KR102376061B1 - Epoxy resin mixture, epoxy resin composition, cured product and semiconductor device - Google Patents

Abstract

Provided is an epoxy resin mixture that can simultaneously satisfy the properties of the cured product, such as mechanical strength, flame retardancy, and elasticity at high temperature, and low viscosity before curing, while having excellent heat resistance of the cured product, which are properties opposite to the heat resistance.
The epoxy resin mixture obtained by making the phenol resin (A) and biphenol (B) represented by following formula (1) react with epihalohydrin simultaneously.
(1) [Wherein, the ratio (molar ratio) of (a) (b) is (a)/(b) = 1 to 3, and n represents the number of repetitions.]

Description

Epoxy resin mixture, epoxy resin composition, cured product, and semiconductor device

The present invention relates to an epoxy resin mixture, an epoxy resin composition, a cured product thereof, and a semiconductor device suitable for use in electrical and electronic materials requiring heat resistance.

Epoxy resin compositions are widely used in the fields of electrical/electronic components, structural materials, adhesives, paints, etc. due to workability and excellent electrical properties of the cured product, heat resistance, adhesiveness, moisture resistance (water resistance), and the like.

However, in recent years, in the field of electricity and electronics, with the development of high purity resin compositions, moisture resistance, adhesion, dielectric properties, low viscosity for high filling of fillers (inorganic or organic fillers), and reactivity to shorten the molding cycle There is a demand for better improvement of various characteristics, such as improvement of Moreover, as a structural material, it is lightweight and excellent in mechanical properties in an aerospace material, a leisure/sports equipment use, etc. are calculated|required. In particular, in the field of semiconductor encapsulation and substrates (the substrate itself or its surrounding materials), it is complicated by thinning, stacking, systemization, and three-dimensionalization according to the change of the semiconductor. . Moreover, especially with the expansion of the use of the vehicle mounting of a plastic package, the improvement request|requirement of heat resistance is becoming stricter. Specifically, heat resistance of 150°C or higher is required due to an increase in the driving temperature of the semiconductor. In general, epoxy resins with a high softening point tend to have high heat resistance, but on the other hand, the tendency to increase in viscosity makes it difficult to use as a sealing material. Moreover, the fall of the thermal decomposition temperature and the fall of a flame retardance become a subject.

"2008 STRJ Report Semiconductor Roadmap Expert Committee Heisei 20 Year Report", Chapter 8, p1-1, [online], March, Heisei 21, JEITA Electronics Information Technology Industry Association Semiconductor Technology Roadmap Specialist Committee, [Pyeongseong] Retrieved May 30, 24], <http://strj-jeita.elisasp.net/strj/nenjihoukoku-2008.cfm> Takakura Nobuyuki et al., Matsushita Denko Jibo Vehicle-related Device Technology Automotive High-Temperature Operation IC, No. 74, Japan, May 31, 2001, pp. 35-40

In general, when the epoxy resin is made high in Tg, the flame retardancy is lowered. This is the effect by which a crosslinking density improves. However, the development of resins having these opposite characteristics is urgently needed while high Tg is required for semiconductor peripheral materials requiring flame retardancy.

In addition, Japanese Patent Laid-Open No. 2013-43958 and International Publication No. 2007/007827 introduce a biphenylene aralkyl type resin using dihydroxybenzenes as a method for solving the present problem.

However, although the said epoxy resin makes high heat resistance and flame retardance compatible, on the other hand, mechanical properties fall. In addition, since the viscosity of the epoxy resin itself was too high, it was difficult to actually use it as a sealing material.

That is, the present invention provides an epoxy resin mixture capable of simultaneously satisfying characteristics such as low viscosity before curing, excellent in mechanical strength, flame retardancy, and elastic modulus at high temperature, which are properties opposite to the heat resistance, while having excellent heat resistance of the cured product. It aims to provide, and also aims to provide the epoxy resin composition, hardened|cured material, and semiconductor device using the said epoxy resin mixture.

MEANS TO SOLVE THE PROBLEM The present inventors came to complete this invention, as a result of earnestly examining in view of the above actual conditions.

That is, the present invention

(One)

An epoxy resin mixture obtained by simultaneously reacting a phenol resin (A) represented by the following formula (1) and a biphenol with epihalohydrin (B);

[Wherein, the ratio (molar ratio) of (a) (b) is (a)/(b) = 1 to 3, and n represents the number of repetitions],

(2) the ratio of the phenol resin (A) to the biphenol (B) with respect to 1 molar equivalent of the hydroxyl equivalent of (A), the hydroxyl group of (B) is 0.08 to 0.33 times moles of the epoxy resin mixture according to the item (1) above,

(3)

The epoxy resin mixture according to the above (1) or (2), wherein the softening point is 80 to 100 ° C;

(4)

The epoxy resin mixture according to any one of (1) to (3), wherein the ICI melt viscosity at 150°C (corn plate method) is 0.05 to 0.30 Pa·s;

(5)

A curable resin composition comprising the epoxy resin mixture according to any one of (1) to (4) and a curing agent as essential components;

(6)

An epoxy resin composition comprising the epoxy resin mixture according to any one of (1) to (4) and a curing catalyst as essential components;

(7)

A cured product obtained by curing the curable resin composition according to the above (5) or (6);

(8)

A semiconductor device obtained by sealing a semiconductor chip using the curable resin composition according to the above (5) or (6);

is about

(Effects of the Invention)

Since the epoxy resin mixture of the present invention has excellent properties such as heat resistance, absorption properties and mechanical properties, the epoxy resin mixture of the present invention is an insulating material for electrical and electronic components, and various composite materials including laminates (printed wiring boards, build-up boards, etc.) and CFRP, adhesives , is useful for paints, etc.

The epoxy resin mixture of the present invention is a mixture of an epoxidized product of a phenol resin (A) represented by the following formula (1) and a glycidylated product of a biphenol (B).

[Wherein, the ratio (molar ratio) of (a) (b) is (a)/(b) = 1 to 3, and n represents the number of repetitions.]

Here, in the epoxy compound of the phenol resin represented by the formula (1) in the epoxy resin mixture of the present invention, the epoxy compound of n=0 in area % as measured by gel permeation chromatography (GPC) is 5-59 It is preferable that it is area%, It is more preferable that it is 10-49 area%, It is also preferable that the epoxy compound of n=1 is 5-35 area%, It is more preferable that it is 5-29 area%.

On the other hand, in the epoxy resin mixture of this invention, it is preferable that it is 5-25 area%, and, as for the epoxide of a biphenol, it is more preferable that it is 5-19 area% in GPC measurement area%.

Moreover, it is preferable that melt viscosity of the epoxy resin mixture of this invention is 0.05-0.30 Pa*s (ICI melt viscosity 150 degreeC corn plate method).

As a phenol resin used for this invention, it is a phenol resin represented by following formula (1).

[Wherein, the ratio (molar ratio) of (a) (b) is (a)/(b) = 1 to 3, and n represents the number of repetitions.]

55-100 degreeC is preferable, as for the softening point of the phenol resin represented by said Formula (1), 55-80 degreeC is more preferable, 60-80 degreeC is preferable.

Moreover, as n which is the number of repetitions, 1.05-3.0 are preferable and 1.05-2.0 are more preferable.

Moreover, as for the ratio (molar ratio) of (a) (b), it is more preferable that it is normally (a)/(b)=1-3, and it is 1-2.5. This is because, when the ratio of (a) is too large, gelation may be caused. In addition, this ratio is computable based on the area ratio of the peak derived from (a) (b) in n=1 in gel permeation chromatography (GPC).

wherein the compound of n=1 in the phenol resin is (i) (resorcin)-(biphenylene)-(resorcin) structure RR structure, (ii) (resorcin)-(biphenylene)-( In the ratio of the RP structure as the phenol) structure and the PP structure as the (iii) (phenol)-(biphenylene)-(phenol) structure, it is preferable that 4>(RP structure)/(RR structure)>0.5. It is because high heat resistance can be ensured by being in this range. Moreover, it is preferable that 4>(RP structure)/(PP structure)>0.5. It is because high flame retardance can be ensured by being in this range.

The biphenol used for this invention has the following structure.

(In the above formula, a plurality of R ₁ is independently present, represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and k represents an integer of 1 to 4.)

As for the biphenol of the said structure, although 2,2' form, 2,4' form, 4,4' form etc. exist, for example, 4,4' form biphenol is especially preferable.

In addition, a purity of 95% or more can be preferably used.

In this invention, the target epoxy resin mixture is obtained by epoxidizing the mixture of the phenol resin and biphenol represented by the said Formula (1) with epihalohydrin simultaneously.

Here, the ratio of the phenol resin (A) and the biphenol (B) represented by the formula (1) is 0.08 to 0.43 times mole of the hydroxyl group of the biphenol (B) with respect to 1 molar equivalent of the hydroxyl group equivalent of the phenol resin (A). It is preferable that it is, More preferably, it is 0.08-0.33 times mole.

When it is 0.08 times mole or more, the viscosity is reduced and the mechanical properties are further improved, and when it is 0.43 times mole or less, crystal precipitation is further reduced during production, the yield is further improved, and the heat resistance is further improved.

Below, it describes about the manufacturing method of a specific epoxy resin mixture.

The epoxy resin mixture of this invention is obtained by making the mixture of the phenol resin (A) and biphenol (B) represented by the said Formula (1) react with epihalohydrin. Hereinafter, the mixture of the phenol resin (A) and the biphenol (B) is referred to as the phenol resin mixture of the present invention.

The epoxy equivalent of the epoxy resin mixture of this invention is 1.02 times - 1.13 times with respect to the theoretical epoxy equivalent of the phenol resin mixture used as a raw material. More preferably, it is 1.03-1.10 times. When it is less than 1.02 times, a great cost may be incurred for the synthesis and purification of the epoxy, and when it exceeds 1.11 times, the same problems due to the amount of chlorine as described above may occur.

Moreover, as total chlorine remaining in the epoxy resin mixture obtained by reaction, it is 5000 ppm or less, More preferably, it is 3000 ppm or less, It is preferable that it is especially 1000 ppm or less. About the adverse effect by the amount of chlorine, it is the same as that mentioned above. Moreover, about a chlorine ion and a sodium ion, 5 ppm or less is preferable, respectively, More preferably, it is 3 ppm or less. Although it goes without saying that chlorine ions are described above, cations such as sodium ions are also a very important factor, particularly in power device applications, and cause one of the failure modes when a high voltage is applied.

Here, the theoretical epoxy equivalent represents the epoxy equivalent computed when the phenolic hydroxyl group of the phenolic resin mixture of this invention glycidylates without excess or deficiency. When an epoxy equivalent exists in the said range, the epoxy resin excellent in the heat resistance and electrical reliability of hardened|cured material can be obtained.

The epoxy resin mixture of the present invention has a dendritic form having a softening point. Here, as a softening point, 70-110 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 a low temperature. Conversely, when the softening point is too high, problems such as poor handling may occur during kneading with other resins (eg, a curing agent). Moreover, as for a melt viscosity, 0.05-0.30 Pa*s (ICI melt viscosity 150 degreeC corn plate method) is preferable, More preferably, it is 0.07-0.20 Pa.s. When an inorganic material (filler, etc.) is mixed and used, problems, such as poor fluidity|liquidity, arise.

As epihalohydrin used for the synthesis method of the epoxy resin mixture of this invention, industrially easy access epichlorohydrin is preferable. The amount of epihalohydrin used is usually 3.0 to 15 mol, preferably 3.0 to 10 mol, more preferably 3.5 to 8.5 mol, particularly preferably 4.5 to 1 mol of the hydroxyl group of the phenol resin mixture of the present invention. 8.5 moles.

When it is less than 3.0 mol, the epoxy equivalent of the epoxy resin mixture obtained may become large, and the handling workability|operativity of the epoxy resin mixture obtained may worsen. When it exceeds 15 mol, the amount of solvent will become large.

In the said reaction, an alkali metal hydroxide can be used. Examples of alkali metal hydroxides that can be used in the above reaction include sodium hydroxide and potassium hydroxide. A solid material may be used or an aqueous solution thereof may be used. In the present invention, in particular, in terms of solubility and handling, The use of solids is preferred.

The amount of the alkali metal hydroxide used is usually 0.90 to 1.5 moles, preferably 0.95 to 1.25 moles, and more preferably 0.99 to 1.15 moles, based on 1 mole of hydroxyl groups in the phenol resin mixture of the present invention as a raw material.

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. As the usage-amount of a quaternary ammonium salt, it is 0.1-15 g normally with respect to 1 mol of hydroxyl groups of a raw material phenol mixture, Preferably it is 0.2-10 g.

In this reaction, in addition to the epihalohydrin, it is preferable to use together a non-polar proton solvent (dimethyl sulfoxide, dioxane, dimethylimidazolidinone, etc.) or an alcohol having 1 to 5 carbon atoms. Examples of the alcohol having 1 to 5 carbon atoms include alcohols such as methanol, ethanol and isopropyl alcohol. The amount of the non-polar protonic solvent or alcohol having 1 to 5 carbon atoms used is usually 2 to 50 wt%, preferably 4 to 25 wt%, based on the amount of epihalohydrin used. In addition, you may perform epoxidation while controlling the water|moisture content in a system by methods, such as azeotropic dehydration.

When there is much moisture in the system, electrical reliability may deteriorate in the cured product of the obtained epoxy resin mixture, and it is preferable to control the moisture to 5% or less for synthesis. In addition, when an epoxy resin is obtained using a nonpolar proton solvent, since the hardened|cured material of the epoxy resin mixture excellent in electrical reliability is obtained, a nonpolar proton solvent can be used preferably.

Reaction temperature is 30-90 degreeC normally, Preferably it is 35-80 degreeC. In particular, in the present invention, for higher purity epoxidation, 60° C. or higher is preferred, and reaction under conditions close to reflux conditions is particularly preferred. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours, particularly preferably 1 to 3 hours. When the reaction time is short, the reaction does not proceed to the end, and when the reaction time is long, a by-product is generated, which is not preferable.

After or without water washing the reactants of these epoxidation reactions, epihalohydrin, solvent, etc. are removed under heating and reduced pressure. Further, in order to obtain an epoxy resin mixture with less hydrolyzable halogen, the recovered epoxide is treated with a ketone compound having 4 to 7 carbon atoms (eg, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.). ) as a solvent, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to perform the reaction to ensure ring closure. In this case, the usage-amount of an alkali metal hydroxide is 0.01-0.3 mol normally with respect to 1 mol of hydroxyl groups of the phenol resin mixture used for epoxidation, Preferably it is 0.05-0.2 mol. 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 resulting 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 a semi-crystalline dendritic phase.

A normal epoxy resin mixture is not orientated and becomes resin in a transparent amorphous state. In the present invention, the resin mixture has crystallinity and becomes cloudy and not transparent. The semi-crystalline phase indicates this state, and when it becomes a semi-crystalline phase, the hardness of the produced resin becomes hard, so that it is easy to pulverize during kneading and pulverization, resulting in a resin with good productivity. Here, the semi-crystalline phase refers not only to the resin in the cloudy state as described above, but also to the transparent resin in an amorphous state, leaving it for at least 10 minutes after the reaction in the range of 100°C ± 30°C, and then gradually cooling it to become cloudy. do. Crystallization of such a resin is similarly accelerated by kneading or the like at the time of preparation of the resin composition, thereby contributing to productivity.

In the epoxy resin mixture of the present invention, the epoxidized product of the phenol resin represented by the formula (1) and bisglycidyloxybiphenyl (however, when a substituent is provided in the aromatic ring, the number of substituents is 4 or less, and the number of carbon atoms is 4 or less.) exist simultaneously, but in the reaction under the above preferred conditions, there is also a structure in which the phenol resin structure represented by the above formula (1) and the biphenol structure are linked by epihalohydrin. Therefore, the said structure is produced|generated by simultaneous epoxidation of the phenol resin mixture of this invention, and a viscosity becomes low comparatively easily, It is preferable in the improvement of the fluidity|liquidity made into the objective of this invention. Moreover, mechanical properties, such as toughness, are also improved.

Moreover, compared with the case where only biphenol is epoxidized, since the crystallinity of the epoxy resin mixture obtained by such a manufacturing method is low, and since refinement|purification is performed easily, it becomes easy to obtain the epoxy resin mixture with little residual chlorine content.

In the present invention, it is preferable that the epoxy resin having a structure in which the phenolic resin structure represented by the formula (1) and the biphenol structure are connected by epihalohydrin is 0.01 to 10 area% in area% of GPC measurement. And, it is especially preferable that it is 0.1-10 area%.

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

The epoxy resin composition of this invention WHEREIN: You may contain the epoxy resin of other types other than the epoxy resin mixture of this invention. Among all the epoxy resins, the proportion of the epoxy resin mixture of the present invention is preferably 20% by weight or more, more preferably 30% by weight or more, and particularly preferably 40% by weight or more.

As another epoxy resin which can be used together with the epoxy resin mixture of this invention, a novolak-type epoxy resin, a bisphenol-type epoxy resin, a biphenyl-type epoxy resin, a triphenylmethane-type epoxy resin, a phenol aralkyl-type epoxy resin, etc. are mentioned. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorenebisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3',5,5'-tetramethyl -[1,1'-biphenyl]-4,4'-diol, hydroquinone, resorcinol, naphthalenediol, tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis (4 -Hydroxyphenyl)ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxy Roxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis Polycondensates of (methoxymethyl)-1,1'-biphenyl, 1,4-bis(chloromethyl)benzene or 1,4-bis(methoxymethyl)benzene and their modified products, tetrabromobisphenol Glycidyl ether products derived from halogenated bisphenols such as A and alcohols, alicyclic epoxy resins, glycidylamine-based epoxy resins, glycidyl ester-based epoxy resins, silsesquioxane-based epoxy resins (chain, A solid or liquid epoxy resin such as an epoxy resin having a glycidyl group and/or an epoxycyclohexane structure in the siloxane structure of a cyclic, ladder-like, or mixed structure of at least two or more thereof), but is not limited thereto .

Specific examples of the curing catalyst (curing accelerator) that can be used in the present invention include amine compounds such as triethylamine, tripropylamine and tributylamine, pyridine, dimethylaminopyridine, and 1,8-diazabicyclo[5.4.0]unde. Car-7-ene, 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-phenyl Imidazole, 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 of nuric acid, 2-phenylimidazoleisocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5- Various heterocyclic compounds such as methylimidazole and 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and these heterocyclic compounds and phthalic acid, isophthalic acid, terephthalic acid, tri Salts of polyhydric carboxylic acids such as mellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and oxalic acid, amides such as dicyandiamide, 1,8-diaza-bicyclo(5.4.0)undecene Diaza compounds such as -7 and their salts such as tetraphenylborate and phenol novolac, salts with the above polyhydric carboxylic acids or phosphinic acids, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra Propylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetra methylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium acetate, etc. Phosphines such as ammonium salt, triphenylphosphine, tri(toluyl)phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, phosphonium compounds, and phenols such as 2,4,6-trisaminomethylphenol , amine adducts, metal carboxylate salts (zinc salts such as 2-ethylhexanoic acid, stearic acid, behenic acid, and myristic acid, tin salts, zirconium salts) or metal phosphate esters (zinc such as octyl phosphoric acid and stearyl phosphoric acid) salt), metal compounds such as alkoxy metal salts (such as tributylaluminum and tetrapropyl zirconium) and acetylacetone salts (such as acetylacetone zirconium chelate and acetylacetone titanium chelate). In the present invention, phosphonium salts, ammonium salts, and metal compounds are particularly preferable in terms of coloration at the time of curing and changes thereof. In addition, when using a quaternary salt, the salt with a halogen may leave a halogen in the hardened|cured material.

The curing accelerator is used as needed in an amount of 0.01 to 5.0 parts by weight based on 100 of the epoxy resin.

It is preferable to contain a hardening|curing agent in the epoxy resin composition of this invention. For example, an amine type compound, an acid anhydride type compound, an amide type compound, a phenol resin, a carboxylic acid type compound, etc. are mentioned. Specific examples of the curing agent that can be used include a polyamide resin synthesized from diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, a dimer of linolenic acid and ethylenediamine. nitrogen-containing compounds such as amines and amide compounds; Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetra Carboxylic anhydride, bicyclo[2,2,1]heptane-2,3-dicarboxylic acid anhydride, methylbicyclo[2,2,1]heptane-2,3-dicarboxylic acid anhydride, cyclohexane acid anhydrides such as -1,3,4-tricarboxylic acid-3,4-anhydride; Carboxylic acid resin obtained by addition reaction of various alcohols, a carbinol-modified silicone, and the above-mentioned acid anhydride; Bisphenol A, bisphenol F, bisphenol S, fluorenebisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3',5,5'-tetramethyl-[1,1 '-biphenyl]-4,4'-diol, hydroquinone, resorcinol, naphthalenediol, tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl) Ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p- Hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl) Polycondensates such as -1,1'-biphenyl, 1,4'-bis(chloromethyl)benzene, or 1,4'-bis(methoxymethyl)benzene, modified products thereof, tetrabromobisphenol A, etc. phenol resins such as halogenated bisphenols and condensates of terpenes and phenols; Although imidazole, a trifluoroborane-amine complex, the compound of a guanidine derivative, etc. are mentioned, It is not limited to these. These may be used independently and may use 2 or more types.

In this invention, since it uses especially for an electronic material use, the above-mentioned phenol resin is preferable.

As for the usage-amount of the hardening|curing agent in the epoxy resin composition of this invention (it is also called curable resin composition hereafter), 0.7-1.2 equivalent is preferable with respect to 1 equivalent of the epoxy group of an epoxy resin. When it does not reach 0.7 equivalent with respect to 1 equivalent of epoxy group, or when it exceeds 1.2 equivalent, hardening becomes incomplete in all and good hardening property may not be obtained.

Moreover, use of a cyanate ester compound as another component is preferable. A cyanate ester compound can be made into a heat-resistant hardened|cured material with a higher crosslinking density by reaction with an epoxy resin in addition to individual hardening reaction. As cyanate ester resin, for example, 2,2-bis (4-cyanate phenyl) propane, bis (3,5-dimethyl-4- cyanate phenyl) methane, 2, 2-bis (4-cyanate phenyl) ) ethane, derivatives thereof, aromatic cyanate ester compounds, and the like. In addition, synthesis is also possible, for example, by reaction of various phenol resins and cyanide or salts thereof as described in the above-mentioned hardening material. In the present invention, it is particularly preferable to have a structure that does not have a methylene structure at the benzyl position in the molecule, such as 2,2-bis(4-cyanatephenyl)propane or a derivative thereof (partially polymerized product, etc.), You may use 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 imparting component. The phosphorus-containing compound may be a reactive compound or an additive compound. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1, 3-phenylene bis ( phosphoric acid esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), and 4,4'-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide phosphanes, such as; Phosphorus-containing epoxy compounds obtained by reacting an epoxy resin with active hydrogen of the phosphanes, red phosphorus, and the like are mentioned. Phosphoric acid esters, phosphanes, or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis(dicyl) Relenyl phosphate), 1,4-phenylenebis (dicyrylenyl phosphate), 4,4'-biphenyl (dicyrylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. As for content of a phosphorus containing compound, phosphorus containing compound/all epoxy resins =0.1-0.6 (weight ratio) are preferable. If it is less than 0.1, the flame retardance is insufficient, and if it exceeds 0.6, the hygroscopicity and dielectric properties of the cured product may be adversely affected.

Moreover, binder resin can also be mix|blended with the epoxy resin composition of this invention as needed. Examples of the binder resin include butyral-based resins, acetal-based resins, acrylic resins, epoxy-nylon-based resins, NBR-phenolic resins, epoxy-NBR-based resins, polyamide-based resins, polyimide-based resins, silicone-based resins, and the like. 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 0.05 to 20 parts by weight, based on 100 parts by weight of the total of the epoxy resin and the curing agent. do.

An inorganic filler can be added to the epoxy resin composition of this invention as needed. Examples of the inorganic filler include powders such as crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, steatite, spinel, titania, talc, or a spherical form of these. Although beads etc. are mentioned, It is not limited to these. These fillers may be used independently and may use 2 or more types. In the epoxy resin composition of the present invention, the content of these inorganic fillers depends on the application, but is generally used in an amount that accounts for 0 to 95% by weight, particularly preferably 50 to 95% by weight, particularly preferably for use as a sealing material. In the range of 65 to 95% by weight, it is preferable to use it separately according to the shape of the package. In addition, to the epoxy resin composition of the present invention, antioxidants, light stabilizers, silane coupling agents, stearic acid, palmitic acid, zinc stearate, release agents such as calcium stearate, various compounding agents such as pigments, and various thermosetting resins can be added. can In particular, to the coupling material, it is preferable to add a coupling material having an epoxy group or a coupling material having a thiol.

The epoxy resin composition of this invention is obtained by mixing each component uniformly. The epoxy resin composition of this invention can be easily made into the hardened|cured material by the method similar to the method known conventionally. For example, the epoxy resin component and the curing agent component and, if necessary, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent, etc. are uniformly prepared using an extruder, a kneader, a roll, a planetary mixer, etc. The epoxy resin composition is obtained by sufficiently mixing until In addition, when the obtained epoxy resin composition is solid, it shape|molds using a casting_mold|template or a transfer molding machine etc. after melting, and also makes it harden|cure by heating. As curing temperature and time, it is 2-10 hours at 80-200 degreeC. As a hardening method, although hardening can also be carried out at once at high temperature, it is preferable to heat up stepwise and to advance hardening reaction. Specifically, initial curing is performed at 80 to 150°C, and post-curing is performed at 100°C to 200°C. As a stage of hardening, it is preferable to divide into 2 to 8 steps, and to raise the temperature, More preferably, it is 2 to 4 steps.

In addition, 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, , glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, a cured product of the epoxy resin composition of the present invention by hot press molding a prepreg obtained by impregnating a substrate such as paper and heating and drying. In this case, the solvent 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 is used.

Specific uses of these compositions include adhesives, paints, coatings, molding materials (including sheets, films, FRP, etc.), insulating materials (other than sealing materials including printed circuit boards and electric wire coverings, sealing materials, and cyanate resin compositions for substrates) Examples of the curing agent for resist include additives such as acrylic acid ester-based resins and other resins. In the present invention, use as an insulating material for electronic materials (other than a sealing material including a printed circuit board, an electric wire covering, etc., a sealing material, and the cyanate resin composition for board|substrates) is especially preferable.

Examples of the adhesive include adhesives for civil engineering, construction, automobiles, general office use, and medical use, as well as adhesives for electronic materials. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfill, underfill for BGA reinforcement, anisotropic conductive film (ACF), anisotropic conductive paste (ACP), etc. Adhesives for mounting, etc. are mentioned.

As an encapsulant and substrate, potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, etc., potting sealing for IC and LSI types of COB, COF, TAB, etc., underfill for flip chips, etc.; and sealing (including reinforcing underfill) and package substrates at the time of mounting IC packages such as QFP, BGA, and CSP. Moreover, it is suitable also for the board|substrate use which requires functionality, such as a network board|substrate or a module board|substrate.

It is preferable that the epoxy resin composition of this invention is used especially for a semiconductor device.

The semiconductor device is the group of IC packages exemplified above.

The semiconductor device of the present invention is obtained by sealing a silicon chip provided on a support such as a package substrate or die with the epoxy resin composition of the present invention. The molding temperature and the molding method are as described above.

Example

Next, the present invention will be more specifically described by way of examples, but in the following, parts are parts by weight unless otherwise specified. In addition, this invention is not limited to these Examples.

Various analysis methods used in Examples are described below.

Epoxy equivalent: Conforms to JIS K 7236 (ISO 3001)

ICI melt viscosity: Conforms to JIS K 7117-2 (ISO 3219)

Softening point: Conforms to JIS K 7234

All chlorine: Conforms to JIS K 7243-3 (ISO 21672-3)

Chloride ion: Conforms to JIS K 7243-1 (ISO 21672-1)

GPC:

Columns (Shodex KF-603, KF-602.5, KF-602, KF-601x2)

The linking eluent is tetrahydrofuran

The flow rate was 0.5 ml/min.

Column temperature is 40℃

Detection: RI (Differential Refraction Detector)

(Example 1)

A phenolic resin prepared in accordance with International Publication No. 2007/007827 [(a)/(b) = 1.3, n = 1.5, (RP structure )/(RR structure) = 2.15, (RP structure)/(PP structure) = 2.1 (GPC measurement), hydroxyl equivalent 134 g/eq., softening point 93 ° C.] 132 parts, 4,4'-biphenol 29.3 parts [phenol With respect to 1 molar equivalent of hydroxyl equivalent of resin (A), 0.32 times mole of hydroxyl group of biphenol (B)], 541 parts of epichlororohydrin (4.5 molar equivalents to phenol resin), and 124 parts of dimethyl sulfoxide were added under stirring. It melted and heated up to 40-45 degreeC. Then, 54.6 parts of flaky sodium hydroxide was added in portions over 90 minutes, and then, the reaction was further performed at 40°C for 1 hour, at 60°C for 1 hour, and at 70°C for 1 hour. After completion of the reaction, excess solvents such as epichlorohydrin were distilled off under reduced pressure using a rotary evaporator. To the residue, 500 parts of methyl isobutyl ketone was added and dissolved, and after washing with 300 parts of water, the temperature was raised to 70°C. After adding 17 parts of 30 wt% sodium hydroxide aqueous solution under stirring and reacting for 1 hour, washing with water until the washing water of the oil layer becomes neutral. By distilling off, 201 parts of the epoxy resin mixture (EP1) of this invention were obtained. The epoxy equivalent of the obtained epoxy resin mixture (EP1) was 192 g/eq. The melt viscosity (ICI melt viscosity cone #1) in a softening point of 95 degreeC and 150 degreeC was 0.11 Pa.s. In addition, as a result of measuring the obtained epoxy resin mixture (EP1) by gel permeation chromatography, it was confirmed that the biphenol epoxy resin was contained in 15.3 area%, and in the above formula (1), n = 0 epoxide was It was confirmed that 28.8 area% and 17.6 area% of the epoxide of n=1 were contained.

(Example 2 and Comparative Example 1)

Using the epoxy resin mixture (EP1) obtained above to the comparative epoxy resin (EP2: in Example 1, the phenol resin was changed to 172 parts and no biphenol was added), an epoxy resin and a curing agent {P-1 : Phenol aralkyl resin [KAYAHARD GPH-65 manufactured by Nippon Kayaku Co., Ltd.], P-2: Phenol aralkyl resin [Milex XLC-3L manufactured by Mitsui Chemicals Co., Ltd.]) was blended in equal amounts and cured Catalyst {curing accelerator: triphenylphosphine [TPP manufactured by Hoko Chemical Co., Ltd.]} and a filler (fusible silica Takimori MSR-2122 table, the percentage of filler in the table is the proportion of the total epoxy resin composition) and uniformly mixed and kneaded using a mixing roll to obtain a curable resin composition. This curable resin composition was grind|pulverized by the mixer, and also tablet-formed with the tablet machine. This tablet-formed curable resin composition was transfer-molded (175 degreeC x 60 second), and also after demolding, hardening and the test piece for evaluation were obtained on the conditions of 160 degreeC x 2 hours + 180 degreeC x 6 hours.

Using this test piece for evaluation, the physical property of hardened|cured material was measured in the following way. In addition, according to the evaluation items of the physical properties of the cured product, the type of curing agent used is as shown in Table 1 below, and the amount of the curing accelerator used is 1% based on the weight of the epoxy resin in the sample used for evaluation of heat resistance and shrinkage, and evaluation of flame retardancy In the sample used for , it was set to 2% with respect to the weight of the epoxy resin. The test results are also shown in Table 1 below.

<TMA measurement conditions>

Thermomechanical measuring device made by TA-instruments, Q400EM

Measuring temperature range: 40℃~280℃

Temperature increase rate: 2°C/min

<flame retardancy test>

- Judgment of flame retardance: It performed based on UL94. However, the sample size made the width 12.5 mm x length 150 mm, and thickness tested it by 0.8 mm.

・Afterflame time: the sum of the after-flame time after contacting 5 samples in one set 10 times

<Cure shrinkage>

Conforms to JISK-6911 (molding shrinkage)

With respect to Comparative Example 1, the epoxy resin composition of the present invention maintains heat resistance despite containing the epoxide of biphenol, improves shrinkage, and shortens the combustion time even if the curing agent is changed in the flame retardant test. In the epoxy resin composition of the present invention, high heat resistance and flame retardancy can be achieved.

(Example 3)

A phenolic resin [(a)/(b)=1.3, n=1.5, (RP structure) prepared in accordance with International Publication No. 2007/007827 while nitrogen purge was applied to a flask equipped with a stirrer, a reflux cooling tube, and a stirring device )/(RR structure) = 2.15, (RP structure)/(PP structure) = 2.1 (GPC measurement), hydroxyl equivalent 134 g/eq., softening point 93 ° C.] 97.8 parts, 4,4'-biphenol 25.1 parts [phenol With respect to 1 molar equivalent of hydroxyl equivalent of resin (A), 0.37 times mole of hydroxyl group of biphenol (B)], 555 parts of epichlorohydrin (6 molar equivalents to phenol resin), and 55.5 parts of methanol are added and dissolved under stirring; It heated up to 70 degreeC. Then, after adding 42 parts of flake-form sodium hydroxide in portions over 90 minutes, reaction was performed at 70 degreeC for 1 hour. After completion of the reaction, the organic layer obtained after washing with water was evaporated under reduced pressure using a rotary evaporator to remove excess solvents such as epichlorohydrin. To the residue, 500 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70°C. After adding 10 parts of 30% by weight sodium hydroxide aqueous solution under stirring and reacting for 1 hour, washing with water until the washing water of the oil layer becomes neutral. From the resulting solution, methyl isobutyl ketone, etc. By distilling off, 161 parts of the epoxy resin mixture (EP3) of this invention were obtained. The epoxy equivalent of the obtained epoxy resin mixture (EP3) was 192 g/eq. The melt viscosity (ICI melt viscosity cone #1) in softening point 82 degreeC and 150 degreeC was 0.07 Pa*s. In addition, as a result of measuring the obtained epoxy resin mixture (EP3) by gel permeation chromatography, it was confirmed that the biphenol epoxy resin was contained in 12.0 area %, and in the above formula (1), n = 0 epoxide was It was confirmed that 24.4 area % and 16.5 area % of the epoxide of n=1 were contained.

(Example 4)

A phenolic resin prepared in accordance with International Publication No. 2007/007827 [(a)/(b) = 1.3, n = 1.5, (RP structure )/(RR structure) = 2.15, (RP structure)/(PP structure) = 2.1 (GPC measurement), hydroxyl equivalent 134 g/eq., softening point 93 ° C.] 101.8 parts, 4,4'-biphenol 22.3 parts [phenol With respect to 1 molar equivalent of hydroxyl equivalent of resin (A), 0.316 times mole of hydroxyl group of biphenol (B)], 555 parts of epichlorohydrin (6 molar equivalents to phenol resin), and 125 parts of dimethyl sulfoxide are added and dissolved under stirring. and heated up to 40-45°C. Then, after adding 42 parts of flake-form sodium hydroxide in portions over 90 minutes, reaction was further performed at 40 degreeC for 1 hour, 60 degreeC for 1 hour, and 70 degreeC for 1 hour. After completion of the reaction, excess solvents such as epichlorohydrin were distilled off under reduced pressure using a rotary evaporator. To the residue, 500 parts of methyl isobutyl ketone was added and dissolved, and after washing with 300 parts of water, the temperature was raised to 70°C. After adding 10 parts of 30% by weight sodium hydroxide aqueous solution under stirring and reacting for 1 hour, washing with water until the washing water of the oil layer becomes neutral. From the resulting solution, methyl isobutyl ketone, etc. By distilling off, 159 parts of the epoxy resin mixture (EP4) of this invention were obtained. The epoxy equivalent of the obtained epoxy resin mixture (EP4) was 189 g/eq. The melt viscosity (ICI melt viscosity cone #1) in the softening point 98 degreeC and 150 degreeC was 0.08 Pa*s. In addition, as a result of measuring the obtained epoxy resin mixture (EP4) by gel permeation chromatography, it was confirmed that the biphenol epoxy resin was contained in 14.9 area%, and in the above formula (1), n = 0 epoxide was It was confirmed that 29.3 area% and 18.6 area% of an epoxide of n=1 were contained.

(Examples 5 and 6)

The epoxy resin mixtures (EP3, EP4) obtained above - the epoxy resin for comparison (EP2) were treated with a curing agent {P-3: phenol novolac [Meiwaka Seiko Co., Ltd. H-1]}, a curing catalyst {curing accelerator : Triphenylphosphine [Hoko Chemical Co., Ltd. TPP]} was mix|blended in the ratio (equivalent) of Table 2, and it mixed and kneaded uniformly using the mixing roll, and the curable resin composition was obtained. This curable resin composition was grind|pulverized by the mixer, and also tablet-formed with the tablet machine. This tablet-formed curable resin composition was transfer-molded (175 degreeC x 60 second), and also after demolding, hardening and the test piece for evaluation were obtained on the conditions of 160 degreeC x 2 hours + 180 degreeC x 6 hours. Using this test piece for evaluation, the physical property of hardened|cured material was measured in the following way. The test results are also shown in Table 2.

<TMA measurement conditions>

Thermomechanical measuring device made by TA-instruments, Q400EM

Measuring temperature range: 40℃~280℃

Temperature increase rate: 2°C/min

<Peel strength>

・Use of rolled copper foil according to 180°C peel test JIS K-6854-2

It turns out that toughness is improved in the state which maintained high heat resistance of the hardened|cured material of the epoxy resin composition of this invention from the above result. That is, in the epoxy resin composition of this invention, the high heat resistance and toughness of hardened|cured material can be made compatible.

(Example 7)

A phenolic resin prepared in accordance with International Publication No. 2007/007827 [(a)/(b) = 1.3, n = 1.5, (RP structure )/(RR structure) = 2.15, (RP structure)/(PP structure) = 2.1 (GPC measurement), hydroxyl equivalent 134 g/eq., softening point 93° C.] 109.9 parts, 4,4'-biphenol 16.8 parts [phenol With respect to 1 molar equivalent of hydroxyl equivalent of resin (A), 0.22 times mole of hydroxyl group of biphenol (B)], 463 parts of epichlorohydrin (5 molar equivalents to phenol resin), and 100 parts of dimethyl sulfoxide are added and stirred under stirring. After dissolution, the temperature was raised to 40-45°C. Then, after adding 42 parts of flake-form sodium hydroxide in portions over 90 minutes, reaction was further performed at 40 degreeC for 1 hour, 60 degreeC for 1 hour, and 70 degreeC for 1 hour. After completion of the reaction, excess solvents such as epichlorohydrin were distilled off under reduced pressure using a rotary evaporator. To the residue, 500 parts of methyl isobutyl ketone was added and dissolved, and after washing with water 300 parts, the temperature was raised to 70°C. After adding 10 parts of 30 wt% sodium hydroxide aqueous solution under stirring and reacting for 1 hour, washing with water until the washing water of the oil layer becomes neutral. From the resulting solution, methyl isobutyl ketone, etc. By distilling off, 169 parts of the epoxy resin mixture (EP5) of this invention was obtained. The epoxy equivalent of the obtained epoxy resin mixture (EP5) was 189 g/eq. The melt viscosity (ICI melt viscosity cone #1) in softening point 83 degreeC and 150 degreeC was 0.07 Pa*s. In addition, as a result of measuring the obtained epoxy resin mixture (EP5) by gel permeation chromatography, it was confirmed that the biphenol epoxy resin was contained in 11.0 area%, and in the formula (1), n = 0 epoxide was It was confirmed that 29.1 area % and 17.7 area % of the epoxide of n=1 were contained.

(Example 8)

The epoxy resin mixture (EP5) obtained above - the epoxy resin for comparison (EP2) were used as a curing agent {P-4: A phenol resin prepared in accordance with International Publication No. 2007/007827 of phenol resin used in Example 1 [(a) /(b)=1.3, n=1.5, (RP structure)/(RR structure)=2.15, (RP structure)/(PP structure)=2.1 (GPC measurement), hydroxyl equivalent 134 g/eq., softening point 93°C] }, curing catalyst {curing accelerator: triphenylphosphine [Hoko Chemical Co., Ltd. TPP]} was blended in the ratio (equivalent) in Table 3, and uniformly mixed and kneaded using a mixing roll to obtain a curable resin composition got it This curable resin composition was grind|pulverized with the mixer, and also tablet-formed with the tablet machine. This tablet-formed curable resin composition was transfer-molded (175 degreeC x 60 second), and also hardened|cured and obtained the test piece for evaluation under the conditions of 160 degreeC x 2 hours + 180 degreeC x 6 hours after demolding.

Using this test piece for evaluation, the physical property of hardened|cured material was measured in the following way. The test results are also shown in Table 2.

<TMA measurement conditions>

Thermomechanical measuring device made by TA-instruments, Q400EM

Measuring temperature range: 40℃~280℃

Temperature increase rate: 2°C/min

<Hygroscopicity>

Evaluated as % of weight increase after standing for 24 hours in a high-temperature, high-humidity tank at 85°C and 85%

<Measurement conditions for thermal decomposition properties>

A part of the obtained test piece is pulverized by a cycle mill to a powder form, filtered through a sieve, and a sample of 5-10 mg is taken according to the particle size of a 100 μm mesh pass and a 75 μm mesh on, and the thermogravimetric reduction temperature is checked with TG-DTA. did. A weight loss temperature of 5% was taken as an index.

Measured by TG-DTA (Td5)

Measurement sample: 5-10 mg of powder (through 100 μm mesh, 75 μm mesh on)

Measurement conditions: Temperature increase rate 10 degreeC/min Air flow 200 mL/min 5% Weight loss|decrease temperature was measured.

From the above results, it can be seen that the epoxy resin of the present invention can maintain high heat resistance in spite of significant reduction in viscosity of less than half, and high properties in other properties. That is, the epoxy resin of the present invention becomes a resin capable of improving various properties with heat resistance that is difficult to be compatible with.

Although this invention was demonstrated in detail with reference to the specific form, it is clear for those skilled in the art that various changes and correction are possible without departing from the mind and range of this invention.

In addition, this application is based on the JP Patent application (Japanese Patent Application No. 2013-189035) for which it applied on September 12, 2013, The whole is used by reference. Also, all references cited herein are incorporated in their entirety.

<Industrial Applicability>

Since the epoxy resin mixture of the present invention has excellent properties such as heat resistance, absorption properties and flame retardancy, the epoxy resin mixture of the present invention includes insulating materials for electrical and electronic components and laminates (printed wiring boards, build-up boards, etc.) and various composite materials including CFRP, adhesives, Useful for paints, etc.

Claims (8)

It is an epoxy resin mixture obtained by simultaneously reacting the phenol resin (A) and biphenol (B) represented by the following formula (1) with epihalohydrin,
A compound having a structure in which the structure of the phenol resin (A) represented by the following formula (1) and the structure of the biphenol (B) are linked by epihalohydrin;
In the area % of gel permeation chromatography (GPC) measurement, the content ratio of the epoxide of n=0 in the phenol resin represented by the following formula (1) is 5 to 59 area%, and the epoxide of n=1 Epoxy resin mixture, characterized in that the content ratio of 5 to 35 area%.

[Wherein, the ratio (molar ratio) of (a) (b) is (a)/(b) = 1 to 3, and n represents the number of repetitions.] The method of claim 1,
Epoxy resin mixture, characterized in that the ratio of the phenol resin (A) to the biphenol (B) is 0.08 to 0.33 times mole of the hydroxyl group of (B) with respect to 1 mole equivalent of the hydroxyl group equivalent of (A). 3. The method of claim 1 or 2,
Epoxy resin mixture, characterized in that the softening point is 80 ~ 100 ℃. 3. The method of claim 1 or 2,
ICI melt viscosity (corn plate method) at 150 degreeC is 0.05-0.30 Pa*s, The epoxy resin mixture characterized by the above-mentioned. A curable resin composition comprising the epoxy resin mixture according to claim 1 or 2 and a curing agent. An epoxy resin composition comprising the epoxy resin mixture according to claim 1 or 2 and a curing catalyst. A cured product obtained by curing the curable resin composition according to claim 5. It is obtained by sealing a semiconductor chip using the curable resin composition of Claim 5, The semiconductor device characterized by the above-mentioned.