TWI618744B - Epoxy resin mixture, epoxy resin composition, hardened material, and semiconductor device - Google Patents

Abstract

The present invention provides an epoxy resin mixture, which has excellent heat resistance of a hardened material, and can simultaneously satisfy the properties opposite to the heat resistance, that is, the mechanical strength of the hardened material, flame resistance, and excellent elastic modulus at high temperature. And low viscosity before hardening and other characteristics. The epoxy resin mixture of the present invention is obtained by simultaneously reacting a phenol resin (A) and biphenol (B) represented by the following formula (1) with an epihalohydrin.

(In the formula, 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, hardened material, 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 that require heat resistance.

Epoxy resin compositions are widely used in electrical, electronic parts, structural materials, adhesives, coatings, etc. due to their excellent electrical properties, heat resistance, adhesion, and moisture resistance (water resistance), etc. field.

However, in recent years, in the electrical and electronic fields, along with its development, we have sought to improve the moisture resistance, adhesion, and dielectric properties of resin compositions, including high-purity resins, and to increase fillers (inorganic or organic fillers). Further improvement of various characteristics such as low viscosity of the filling and improvement of reactivity for shortening the molding cycle. In addition, as a structural material, materials that are lightweight and excellent in mechanical properties are used in aerospace materials, leisure, and sports equipment applications. Especially in the field of semiconductor sealing, substrates (the substrate itself or its surrounding materials), the thinning, stacking, systemization, and three-dimensionality have become complicated with the changes in its semiconductors, which require very high levels of heat resistance or high fluidity. And other required characteristics. Furthermore, especially with the expansion of plastic packaging to vehicle applications, the requirements for improving heat resistance have become more stringent. Specifically, heat resistance of 150 ° C. or higher is required due to an increase in driving temperature of a semiconductor. In general, epoxy resins tend to have high heat resistance, but on the other hand, they tend to increase viscosity, making them difficult to use as sealing materials. In addition, a reduction in thermal decomposition temperature and a reduction in flame resistance have become problems.

Non-Patent Document 1: "2008 Annual Report of the Special Committee on Semiconductor Technology Blueprints of the 2008 STRJ Report", Chapter 8, p1-1, [online], March, 2011, JEITA (Company) Electronic Information Technology Industry Association, Semiconductors Technical Blueprint Special Committee, [Retrieved on May 30, 2012], <http://strj-jeita.elisasp.net/strj/nenjihoukoku-2008.cfm>

Non-Patent Literature 2: Takakura Nobuyuki, Matsushita Electric Works Bulletin Vehicle-Related Equipment Technology Vehicle High-Temperature Action IC, No. 74, Japan, May 31, 2001, pages 35-40

When the Tg of an epoxy resin is generally increased, the flame retardancy is reduced. It is caused by the increase in crosslinking density. However, when high Tg is required for a semiconductor peripheral material that requires flame retardancy, it is urgent to develop a resin having the opposite characteristics.

In addition, in Japanese Patent Application Laid-Open No. 2013-43958 and International Publication No. 2007/007827, as a method for solving this problem, a diphenylphenyl aralkyl type resin using dihydroxybenzenes is introduced.

However, the above-mentioned epoxy resin has both high heat resistance and flame resistance, but on the other hand, the mechanical properties are reduced. In addition, since the viscosity of the epoxy resin itself is too high, it is actually difficult to use it as a sealing material.

That is, an object of the present invention is to provide an epoxy resin mixture which has excellent heat resistance of a hardened material and can simultaneously satisfy the characteristics opposite to the heat resistance, namely, mechanical strength, flame resistance, and elasticity at high temperature of the hardened material. The modulus is excellent, and the viscosity before curing is low. Furthermore, an object of the present invention is to provide an epoxy resin composition, a cured product, and a semiconductor device using the epoxy resin mixture.

The present inventors have made intensive studies in view of the actual situation as described above, and as a result, have completed the present invention.

That is, the present invention relates to the following: (1) An epoxy resin mixture in which a phenol resin (A) and biphenol represented by the following formula (1) are simultaneously used with epihalohydrin (B) Obtained by reaction;

(In the formula, the ratio (molar ratio) of (a) (b) is (a) / (b) = 1 ~ 3, n represents the repeating number); (2) the epoxy resin mixture as described in (1) above, Among them, the ratio of the phenol resin (A) to the biphenol (B) is 1 mole equivalent to the hydroxyl equivalent of (A), and the hydroxyl group of (B) is 0.08 to 0.33 times mole; (3) As described in the above item (1) Or (2) the epoxy resin mixture having a softening point of 80 to 100 ° C; (4) the epoxy resin mixture according to any one of the items (1) to (3) above, whose ICI melt viscosity at 150 ° C ( Cone plate method) is 0.05 ~ 0.30Pa. s; (5) a curable resin composition, which is an epoxy resin mixture and a hardener of any one of the foregoing items (1) to (4) as essential components; (6) an epoxy resin composition, which The epoxy resin mixture and hardening catalyst according to any one of the preceding items (1) to (4) as essential components; (7) a hardened product comprising the hardening resin of the preceding item (5) or (6) (8) A semiconductor device obtained by sealing a semiconductor wafer with a curable resin composition according to the item (5) or (6) above.

The epoxy resin mixture of the present invention has heat resistance and water absorption properties due to its hardened material. Because of its excellent properties and mechanical properties, it is useful for insulating materials for electrical and electronic parts, multilayer boards (printed wiring boards, buildup substrates, etc.) or various composite materials such as CFRP, adhesives, and coatings.

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

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

Here, in the epoxy resin mixture of the present invention, among the epoxy compounds of the phenol resin represented by the above formula (1), in the area% measured by gel permeation chromatography (GPC), epoxy with n = 0 The compound is preferably 5 to 59 area%, more preferably 10 to 49 area%, and the epoxy compound of n = 1 is preferably 5 to 35 area%, and more preferably 5 to 29 area%.

On the other hand, the epoxide of biphenol is in the epoxy resin mixture of the present invention, and it is preferably 5 to 25 area%, and more preferably 5 to 19 area% in the area% determined by GPC.

In addition, the epoxy resin mixture of the present invention preferably has a melt viscosity of 0.05 to 0.30 Pa. s (ICI Melt viscosity 150 ° C cone plate method).

The phenol resin used in the present invention is a phenol resin represented by the following formula (1).

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

The softening point of the phenol resin represented by the above formula (1) is preferably 55 to 100 ° C, more preferably 55 to 80 ° C, and even more preferably 60 to 80 ° C.

Further, n as the number of repetitions is preferably 1.05 to 3.0, and more preferably 1.05 to 2.0.

Furthermore, the ratio (molar ratio) of (a) (b) is usually (a) / (b) = 1 to 3, more preferably 1 to 2.5. The reason is that if the ratio of (a) is too large, gelation may occur. The ratio can be calculated in a gel permeation chromatography (GPC) based on the area ratio of the peaks generated by (a) and (b) when n = 1.

Here, the compound of n = 1 in the phenol resin is the RR structure of (i) (resorcinol)-(biphenylene)-(resorcinol) structure, (ii) (resorcinol)- Among the ratios of the RP structure of the (biphenylene)-(phenol) structure and the PP structure of (iii) (phenol)-(biphenylene)-(phenol) structure, the ratio is preferably 4> (RP structure) / (RR Structure)> 0.5. The reason for this is that by setting it within this range, high heat resistance can be secured. In addition, 4> (RP structure) / (PP structure)> 0.5 is preferable. The reason for this is that by keeping it within this range, high flame resistance can be ensured.

The biphenol used in the present invention has the following structure.

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

The biphenol having the above structure includes, for example, a 2,2 'body, a 2,4' body, a 4,4 'body, and the like, and among them, a 4,4' body is preferred.

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

In the present invention, a target epoxy resin mixture is obtained by simultaneously epoxidizing a mixture of a phenol resin and biphenol represented by the above formula (1) with epihalohydrin.

Here, the ratio of the phenol resin (A) and the biphenol (B) represented by the above formula (1) is preferably 0.08 with respect to the hydroxyl equivalent of the phenol resin (A), and the hydroxyl group of the biphenol (B) is preferably 0.08 ~ 0.43 times mole, more preferably 0.08 ~ 0.33 times mole.

If it is 0.08 times mole or more, the viscosity is lowered and the mechanical properties are further improved. If it is less than 0.43 times mole, the precipitation of crystals during production is less, the yield is further improved, and the heat resistance is further improved.

Hereinafter, the specific manufacturing method of an epoxy resin mixture is described.

The epoxy resin mixture of the present invention is obtained by reacting a mixture of the phenol resin (A) and biphenol (B) represented by the formula (1) with epihalohydrin. Hereinafter, the mixture of phenol resin (A) and biphenol (B) is referred to as the phenol resin mixture of the present invention.

The epoxy equivalent of the epoxy resin mixture of the present invention is 1.02 times to 1.13 times the theoretical epoxy equivalent of the phenol resin mixture as a raw material. It is more preferably 1.03 to 1.10 times. When it is less than 1.02 times, it may cost a lot of money to synthesize and purify epoxy, and when it is more than 1.11 times, it may cause problems caused by the same amount of chlorine as described above.

The total chlorine remaining in the epoxy resin mixture obtained by the reaction is preferably 5000 ppm or less, more preferably 3000 ppm or less, and even more preferably 1000 ppm or less. The adverse effects caused by the amount of chlorine are the same as described above. The chloride ion and sodium ion are each preferably 5 ppm or less, and more preferably 3 ppm or less. Chloride ions are described above and needless to say, but cations such as sodium ions are also very important factors especially in power device applications, and become one of the reasons for the poor mode when high voltage is applied.

Here, the theoretical epoxy equivalent is an epoxy equivalent calculated when the phenolic hydroxyl group of the phenol resin mixture of the present invention is not epoxidized in a large amount. When the epoxy equivalent is within the above range, an epoxy resin having excellent heat resistance and electrical reliability can be obtained.

The epoxy resin mixture of the present invention has a resinous form having a softening point. Here, the softening point is preferably 70 to 110 ° C, and more preferably 80 to 100 ° C. If the softening point is too low, blocking during storage becomes a problem, and there are many problems such as having to operate at a low temperature. Conversely, when the softening point is too high, problems such as poor workability may occur when kneaded with other resins (for example, hardeners). The melt viscosity is preferably 0.05 to 0.30 Pa. s (ICI 150 ° C cone-plate method), more preferably 0.07 ~ 0.20Pa. s. When an inorganic material (a filler, etc.) is mixed and used, problems such as poor fluidity arise.

As the epihalohydrin used in the method for synthesizing the epoxy resin mixture of the present invention, epichlorohydrin which is easily available industrially is preferred. The amount of epihalohydrin used is 1 mole relative to the hydroxyl group of the phenol resin mixture of the present invention, which is generally 3.0 to 15 moles, preferably 3.0 to 10 moles, more preferably 3.5 to 8.5 moles, and even more preferably 4.5. ~ 8.5 Mol.

If it is less than 3.0 mol, the epoxy equivalent of the obtained epoxy resin mixture may become large, and the workability of the obtained epoxy resin mixture may be deteriorated. If it exceeds 15 mol, the amount of the solvent increases.

An alkali metal hydroxide can be used in the above reaction. Examples of the alkali metal hydroxide that can be used in the above reaction include sodium hydroxide, potassium hydroxide, and the like. A solid substance may be used, or The aqueous solution is used. In the present invention, in terms of solubility and handling, it is particularly preferable to use a solid formed into a sheet shape.

The amount of the alkali metal hydroxide used is 1 mole relative to the hydroxyl group of the phenol resin mixture of the present invention, which is usually 0.90 to 1.5 moles, preferably 0.95 to 1.25 moles, and more preferably 0.99 to 1.15 moles.

To promote the reaction, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, and trimethylbenzylammonium chloride can be added as catalysts. The used amount of the quaternary ammonium salt is generally 0.1 to 15 g, preferably 0.2 to 10 g, relative to 1 mole of the hydroxyl group of the raw material phenol mixture.

In this reaction, in addition to the above epihalohydrin, it is preferred to use a non-polar protic solvent Alkanes, dimethyl imidazolidone, etc.) or alcohols having 1 to 5 carbon atoms. Examples of the alcohol having 1 to 5 carbon atoms include alcohols such as methanol, ethanol, and isopropanol. The amount of the non-polar protic solvent or the alcohol having 1 to 5 carbons is usually 2 to 50% by weight, preferably 4 to 25% by weight, relative to the amount of epihalohydrin. In addition, the epoxidation can also be performed while controlling the moisture in the system by methods such as azeotropic dehydration.

When there is a large amount of water in the system, the electrical reliability of the hardened product of the epoxy resin mixture obtained may be deteriorated, and it is preferable to synthesize by controlling the water content to 5% or less. In addition, when an epoxy resin is obtained using a non-polar proton solvent, a cured product of an epoxy resin mixture having excellent electrical reliability can be obtained. Therefore, a non-polar 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, in order to perform epoxidation with higher purity, it is preferably 60 ° C or higher, and it is particularly preferable to perform the reaction under conditions close to reflux conditions. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours, and particularly preferably 1 to 3 hours. If the reaction time is short, the reaction is not completed, and if the reaction time is long, by-products are generated, which is not preferable.

After washing the reactants of the epoxidation reaction with water, or without washing, the epihalohydrin or the solvent is removed under heating and reduced pressure. In addition, in order to further prepare an epoxy resin mixture with less hydrolyzable halogen, a ketone compound having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, and cyclic Pentanone, cyclohexanone, etc.) are dissolved as a solvent to dissolve the recovered epoxide, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to react to make the ring closed reliably. In this case, the amount of the alkali metal hydroxide used is 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, relative to 1 mol of the hydroxyl group of the phenol resin mixture used in the epoxidation. The reaction temperature is usually 50 to 120 ° C, and the reaction time is usually 0.5 to 2 hours.

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

The epoxy resin mixture of the present invention exhibits a semi-crystalline resinous shape.

Common epoxy resin mixtures are non-aligned and transparent amorphous resins. In the present invention, the resin mixture has crystallinity and is in a cloudy and opaque state. The so-called semi-crystalline state means this state, and the hardness of the resin produced by making it semi-crystalline is hardened, and it is easy to pulverize during kneading and pulverization, and it becomes a resin with good productivity. Here, the semi-crystalline state means not only the resin in a state of white turbidity as described above, but also a transparent resin in an amorphous state, which is left to stand for more than 10 minutes after reacting in a range of 100 ° C ± 30 ° C, and then slowly Cool, so that those who are cloudy. Such a resin also promotes crystallization by kneading and the like when making a resin composition, and contributes to productivity.

In the epoxy resin mixture of the present invention, both the epoxide of the phenol resin represented by the above formula (1) and diglycidoxybiphenyl (where the aromatic ring has a substituent, the substitution The number of groups is 4 or less and the number of carbons is 4 or less), but in the reaction under the preferable conditions as described above, the phenol resin structure and the biphenol structure represented by the above formula (1) also exist due to epihalohydrin. The structure. Therefore, by simultaneously epoxidizing the phenol resin mixture of the present invention to produce the structure, the relative viscosity tends to be low, which is better in terms of improving the target fluidity of the present invention. In addition, mechanical properties such as toughness are also improved.

In addition, compared with the case where only biphenol is epoxidized, the epoxy resin mixture obtained by this method has low crystallinity and can be easily purified. Therefore, an epoxy resin mixture having a small amount of residual chlorine can be easily obtained. .

In the present invention, an epoxy resin having a structure in which the phenol resin structure and the biphenol structure represented by the above formula (1) are connected by epihalohydrin is determined by GPC, and is preferably 0.01 to 10 area%, and particularly preferably It is 0.1 to 10 area%.

The epoxy resin composition of this invention contains the epoxy resin mixture of this invention, a hardening catalyst, and / or a hardener. 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. In the total epoxy resin, 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 even more preferably 40% by weight or more.

Examples of other epoxy resins that can be used in combination with the epoxy resin mixture of the present invention include novolac epoxy resin, bisphenol epoxy resin, biphenyl epoxy resin, triphenylmethane epoxy resin, and phenol. Aralkyl-type epoxy resin and the like. Specific examples include bisphenol A, bisphenol S, thiobiphenol, bisphenol hydrazone, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5 , 5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcinol, naphthalene glycol, tri- (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 1,1'-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4-bis (chloromethyl) benzene or 1,4-bis (methoxy) Polycondensates of methyl) benzene, etc., and their modifications, halogenated bisphenols such as tetrabromobisphenol A, and epoxypropyl etherate, alicyclic epoxy resin, and propylene oxide derived from alcohols Based amine epoxy resin, epoxy propyl ester epoxy resin, silsesquioxane epoxy resin (chain, cyclic, stepped, or a mixed structure of at least two or more of these siloxane structures) With epoxy and / or Epoxy cyclohexane structure epoxy resin) and other solid or liquid epoxy resins are not limited to these.

Specific examples of the hardening catalyst (hardening accelerator) usable in the present invention include amine compounds such as triethylamine, tripropylamine, and tributylamine; pyridine, dimethylaminopyridine, and 1,8-diamine. Azabicyclo [5.4.0] -7-undecene, 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-symmetric tris , 2,4-diamino-6 (2'-undecylimidazole (1 ')) ethyl-symmetric tris , 2,4-diamino-6 (2'-ethyl, 4-methylimidazole (1 ')) ethyl-symmetric tris , 2,4-diamino-6 (2'-methylimidazole (1 ')) ethyl-symmetric tris -Isotricyanic acid adduct, 2-methylimidazole isotricyanic acid 2: 3 adduct, 2-phenylimidazole isotricyanic acid adduct, 2-phenyl-3,5 -Dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, etc. Heterocyclic compounds; and these heterocyclic compounds with phthalic acid, isophthalic acid, terephthalic acid, 1,2,4-benzenetricarboxylic acid, pyromelic acid, naphthalenedicarboxylic acid, horse Salts of polycarboxylic acids such as maleic acid and oxalic acid; ammoniums such as dicyandiamide; diaza compounds such as 1,8-diazabicyclo (5.4.0) undecene-7; and tetraphenyl Borates, phenolic novolacs and other salts; salts with the above polycarboxylic acids or phosphonic acids; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide , Trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylhexadecylammonium hydroxide, trioctylmethylammonium hydroxide, chloride Tetramethylammonium, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, ethyl Ammonium salts such as trioctylmethylammonium; phosphines or phosphonium compounds such as triphenylphosphine, tris (tolylmethyl) phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate; 2,4, 6-triaminomethylphenol and other phenols; amine adducts; carboxylic acid metal salts (zinc, tin and zirconium salts of 2-ethylhexanoic acid, stearic acid, rosic acid, myristic acid, etc.) Or phosphate metal (zinc salt of octyl phosphate, stearyl phosphate, etc.), metal alkoxy salt (tributylaluminum, tetrapropylzirconium, etc.), acetamidine acetone (acetamidine zirconium chelate, Metal compounds such as acetoacetone titanium chelate and the like). In the present invention, sulfonium salts, ammonium salts, and metal compounds are particularly preferred in terms of coloring or changes during curing. In the case where a quaternary salt is used, halogen may remain in a hardened substance with a salt of halogen.

The hardening 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 hardener. Examples include amine-based compounds, acid anhydride-based compounds, amidine-based compounds, phenol resins, and carboxylic acid-based compounds. Specific examples of usable hardeners include diaminodiphenylmethane, diethylenetriamine, triethylenetriamine, diaminodiphenylphosphonium, isophoronediamine, Nitrogen compounds (amines, amidine compounds) such as dicyandiamide, polyamine resins synthesized from the dimer of linolenic acid and ethylenediamine; phthalic anhydride, 1,2,4-benzene Tricarboxylic anhydride, 1,2,4-benzenetricarboxylic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl dianhydride, phthalic anhydride, hexahydrophthalic anhydride Phthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic dianhydride, bicyclic [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclic [2,2, 1] Acid anhydrides such as heptane-2,3-dicarboxylic anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride; modification of polysiloxane with various alcohols and methanol Carboxylic acid resin obtained by addition reaction; bisphenol A, bisphenol F, bisphenol S, bisphenol hydrazone, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ' , 5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcinol, naphthalene glycol, tri- (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) -1,1'-biphenyl, 1,4'-bis (chloromethyl) benzene, or 1,4'-bis (methoxymethyl) benzene Polycondensates and their modified products, halogenated bisphenols such as tetrabromobisphenol A, phenol resins such as condensates of terpenes and phenols; imidazole, trifluoroborane-amine complexes, guanidine derivatives But not limited to these. These can be used alone or in combination of two or more.

In the present invention, in order to be used especially for electronic material applications, the aforementioned phenol resin is preferred.

The usage-amount of the hardening | curing agent in the epoxy resin composition (henceforth a curable resin composition) of this invention is 0.7-1.2 equivalent with respect to 1 equivalent of epoxy groups of an epoxy resin. When the equivalent of epoxy equivalent is less than 0.7 equivalent or exceeds 1.2 equivalent, there are cases where the hardening is incomplete and good hardened physical properties cannot be obtained.

Moreover, it is preferable to use a cyanate ester compound as another component. In addition to the cyanate ester compound undergoing a hardening reaction alone, it can be made into a heat-resistant hardened material with a higher crosslink density by reaction with an epoxy resin. Examples of the cyanate resin include 2,2-bis (4-cyanatephenyl) propane, bis (3,5-dimethyl-4-cyanatephenyl) methane, and 2, 2-bis (4-cyanatophenyl) ethane, derivatives thereof, aromatic cyanate compounds, and the like. Moreover, it can synthesize | combine by reaction of various phenol resin as described in the said hardening material with cyanic acid or its salt, for example. Particularly preferred in the present invention is a structure that does not have a methylene structure in the molecule like a 2,2-bis (4-cyanatephenyl) propane or a derivative thereof (partial polymer, etc.). These can be used alone or in combination of two or more.

The epoxy resin composition of the present invention may contain a phosphorus-containing compound as a flame retardancy-imparting component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresol phosphate, tricresyl phosphate, cresol phosphate diphenyl ester, and cresol phosphate-2,6. -Di (xylene) ester, 1,3-phenylene bis (di (xylyl) phosphate), 1,4-phenylene bis (di (xyl) phosphate), 4,4'-diphenyl Phosphoric acid esters such as phenyl (bis (xylyl phosphate)); 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide and other phosphines; phosphorus-containing epoxy compounds, red phosphorus, etc. obtained by reacting epoxy resin with the above-mentioned phosphine active hydrogen, preferably phosphoric acid Esters, phosphines or phosphorus-containing epoxy compounds, particularly preferably 1,3-phenylene bis (dimethyl (xyl) phosphate), 1,4-phenylene bis (dimethyl (xyl) phosphate) , 4,4'-biphenyl (di (xylyl phosphate)) or a phosphorus-containing epoxy compound. The content of the phosphorus-containing compound is preferably phosphorus-containing compound / total epoxy resin = 0.1 to 0.6 (weight ratio). If not reached If 0.1, the flame retardance may be insufficient. If it exceeds 0.6, the moisture absorption and dielectric properties of the cured product may be adversely affected.

Further, an adhesive resin may be blended into the epoxy resin composition of the present invention as necessary. Examples of the binder resin include a butyral resin, an acetal resin, an acrylic resin, an epoxy-nylon resin, an NBR-phenol resin, an epoxy-NBR resin, a polyamide resin, and a polyfluorene resin. The imine-based resin, the polysiloxane-based resin, and the like are not limited thereto. The blending amount of the binder resin is preferably in a range that does not damage the flame retardancy and heat resistance of the hardened material. It is generally used in an amount of 0.05 to 50 parts by weight based on 100 parts by weight of the total amount of the epoxy resin and the hardener. 0.05 ~ 20 parts by weight.

In the epoxy resin composition of the present invention, an inorganic filler may be added as necessary. Examples of the inorganic filler include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, and talc , Spinel, titanium dioxide, talc and other powders or beads made of these spheres, but it is not limited to these. These fillers can be used alone or in combination of two or more. Although the content of these inorganic fillers also depends on the application, it is generally used in an amount of 0 to 95% by weight in the epoxy resin composition of the present invention, especially when it is used in the application of a sealing material. According to the shape of the package, it is preferably used in a range of preferably 50 to 95% by weight, particularly preferably 65 to 95% by weight. Furthermore, to the epoxy resin composition of the present invention, various additives such as antioxidants, light stabilizers, silane coupling agents, stearic acid, palmitic acid, zinc stearate, calcium stearate, and pigments can be added. Compounding agents and various thermosetting resins. The coupling material is particularly preferably a coupling material having an epoxy group or a coupling material having a thiol group.

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 the same method as the conventionally known method. For example, if necessary, an extruder, a kneader, a roller, a planetary mixer, etc. are used to combine the epoxy resin component and the hardener component, and the hardening accelerator, phosphorus compound, The mixture resin, the inorganic filler, and the admixture are sufficiently mixed until uniform to obtain an epoxy resin composition. When the obtained epoxy resin composition is liquid, the composition is impregnated by pouring or casting. It is cast on a substrate or poured into a mold, and is hardened by heating. In the case where the obtained epoxy resin composition is solid, it is casted after being melted, or molded using a transfer molding machine or the like, and then hardened by heating. The hardening temperature and time are 80 ~ 200 ℃ and 2 ~ 10 hours. As a hardening method, it may be hardened instantaneously at a high temperature, but it is preferable to gradually increase the temperature and advance the hardening reaction. Specifically, initial hardening is performed at 80 to 150 ° C, and post-hardening is performed at 100 to 200 ° C. The hardening stage is preferably divided into 2 to 8 stages, and more preferably 2 to 4 stages.

The epoxy resin composition of the present invention is dissolved in toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, and N-formaldehyde. A solvent such as pyrrolidone is used to prepare a hardening resin composition varnish, which is impregnated with glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, and other substrates, and dried by heating to obtain a preliminary The hardened body of the epoxy resin composition of the present invention can be prepared by hot pressing forming the obtained prepreg. The solvent used at this time in the mixture of the epoxy resin composition of the present invention and the solvent usually accounts for 10 to 70% by weight, preferably 15 to 70% by weight.

Specific applications of these compositions include adhesives, coatings, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (including printed circuit boards, wire coatings, etc., in addition to sealing materials, And sealing materials, cyanate resin compositions for substrates), additives to other resins such as acrylate resins as hardeners for resists, and the like. In the present invention, it is particularly preferred that it is an insulating material for electronic materials (including printed circuit boards, wire coatings, etc., in addition to sealing materials, and sealing materials, and cyanate resin compositions for substrates).

Examples of the adhesive include adhesives for civil engineering, construction, automotive, general office, and medical use, and adhesives for electronic materials. Examples of such adhesives for electronic materials include indirect coating of layers of multilayer substrates such as build-up substrates, and die bonding. Adhesives, semiconductor adhesives such as underfills, BGA reinforcement primers, anisotropic conductive films (ACF), anisotropic conductive pastes (ACP), and other mounting adhesives.

Examples of the sealant and substrate include capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, etc. used for potting, dipping, injection molding, and IC, LSI-based COB, COF, and TAB. Primers for potting and sealing, flip-chips, etc., IC packaging such as QFP, BGA, CSP, etc. (including primers for reinforcement) and package substrates for mounting. In addition, it is also suitable for network substrates or module substrates that require functionality.

The epoxy resin composition of the present invention is particularly preferably used in a semiconductor device.

The semiconductor device becomes the IC package group listed above.

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

[Example]

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

Various analysis methods used in the examples are described below.

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

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

Softening point: According to JIS K 7234

Total chlorine: according to JIS K 7243-3 (ISO 21672-3)

Chloride: in accordance with JIS K 7243-1 (ISO 21672-1)

GPC:

Columns (Shodex KF-603, KF-602.5, KF-602, KF-601 × 2)

Tetrahydrofuran

Flow rate is 0.5ml / min

40 ° C column temperature

Detection: RI (differential refractive index detector)

(Example 1)

Add a phenol resin ((a) / (b) = 1.3, n = 1.5, (RP structure) manufactured according to International Publication No. 2007/007827 to a flask equipped with a stirrer, a reflux cooling tube, and a stirring device while purging with nitrogen. ) / (RR structure) = 2.15, (RP structure) / (PP structure) = 2.1 (determined by GPC), hydroxyl equivalent 134g / eq., Softening point 93 ° C) 132 parts, 4,4'-biphenol 29.3 parts ( 1 mol equivalent with respect to the hydroxy equivalent of phenol resin (A), 0.32 times mol equivalent with biphenol (B)), 541 parts of epichlorohydrin (4.5 mol equivalent with respect to phenol resin), dimethylene碸 124 parts, dissolve them with stirring, and raise the temperature to 40 ~ 45 ° C. Then, 54.6 parts of flake-shaped sodium hydroxide was added in portions over 90 minutes, and then reacted at 40 ° C for 1 hour, 60 ° C for 1 hour, and 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. 17 parts of a 30% by weight sodium hydroxide aqueous solution was added under stirring, and the reaction was performed for 1 hour, followed by water washing until the cleaning solution of the oil layer became neutral, and the formazan was distilled off from the obtained solution under reduced pressure using a rotary evaporator. Based on isobutyl ketone, etc., thereby obtaining 201 parts of the epoxy resin mixture (EP1) of the present invention. The epoxy equivalent of the obtained epoxy resin mixture (EP1) was 192 g / eq., And the melt viscosity (ICI melt viscosity cone plate # 1) at a softening point of 95 ° C and 150 ° C was 0.11 Pa. s. The obtained epoxy resin mixture (EP1) was measured by gel permeation chromatography. As a result, it was confirmed that the epoxy resin containing biphenol contained 15.3 area%, and it was confirmed that the ring containing n = 0 in the formula (1) was contained. 28.8 area% of oxide, 17.6 area% of epoxide with n = 1.

(Example 2 and Comparative Example 1)

Using the epoxy resin mixture (EP1) obtained above or the comparative epoxy resin (EP2: the phenol resin was changed to 172 parts in Example 1 without adding biphenol), and blended in equivalent amounts Epoxy resin and hardener (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.) )), And blending hardening catalyst (hardening accelerator: triphenylphosphine (TPP manufactured by Beixing Chemical Co., Ltd.)) and fillers as needed (filler content in the table of MSR-2122 manufactured by Fused Silica Mori The proportion of the entire epoxy resin composition) is uniformly mixed and kneaded using a mixing roller to obtain a curable resin composition. This curable resin composition was pulverized by a mixer, and further tabletted by a tableting machine. The tablet-shaped curable resin composition was transferred to a mold (175 ° C × 60 seconds) and further demolded, and then cured at 160 ° C × 2 hours + 180 ° C × 6 hours to obtain an evaluation test. sheet.

Using this test piece for evaluation, the physical properties of the cured product were measured in accordance with the following points. In addition, according to the evaluation items of the physical properties of the hardened material, the types of hardener used are as shown in Table 1 below. Among the samples used in the evaluation of the amount of hardening accelerator, heat resistance, and shrinkage, The weight of the oxygen resin was 1%, and the sample used for the evaluation of the flame retardancy was 2% relative to the weight of the epoxy resin. The test results are also shown in Table 1 below.

<TMA measurement conditions>

Manufacture of thermo-mechanical measuring device TA-instruments, Q400EM

Measuring temperature range: 40 ℃ ~ 280 ℃

Heating rate: 2 ° C / min

<Flammability test>

． Judgment of flame retardancy: According to UL94. The test was performed under the conditions that the sample size was 12.5 mm in width × 150 mm in length and 0.8 mm in thickness.

． Residual flame time: The total amount of residual flame time after 5 samples of a group are exposed to the flame 10 times

<Hardening shrinkage>

According to JISK-6911 (molding shrinkage)

Compared with Comparative Example 1, epoxide containing or without biphenol can maintain heat resistance and improve shrinkage. In addition, even if the hardener is changed in the flame retardancy test, the burning time is shortened. Therefore, the epoxy resin of the present invention The resin composition can have both high heat resistance and flame resistance.

(Example 3)

Add a phenol resin ((a) / (b) = 1.3, n = 1.5, (RP structure) manufactured according to International Publication No. 2007/007827 to a flask equipped with a stirrer, a reflux cooling tube, and a stirring device while purging with nitrogen. ) / (RR structure) = 2.15, (RP structure) / (PP structure) = 2.1 (determined by GPC), hydroxyl equivalent 134g / eq., Softening point 93 ° C) 97.8 parts, 2,4'-biphenol 25.1 parts ( The hydroxyl equivalent of phenol resin (A) is 1 mole equivalent, the hydroxyl group of biphenol (B) is 0.37 moles), 555 parts of epichlorohydrin (6 mole equivalents to phenol resin), and 55.5 parts of methanol. These were dissolved under stirring, and the temperature was raised to 70 ° C. Then, 42 parts of flake-shaped sodium hydroxide was added in portions over 90 minutes, and then reacted at 70 ° C for 1 hour. After completion of the reaction, the resultant was washed with water, and then the excess organic solvent such as epichlorohydrin was distilled off under reduced pressure using a rotary evaporator. 500 parts of methyl isobutyl ketone was added to the residue to dissolve it, and the temperature was raised to 70 ° C. 10 parts of a 30% by weight aqueous solution of sodium hydroxide was added under stirring, and the reaction was performed for 1 hour, followed by washing with water until the cleaning solution of the oil layer became neutral, and the resulting solution was distilled off under reduced pressure using a rotary evaporator. By removing methyl isobutyl ketone and the like, 161 parts of the epoxy resin mixture (EP3) of the present invention was obtained. The epoxy equivalent of the obtained epoxy resin mixture (EP3) was 192 g / eq., And the melt viscosity (ICI melt viscosity cone plate # 1) at a softening point of 82 ° C and 150 ° C was 0.07 Pa. s. The obtained epoxy resin mixture (EP3) was measured by gel permeation chromatography. As a result, it was confirmed that the epoxy resin containing biphenol contained 12.0 area%, and it was confirmed that the ring containing n = 0 in the above formula (1) was contained. 24.4 area% of oxide, 16.5 area% of epoxide with n = 1.

(Example 4)

Add a phenol resin ((a) / (b) = 1.3, n = 1.5, (RP structure) manufactured according to International Publication No. 2007/007827 to a flask equipped with a stirrer, a reflux cooling tube, and a stirring device while purging with nitrogen. ) / (RR structure) = 2.15, (RP structure) / (PP structure) = 2.1 (determined by GPC), hydroxyl equivalent 134g / eq., Softening point 93 ° C) 101.8 parts, 4,4'-biphenol 22.3 parts ( 1 mol equivalent with respect to the hydroxyl equivalent of phenol resin (A), 0.316 times mol equivalent with biphenol (B)), 555 parts of epichlorohydrin (6 mol equivalent with respect to phenol resin), dimethylene碸 125 parts, dissolve them under stirring, and raise the temperature to 40 ~ 45 ° C. Then, 42 parts of flake-shaped sodium hydroxide was added in portions over 90 minutes, and then reacted at 40 ° C for 1 hour, 60 ° C for 1 hour, and 70 ° C for 1 hour. After the reaction was completed, excess solvent such as epichlorohydrin was distilled off under reduced pressure using a rotary evaporator. 500 parts of methyl isobutyl ketone was added to the residue to dissolve it, and after washing with 300 parts of water, the temperature was raised to 70 ° C. 10 parts of a 30% by weight sodium hydroxide aqueous solution was added under stirring, and the reaction was performed for 1 hour, followed by water washing until the cleaning solution of the oil layer became neutral, and the formazan was distilled off from the obtained solution using a rotary evaporator under reduced pressure. Butyl isobutyl ketone, etc., thereby obtaining 159 parts of the epoxy resin mixture (EP4) of the present invention. The epoxy equivalent of the obtained epoxy resin mixture (EP4) was 189 g / eq., And its melt viscosity (ICI melt viscosity cone plate # 1) at a softening point of 98 ° C and 150 ° C was 0.08 Pa. s. The obtained epoxy resin mixture (EP4) was measured by gel permeation chromatography. As a result, it was confirmed that the epoxy resin containing biphenol contained 14.9 area%, and it was confirmed that the ring containing n = 0 in the formula (1) was contained. 29.3 area% of oxide, n = 18.6 area of epoxide %.

(Examples 5 and 6)

The hardener (P-3: phenolic novolac (H-1 manufactured by Meiwa Chemical Industry Co., Ltd.)) and hardening catalyst (hardening accelerator: triphenylphosphine (Beixing Chemicals) (Production of TPP))), the epoxy resin mixture (EP3, EP4) or comparative epoxy resin (EP2) obtained as described above was uniformly mixed and kneaded using a mixing roller to obtain a curable resin composition. This curable resin composition was pulverized by a mixer, and further tabletted by a tableting machine. The tablet-shaped curable resin composition was transferred to a mold (175 ° C × 60 seconds) and further demolded, and then cured at 160 ° C × 2 hours + 180 ° C × 6 hours to obtain an evaluation test. sheet. Using this test piece for evaluation, the physical properties of the cured product were measured in accordance with the following points. The test results are also shown in Table 2.

<TMA measurement conditions>

Manufacture of thermo-mechanical measuring device TA-instruments, Q400EM

Measuring temperature range: 40 ℃ ~ 280 ℃

Heating rate: 2 ° C / min

<Peel strength>

． 180 ° C peel test using rolled copper foil in accordance with JIS K-6854-2

From the above results, it can be seen that the cured product of the epoxy resin composition of the present invention can be used in Improved toughness while maintaining high heat resistance. That is, the epoxy resin composition of the present invention can have both high heat resistance and toughness of a cured product.

(Example 7)

Add a phenol resin ((a) / (b) = 1.3, n = 1.5, (RP structure) manufactured according to International Publication No. 2007/007827 to a flask equipped with a stirrer, a reflux cooling tube, and a stirring device while purging with nitrogen. ) / (RR structure) = 2.15, (RP structure) / (PP structure) = 2.1 (determined by GPC), hydroxyl equivalent 134g / eq., Softening point 93 ° C) 109.9 parts, 4,4'-biphenol 16.8 parts ( 1 mol equivalent with respect to the hydroxy equivalent of phenol resin (A), 0.22 times mol equivalent with biphenol (B)), 463 parts of epichlorohydrin (5 mol equivalent with respect to phenol resin), dimethylene碸 100 parts, dissolve them under stirring, and raise the temperature to 40 ~ 45 ° C. Then, 42 parts of flake-shaped sodium hydroxide was added in portions over 90 minutes, and then reacted at 40 ° C for 1 hour, 60 ° C for 1 hour, and 70 ° C for 1 hour. After the reaction was completed, excess solvent such as epichlorohydrin was distilled off under reduced pressure using a rotary evaporator. 500 parts of methyl isobutyl ketone was added to the residue to dissolve it, and after washing with 300 parts of water, the temperature was raised to 70 ° C. 10 parts of a 30% by weight sodium hydroxide aqueous solution was added under stirring, and the reaction was performed for 1 hour, followed by water washing until the cleaning solution of the oil layer became neutral, and the formazan was distilled off from the obtained solution using a rotary evaporator under reduced pressure. Butyl isobutyl ketone, etc., thereby obtaining 169 parts of the epoxy resin mixture (EP5) of the present invention. The epoxy equivalent of the obtained epoxy resin mixture (EP5) was 189 g / eq., And the melt viscosity (ICI melt viscosity cone plate # 1) at a softening point of 83 ° C and 150 ° C was 0.07 Pa. s. Further, the obtained epoxy resin mixture (EP5) was measured by gel permeation chromatography. As a result, it was confirmed that the epoxy resin containing biphenol contained 11.0 area%, and it was confirmed that the ring containing n = 0 in the formula (1) was contained. 29.1 area% of oxide, 17.7 area% of epoxide with n = 1.

(Example 8)

The hardener (P-4: phenol resin used in Example 1 was produced in accordance with the ratio (equivalent) in Table 3 according to 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 134g / eq., Softening point 93 ° C)), hardening catalyst (hardening accelerator: Triphenylphosphine (TPP manufactured by Beixing Chemical Co., Ltd.)), and the epoxy resin mixture (EP5) or comparative epoxy resin (EP2) obtained as described above are uniformly mixed and kneaded with a mixing roller to obtain a hardenable resin composition. Thing. This curable resin composition was pulverized by a mixer, and further tabletted by a tableting machine. The tablet-shaped curable resin composition was transferred to a mold (175 ° C × 60 seconds) and further demolded, and then cured at 160 ° C × 2 hours + 180 ° C × 6 hours to obtain an evaluation test. sheet.

Using this test piece for evaluation, the physical properties of the cured product were measured in accordance with the following points. The test results are also shown in Table 2.

<TMA measurement conditions>

Manufacture of thermo-mechanical measuring device TA-instruments, Q400EM

Measuring temperature range: 40 ℃ ~ 280 ℃

Heating rate: 2 ° C / min

<Hygroscopicity>

Evaluation based on% weight increase after leaving the tank at 85 ° C and 85% for 24 hours

<Measurement conditions for thermal decomposition resistance>

A part of the obtained test pieces was pulverized with a circular mill to make a powder, and the particles were screened through a 100 μm sieve to make the particle size uniformly remain on the 75 μm sieve. Take a 5-10 mg sample. The thermal weight reduction temperature was confirmed by TG-DTA. Take 5% weight reduction temperature as an indicator.

Measurement by TG-DTA (Td5)

Measurement sample: powdery (pass through 100μm sieve hole, leave on 75μm sieve hole) 5-10mg

Measurement conditions: heating rate 10 ℃ / min air flow rate 200ml / min determination 5% weight loss Less temperature.

From the above results, it can be seen that even if the epoxy resin of the present invention is substantially reduced in viscosity by less than half, it can maintain high heat resistance and also maintain high characteristics in other characteristics. That is, the epoxy resin of the present invention is a resin that can improve various characteristics that are difficult to have both heat resistance and heat resistance.

The present invention will be described in detail with reference to specific aspects, but it should be understood that various changes and modifications can be made without departing from the spirit and scope of the present invention.

Furthermore, this application is based on a Japanese patent application filed on September 12, 2013 (Japanese Patent Application No. 2013-189035), the entire contents of which are incorporated by reference. Also, all references cited herein are incorporated herein in their entirety.

[Industrial availability]

The epoxy resin mixture of the present invention is excellent in heat resistance, water absorption properties, and flame retardancy, so it is suitable for insulating materials for electrical and electronic parts and laminated boards (printed wiring boards, build-up substrates, etc.) or CFRP. A variety of composite materials, adhesives, coatings, etc. are useful.

Claims (9)

An epoxy resin mixture obtained by simultaneously reacting a phenol resin (A) and biphenol (B) represented by the following formula (1) with epihalohydrin, and a ring of biphenol (B) The content ratio of the oxide is 5 to 19 area% in the area% measured by gel permeation chromatography (GPC); (In the formula, the ratio (molar ratio) of (a) (b) is (a) / (b) = 1 to 3, and n represents the number of repetitions). For example, the epoxy resin mixture in the first scope of the patent application, wherein the ratio of the phenol resin (A) to the biphenol (B) is 1 mole equivalent with respect to the hydroxyl equivalent of (A), and the hydroxyl group of (B) is 0.08 ~ 0.33 times mole. For example, the softening point of the epoxy resin mixture in the scope of patent application No. 1 or 2 is 80 ~ 100 ℃. For example, the epoxy resin mixture of the first or second patent application range has an ICI melt viscosity measured at 150 ° C by a cone plate method of 0.05 to 0.30 Pa · s. For example, the epoxy resin mixture in the third patent application range has an ICI melt viscosity measured at 150 ° C by a cone plate method of 0.05 to 0.30 Pa · s. A curable resin composition containing an epoxy resin mixture and a curing agent according to any one of claims 1 to 5. An epoxy resin composition containing an epoxy resin mixture and a hardening catalyst according to any one of claims 1 to 5. A hardened product is obtained by hardening a curable resin composition according to item 6 of the patent application or an epoxy resin composition according to item 7. A semiconductor device is obtained by sealing a semiconductor wafer with a hardenable resin composition according to claim 6 or an epoxy resin composition according to claim 7.