JP6366590B2 - Epoxy resin mixture, epoxy resin composition, cured product, and semiconductor device - Google Patents

Description

  The present invention relates to an epoxy resin mixture, an epoxy resin composition, a cured product thereof, and a semiconductor device suitable for electrical and electronic material applications that require heat resistance.

  Epoxy resin compositions are widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. It has been.

However, in recent years, with the development in the electric / electronic field, moisture resistance, adhesion, dielectric properties, low viscosity for high filling of filler (inorganic or organic filler) as well as high purity of resin composition, There is a need for further improvements in various properties such as increased reactivity to shorten the molding cycle. Further, as a structural material, there is a demand for a material that is lightweight and has excellent mechanical properties in applications such as aerospace materials and leisure / sports equipment. Especially in the field of semiconductor encapsulation and substrates (substrate itself or its peripheral materials), as the semiconductor transitions, it becomes increasingly complex with thinning, stacking, systematization, and three-dimensionalization. Required characteristics such as heat resistance and high fluidity are required. In particular, with the expansion of plastic packages to in-vehicle applications, demands for improving heat resistance are becoming more severe. Specifically, heat resistance of 150 ° C. or higher has been required due to an increase in semiconductor driving temperature. In general, the higher the softening point of an epoxy resin, the more the cured product tends to have higher heat resistance. However, on the other hand, since the viscosity tends to increase, it is difficult to use the sealing material. In response to this problem, attempts have been made to provide heat resistance by introducing a naphthalene structure, but there has been a problem that it becomes hard and brittle and the mechanical strength decreases. Moreover, although the polyfunctional epoxy resin is examined, the subject that a flame retardance falls remarkably occurred.
In recent years, resistance to solder shocks such as warping and solder reflow has been extremely demanded. In particular, as the chip becomes thinner, it is required to withstand the temperature of lead-free solder (260 ° C). In order to avoid the stress of this solder shock, the elastic modulus at high temperature is low and the stress is released. There is a need for a sealing material that can be used. Moreover, high heat resistance and low elastic modulus at high temperature are required for suppressing warpage. This low elastic modulus and heat resistance are contradictory properties like flame retardancy, and if the crosslink density is increased in order to increase heat resistance, the elastic modulus at high temperatures will increase, and the stress during reflow cannot be released. This causes problems such as load on the chip and cracks and warpage of the package.

“2008 STRJ Report Semiconductor Roadmap Technical Committee 2008 Report”, Chapter 8, p1-1, [online], March 2009, JEITA Japan Electronics and Information Technology Industries Association Semiconductor Technology Roadmap Specialist Association, [May 30, 2012 search], <http://strj-jeita.elisasp.net/strj/nenjihoukoku-2008.cfm> Nobuyuki Takakura et al., Matsushita Electric Engineering Technical Report Car-related device technology High-temperature operation IC for vehicles, 74, Japan, May 31, 2001, pp. 35-40 Masashi Nakamura, Panasonic Electric Works Technical Report, Technical Trends of Advanced Semiconductor Encapsulation Materials, Vol. 56 No. 4 [Search June 6, 2013] <http://panasonic.co.jp/ptj/pew/564j/pdfs/564_02.pdf> “BGA package warpage analysis” JEITA Japan Electronics and Information Technology Industries Association [searched September 30, 2012] <http://home.jeita.or.jp/ecb/material/No011.html>

One of the properties particularly required for the enhancement of functionality of epoxy resins is the heat resistance of the cured product. Conventionally, the heat resistance of cured epoxy resins has been regarded as important, but as described above, generally, as the heat resistance is increased, it becomes brittle and mechanical strength is deteriorated. Problems such as increase in viscosity, increase in elastic modulus at high temperature (of the cured product) occur at the same time, and it is difficult to satisfy all the characteristics.
Therefore, it has been desired to develop an epoxy resin that can achieve both the heat resistance of the cured product and the characteristics contrary to the heat resistance.
That is, the present invention is excellent in the mechanical strength, flame retardancy, and elastic modulus at high temperature of the cured product, which is a property contrary to the heat resistance while having excellent heat resistance of the cured product. An object of the present invention is to provide an epoxy resin mixture capable of simultaneously satisfying properties such as low resistance, and to provide an epoxy resin composition, a cured product, and a semiconductor device using the epoxy resin mixture.

As a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention.
That is, the present invention

(1)
An epoxy resin mixture containing 60 to 75% (gel permeation chromatography area%) of a compound represented by the following formula (1) and 5 to 30% (same as above) of an epoxidized product of biphenol.

(In the formula, a plurality of G and R are independently present, G represents a glycidyl group, R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. )

(2)
The epoxy resin mixture according to item (1), wherein the softening point is 80 to 100 ° C.
(3)
The epoxy resin mixture according to (1) or (2) above, wherein the ICI melt viscosity (cone plate method) at 150 ° C. is 0.08 to 0.35 Pa · s.
(4)
An epoxy resin composition comprising the epoxy resin mixture according to any one of (1) to (3) and a curing agent.
(5)
An epoxy resin composition comprising the epoxy resin mixture according to any one of (1) to (3) and a curing catalyst.
(6)
Hardened | cured material which hardened | cured the epoxy resin composition of the preceding clause (4) or (5).
(7)
The present invention relates to a semiconductor device obtained by sealing a semiconductor chip using the epoxy resin composition described in the above item (4) or (5).

  The epoxy resin mixture of the present invention has a low viscosity, and the cured product has excellent heat resistance, water absorption characteristics and flame retardancy. Therefore, insulating materials for electrical and electronic parts and laminated boards (printed wiring boards, build-up boards, etc.) ) And CFRP and other composite materials, adhesives, paints and the like.

FIG. 38 shows a 96-Pin QFP lead frame used in Example 22. It is a figure which shows the test piece for test evaluation of the solder crack resistance produced and used in Example 22. FIG.

The epoxy resin mixture of the present invention relates to an epoxy resin mixture containing a compound having a phenolphthalein skeleton derivative structure. The basic skeleton of the compound represented by the formula (1) of the present invention is disclosed in British Patent No. 1158606 (Patent Document 1). According to Patent Document 1, epoxy equivalents per kg is 3.4 (294 g / eq. In terms of current epoxy equivalent), hue is Gardner 8 (40% in methyl glycol), softening point is 66 ° C. (kolfer heater), An epoxy resin having a phenolphthalein skeleton derivative structure having a chlorine content of 2.2% is disclosed. In addition, cured physical properties with DDS (diaminodiphenyl sulfone) are disclosed.
From the above data, the epoxy resin described in Patent Document 1 has a very large amount of chlorine, is unsuitable for use in electronic materials, and is very colored, so it is difficult to use in applications that require color. It is suggested that there is. The epoxy equivalent was 294 g / eq. Is larger than the theoretical value (252.7 g / eq.), And the large amount of chlorine suggests that the epoxy contains many epihalohydrin structures that remain without ring closure. Nevertheless, if such an epoxy ring has not been completed, crosslinking did not proceed well, and curing with a phenol resin, anionic polymerization with a basic catalyst such as imidazole, and cationic polymerization with an onium salt were performed. However, there are many cases where problems arise in the characteristics such as mechanical characteristics and water absorption. Particularly in the case of electronic materials, not only these curings but also amine-based curing is expected to cause corrosion of wiring due to the liberation of chlorine at the time of curing, resulting in a decrease in electrical reliability.
In recent years, in particular, copper wires are increasingly used for bonding a semiconductor chip and a substrate, and such a problem of electrocorrosion is becoming more important and a problem to be solved.
Furthermore, the viscosity of the epoxy resin described in Patent Document 1 increases due to the problem of polarity in the molecule. Furthermore, mechanical strength and adhesion tend to be deteriorated due to the characteristics of the structure, and it has been difficult to develop into applications such as semiconductor sealing materials.

  The present invention is an epoxy resin mixture containing 60 to 75% (gel permeation chromatography area%) of a compound represented by the following formula (1) and 5 to 30% (same as above) of an epoxidized product of biphenol.

(In the formula, a plurality of G and R are independently present, G represents a glycidyl group, R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. )

Here, when the content of the compound represented by the formula (1) exceeds 75%, the crystallinity may be increased or the toughness may be decreased. When the content of the compound represented by the formula (1) is less than 60%, the epoxy ring is not completely closed, and many compounds having no functional group are contained. In addition, many of these compounds that could not be ring-closed often contain chlorine, and as an electronic material application, there is concern about the release of chlorine ions under high-temperature and high-humidity conditions and the resulting corrosion of wiring. Absent.
Most preferred for R is a hydrogen atom. Examples of the alkyl group having 1 to 6 carbon atoms represented by R include alkyl groups having a linear, branched or cyclic structure such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Can be mentioned. Here, R is preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
As a C1-C6 alkoxy group which R shows, the alkoxy group which has linear, branched chain, or cyclic structures, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, is mentioned, for example. Here, R is preferably a methoxy group, an ethoxy group, or a propoxy group, and particularly preferably a methoxy group.

  If the epoxidized product of biphenol exceeds 30%, the heat resistance of the cured product resulting from the structure of the compound represented by the formula (1) cannot be fully utilized, and if it is less than 5%, the viscosity is lowered, the mechanical strength, and the adhesion Less effective in terms of sex. The content of the epoxidized biphenol in the epoxy resin mixture of the present invention is particularly preferably 5 to 25%.

The epoxy equivalent of the epoxy resin mixture of the present invention is usually 1.01 to 1.13 times, preferably 1.02 to 1.10 times the theoretical epoxy equivalent of the phenol skeleton as a raw material. When the ratio is less than 1.01, the epoxy synthesis and purification may be very expensive. When the ratio is more than 1.13, the problem may be caused by the amount of chlorine as described above.
Further, the total chlorine contained in the epoxy resin of the present invention is preferably 5000 ppm or less, more preferably 3000 ppm or less, and particularly preferably 2000 ppm or less. The adverse effect of the chlorine amount is the same as described above. In addition, about chlorine ion and sodium ion, 5 ppm or less is preferable respectively, More preferably, it is 3 ppm or less. Chlorine ions are described above. Needless to say, cations such as sodium ions are also very important factors particularly in power device applications, and contribute to a defective mode when a high voltage is applied.
Here, the theoretical epoxy equivalent indicates an epoxy equivalent calculated when the phenolic hydroxyl group of the phenol compound as a raw material is glycidylated without excess or deficiency.
In addition, specific epoxy equivalent values are preferably 210.0 g / eq. To 280.0 g / eq. When R is all a hydrogen atom, and 220.0 g / eq. To 250.0 g / eq. Particularly preferred. When the epoxy equivalent is within the above range, an epoxy resin excellent in heat resistance and electrical reliability of the cured product can be obtained.

The epoxy resin mixture of the present invention has a resinous form having a softening point. Here, as a softening point, 70-130 degreeC is preferable, More preferably, it is 80-120 degreeC. When all the substituents R are hydrogen atoms, 80-120 degreeC is preferable, More preferably, it is 80-100 degreeC. If the softening point is too low, blocking during storage becomes a problem, and there are many problems such as handling at low temperatures. On the other hand, if the softening point is too high, problems such as poor handling may occur during kneading with other resins.
The melt viscosity is 0.08 to 0.35 Pa · s (ICI melt viscosity 150 ° C. cone plate method), more preferably 0.08 to 0.3 Pa · s, particularly preferably 0.08 to 0.25 Pa · s. It is. When mixing and using inorganic materials (filler etc.), problems, such as poor fluidity, arise.

Hereafter, the manufacturing method of the epoxy resin mixture of this invention is described.
In the epoxy resin mixture of the present invention, the compound represented by the formula (1) and the epoxidized product of biphenol may be mixed at a predetermined ratio, but the phenol compound (DPPI) represented by the following formula (4) It may be synthesized by the reaction of a mixture of bisphenol and biphenol with epihalohydrin.

(Wherein R has the same meaning as R in formula (1)).

  The phenol compound (DPPI) represented by the formula (4) is synthesized from a phenolphthalein derivative and an aminobenzene derivative (for example, Japanese Patent Application Laid-Open No. 2005-290378).

It is known that phenolphthalein derivatives can be synthesized with phthalic acid and various corresponding phenols. If the phenols used are phenol, phenolphthalein is obtained, and if cresols, cresolphthalein is obtained. .
Here, examples of the various phenols include phenol, cresol, ethylphenol, propylphenol, xylenol, and methylbutylphenol. In the present invention, the use of phenolphthalein is preferred.
Moreover, as a phenolphthalein derivative obtained by the said synthesis | combination, the structure represented by following formula (2) is mentioned, for example.

(Wherein R has the same meaning as R in formula (1)).

  Examples of the aminobenzene derivative include those represented by the following formula (3).

(Wherein R has the same meaning as R in formula (1)).

The amount of residual phenolphthalein derivative in the phenol compound (DPPI) is preferably 2% or less, more preferably 1% or less, still more preferably 0.5% or less, and particularly preferably 0.1% or less (high performance liquid chromatography). Measured graphically). When this phenolphthalein derivative remains, coloring tends to increase during the reaction. The same applies to aminobenzene derivatives. Further, the remaining iron content (ICP emission analysis) is one of the factors caused by coloring. The residual iron content is preferably 100 ppm or less, more preferably 50 ppm or less, and particularly preferably 10 ppm or less. The phenol compound (DPPI) as the main body is desired to have a purity of 95% or more, more preferably 98% or more.
The amount of residual phenolphthalein derivative can be adjusted by purification of DPPI (washing, recrystallization, reprecipitation, etc.).
In addition, the DPPI used in the present invention preferably has a softening point of 100 ° C. or higher. When the softening point is 100 ° C. or higher, it contributes to the heat resistance of the resulting epoxy resin mixture. In particular, the DPPI used in the present invention preferably has a melting point, and the melting point is preferably 200 ° C. or higher.

  The biphenol used in the present invention has a structure represented by the following formula (5).

(In Formula (5), a plurality of R _{1 s} exist independently, each representing a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and k represents an integer of 1 to 4)
Examples of the biphenol having the structure represented by the formula (5) include 2,2′-form, 2,4′-form, 4,4′-form, etc., among which 4,4′-form biphenol is preferable.
A purity of 95% or more can be suitably used.

  Below, the method of obtaining the epoxy resin mixture of this invention by reaction with the mixture of a phenolic compound (DPPI) and biphenol, and epihalohydrin is described. Hereinafter, a mixture of a phenol compound (DPPI) and biphenol is referred to as a phenol mixture used in the present invention.

  The phenol mixture used in the present invention may be a mixture of a phenol compound (DPPI) and a biphenol, but the mixing ratio of the phenol compound (DPPI) and the biphenol is a molar ratio, and the phenol compound (DPPI): biphenol is 5: 5-9: 1 is preferable, and 6: 4-8: 2 is more preferable. Moreover, it is preferable that phenol compound (DPPI): biphenol is 6: 4-9: 1 by weight ratio, and it is more preferable that it is 7: 3-8.6: 1.4.

The epihalohydrin used in the method for synthesizing the epoxy resin mixture of the present invention is preferably epichlorohydrin which is easily available industrially. The usage-amount of epihalohydrin is 3.0-15 mol normally with respect to 1 mol of hydroxyl groups of the phenol mixture used by this invention, Preferably it is 3.0-10 mol, More preferably, it is 3.5-8.5 mol, Preferably it is 4.0-6.0 mol.
If the amount is less than 3.0 mol, the epoxy equivalent may increase, and the workability of the resulting epoxy resin may deteriorate. If it exceeds 15 moles, the amount of solvent becomes large, which is not preferable in terms of waste and productivity.

In the above reaction, an alkali metal hydroxide can be used. Examples of the alkali metal hydroxide that can be used in the above reaction include sodium hydroxide, potassium hydroxide and the like, and a solid substance may be used, or an aqueous solution thereof may be used. From the viewpoint of solubility and handling, it is preferable to use a solid material molded into a flake shape.
The amount of the alkali metal hydroxide used is usually 0.90 to 1.5 mol, preferably 0.95 to 1.25 mol, more preferably 1 mol with respect to 1 mol of the hydroxyl group of the phenol mixture used in the present invention as a raw material. Is 0.99 to 1.15 mol.

  In order to accelerate the reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride may be added as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of hydroxyl group in the raw material phenol mixture.

In this reaction, it is preferable to use a nonpolar proton solvent (dimethyl sulfoxide, dioxane, dimethylimidazolidinone, etc.) or an alcohol having 1 to 5 carbon atoms in addition to the epihalohydrin. Examples of the alcohol having 1 to 5 carbon atoms include alcohols such as methanol, ethanol and isopropyl alcohol. The usage-amount of a nonpolar protic solvent or a C1-C5 alcohol is 2-50 weight% normally with respect to the usage-amount of an epihalohydrin, Preferably it is 4-25 weight%. Moreover, epoxidation may be performed while controlling the moisture in the system by a technique such as azeotropic dehydration.
When there is a lot of moisture in the system, the electrical reliability of the cured product of the obtained epoxy resin mixture may be deteriorated, and it is preferable to synthesize by controlling the moisture to 5% or less. Further, when an epoxy resin is obtained using a nonpolar proton solvent, a cured product of the epoxy resin having excellent electrical reliability can be obtained, and therefore a nonpolar proton solvent can be preferably used.

The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. In particular, in the present invention, 60 ° C. or higher is preferable for higher-purity epoxidation, and reaction under conditions close to reflux conditions is particularly preferable. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours, particularly preferably 1 to 3 hours. If the reaction time is short, the reaction cannot proceed, and if the reaction time is long, a by-product may be formed.
After the reaction product of these epoxidation reactions is washed with water or without washing with water, the epihalohydrin, the solvent and the like are removed under heating and reduced pressure. Further, in order to obtain an epoxy resin mixture with less hydrolyzable halogen, the recovered epoxidized product is a ketone compound having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.). It can be dissolved as a solvent and reacted by adding an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide to ensure ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, based on 1 mol of the hydroxyl group of the phenol mixture used in the present invention used for epoxidation. It is. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

  After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin mixture of the present invention.

  The epoxy resin mixture of the present invention exhibits an amorphous resinous or semicrystalline resinous form. In the epoxy resin mixture of the present invention, a semi-crystalline resin is preferable because it has low viscosity and high mechanical strength and adhesion.

In the epoxy resin mixture of the present invention, the compound represented by the formula (1) and bisglycidyloxybiphenyl (however, when the aromatic ring has a substituent, the number of substituents is 4 or less and the number of carbons is 4 or less. In the reaction under the preferable conditions as described above, there is also a structure in which the phenol resin structure represented by the above formula ( 4 ) and the biphenol structure are connected by epihalohydrin. Therefore, by epoxidizing the phenol mixture at the same time, the above structure is formed and the viscosity tends to be relatively low, which is preferable in improving the fluidity of the present invention.
Compared to the case of epoxidizing only biphenol, the epoxy resin mixture obtained by such a method has low crystallinity and can be easily purified to obtain an epoxy resin mixture with a small amount of residual chlorine. Becomes easy.

  The epoxy resin composition of the present invention contains the epoxy resin mixture of the present invention and a curing catalyst (curing accelerator) and / or a curing agent. Moreover, it is preferable to contain another epoxy resin as an arbitrary component.

  The epoxy resin composition of the present invention may contain other types of epoxy resins in addition to the epoxy resin mixture of the present invention. The proportion of the epoxy resin mixture of the present invention in the total epoxy resin is preferably 20% by weight or more, more preferably 30% by weight or more, and particularly preferably 40% by weight or more.

  Other epoxy resins that can be used in combination with the epoxy resin mixture of the present invention include novolac type epoxy resins, bisphenol type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol aralkyl type epoxy resins and the like. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetaldehyde Non, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene or 1,4-bis (methoxymethyl) benzene and their modified products, halogenated bisphenols such as tetrabromobisphenol A, and alcohols , Cycloaliphatic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, silsesquioxane epoxy resin (chain structure, cyclic structure, ladder structure, or a mixed structure of at least two of these) Has glycidyl group and / or epoxycyclohexane structure Epoxy resin) solid or liquid epoxy resins and the like that, but not limited thereto.

Specific examples of the curing catalyst that can be used in the present invention include amine compounds such as triethylamine, tripropylamine, and tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, and imidazole. , Triazole, tetrazole, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2 -Methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1 ')) Ethyl-s Triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl, 4-methylimidazole (1 ′)) ethyl -S-triazine, 2,4-diamino-6 (2'-methylimidazole (1 ')) ethyl-s-triazine-isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenyl Such as imidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, etc. Various heterocyclic compounds, and these heterocyclic compounds and phthalic acid, isophthalic acid, terephthalic acid, Mellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, salts with polyvalent carboxylic acids such as succinic acid, amides such as dicyandiamide, 1,8-diaza-bicyclo (5.4.0) undecene-7, etc. Diaza compounds and salts thereof such as tetraphenylborate and phenol novolak, salts with the above polyvalent carboxylic acids or phosphinic acids, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide , Trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide Ammonium salts such as droxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium acetate, triphenylphosphine, tri (toluyl) phosphine, tetraphenylphosphonium bromide, tetraphenyl Phosphines such as phosphonium tetraphenylborate, phosphonium compounds, phenols such as 2,4,6-trisaminomethylphenol, amine adducts, carboxylic acid metal salts (2-ethylhexanoic acid, stearic acid, behenic acid, mytilic acid, etc. Zinc salts, tin salts, zirconium salts), phosphate ester metals (zinc salts such as octyl phosphate and stearyl phosphate), alkoxy metal salts (trib Le aluminum, tetrapropyl zirconium, etc.), acetylacetonates (acetylacetone zirconium chelate, a metal compound such as acetylacetone titanium chelate) and the like, can be mentioned. In the present invention, phosphonium salts, ammonium salts, and metal compounds are particularly preferable in terms of coloring at the time of curing and changes thereof. When a quaternary salt is used, the salt with halogen may leave halogen in the cured product.
The curing accelerator is used in an amount of 0.01 to 5.0 parts by weight with respect to the epoxy resin 100 as necessary.

The epoxy resin composition of the present invention preferably contains a curing agent. Examples thereof include amine compounds, acid anhydride compounds, amide compounds, phenol resins, carboxylic acid compounds, and the like. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and nitrogen-containing compounds such as polyamide resins synthesized from linolenic acid and ethylenediamine (amine, Amide compounds); phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methyl hexahydro Phthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, Cyclohe Acid anhydrides such as sun-1,3,4-tricarboxylic acid-3,4-anhydride; carboxylic acid resins obtained by addition reaction of various alcohols, carbinol-modified silicones and the above-mentioned acid anhydrides; bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [1,1′-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol) , Naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphth ) And formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1 Polycondensation with '-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4'-bis (chloromethyl) benzene or 1,4'-bis (methoxymethyl) benzene And modified products thereof, phenol resins such as halogenated bisphenols such as tetrabromobisphenol A, condensates of terpenes and phenols; imidazole, trifluoroborane-amine complexes, guanidine derivative compounds, etc. Limited to is not. These may be used alone or in combination of two or more.
In the present invention, the above-described phenol resin is preferable because it is used particularly for electronic materials.

  As for the usage-amount of the hardening | curing agent in the epoxy resin composition of this invention, 0.7-1.2 equivalent is preferable with respect to 1 equivalent of epoxy groups of an epoxy resin. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.

  The use of cyanate ester compounds as other components is preferred. The cyanate ester compound can be made into a heat-resistant cured product having a higher crosslinking density by a reaction with an epoxy resin in addition to a curing reaction alone. Examples of the cyanate ester resin include 2,2-bis (4-cyanatephenyl) propane, bis (3,5-dimethyl-4-cyanatephenyl) methane, 2,2-bis (4-cyanatephenyl) ethane, These derivatives, aromatic cyanate ester compounds, etc. are mentioned. Further, for example, as described in the above-mentioned curing agent, synthesis can be performed by reaction of various phenol resins with hydrocyanic acid or salts thereof. In the present invention, those having a structure having no methylene structure at the benzyl position in the molecule, such as 2,2-bis (4-cyanatephenyl) propane and derivatives thereof (partially polymerized products, etc.) are particularly preferred. You may use independently and may use 2 or more types together.

  The epoxy resin composition of the present invention may contain a phosphorus-containing compound as a flame retardant component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric acid esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; epoxy resin and active hydrogen of the phosphanes A phosphorus-containing product obtained by reacting with Poxy compounds, red phosphorus and the like can be mentioned, and phosphoric esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. The phosphorus-containing compound content is preferably phosphorus-containing compound / total epoxy resin = 0.1 to 0.6 (weight ratio). If it is less than 0.1, the flame retardancy is insufficient, and if it exceeds 0.6, it may adversely affect the hygroscopicity and dielectric properties of the cured product.

  Furthermore, a binder resin can also be mix | blended with the epoxy resin composition of this invention as needed. Examples of the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. However, it is not limited to these. The blending amount of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 100 parts by weight in total of the epoxy resin and the curing agent, 0.05 to 20 parts by weight is used as necessary.

  If necessary, an inorganic filler can be added to the epoxy resin composition of the present invention. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These fillers may be used alone or in combination of two or more. In the epoxy resin composition of the present invention, the content of these inorganic fillers is generally 0 to 95% by weight, although it depends on the use. It is preferable to use properly depending on the shape of the package in the range of 50 to 95% by weight, particularly preferably 65 to 95% by weight. Furthermore, the epoxy resin composition of the present invention includes an antioxidant, a light stabilizer, a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate and calcium stearate, various compounding agents such as pigments, Various thermosetting resins can be added. Particularly for the coupling agent, it is preferable to add a coupling material having an epoxy group or a coupling agent having a thiol.

  The epoxy resin composition of this invention is obtained by mixing each component uniformly. The epoxy resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, an epoxy resin component, a curing agent component, and a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, a compounding agent, and the like, if necessary, uniformly using an extruder, kneader, roll, planetary mixer, etc. Mix thoroughly until the epoxy resin composition is obtained. If the resulting epoxy resin composition is liquid, the substrate is impregnated with a potting or casting, or poured into a mold and cast. Or cured by heating. When the obtained epoxy resin composition is solid, it is molded using a cast after casting or a transfer molding machine, and further cured by heating. The curing temperature and time are 80 to 200 ° C. and 2 to 10 hours. As a curing method, it is possible to cure at a high temperature at a stretch, but it is preferable to increase the temperature stepwise to advance the curing reaction. Specifically, initial curing is performed between 80 and 150 ° C., and post-curing is performed between 100 and 200 ° C. As the curing stage, the temperature is preferably divided into 2 to 8 stages, more preferably 2 to 4 stages.

  Further, the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. to obtain a curable resin composition varnish, which contains glass fiber, -Making the cured product of the epoxy resin composition of the present invention by hot press molding a prepreg obtained by impregnating a base material such as bon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating. Can do. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the epoxy resin composition of the present invention and the solvent.

  Moreover, the epoxy resin composition of this invention can also be used as a film type sealing composition. When obtaining such a film-type resin composition, the curable resin composition of the present invention is coated on the release film with the varnish, the solvent is removed under heating, and a B-stage adhesive is formed. Get. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like, and a batch film sealing of an optical semiconductor.

  Specific applications of these compositions include adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (including printed circuit boards, wire coatings, sealing materials, Sealants, cyanate resin compositions for substrates) and resist curing agents include additives to other resins such as acrylic ester resins. In the present invention. The use for the insulating material for electronic materials (a sealing material including a printed circuit board, an electric wire coating | cover etc., a sealing material, cyanate resin composition for a board | substrate) is especially preferable.

  Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

  As sealing agent and substrate, potting sealing for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, etc., dipping, transfer mold sealing, ICs, LSIs for COB, COF, TAB, etc. Examples include underfill for flip chip, sealing (including reinforcing underfill) and package substrate when mounting IC packages such as QFP, BGA, and CSP. Moreover, it is suitable also for the board | substrate use as which a functionality, such as a network board | substrate and a module board, is calculated | required.

The epoxy resin composition of the present invention is particularly preferably used for a semiconductor device.
The semiconductor device is a group of IC packages mentioned above.
The semiconductor device of the present invention can be obtained by sealing a silicon chip installed on a package substrate or a support such as a die with the epoxy resin composition of the present invention. The molding temperature and molding method are as described above.

EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples.
The various analysis methods used in the examples are described below.
Epoxy equivalent: Conforms to JIS K 7236 (ISO 3001)
ICI melt viscosity: compliant with JIS K 7117-2 (ISO 3219) Softening point: compliant with JIS K 7234 Total chlorine: compliant with JIS K 7243-3 (ISO 21672-3) Chlorine ion: JIS K 7243-1 (ISO 21672) -1) GPC:
Column (Shodex KF-603, KF-602x2, KF-601x2)
The coupled eluent is tetrahydrofuran. The flow rate is 0.5 ml / min.
Column temperature is 40 ° C
Detection: RI (differential refraction detector)
Glass transition point (Tg):
TMA thermomechanical measuring device manufactured by TA-instruments, Q400EM
Measurement temperature range: 40 ° C to 280 ° C
Temperature increase rate: 2 ° C / min

Example 1
In a 1 L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer, phenol compound (DPPI1) (compound ( 4 ) in which all substituents R are hydrogen atoms SABIC PPPBP) 137.7 parts, biphenol 27 .9 parts, 555 parts of epichlorohydrin and 139 parts of dimethyl sulfoxide were added, and the temperature of the water bath was raised to 50 ° C. When the internal temperature exceeded 45 ° C., 44 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C. for 2 hours and at 70 ° C. for 1 hour. After completion of the reaction, washing was performed, and excess solvent such as epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 ° C. using a rotary evaporator. To the residue is added 505 parts of methyl isobutyl ketone and dissolved, and after removing sodium chloride and the like produced by washing with water, the organic layer is heated to 70 ° C., and 20 parts of 30 wt% aqueous sodium hydroxide solution is added with stirring. After reacting for 1 hour, washing is performed until the washing water becomes neutral, and the resulting solution is subjected to the present invention by distilling off methyl isobutyl ketone and the like under reduced pressure at 180 ° C. using a rotary evaporator. 210 parts of an epoxy resin mixture (EP1) was obtained. The epoxy equivalent of the obtained epoxy resin mixture was 226 g / eq. The softening point was 92 ° C., the ICI melt viscosity was 0.15 Pa · s (150 ° C.), the total chlorine content was 505 ppm, the hydrolyzable chlorine was 480 ppm, the chlorine ions were 0.1 ppm, and the sodium ions were 0.1 ppm. The compound of the formula (1) was 72 area% (GPC), and the epoxidized biphenol was 16 area% (GPC). Furthermore, the compound (a) of the formula (1) and the epoxidized product (b) of biphenol are (a) / (b) = 4.5 by weight ratio and 2.64 by mole ratio. Between compounds of the formula for other structures (4), biphenol each other, the equation (4) and biphenol was comprise a compound bound mixed.

Synthesis example 1
Stirrer, reflux condenser, phenol compound four-necked flask 1L equipped with a stirrer (DPPI1) (the compound of the substituents R are all hydrogen atoms in the formula (4) SABIC PPPBP) 295 parts of epichlorohydrin 971 parts and 165 parts of dimethyl sulfoxide were added, and the water bath was heated to 45 ° C. When the internal temperature exceeded 40 ° C., 66 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C. for 2 hours and at 70 ° C. for 1 hour. After completion of the reaction, washing was performed, and excess solvent such as epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 ° C. using a rotary evaporator. 760 parts of methyl isobutyl ketone was added to the residue and dissolved, and after removing sodium chloride and the like produced by washing with water, the organic layer was heated to 70 ° C. and 30 parts by weight of 30 wt% sodium hydroxide aqueous solution was added with stirring. After reacting for 1 hour, washing is carried out until the washing water becomes neutral, and the obtained solution is subjected to the above formula by distilling off methyl isobutyl ketone and the like under reduced pressure at 180 ° C. using a rotary evaporator. 353 parts of epoxy resin (EP4) which has a structure represented by (1) was obtained. The epoxy equivalent of the obtained epoxy resin is 267 g / eq. The softening point was 99 ° C., the ICI melt viscosity was 0.91 Pa · s (150 ° C.), the total chlorine amount was 540 ppm, the hydrolyzable chlorine was 430 ppm, the chlorine ions were 0.1 ppm, and the sodium ions were 0.1 ppm. The compound having the structure of the formula (1) contained 88 area% (GPC), and the remaining 12 area% contained a compound in which the compounds having the structure of the formula ( 4 ) were bonded to each other.

Example 2 and Comparative Examples 1 and 2
Epoxy resin mixture (EP1) of the present invention obtained in Example 1 and comparative epoxy resin (EP2: phenol-biphenylene aralkyl type epoxy resin, NC-3000, EP3; trisphenolmethane type epoxy resin manufactured by Nippon Kayaku Co., Ltd. EPPN-502H manufactured by Nippon Kayaku Co., Ltd., and epoxy resin and curing agent (phenol novolak (M-1 made by Meiwa Kasei Kogyo Co., Ltd.) or phenol aralkyl resin (Mitsui Chemicals Co., Ltd., Millex XLC-3L) )) At equal equivalents, and a curing catalyst (curing accelerator, triphenylphosphine (TPP manufactured by Hokuko Chemical Co., Ltd.)) and a filler (fused silica, manufactured by Ashimori MSR-2122, if necessary)% in the table Is a proportion of the total epoxy resin composition) and mixed and kneaded uniformly using a mixing roll. To obtain a epoxy resin composition for sealing. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy resin composition of the present invention and the comparative composition were transfer molded (175 ° C. × 60 seconds), and after demolding, cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours, a test piece for evaluation Got.
In addition, the physical property of hardened | cured material was measured in the following ways. Also, depending on the evaluation items of the physical properties of the cured product, the type of curing agent to be used is as shown in Table 1 below. The amount of curing accelerator used is 1 for the weight of the epoxy resin in the sample used for evaluation of heat resistance and shrinkage. % And 2% with respect to the weight of the epoxy resin in the sample used for evaluation of flame retardancy.

<Curing shrinkage>
Conforms to JISK-6911 (mold shrinkage) <Flame retardance test>
-Determination of flame retardancy: performed in accordance with UL94. However, the test was conducted with a sample size of 12.5 mm wide × 150 mm long and a thickness of 0.8 mm.
・ Afterflame time: Total afterflame time after 10 times contact with 5 samples

  The cured product of Comparative Example 1 is excellent in flame retardancy but has low heat resistance. In the cured product of Comparative Example 2, the heat resistance is high but there is no flame retardancy, and the result is that the flame retardant test completely burns, whereas the cured product of the epoxy resin composition of the present invention is high. Both heat resistance and flame retardancy can be achieved. It can also be seen that the shrinkage during curing is good and the dimensional stability is excellent.

Example 3 and Comparative Example 3
Using the epoxy resin mixture (EP1) of the present invention obtained in Example 1 and the comparative epoxy resin (EP4) obtained in Synthesis Example 1, an epoxy resin and a curing agent (phenol novolak (Maywa Kasei Kogyo Co., Ltd.) ) H-1) or phenol aralkyl resin (Mitsui Chemicals Co., Ltd. Milex XLC-3L)) is blended in equal equivalents, and a curing catalyst (curing accelerator, triphenylphosphine (Hokuko Chemical Co., Ltd., TPP)) And filler (fused silica, manufactured by Ashimori MSR-2122, the filler amount% in the table is a ratio with respect to the whole epoxy resin) as necessary, and uniformly mixed and kneaded using a mixing roll, and an epoxy resin composition for sealing Got. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy resin composition of the present invention and the comparative composition were transfer molded (175 ° C. × 60 seconds), and after demolding, cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours, a test piece for evaluation Got.
In addition, the physical property of hardened | cured material was measured in the following ways. In addition, depending on the evaluation items of the physical properties of the cured product, the type of curing agent to be used is as shown in Table 2 below, and the amount of curing accelerator used is the weight of the epoxy resin in the sample used for the evaluation of heat resistance, mechanical strength and adhesion. 1% relative to the weight of the epoxy resin in the sample used for evaluation of flame retardancy.

<TMA measurement conditions>
・ Thermo-mechanical measuring device, TA-instruments, Q400EM
-Measurement temperature range: 40 ° C-280 ° C
・ Temperature increase rate: 2 ° C./min <bending test>
-According to JIS K 6911 The test was performed at room temperature and 120 ° C.
<Peel strength>
180 ° C peel test JIS K-6854-2 compliant Use of rolled copper foil <Flame retardance test>
-Determination of flame retardancy: performed in accordance with UL94. However, the test was conducted with a sample size of 12.5 mm wide × 150 mm long and a thickness of 0.8 mm.
・ Afterflame time: Total afterflame time after 10 times contact with 5 samples

  The epoxy resin composition of the present invention has a very low melt viscosity, and the cured product maintains the heat resistance derived from the structure of the formula (1). Furthermore, since the after flame time is shortened in flame retardancy, it is clear that the flame retardancy is improved, and the bending strength and peel strength are better than those of the cured epoxy resin composition.

Synthesis example 2
Stirrer, reflux condenser, phenol compounds in a flask equipped with a stirring device (DPPI1) (Formula (substituent R are all compounds SABIC PPPB P of the hydrogen atoms in 4)) 256 parts, 971 parts of epichlorohydrin, benzyl 3 parts of trimethylammonium chloride was added and the water bath was heated to 70 ° C. To this, 100 parts of a 49% aqueous sodium hydroxide solution was added dropwise over 90 minutes, followed by further reaction at 70 ° C. for 4 hours. After completion of the reaction, washing with water was carried out, and an epoxy resin (EP5) having a structure represented by the above formula (1) was obtained by distilling off excess epichlorohydrin and the like from the oil layer under reduced pressure at 140 ° C. using a rotary evaporator. 290 parts were obtained. The epoxy resin having the structure represented by the formula (1) obtained has an epoxy equivalent of 297 g / eq. The softening point was 95 ° C., the ICI melt viscosity was 0.70 Pa · s (150 ° C.), the total chlorine content was 10450 ppm, and the hydrolyzable chlorine was 9700 ppm.

Example 4 and Comparative Example 4
Using the epoxy resin mixture (EP1) of the present invention obtained in Example 1 and the comparative epoxy resin (EP5) obtained in Synthesis Example 2, an epoxy resin and a curing agent (phenol novolak (Maywa Kasei Kogyo Co., Ltd.) H-1)) is blended in an equivalent amount, and 1% of triphenylphosphine (TPP manufactured by Hokuko Chemical Co., Ltd.) is added as a curing catalyst (curing accelerator) with respect to the weight of the epoxy resin, and a mixing roll is used. Were mixed and kneaded uniformly to obtain an epoxy resin composition for sealing. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy resin composition was transfer-molded (175 ° C. × 60 seconds), and after demolding, cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours to obtain a test piece for evaluation.
In addition, the physical property of hardened | cured material was measured in the following ways.

<TMA measurement conditions>
・ Thermo-mechanical measuring device, TA-instruments, Q400EM
-Measurement temperature range: 40 ° C-280 ° C
・ Temperature increase rate: 2 ℃ / min

  The epoxy resin composition of the present invention has a significantly lower viscosity than the conventionally known epoxy resin compositions, and it was confirmed that the cured product was excellent in heat resistance.

Example 5
100 parts of biphenol, 971 parts of epichlorohydrin and 97 parts of methanol were added to a flask equipped with a stirrer, a reflux condenser, and a stirrer, and the temperature of the water bath was raised to 70 ° C. After 41 parts of flaky sodium hydroxide was added in portions over 90 minutes, the reaction was further carried out at 70 ° C. for 1 hour. After the reaction, a mixture of the precipitated epoxy resin and sodium chloride was filtered off from the solvents. By washing 5 times with 200 parts of warm water of 70 ° C. and drying, 121 parts of biphenol type epoxy resin (EP7) represented by the above formula (5) was obtained.
The obtained epoxy resin (EP7) and the epoxy resin (EP4) obtained in Synthesis Example 1 were added to 300 parts of tetrahydrofuran at a ratio of 20 parts and 80 parts, respectively, and tetrahydrofuran was added as it was at 180 ° C. under reduced pressure using a rotary evaporator. Was distilled off to obtain an epoxy resin mixture (EP8) of the present invention. The obtained epoxy resin mixture (EP8) was semi-crystalline and its epoxy equivalent was 247 g / eq. The softening point was 95 ° C., the ICI melt viscosity was 0.18 Pa · s (150 ° C.), the total chlorine content was 1820 ppm, and the hydrolyzable chlorine was 1670 ppm.

Examples 6 and 7
Using the epoxy resin mixture (EP1) obtained in Example 1 and the epoxy resin (EP8) obtained in Example 5, an epoxy resin and a curing agent (phenol aralkyl resin (KAYAHARD manufactured by Nippon Kayaku Co., Ltd.) GPH-65)) with equal equivalents, curing catalyst (curing accelerator, triphenylphosphine (TPP manufactured by Hokuko Chemical Co., Ltd. 2% added to the weight of the epoxy resin) and filler (melting) as required Silica MSM-2122, filler amount% in the table is a ratio with respect to the whole epoxy resin composition), and mixed and kneaded uniformly using a mixing roll to obtain an epoxy resin composition for sealing. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy resin composition was transfer-molded (175 ° C. × 60 seconds), and after demolding, cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours to obtain a test piece for evaluation.
In addition, the physical property of hardened | cured material was measured in the following ways.

<TMA measurement conditions>
・ Thermo-mechanical measuring device, TA-instruments, Q400EM
-Measurement temperature range: 40 ° C-280 ° C
・ Temperature increase rate: 2 ° C./min <flame retardant test>
-Determination of flame retardancy: performed in accordance with UL94. However, the test was conducted with a sample size of 12.5 mm wide × 150 mm long and a thickness of 0.8 mm.
・ Afterflame time: Total afterflame time after 10 times contact with 5 samples

  It is clear that the cured product of the epoxy resin composition of the present invention has improved flame retardancy and good heat resistance.

  From the above results, it is clear that the epoxy resin mixture of the present invention is excellent in fluidity, and that the cured product is particularly excellent in flame retardancy and heat resistance, and a semiconductor encapsulant that requires high functionality, It can be seen that it is useful for thin film substrate materials (including interlayer insulating films) that require high filler filling.

Example 8
A 1-L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer is charged with a phenol compound (based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content <5 ppm, melting point 289-290 ° C.) 137.7 parts, 27.9 parts of biphenol, 470 parts of epichlorohydrin and 120 parts of dimethyl sulfoxide were added, and the temperature of the water bath was raised to 50 ° C. When the internal temperature exceeded 45 ° C., 44 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C. for 2 hours and at 70 ° C. for 1 hour. After completion of the reaction, excess solvent such as epichlorohydrin was distilled off under reduced pressure at 140 ° C. using a rotary evaporator. 505 parts of methyl isobutyl ketone is added to the residue and dissolved, and after removing sodium chloride and the like produced by washing with water, the organic layer is heated to 70 ° C., and 10 parts of 30 wt% aqueous sodium hydroxide solution is added with stirring. After reacting for 1 hour, washing is performed until the washing water becomes neutral, and the resulting solution is subjected to the present invention by distilling off methyl isobutyl ketone and the like under reduced pressure at 180 ° C. using a rotary evaporator. 205 parts of an epoxy resin mixture (EP13) was obtained. The epoxy equivalent of the obtained epoxy resin mixture was 236 g / eq. The softening point was 92 ° C., the ICI melt viscosity was 0.15 Pa · s (150 ° C.), the total chlorine content was 309 ppm, the hydrolyzable chlorine was 278 ppm, the chlorine ions were 0.1 ppm, and the sodium ions were 0.1 ppm. The content ratio of the compound of the formula (1) was 65 area% (GPC), and the content ratio of the epoxidized biphenol was 15 area% (GPC). Furthermore, the compound (a) of the above formula (1) and the epoxidized product (b) of biphenol are (a) / (b) = 4.3 by weight ratio and 2.55 by mole ratio. About other structures, the compound of the said Formula (1), biphenols, and the compound which the compound of the said Formula (1) and biphenol mixed and couple | bonded were included.

Example 9
A 1-L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer is charged with a phenol compound (based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content <5 ppm, melting point 289-290 ° C.) 125.7 parts, biphenol 33.6 parts, epichlorohydrin 463 parts, dimethyl sulfoxide 116 parts were added, and the temperature of the water bath was raised to 50 ° C. When the internal temperature exceeded 45 ° C., 44 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C. for 2 hours and at 70 ° C. for 1 hour. After completion of the reaction, excess solvent such as epichlorohydrin was distilled off under reduced pressure at 140 ° C. using a rotary evaporator. 505 parts of methyl isobutyl ketone is added to the residue and dissolved, and after removing sodium chloride and the like produced by washing with water, the organic layer is heated to 70 ° C., and 10 parts of 30 wt% aqueous sodium hydroxide solution is added with stirring. After reacting for 1 hour, washing is performed until the washing water becomes neutral, and the resulting solution is subjected to the present invention by distilling off methyl isobutyl ketone and the like under reduced pressure at 180 ° C. using a rotary evaporator. 195 parts of an epoxy resin mixture (EP14) was obtained. The epoxy equivalent of the obtained epoxy resin mixture was 225 g / eq. The softening point was 81 ° C., ICI melt viscosity 0.09 Pa · s (150 ° C.), total chlorine amount 377 ppm, hydrolyzable chlorine 281 ppm, chlorine ion 0.1 ppm, sodium ion 0.1 ppm. The content ratio of the compound of the formula (1) was 63 area% (GPC), and the content ratio of the epoxidized biphenol was 19 area% (GPC). Further, the compound (a) of the formula (1) and the epoxidized product (b) of biphenol are (a) / (b) = 3.3 in weight ratio and 1.96 in molar ratio. About other structures, the compound of the said Formula (1), biphenols, and the compound which the compound of the said Formula (1) and biphenol mixed and couple | bonded were included.

Example 10
A 1-L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer is charged with a phenol compound (based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content <5 ppm, melting point 289-290 ° C.) 151.5 parts, biphenol 21.4 parts, epichlorohydrin 463 parts, dimethyl sulfoxide 116 parts were added, and the temperature of the water bath was raised to 50 ° C. When the internal temperature exceeded 45 ° C., 44 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C. for 2 hours and at 70 ° C. for 1 hour. After completion of the reaction, excess solvent such as epichlorohydrin was distilled off under reduced pressure at 140 ° C. using a rotary evaporator. 505 parts of methyl isobutyl ketone is added to the residue and dissolved, and after removing sodium chloride and the like produced by washing with water, the organic layer is heated to 70 ° C., and 10 parts of 30 wt% aqueous sodium hydroxide solution is added with stirring. After reacting for 1 hour, washing is performed until the washing water becomes neutral, and the resulting solution is subjected to the present invention by distilling off methyl isobutyl ketone and the like under reduced pressure at 180 ° C. using a rotary evaporator. 210 parts of an epoxy resin mixture (EP15) was obtained. The epoxy equivalent of the obtained epoxy resin mixture was 248 g / eq. The softening point was 83 ° C., the ICI melt viscosity was 0.31 Pa · s (150 ° C.), the total chlorine content was 410 ppm, the hydrolyzable chlorine was 299 ppm, the chlorine ions were 0.1 ppm, and the sodium ions were 0.1 ppm. The content of the compound of the formula (1) was 72 area% (GPC), and the content of the epoxidized biphenol was 12 area% (GPC). Furthermore, the compound (a) of the formula (1) and the epoxidized product (b) of biphenol are (a) / (b) = 6.0 by weight ratio and 3.56 by mole ratio. About other structures, the compound of the said Formula (1), biphenols, and the compound which the compound of the said Formula (1) and biphenol mixed and couple | bonded were included.

Examples 11-13 and Comparative Examples 8-10
Epoxy resin mixture (EP13, 14, 15) obtained in Examples 8-10, comparative epoxy resin EP10-12 (EP10: Nippon Kayaku Orthocresol Novolac Epoxy Resin EOCN-1020-70, EP11: Mitsubishi Chemical Use biphenyl type epoxy resin YX-4000H, EP12: Nippon Kayaku biphenyl aralkyl epoxy resin NC-3000), and mix epoxy resin and curing agent (phenol novolac: H-1 made by Meiwa Kasei Kogyo Co.) Then, 1% of triphenylphosphine as a curing accelerator was added to the weight of the epoxy resin, and the mixture was uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition for sealing. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy resin composition was transfer-molded (175 ° C. × 60 seconds), and after demolding, cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours to obtain a test piece for evaluation.
In addition, the physical property of hardened | cured material was measured in the following ways.

<Elastic modulus and heat resistance (DMA)>
Dynamic viscoelasticity measuring device: TA-instruments, DMA-2980
Measurement temperature range: -30 to 280 ° C
Temperature rate: 2 ° C./min Test piece size: 5 mm × 50 mm cut out (thickness is about 800 μm)
Tg: Tan-δ peak point was defined as Tg.

  From Table 5, the cured product of the epoxy resin composition of the present invention was measured by the same DMA even though it had higher heat resistance than the cured product of the conventionally used epoxy resin composition. It can be seen that the elastic modulus at 250 ° C. is greatly reduced.

Examples 14 to 16 and Comparative Example 11
In Examples 11 to 13 and Comparative Example 10, the same operation was performed except that the curing agent was changed to biphenyl type phenol aralkyl resin (KAYAHARD GPH-65 manufactured by Nippon Kayaku Co., Ltd.).

  From Table 6, even if it changed the hardening | curing agent, it has confirmed that the lower elasticity modulus was shown in the hardened | cured material of the epoxy resin composition of this invention.

Example 17 and Comparative Example 12
Using the epoxy resin mixture (EP13) obtained in Example 8 and a comparative epoxy resin (EP16; trisphenolmethane type epoxy resin, Nippon Kayaku Co., Ltd. EPPN-501H), each epoxy resin and curing agent (Biphenyl type phenol aralkyl resin: softening point 73 ° C., Japanese Patent Laid-Open No. 2003-113225, synthesized using the method described in Example 1, hydroxyl equivalent 207 g / eq.) Is blended in an equivalent amount, and tri-p is used as a curing accelerator. -Tolylphosphine (1% based on the weight of the epoxy resin) was added, and the mixture was uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition for sealing. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. This tableted epoxy resin composition was transfer molded (175 ° C. × 60 seconds), and after demolding, cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours to obtain a test piece for evaluation. Was done.

<TMA measurement conditions>
Thermomechanical measuring device, TA-instruments, Q400EM
Measurement temperature range: 40 ° C to 280 ° C
Temperature increase rate: 2 ° C / min

<DMA measurement conditions>
Dynamic viscoelasticity measuring instrument: manufactured by TA-instruments, DMA-2980
Measurement temperature range: -30 ° C to 280 ° C
Temperature rate: 2 ° C./min Test piece size: 5 mm × 50 mm cut out (thickness is about 800 μm).
Analysis condition Tg: Tanδ peak point (tanδMAX) in DMA measurement was defined as Tg.

<Measurement conditions for thermal decomposition characteristics>
Part of the obtained test piece was pulverized by a cycle mill, powdered, passed through a 100 μm mesh and aligned to a particle size of 75 μm mesh-on, and a 5-10 mg sample was taken. It was confirmed. The weight loss temperature of 5% was used as an index.
Measured with TG-DTA (Td5)
Measurement sample: Powdery (100μm mesh passed, 75μm mesh on) 5-10mg
Measurement conditions: Temperature rising rate 10 ° C./min Air flow 200 ml / min 5% weight loss temperature was measured.

  From Table 7, it can be seen that the cured product of the epoxy resin composition of the present invention has not only high heat resistance but also high thermal decomposition characteristics.

Example 18
A 1-L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer is charged with a phenol compound (based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content <5 ppm, melting point 289-290 ° C.) 138 parts, biphenol 28 parts, epichlorohydrin 463 parts, dimethyl sulfoxide 115 parts were added, and the temperature of the water bath was raised to 50 ° C. When the internal temperature exceeded 45 ° C., 44 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C. for 2 hours and at 70 ° C. for 1 hour. After completion of the reaction, excess solvent such as epichlorohydrin was distilled off under reduced pressure at 140 ° C. using a rotary evaporator. 505 parts of methyl isobutyl ketone is added to the residue and dissolved, and after removing sodium chloride and the like produced by washing with water, the organic layer is heated to 70 ° C., and 10 parts of 30 wt% aqueous sodium hydroxide solution is added with stirring. After reacting for 1 hour, washing is carried out until the washing water becomes neutral, and the resulting solution is epoxy resin by distilling off methyl isobutyl ketone and the like under reduced pressure at 180 ° C. using a rotary evaporator. 189 parts of (EP17) were obtained. The epoxy equivalent of the obtained epoxy resin is 241 g / eq. The softening point was 85.3 ° C., the ICI melt viscosity was 0.15 Pa · s (150 ° C.), the total chlorine content was 460 ppm, the hydrolyzable chlorine was 394 ppm, the chlorine ions were 0.6 ppm, and the sodium ions were 0.7 ppm. The structure of the formula (1) was 69.5 area% (GPC), and the epoxidized biphenol was 15.0 area% (GPC). Further, the compound (a) of the formula (1) and the epoxidized product (b) of biphenol are (a) / (b) = 4.6 by weight ratio and 2.73 in molar ratio. About other structures, the compound of the said Formula (1), biphenols, and the compound which the compound of the said Formula (1) and biphenol mixed and couple | bonded were included.

Example 19
A 1-L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer is charged with a phenol compound (based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content <5 ppm, melting point 289-290 ° C.) 126 parts, biphenol 34 parts, epichlorohydrin 463 parts, dimethyl sulfoxide 116 parts were added, and the temperature of the water bath was raised to 50 ° C. When the internal temperature exceeded 45 ° C., 43 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 45 ° C. for 2 hours and at 70 ° C. for 1 hour. After completion of the reaction, excess solvent such as epichlorohydrin was distilled off under reduced pressure at 140 ° C. using a rotary evaporator. After adding 600 parts of methyl isobutyl ketone to the residue and dissolving it, removing sodium chloride and the like produced by washing with water, the organic layer was heated to 70 ° C., and 10 parts of a 30 wt% aqueous sodium hydroxide solution were added with stirring. After reacting for 1 hour, washing is carried out until the washing water becomes neutral, and the resulting solution is epoxy resin by distilling off methyl isobutyl ketone and the like under reduced pressure at 180 ° C. using a rotary evaporator. 190 parts of (EP18) were obtained. The epoxy equivalent of the obtained epoxy resin was 235 g / eq. The softening point was 93.0 ° C., ICI melt viscosity 0.09 Pa · s (150 ° C.), total chlorine amount 467 ppm, hydrolyzable chlorine 388 ppm, chlorine ion 0.3 ppm, sodium ion 0.4 ppm. The structure of the formula (1) was 65.0 area% (GPC), and the epoxidized biphenol was 18.6 area% (GPC). Further, the compound (a) of the formula (1) and the epoxidized product (b) of biphenol are (a) / (b) = 3.5 by weight ratio and 2.08 molar ratio. About other structures, the compound of the said Formula (1), biphenols, and the compound which the compound of the said Formula (1) and biphenol mixed and couple | bonded were included.

Comparative Example 13
A 1-L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer is charged with a phenol compound (based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content <5 ppm, melting point 289-290 ° C.) 102 parts, biphenol 45 parts, epichlorohydrin 462 parts, dimethyl sulfoxide 116 parts were added, and the temperature of the water bath was raised to 50 ° C. When the internal temperature exceeded 45 ° C., 44 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C. for 2 hours and at 70 ° C. for 1 hour. After completion of the reaction, excess solvent such as epichlorohydrin was distilled off under reduced pressure at 140 ° C. using a rotary evaporator. 505 parts of methyl isobutyl ketone is added to the residue and dissolved, and after removing sodium chloride and the like produced by washing with water, the organic layer is heated to 70 ° C., and 10 parts of 30 wt% aqueous sodium hydroxide solution is added with stirring. After reacting for 1 hour, washing is carried out until the washing water becomes neutral, and the resulting solution is epoxy resin by distilling off methyl isobutyl ketone and the like under reduced pressure at 180 ° C. using a rotary evaporator. 177 parts of (EP19) were obtained. The epoxy equivalent of the obtained epoxy resin is 220 g / eq. The softening point was 109 ° C., the ICI melt viscosity was 0.03 Pa · s (150 ° C.), the total chlorine amount was 457 ppm, the hydrolyzable chlorine was 401 ppm, the chlorine ion was 0.9 ppm, and the sodium ion was 0.8 ppm. The structure of the formula (1) was 58.0 area% (GPC), and the epoxidized biphenol was 26.8 area% (GPC). Furthermore, the compound (a) of the formula (1) and the epoxidized product (b) of biphenol are (a) / (b) = 2.2 by weight ratio and 1.31 molar ratio. The other structures mainly include compounds in which the compound of the formula (1), biphenols, and a compound in which the compound of the formula (1) and biphenol are mixed and bonded.

Examples 20 to 21, Comparative Example 14
Using the epoxy resin mixture (EP17, EP18, EP19) obtained in Examples 18 and 19 and Comparative Example 13, biphenyl type phenol aralkyl resin (KAYAHARD GPH-65 manufactured by Nippon Kayaku Co., Ltd.) is blended in an equivalent equivalent amount as a curing agent. Then, a curing accelerator (triphenylphosphine manufactured by Hokuko Chemical Co., Ltd.) was added at 1% with respect to the weight of the epoxy resin, and uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy resin composition was transfer-molded (175 ° C. × 60 seconds), and after demolding, cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours to obtain a test piece for evaluation.
Using this test specimen for evaluation, the shrinkage rate and heat resistance were evaluated. The degree of shrinkage was confirmed by measuring the difference between the mold and the mold of the obtained molding. The heat resistance was measured as follows.

<TMA measurement conditions>
Thermomechanical measuring device, TA-instruments, Q400EM
Measurement temperature range: 40 ° C to 280 ° C
Temperature increase rate: 2 ° C./min <curing shrinkage>
Conforms to JISK-6911 (mold shrinkage)

  From Table 8, it was confirmed that the cured product using the comparative epoxy resin mixture had larger molding shrinkage than the epoxy resin mixture of the present invention.

Example 22
The epoxy resin composition of the present invention having the composition of Example 6 was tested for solder crack resistance. 96PinQFP (chip size: 7 × 7 × thickness 0.1 mm, package size: 14 × 14 × thickness 1.35 mm) lead frame (surface is sufficiently wiped with acetone before use, as shown in FIG. (Use a soiled product) Use a lead frame for solder crack resistance evaluation, set the lead frame in a transfer mold and transfer the tableted epoxy resin composition in the same way as above (175 ° C x 60 seconds) Further, after demolding, three samples were obtained for test evaluation for curing and solder crack resistance under conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours (FIG. 2). The obtained three test pieces were allowed to stand for 5 hours in a thermostat set to a relative humidity of 60 ° C./85% RH for moisture absorption, and after this moisture absorption, a solder reflow test at 280 ° C. for 10 seconds was performed. The generation of cracks was visually confirmed for the package cracks caused by the thermal shock at this time, but no cracks were found in any of the samples.

Examples 23 and 24
The epoxy resin mixture (EP18, 19) of the present invention obtained in Examples 18 and 19 and a curing agent (phenol novolak (H-1 manufactured by Meiwa Kasei Kogyo Co., Ltd.)) were blended in equal equivalents, and a curing catalyst (curing) Add 1% of triphenylphosphine (TPP manufactured by Hokuko Chemical Co., Ltd.) as the accelerator) to the weight of the epoxy resin, and mix and knead uniformly using a mixing roll to obtain an epoxy resin composition for sealing. Obtained. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy resin composition was transfer-molded (175 ° C. × 60 seconds), and after demolding, cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours to obtain a test piece for evaluation. Table 9 shows the evaluation results.

<TMA measurement conditions>
Heat resistance and dimensional stability (linear expansion rate)
Thermomechanical measuring device, TA-instruments, Q400EM
Measurement temperature range: 40 ° C to 280 ° C
Temperature increase rate: 2 ° C / min

<DMA measurement conditions>
Dynamic viscoelasticity measuring instrument: manufactured by TA-instruments, DMA-2980
Measurement temperature range: -30 ° C to 280 ° C
Temperature rate: 2 ° C./min Test piece size: 5 mm × 50 mm cut out (thickness is about 800 μm).
Analysis condition Tg: Tanδ peak point (tanδMAX) in DMA measurement was defined as Tg.
<Dielectric constant, dielectric loss tangent>
Measured using a cavity resonator and a 1 GHz jig manufactured by Kanto Denshi Kagaku Kagaku (using one cut into 0.5 mm x 70 mm)
<Bending test>
・ Compliant with JIS K 6911 Tested at 120 ° C. at room temperature <Peel strength>
180 ° C peel test JIS K-6854-2 compliant Use of rolled copper foil <Water absorption / moisture absorption>
・ Evaluation based on weight increase after standing for 24 hours in a high-temperature and high-humidity tank at 85 ° C. and 85% <KIC: fracture toughness test>
・ Compact compliant with ASTME-399

  From this result, it can be seen that the epoxy resin of the present invention gives a cured product having high heat resistance, high mechanical properties, low linear expansion, and high moisture and water resistance properties and excellent dielectric properties for the level of heat resistance. .

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
In addition, this application is a Japanese patent application filed on September 10, 2013 (Japanese Patent Application No. 2013-186859) and a Japanese patent application filed on July 14, 2014 (Japanese Patent Application No. 2014-143791). Which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.

In the epoxy resin mixture of the present invention, since the cured product has excellent heat resistance, water absorption characteristics and flame retardancy, insulating materials for electrical and electronic parts, laminated boards (printed wiring boards, build-up boards, etc.) and CFRP are used. It is useful for various composite materials, adhesives, paints, etc.

Claims (7)

An epoxy resin mixture containing 60 to 75% (gel permeation chromatography area%) of a compound represented by the following formula (1) and 5 to 25 % (same as above) of an epoxidized biphenol.

(In the formula, a plurality of G and R are independently present, G represents a glycidyl group, R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. )   The epoxy resin mixture according to claim 1, which has a softening point of 80 to 100 ° C.   The epoxy resin mixture according to claim 1 or 2, wherein the ICI melt viscosity (cone plate method) at 150 ° C is 0.08 to 0.35 Pa · s.   The epoxy resin composition containing the epoxy resin mixture and hardening | curing agent as described in any one of Claims 1-3.   The epoxy resin composition containing the epoxy resin mixture and curing catalyst as described in any one of Claims 1-3.   Hardened | cured material which hardened | cured the epoxy resin composition of Claim 4 or 5.   The semiconductor device obtained by sealing a semiconductor chip using the epoxy resin composition of Claim 4 or 5.

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