TWI651359B - Epoxy resin composition, cured product thereof and semiconductor device - Google Patents

Abstract

An object of the present invention is to provide an epoxy resin composition excellent in heat resistance and flame retardancy, a cured product thereof, and a semiconductor device using the same. The epoxy resin composition of the present invention contains an epoxy resin having an epoxy resin represented by the formula (1) and an epoxy compound represented by the following formula (2) at a softening point (according to ASTM D 3104) of 100 to 120 ° C. A mixture, a biphenyl aralkyl type phenol resin, and an inorganic filler.

(In the formula (1), n represents the average value of 5 to 20)

Description

Epoxy resin composition, cured product thereof and semiconductor device

The present invention relates to an epoxy resin composition which provides a cured product excellent in heat resistance and flame retardancy.

Further, the present invention relates to an epoxy resin composition and a cured product thereof, which are preferable as a sealing material for a semiconductor, a film substrate material, and a cured product thereof, and a semiconductor device using the same.

The epoxy resin composition is excellent in electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. in electrical/electronic parts, structural materials, adhesives, paints, and the like due to workability and excellent electrical properties, heat resistance, adhesion, and moisture resistance (water resistance). It is used in a wide range.

However, in recent years, in the field of electric and electronic fields, moisture resistance, adhesion, dielectric properties represented by high purity of a resin composition, and high filler (inorganic or organic filler) have been sought. Further improvement in various characteristics such as low viscosity of filling and improvement in reactivity for shortening the molding cycle. In addition, as a structural material, it is a material that is lightweight and excellent in mechanical properties in aerospace materials, entertainment/sports applications, and the like. In particular, in recent years, power devices have received increasing attention from the viewpoint of energy saving (Non-Patent Document 1).

In the past, the power device has been sealed with silicone rubber. In the future, in terms of productivity and cost, the conversion to a thermosetting resin has been greatly progressed in terms of strength and reliability. Moreover, the driving temperature of the power device tends to increase year by year, such as the tethering system. The semiconductor system is designed to have a driving temperature of 150 ° C or higher, and heat resistance at a very high temperature exceeding 150 ° C is sought (Non-Patent Document 2).

Non-Patent Document 1: "2008 STRJ Report Semiconductor Blueprint Special Committee 2008 Annual Report", Chapter 8, p1-17, [online], March 2009, JEITA (Company) Electronic Information Technology Industry Association Semiconductor Technology Blueprint Special Committee , [Search on May 30, 2012], Internet <URL: http://strj-jeita.elisasp.net/strj/nenjihoukoku-2008.cfm>

Non-Patent Document 2: Takakura Shinji et al., Matsushita Electric Technology Car Related Device Technology Automotive High Temperature Action IC, No. 74, Japan, May 31, 2001, 35-40 pages

An epoxy resin having high heat resistance is generally an epoxy resin having a high crosslinking density.

Further, the epoxy resin having a high crosslinking density has a high water absorption rate and is brittle, and the thermal decomposition property is deteriorated. Moreover, there is a tendency that electrical characteristics are deteriorated. In the case of a semiconductor driven at a high temperature, not only the thermal decomposition property is important but also the electrical characteristics are important, and therefore, an epoxy resin having a high crosslinking density is not preferable. If the crosslinking density is lowered, these unfavorable characteristics are improved, but the heat resistance is lowered and the glass transition point (Tg) is lowered. When the driving temperature exceeds the glass transition point, the volume resistivity generally decreases at a temperature exceeding Tg, and thus the electrical characteristics are deteriorated.

In the case where such a characteristic is to be improved, there is a case where a method of improving the heat resistance by increasing the molecular weight of the resin itself is used, but the viscosity is extremely high. Therefore, since it is difficult to completely cover at a high viscosity, when it is necessary to completely cover the entire semiconductor in the sealing of the semiconductor, an unfilled portion such as a void is formed, which is not suitable as a semiconductor sealing material.

Further, in general, a cured product having high heat resistance tends to have poor flame retardancy.

In particular, a compound having a Tg having a thermomechanical property of 150 ° C or higher is often inferior in flame retardancy, and both heat resistance and flame retardancy are required.

That is, an object of the present invention is to provide an epoxy resin composition which is suitable for fluidity in semiconductor sealing applications and which is excellent in heat resistance and flame retardancy, a cured product thereof, and a semiconductor device using the same.

The present inventors conducted intensive studies in view of the above-described status quo, and as a result, completed the present invention.

That is, the present invention relates to the following [1] to [4].

[1] An epoxy resin composition comprising a softening point (according to ASTM D 3104) of an epoxy resin represented by the formula (1) and an epoxy compound represented by the following formula (2) at 100 to 120 ° C Epoxy resin mixture, biphenyl aralkyl type phenol resin and inorganic filler.

(In the formula (1), n represents the average value of 5 to 20)

[2] The epoxy resin composition according to [1], wherein the epoxy tree represented by the above formula (1) The epoxy resin obtained by reacting epihalohydrin with o-cresol novolac, the total content of the 2 nucleus and the 3 nucleus in the o-cresol novolac is subjected to gel permeation chromatography. The area percentage of the method (GPC) is 10 area% or less.

[3] A cured product obtained by hardening an epoxy resin composition of [1] or [2].

[4] A semiconductor device in which a semiconductor wafer is covered with an epoxy resin composition [1] or [2] formed into a granular or plate shape, and molded at 175 to 250 °C.

According to the present invention, it is possible to provide an epoxy resin composition which is excellent in heat resistance and flame retardancy, which is suitable for fluidity for semiconductor sealing, a cured product thereof, and a semiconductor device using the same.

In particular, the epoxy resin composition of the present invention can be used for sealing a semiconductor, particularly a semiconductor device for a power device, and can provide a highly reliable semiconductor device having high heat resistance and flame retardancy.

The epoxy resin composition of the present invention contains a specific epoxy resin mixture, a specific hardener, and an inorganic filler. Further, in the present specification, the softening point is a value measured in accordance with ASTM D 3104 (METTLER method) unless otherwise specified.

The epoxy resin mixture of the present invention contains an o-cresol novolak type epoxy resin and 4,4'-bisgoxypropoxy biphenyl. The epoxy resin mixture of the present invention contains an o-cresol novolac type epoxy resin as a main component. The content of 4,4'-bisgoxypropoxybiphenyl in epoxy resin mixture Preferably, it is 10 to 25 area% (calculated by a gel permeation chromatography (hereinafter referred to as GPC) (detector: RI)), more preferably 10 to 23 area%, and particularly preferably 10%. 20 area%. The preferred ratio of 4,4'-bis-glycidoxybiphenyl to o-cresol novolac-type epoxy resin is 9:1~3:1 in terms of area ratio of GPC (o-cresol novolac type ring) Oxygen resin: 4,4'-diepoxypropoxybiphenyl), especially preferably in a ratio of 9:1 to 4:1.

The 4,4'-bis-glycidoxybiphenyl is effective for improving fluidity by containing 10% by area or more, and is effective for maintaining heat-resistant decomposition characteristics and water resistance characteristics by a content of 25% by area or less.

In the epoxy resin mixture of the present invention, when an ortho-cresol novolac type epoxy resin is used as a main component as described above, the o-cresol novolac type epoxy resin is an epoxy compound represented by the following formula (1). Resin.

(In the formula (1), n represents the average value of 5 to 20)

In the o-cresol novolac type epoxy resin in the epoxy resin mixture of the present invention, the average value of n is 5 to 20, preferably 5 to 10. Further, the ortho-cresol novolac type epoxy resin is preferably used in the measurement by GPC, and the number average molecular weight is preferably from 100 to 10,000, more preferably from 1,000 to 5,000, still more preferably from 1300 to 2,000. Further, the softening point of the o-cresol novolac type epoxy resin in the epoxy resin composition of the present invention is from 100 to 120 ° C, preferably from 100 to 115 ° C. If the softening point is less than 100 The resin of °C reduces the heat resistance or thermal decomposition resistance of the epoxy resin composition formed, and in the case of an epoxy resin exceeding 120 ° C, even if it is a composition of an epoxy resin with biphenol, its melt viscosity It is also impossible to reduce the liquidity in applications such as semiconductor sealing applications, and it is a cause of voids.

As the shape of the epoxy resin mixture of the present invention, in the case of homogeneously mixing, it is preferred to have a crystalline solid resin shape, with respect to softening point (according to ASTM D 3104), workability, and hardening. The problem of formability is preferably from 100 to 120 ° C, more preferably from 100 to 110 ° C. Generally, the resin tends to have a sticky feeling when it is operated at room temperature, and is preferably used at a temperature of at least 50 ° C below the softening point. In particular, in view of the production of electronic materials in the Southeast Asia, it is assumed that the indoor temperature exceeds 40 ° C. Therefore, by making the softening point exceed 100 ° C, not only the operation at room temperature is extremely simple, but also the pulverization and kneading property are excellent. However, when the softening point is too high, there is a problem that it is not completely dissolved at the time of kneading, and if the temperature is excessively applied when melting, the possibility of reaction at the time of kneading is high. Therefore, it is preferably a softening point of 120 ° C or less.

In addition, the resin having crystallinity refers to a resin which has crystallinity and is not white turbid, and does not exhibit crystallinity at a time, and is left at 25 to 100 ° C for 8 hours or more. Also, the resin from the transparent becomes cloudy.

The epoxy resin mixture of the present invention preferably has a melt viscosity at 150 ° C of 0.11 Pa·s or more and 1.0 Pa·s or less, more preferably 0.11 Pa·s or more and 0.8 Pa·s or less, and particularly preferably 0.11 Pa. ‧s or more below 0.7Pa‧s.

In particular, in the power device, since the wire is thick, even if the viscosity is high, the sealing can be performed. However, if it exceeds 1.0 Pa·s, there is a problem in moldability. On the contrary, in the case of being too low, there is a problem that the air is directly entrained and hardened, and a weld void is formed, which has a certain degree of stickiness. The degree, that is, the viscosity of 0.11 Pa·s or more, is preferable because the air is easily extruded from the vent hole to the outside of the mold.

The epoxy resin mixture of the present invention may also uniformly mix the epoxy resins, but in the present invention, it is preferred to carry out the mixing of the cresol novolak with 4,4'-biphenol and with epihalohydrin. Obtained by reaction. As the cresol novolac, an o-cresol novolac is preferred.

Further, in the cresol novolac or o-cresol novolak to be used, the content of the two-core body and the three-core body is preferably 15% by area or less, and particularly preferably 10% by area or less, based on the measurement by GP °C. . Further, the two-core body is preferably 10% by area or less, and more preferably 5% by area or less. Further, the three-core body is preferably 10% by area or less, and more preferably 5% by area or less.

In the case of simple mixing, epoxidation of cresol novolac and epoxidation of 4,4'-biphenol are carried out separately. In this case, a reaction is produced in which the cresol novolacs are partially bonded to each other upon epoxidation, and the 4,4'-biphenol is partially bonded to each other. In this case, the cresol novolac varnish is partially polymerized, and the degree of viscosity rise is remarkable. Further, since 4,4'-biphenol is bonded to each other, the crystallinity is extremely high and the compatibility is poor, so that it is difficult to dissolve homogeneously. Moreover, it also causes a decrease in heat resistance.

On the other hand, when the mixture of the cresol novolak and the 4,4′-biphenol is epoxidized, the cresol can be inhibited by forming a compound in which the cresol novolak is bonded to the biphenol moiety. The novolacs are polymerized with each other to promote low viscosity. Further, the present compound has characteristics of both a cresol novolak and a biphenol, and is excellent in compatibility, and further suppresses a decrease in heat resistance.

The cresol novolak resin which can be used in the present invention can be used as a commercially available product, and can be produced by a reaction of cresol and formaldehyde (see JP-A-2002-179750, JP-A-2004-131585). As the softening point of the cresol novolak resin (according to ASTM D 3104), preferably 120 to 150 ° C, more preferably 120 to 145 ° C, and particularly preferably 120 to 140 ° C.

Further, as the structure, an o-cresol novolac, in particular, a bifunctional biscresol F is 5 area% or less in the measurement of GPC, and a trifunctional cresol novolac is 5 area% or less.

Further, the Mw (average molecular weight) is preferably 1,000 or more and less than 10,000, and more preferably 1,000 or more and less than 5,000. In the present range, there is a tendency that the balance of fluidity, compatibility, heat resistance, and heat decomposition resistance is excellent. Further, in the molecular weight distribution (Mw/Mn), it is preferably used in the range of 1.8 to 2.5. Especially good is 1.85~2.15.

Regarding 4,4'-biphenol, the purity is preferably 99% or more. The reason for this is that when it is partially oxidized by oxidation or the like, it becomes monofunctional, and thus the heat resistance is lowered.

The method of reacting the mixture of the cresol novolak and the 4,4'-biphenol with the epihalohydrin is not particularly limited, and an example of the synthesis method will be described below.

In the reaction for obtaining the epoxy resin mixture of the present invention, an epoxy resin mixture can be prepared by simultaneously reacting a cresol novolac (CN) and 4,4'-biphenol (BP) with an epihalohydrin. Here, as the ratio (weight ratio) of (CN) to (BP), CN/BP = 3 to 9, more preferably 3.5 to 5.7, and particularly preferably 3.5 to 4.5. In terms of heat resistance, flame retardancy, and fluidity balance, the present invention is preferred. Further, a mixture of (CN) and (BP) is hereinafter referred to as a phenol mixture in the present invention.

In the reaction for obtaining the epoxy resin mixture of the present invention, as the epihalohydrin, epichlorohydrin which is industrially easily available is preferred. The amount of the epihalohydrin used is usually 3.0 to 15 moles, preferably 3.0 to 10 moles, more preferably 3.5 to 8.5 moles, relative to the hydroxyl group of the phenol mixture of the present invention. 4.0 to 6.0 moles.

If it is less than 3.0 m, the epoxy equivalent becomes large, and the epoxy resin is formed. If the workability is deteriorated, if it exceeds 15 m, the amount of the solvent may be excessive.

In particular, in the present invention, the reactant of the cresol novolac and the biphenol contributes to the characteristics, and therefore it is preferably an amount of epichlorohydrin of 6.0 mol or less. Thereby, the bonding of the cresol novolak to the biphenol is adjusted.

In this case, the amount of incorporation of biphenol into the cresol novolak is preferably from 1 to 10%, particularly preferably from 1 to 8%. The amount can be calculated based on the number of moles of biphenol and cresol and GPC data based on NMR, and can be calculated from the theoretical reaction ratio at the time of synthesis and the area % of GPC. The specific calculation method is as follows. The amount of theoretical diglycidoxybiphenyl was confirmed based on the amount of addition. On the other hand, the content was confirmed by the peak area of the diglycidoxybiphenyl (detector: RI) according to the area ratio of GPC. This difference becomes the amount of incorporation. If it is only biphenol, the biphenols are preferentially bonded to each other, but in the case of a large amount of cresol novolac, it is preferentially incorporated into the cresol novolac in terms of probability theory, so the judgment can judge the difference. It is fine for the amount of incorporation. On the other hand, in the measurement based on NMR, the molar ratio was calculated from the peak area ratio of protons or carbon of each benzene nucleus. The theoretical amount of diglycidoxybiphenyl was confirmed based on the molar ratio. This is the same as above. Further, it can be roughly calculated from the difference between the actual epoxy equivalent and the theoretical epoxy equivalent calculated from the addition ratio.

In the above reaction, an alkali metal hydroxide is preferably used in the reaction with the epihalohydrin. Examples of the alkali metal hydroxide which can be used include sodium hydroxide, potassium hydroxide, and the like, and a solid matter or an aqueous solution thereof can be used. In the present invention, in terms of moisture, solubility, and handleability, It is particularly preferable to use a solid material formed into a sheet shape.

The amount of the alkali metal hydroxide to be used is usually 0.90 to 1.5 moles, preferably 0.95 to 1.25 moles, more preferably 0.99 to 1.15 moles, per mole of the hydroxyl group of the phenol mixture.

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

In the present reaction, it is preferred to use a nonpolar protic solvent (dimethyl sulfoxide, two in addition to the above epihalohydrin). An alkane, a dimethylimidazolidinone, etc., in the present invention, preferably a dimethyl hydrazine, two Alkane), 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 isopropanol (in the present invention, methanol is preferred). The amount of the nonpolar protic solvent or the alcohol having 1 to 5 carbon atoms is usually 2 to 50% by weight, preferably 4 to 25% by weight based on the amount of the epihalohydrin used. Further, epoxidation can be carried out while controlling the moisture in the system by azeotropic dehydration or the like.

In the case where the amount of water in the reaction system is large, there is a case where electrical reliability is lowered in the obtained epoxy resin mixture, and it is preferred to carry out the synthesis by controlling the moisture to 5% or less. Further, when an epoxy resin mixture is obtained by using a nonpolar protic solvent, an epoxy resin mixture excellent in electrical reliability can be obtained, and therefore a nonpolar protic solvent can be preferably used.

The reaction temperature is usually from 30 to 90 ° C, preferably from 35 to 80 ° C. In particular, in the present invention, in order to carry out epoxidation of higher purity, it is preferably 60 ° C or more, and particularly preferably under conditions of reflux conditions. The reaction time is usually from 0.5 to 10 hours, preferably from 1 to 8 hours, and particularly preferably from 1 to 3 hours. There is a case where the reaction does not proceed completely if the reaction time is short, and by-products are generated if the reaction time becomes long.

After the reactants of the epoxidation reaction are washed with water or not, the epihalohydrin or solvent is removed under heating and reduced pressure. Further, in order to obtain an epoxy resin mixture having a small amount of hydrolyzable halogen, the recovered epoxy resin mixture may be a ketone compound having 4 to 7 carbon atoms (for example, methyl isobutyl ketone or methyl ethyl ketone) , cyclopentanone, cyclohexanone, etc.) dissolved as a solvent, adding hydroxide The aqueous solution of an alkali metal hydroxide such as sodium or potassium hydroxide is reacted to make the ring closure. In this case, the amount of the alkali metal hydroxide to be used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, relative to the hydroxyl group of the phenol mixture used in the epoxidation of the invention. . 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 an epoxy resin mixture of the present invention. Further, it is preferably a plate-shaped body (plate shape, sheet shape, strip shape, etc.) which is preferably distilled at 110 to 170 ° C and then at 100 ° C or lower, more preferably 80 ° C or lower, after the solvent is distilled off under heating and reduced pressure. The film is formed into a plate shape, a drop shape (ball shape), and the like, and is taken out and taken out. Further, it may be a stepwise cooling method in which cooling is carried out at 80 ° C or lower and then at 60 ° C or lower. The solid matter obtained in this step exhibits a transparent amorphous shape or a white turbid shape in which crystals are dispersed. It is assumed that even if the solid matter is transparent and amorphous, it is crystallized by heating at 50 to 100 ° C for 30 minutes to 10 hours. The shape of white turbidity.

As the preferable resin characteristics of the epoxy resin mixture of the present invention, the epoxy equivalent is preferably from 175 to 215 g/eq., more preferably from 175 to 210 g/eq. When the epoxy equivalent is in the above range, an epoxy resin mixture excellent in heat resistance and electrical reliability of the cured product can be more easily obtained. In the case where the epoxy equivalent exceeds 215 g/eq., the ring of the epoxy group is not completely closed, and a plurality of compounds having no functional group are contained, and the epoxy equivalent is not lowered. Further, in many cases, most of the compounds which are not completely closed are contained in chlorine, and as an electronic material, there is a case where chlorine ions are generated under high-temperature and high-humidity conditions and corrosion of wiring due thereto is caused.

Further, as the total chlorine remaining in the epoxy resin mixture, it is preferably 1500 ppm. Hereinafter, it is more preferably 1200 ppm or less, and particularly preferably 900 ppm or less. Further, the chloride ion and the sodium ion are each preferably 5 ppm or less, more preferably 3 ppm or less. Regarding the chloride ion, it has been described above, and it is needless to say that a cation such as a sodium ion is a very important factor particularly in the use of a power device, and is one of the bad modes when a high voltage is applied.

In the epoxy resin composition of the present invention, as the curing agent, a phenol resin of a biphenyl aralkyl type is used as an essential component.

The curing agent in the present invention is not particularly limited as long as it is a structure in which a phenol is bonded to a phenyldiyl group, specifically, 4,4'-bis(chloromethyl)-1,1'- Substituted methylene group such as biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 4,4'-bis(hydroxymethyl)-1,1'-biphenyl Benzene compound and phenol: phenol, alkyl substituted phenol with 1-2 carbon atoms (cresol, ethyl phenol, etc.), dihydroxybenzene (resorcinol, hydroquinone, catechol, etc.), three A phenol resin obtained by the reaction of hydroxybenzene (m-phloroglucinol, etc.). As a preferable structure, the following are mentioned, for example.

(In the above formula, R each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyl group, and n represents a number of repetitions of 1 to 10)

In the present invention, the phenylene aralkyl type phenol resin is preferably a resin having a softening point (according to JIS K-7234) of 50 to 120 ° C, more preferably 55 to 90 ° C, and particularly preferably 50 to 84 ° C. If the softening point is lower than 50 ° C, there is a strong feeling of stickiness at room temperature and difficulty in handling. Also, if it exceeds At 120 ° C, there is a partial reaction between the hardener and the epoxy resin during the kneading.

Further, the melt viscosity at 150 ° C is preferably from 0.01 to 1.0 Pa s, more preferably from 0.01 to 0.5 Pa ‧ s. If it exceeds 1.0 Pa s, the fluidity is deteriorated and the unfilled portion is increased, which is not preferable. Further, it is considered that the molecular weight of the compound which is less than 0.01 Pa‧s is too low, or the residual phenol monomer has a problem that volatilization and crystallinity are difficult to obtain a homogeneous composition, which is not preferable.

In the epoxy resin composition of the present invention, the preferred range of the amount of the hardener used in the present invention is preferably an epoxy resin in the present invention in the weight ratio: the hardener in the present invention = 0.5 :1~2:1, more preferably 0.7:1~1.1:1, especially 0.7:1~0.9:1. Further, the content of the curing agent is preferably from 0.7 to 1.2 equivalents per equivalent of the epoxy group of the entire epoxy resin. When the amount is less than 0.7 equivalents per equivalent of the epoxy group, or when it exceeds 1.2 equivalents, there is a case where the hardening is incomplete and good hardenability is not obtained.

Here, in the case of the biphenyl aralkyl type phenol resin, the biphenyl aralkyl type phenol resin is preferably from 0.8 to 1.1, particularly preferably from 0.85 to 1.05, based on 1 mole of the epoxy resin mixture.

The epoxy resin composition of the present invention contains an inorganic filler. Examples of the inorganic filler include crystalline vermiculite, molten vermiculite, alumina, zircon, calcium silicate, calcium carbonate, tantalum carbide, tantalum nitride, boron nitride, zirconium oxide, forsterite, and talc. A powder such as spinel, titanium oxide or talc, or a bead formed by spheroidizing the same, but is not limited thereto. Here, in order to improve the cured property such as the water absorption rate and the linear expansion ratio, the filler which is combined with the epoxy resin mixture in the present invention and the curing agent in the present invention is preferably a vermiculite, molten vermiculite or alumina. . These may be used alone or in combination of two or more. The content of the inorganic filler is usually from 60 to 95% by weight, preferably from 70 to 90% by weight, based on the epoxy resin composition of the present invention.

There are defects such as the following: if it is less than 60% by weight, the water absorption rate and the linear expansion ratio If it is too high, if it exceeds 95% by weight, it cannot be kneaded evenly. Further, there is a problem in fluidity, and it is difficult to seal without filling.

Hereinafter, the blending ratio of the epoxy resin composition of the present invention and other blends will be described.

Specific examples of the hardening accelerator (also referred to as a curing catalyst or a polymerization catalyst) which can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole. a tertiary amine such as 2-(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5.4.0]undecene-7; a phosphine such as triphenylphosphine; tetrabutylammonium a quaternary ammonium salt such as a salt, a triisopropylmethylammonium salt, a trimethylsulfonium ammonium salt or a cetyltrimethylammonium salt; a triphenylbenzyl phosphonium salt, a triphenylethyl phosphonium salt, a tetradecyl phosphonium salt such as a tetrabutyl phosphonium salt (the relative ions of the tetrabasic salt are halogen, an organic acid ion, a hydroxide ion, etc., and are not particularly specified, and are particularly preferably an organic acid ion or a hydroxide ion); stannous octoate; Metal compounds, etc. In the case of using a hardening accelerator, 0.01 to 5.0 parts by weight is used as needed, based on 100 parts by weight of the epoxy resin.

In the epoxy resin composition, in addition to the epoxy resin mixture of the present invention, other epoxy resins may be used in combination. When used in combination, the ratio of the total epoxy resin is preferably 30% by weight or more, and particularly preferably 40% by weight or more.

Specific examples of the other epoxy resin include a novolac type epoxy resin, a bisphenol A type epoxy resin, a biphenyl type epoxy resin, a triphenylmethane type epoxy resin, and a phenol aralkyl type epoxy resin. Resin, etc. Specific examples thereof include bisphenol A, bisphenol S, thiodiphenol, bisphenol, stilbene, 4,4'-biphenol, 2,2'-biphenol, 3,3 ',5,5'-Tetramethyl-[1,1'-biphenyl]-4,4'-diol, hydroquinone, resorcinol, naphthalenediol, tris-(4-hydroxybenzene Methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, Dihydroxybenzene, dihydroxynaphthalene, etc.) with 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) a polycondensate of benzene, 1,4-bis(methoxymethyl)benzene or the like, a modified substance thereof, a halogenated bisphenol such as tetrabromobisphenol A, a glycidyl ether derived from an alcohol, or an alicyclic ring A sesquisesquioxane-based epoxy resin such as an epoxy resin, a glycidylamine epoxy resin or a glycidyl acrylate epoxy resin (in the form of a chain, a ring, a ladder or a mixture of at least two of these) A solid or liquid epoxy resin having a structure of a siloxane having an epoxy group and/or an epoxycyclohexane structure, but is not limited thereto.

The curing agent contained in the epoxy resin composition of the present invention may further contain a curing agent other than the biphenyl aralkyl type phenol resin. For example, a phenol resin, a phenol type compound, an amine type compound, an acid anhydride type compound, a guanamine type compound, a carboxylic acid type compound, etc. are mentioned. When used in combination, the ratio in the hardener is preferably 30% by weight or more, and particularly preferably 40% by weight or more.

Specific examples of the hardener which can be used are as follows.

Phenol resins and phenolic compounds: bisphenol A, bisphenol F, bisphenol S, bismuth bisphenol, stilbene, 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, 1,4'-bis(chloromethyl)benzene, a polycondensate such as 1,4'-bis(methoxymethyl)benzene or the like, a halogenated bisphenol such as tetrabromobisphenol A, a polyphenol such as a condensate of decene and a phenol, but It is not limited to these. These may be used alone or in combination of two or more.

The phenol resin which is preferably used in combination is phenol aralkyl resin (resin having an aromatic alkylene structure), and particularly preferably a resin having at least one selected from the group consisting of phenol, naphthol and cresol. A structure in which at least one alkyl group of the linker is selected from a benzene structure or a naphthalene structure (specifically, a xyloc-based resin, naphthol-phenol aryl) Alkyl, phenol-naphthaldehyde novolak resin, etc.).

Examples thereof include an amine compound, a guanamine compound, a diaminodiphenylmethane, a diethylidene triamine, a tris-ethyltetramine, a diaminodiphenylphosphonium, an isophorone diamine, and a dicyandiamide. A nitrogen-containing compound such as an amine or a polyamine resin synthesized from a dimer of linoleic acid and ethylenediamine, but is not limited thereto. These may be used alone or in combination of two or more.

Examples of the acid anhydride-based compound and the carboxylic acid-based compound include phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, and methyltetrahydrophthalic acid. Methylic anhydride, methylic acid anhydride, ceric anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butane tetracarboxylic anhydride, bicyclo [2.2.1] heptane-2,3- An acid anhydride such as a dicarboxylic acid anhydride, a methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, or a cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride; The carboxylic acid resin obtained by the addition reaction of methanol-modified polyfluorene oxide with the above acid anhydride is not limited thereto. These may be used alone or in combination of two or more.

Examples of the other hardening agent which can be used together include, but are not limited to, an imidazole, a boron trifluoride-amine complex, and a compound of an anthracene derivative. These may be used alone or in combination of two or more.

In the present invention, a phenol resin is preferably used in terms of reliability.

In the epoxy resin composition of the present invention, the amount of the curing agent used is preferably from 0.7 to 1.2 equivalents per equivalent of the epoxy group of the entire epoxy resin. Relative to epoxy 1 In the case where the equivalent amount is less than 0.7 equivalent or more than 1.2 equivalent, there is a case where hardening is incomplete and good hardenability is not obtained.

In the epoxy resin composition of the present invention, a hardening accelerator may be used together with the hardener. Specific examples of the hardening accelerator which can be used include the above. In the case of using a hardening accelerator, 0.01 to 5.0 parts by weight is used as needed, based on 100 parts by weight of the epoxy resin.

The epoxy resin composition of the present invention may further contain a phosphorus-containing compound as a flame retardancy imparting component. As the phosphorus-containing compound, it may be a reactive type or an additive type. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, and cresyl phosphate. -2,6-bis(xylene) ester, 1,3-phenylene bis(di(xylylene) phosphate), 1,4-phenylene bis(di(xylylene phosphate), 4, Phosphates such as 4'-biphenyl (di(xylylene phosphate) phosphate; 9,10-dihydro-9-oxa-10-phosphinophen-10-oxide, 10(2,5-dihydroxybenzene a phosphine such as -10H-9-oxa-10-phosphaphenanthrene-10-oxide; a phosphorus-containing epoxy compound obtained by reacting an epoxy resin with an active hydrogen of the above phosphine; red phosphorus; Preferred are phosphates, phosphines or phosphorus-containing epoxy compounds, particularly preferably 1,3-phenylene bis(di(xylylene) phosphate), 1,4-phenylene bis(phosphine di(xylene) phosphate ) ester), 4,4'-biphenyl (bis(xylene) phosphate) or phosphorus-containing epoxy compound. The content of the phosphorus-containing compound is preferably a phosphorus-containing compound / all epoxy resins = 0.1 to 0.6 (weight ratio). When it is 0.1 or less, the flame retardancy is insufficient, and when it is 0.6 or more, the hygroscopic property and dielectric properties of the cured product are lowered.

Further, in the epoxy resin composition of the present invention, an antioxidant may be added as needed. Examples of the antioxidant that can be used include a phenol-based, sulfur-based, and phosphorus-based antioxidant. The antioxidant may be used singly or in combination of two or more. About the use of antioxidants, relative to the hair 100 parts by weight of the resin component in the epoxy resin composition is usually 0.008 to 1 part by weight, preferably 0.01 to 0.5 part by weight.

Specific examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, and β-( 3,5-di-t-butyl-4-hydroxyphenyl)propionic acid stearyl ester, 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid isooctyl ester, 2,4 - bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-three Monophenols such as 2,4-bis[(octylthio)methyl]o-cresol; 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2 '-Methylene bis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-Adenine Bis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di Tert-butyl-4-hydroxy-phenylpropanamide), 2,2-thio-diethylidene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate ], 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3-third 4--4-hydroxy-5-methylphenyl)propanoxy}ethyl]2,4,8,10-tetraoxaspiro[5.5]undecane, bis(3,5-di-third Bisphenol 4-hydroxybenzylsulfonate) bisphenols such as calcium; 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3 ,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetra-[methylene-3-(3',5'-di Tert-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'- -(4'-hydroxy-3'-t-butylphenyl)butyric acid]diol, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanate 1,3,5-tris(3',5'-di-t-butyl-4'-hydroxybenzyl) symmetry three -2,4,6-(1H,3H,5H) triols, polymer phenols such as tocopherols.

Specific examples of the sulfur-based antioxidant include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and 3,3'-thiodipropionic acid. Distearyl ester and the like.

Specific examples of the phosphorus-based antioxidant include triphenyl phosphite and phosphorous. Diphenylisodecyl phthalate, phenyl diisononyl phosphite, tris(nonylphenyl) phosphite, diisodecyl neopentyl phosphite, tris(2,4-phosphite) Di-tert-butylphenyl)ester, cyclic neopentane tetrakis(bis-octadecyl)phosphite, cyclic neopentyltetrakis(2,4-di-t-butylphenyl) Phosphate ester, cyclic neopentyltetrakis(2,4-di-t-butyl-4-methylphenyl)phosphite, bis[2-t-butyl-6-methyl-4-{ a phosphite such as 2-(octadecyloxycarbonyl)ethyl}phenyl]hydrogen phosphite; 9,10-dihydro-9-oxa-10-phosphinophen-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10- Oxaphosphonium phenanthrene oxides such as dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

These antioxidants may be used alone or in combination of two or more. In particular, a phosphorus-based antioxidant is preferred in the present invention.

Further, in the epoxy resin composition of the present invention, a light stabilizer may be added as needed.

As the light stabilizer, a hindered amine light stabilizer, particularly HALS or the like is preferable. The HALS is not particularly limited, and examples thereof include dibutylamine/1,3,5-three. /N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine and N-(2,2,6,6-tetramethyl- Polycondensate of 4-piperidinyl)butylamine, dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, polycondensation [{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-three -2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imido}hexamethylene {(2,2,6,6-tetramethyl-) 4-piperidinyl)imido}], malonic acid bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-di) Methyl ethyl)-4-hydroxyphenyl]methyl]butyl ester, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, sebacic acid bis(1, 2,2,6,6-pentamethyl-4-piperidinyl) bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate , 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid bis(1,2,2,6,6-pentamethyl-4-piperidinyl ) esters, etc. HALS may be used alone or in combination of two or more.

Further, in the epoxy resin composition of the present invention, a binder resin may be blended as needed. 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 polyruthenium resin. An amine resin, a polysiloxane resin, or the like is not limited thereto. The blending amount of the binder resin is preferably in the range of flame retardancy and heat resistance of the non-destructive 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 epoxy resin component. Share.

Moreover, in the epoxy resin composition of the present invention, a cyanate resin, a maleimide resin, a benzo can also be blended as needed. The resin for improving the heat resistance is usually used in an amount of 10 to 50 parts by weight, preferably 15 to 40 parts by weight, based on 100 parts by weight of the epoxy resin component.

Further, in the epoxy resin composition of the present invention, a mold release agent such as a decane coupling agent, stearic acid, palmitic acid, zinc stearate or calcium stearate, a surfactant, a dye, a pigment, and an ultraviolet absorbing agent may be added. The various blending agents and the various thermosetting resins are usually used in an amount of 0.05% by weight to 1.5% by weight, preferably 0.05% by weight to 1.0% by weight based on the total amount of the epoxy resin composition.

The epoxy resin composition of the present invention can be obtained by uniformly mixing the components. The epoxy resin composition of the present invention can be easily produced into a cured product by the same method as a conventionally known method. For example, if necessary, the modified epoxy resin, the curing agent and/or the hardening accelerator, the phosphorus-containing compound, the binder resin, the inorganic filler, and the blending agent are pulverized, and then an extruder, a kneader, a roll, or the like is used. The epoxy resin composition is obtained by mixing, and the epoxy resin composition is further pulverized into a plate shape or a granular shape, and is formed by a transfer molding machine or a compression molding machine at 140 to 220 ° C, and further at 100 to 220 ° C. Heat up for 1~10 hours to get the hair Hardened matter of the Ming.

The semiconductor device of the present invention is obtained by mounting a semiconductor element on a printed wiring board and sealing it with the epoxy resin composition of the present invention. The method of mounting the semiconductor element and the sealing method are not particularly limited. For example, the connection electrode portion on the multilayer printed wiring board is aligned with the solder bump of the semiconductor element using a flip chip bonding machine or the like. Thereafter, the solder bumps are heated to a temperature higher than the melting point by heating, and the printed wiring board is joined to the solder bumps by fusion bonding. Next, a liquid sealing resin is filled between the printed wiring board and the semiconductor element and hardened. Thereby, a semiconductor device is obtained. The semiconductor device thus obtained has excellent heat resistance and thermal decomposition resistance, and is therefore particularly useful for a vehicle power device or the like.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, and the following parts are parts by weight unless otherwise specified. Furthermore, the invention is not limited to the embodiments. In the following, unless otherwise stated, the area % indicates the area percentage calculated based on the measurement value by gel permeation chromatography (GPC).

Hereinafter, various analysis methods used in the examples will be described.

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

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

Softening point: according to ASTM D 3104

GPC:

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

Linked Solvent: Tetrahydrofuran

Flow rate: 0.5ml/min

Column temperature: 40 ° C

Detection: RI (differential refraction detector)

Hereinafter, the present invention will be specifically described by way of examples and comparative examples.

(Synthesis Example 1)

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, an o-cresol novolak was added while performing a nitrogen purge (softening point 138 ° C 2 nucleus 2.5 area% 3 nucleus 3.4 area % hydroxyl equivalent 120 g / eq.) 92.6 A solution of 21.2 parts of 4,4'-biphenol, 416 parts of epichlorohydrin, and 95.8 parts of dimethyl hydrazine were dissolved under stirring, and the temperature was raised to 45 °C. Then, 42 parts of flaky sodium hydroxide was added in portions over 90 minutes, and then the reaction was further carried out at 45 ° C for 2 hours, and at 70 ° C for 75 minutes. After the completion of the reaction, excess solvent such as epichlorohydrin was distilled off from the oil layer under reduced pressure using a rotary evaporator. 352 parts of methyl isobutyl ketone was added to the residue and dissolved, and the mixture was heated to 75 ° C after washing with water. 13 parts of a 30% by weight aqueous sodium hydroxide solution was added under stirring, and the reaction was carried out for 1 hour, and then washed with water until the washing water of the oil layer became neutral, and the methyl group was obtained from the obtained solution under reduced pressure using a rotary evaporator. Isobutyl ketone or the like was distilled off, whereby 153 parts of the epoxy resin mixture (EP1) of the present invention was obtained. The epoxy resin obtained had an epoxy equivalent of 187 g/eq., a softening point of 108 ° C, and an ICI melt viscosity of 150 ° C of 0.60 Pa s.

The theoretical amount of diglycidoxybiphenyl calculated from the starting materials was 20%. On the other hand, the amount of the diglycidoxybiphenyl calculated by the gel permeation chromatography was 16.2%. From this fact, it was found that 3.8% of the biphenol structure was incorporated into the cresol novolak structure. Further, the average molecular weight Mw was 2517.

(Synthesis Example 2)

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, an o-cresol novolac was added while performing a nitrogen purge (softening point 138 ° C 2 nucleus 1.8 area% 3 nucleus 3.0 area%) 92.6 parts of hydroxyl group equivalent: 122.6 parts, 21.2 parts of 4,4'-biphenol, 602 parts of epichlorohydrin, and 95.8 parts of dimethyl hydrazine were dissolved under stirring, and the temperature was raised to 45 °C. Then, 42 parts of flaky sodium hydroxide was added in portions over 90 minutes, and then the reaction was further carried out at 45 ° C for 2 hours, and at 70 ° C for 75 minutes. After the completion of the reaction, excess solvent such as epichlorohydrin was distilled off from the oil layer under reduced pressure using a rotary evaporator. 352 parts of methyl isobutyl ketone was added to the residue and dissolved, and the mixture was heated to 75 ° C after washing with water. 13 parts of a 30% by weight aqueous sodium hydroxide solution was added under stirring, and the reaction was carried out for 1 hour, and then washed with water until the washing water of the oil layer became neutral, and the methyl group was obtained from the obtained solution under reduced pressure using a rotary evaporator. Isobutyl ketone or the like was distilled off, whereby 158 parts of the epoxy resin mixture (EP2) of the present invention was obtained. The epoxy resin obtained had an epoxy equivalent of 185 g/eq., a softening point of 118 ° C, and an ICI melt viscosity of 150 ° C of 0.53 Pa ‧ .

The theoretical amount of diglycidoxybiphenyl calculated from the starting materials was 20%. On the other hand, the amount of the diglycidoxybiphenyl calculated by the gel permeation chromatography was 18.7%. From this situation, it was found that 1.3% of the biphenol structure was incorporated into the cresol novolak structure. Further, the average molecular weight Mw was 2,368.

(Synthesis Example 3)

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, an o-cresol novolak was added while performing a nitrogen purge (softening point 139 ° C 2 nucleus 1.7 area % 3 nucleus 2.9 area % hydroxyl equivalent 120 g / eq.) 90.0 A solution of 23.3 parts of 4,4'-biphenol, 416 parts of epichlorohydrin, and 95.8 parts of dimethyl hydrazine were dissolved under stirring, and the temperature was raised to 45 °C. Then, after adding 42 parts of flaky sodium hydroxide in batches for 90 minutes, the reaction was further carried out at 45 ° C for 2 hours, and the reaction was carried out at 70 ° C for 75 minutes. After the completion of the reaction, excess solvent such as epichlorohydrin was distilled off from the oil layer under reduced pressure using a rotary evaporator. 352 parts of methyl isobutyl ketone was added to the residue and dissolved, and the mixture was heated to 75 ° C after washing with water. Adding 13 parts of a 30% by weight aqueous sodium hydroxide solution under stirring After the reaction for 1 hour, the water was washed until the washing water of the oil layer became neutral, and methyl isobutyl ketone or the like was distilled off from the obtained solution under reduced pressure using a rotary evaporator, whereby the epoxy of the present invention was obtained. 149 parts of resin mixture (EP3). The obtained epoxy resin had an epoxy equivalent of 179 g/eq., a softening point of 111 ° C, and an ICI melt viscosity of 150 ° C of 0.43 Pa·s.

The theoretical amount of diglycidoxybiphenyl calculated from the starting materials was 22%. On the other hand, the amount of the diglycidoxybiphenyl calculated by the gel permeation chromatography was 19.3%. From this fact, it was found that 2.7% of the biphenol structure was incorporated into the cresol novolak structure. Further, the average molecular weight Mw was 2410.

(Synthesis Example 4)

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, an o-cresol novolak was added while performing a nitrogen purge (softening point 100 ° C 2 nucleus 8.2 area % 3 nucleus 9.1 area % hydroxyl equivalent 120 g / eq.) 96 A portion, 18.6 parts of 4,4'-biphenol, 416 parts of epichlorohydrin, and 95.8 parts of dimethyl hydrazine were dissolved under stirring, and the temperature was raised to 45 °C. Then, after adding 42 parts of flaky sodium hydroxide in batches for 90 minutes, the reaction was further carried out at 45 ° C for 2 hours, and the reaction was carried out at 70 ° C for 75 minutes. After the completion of the reaction, excess solvent such as epichlorohydrin was distilled off from the oil layer under reduced pressure using a rotary evaporator. 352 parts of methyl isobutyl ketone was added to the residue and dissolved, and the mixture was heated to 75 ° C after washing with water. 13 parts of a 30% by weight aqueous sodium hydroxide solution was added under stirring, and the reaction was carried out for 1 hour, and then washed with water until the washing water of the oil layer became neutral, and the methyl group was obtained from the obtained solution under reduced pressure using a rotary evaporator. Isobutyl ketone or the like was distilled off, whereby 165 parts of the epoxy resin mixture (EP4) for comparison was obtained. The epoxy resin obtained had an epoxy equivalent of 187 g/eq., a softening point of 95 ° C, and an ICI melt viscosity of 150 Pa s at 150 ° C.

The theoretical amount of diglycidoxybiphenyl calculated from the starting material was 17.5%. On the other hand, the amount of the diglycidoxybiphenyl calculated by the gel permeation chromatography was 15.9%. As can be seen from this situation, The 1.6% biphenol structure was incorporated into the cresol novolac structure. Further, the average molecular weight Mw was 1,087.

(Synthesis Example 5)

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, o-cresol novolac (softening point 138 ° C 2 nucleus 2.2 area % 3 nucleus 3.6 area % hydroxyl equivalent 120 g / eq.) was added while performing nitrogen purge. A portion, 600 parts of epichlorohydrin, and 95.8 parts of dimethyl hydrazine were dissolved under stirring, and the temperature was raised to 45 °C. Then, after adding 42 parts of flaky sodium hydroxide in batches for 90 minutes, the reaction was further carried out at 45 ° C for 2 hours, and the reaction was carried out at 70 ° C for 75 minutes. After the completion of the reaction, excess solvent such as epichlorohydrin was distilled off from the oil layer under reduced pressure using a rotary evaporator. 352 parts of methyl isobutyl ketone was added to the residue and dissolved, and the mixture was heated to 75 ° C after washing with water. 13 parts of a 30% by weight aqueous sodium hydroxide solution was added under stirring, and the reaction was carried out for 1 hour, and then washed with water until the washing water of the oil layer became neutral, and the methyl group was obtained from the obtained solution under reduced pressure using a rotary evaporator. Isobutyl ketone or the like was distilled off, whereby 166 parts of an epoxy resin (EP-A) was obtained. The obtained epoxy resin had an epoxy equivalent of 202 g/eq., a softening point of 103 ° C, and an ICI melt viscosity of 150 ° C of 3.1 Pa ‧ . Further, the average molecular weight Mw was 3073.

(Synthesis Example 6)

In Synthesis Example 5, "o-cresol novolac (softening point 138 ° C 2 nucleus 2.2 area% 3 nucleus 3.6 area% hydroxyl equivalent 120 g / eq.) 120 parts" was changed to "o-cresol novolac (softening The synthesis was carried out in the same manner except that the ratio of 130 ° C 2 nucleus <5% 3 nucleus < 5% hydroxyl equivalent 130 g / eq.) was 130 parts. The obtained epoxy resin (EP-B) had an epoxy equivalent of 202 g/eq., a softening point of 101 ° C, and an ICI melt viscosity of 2.9 Pa·s at 150 ° C. Further, the average molecular weight Mw was 2,980.

(Synthesis Example 7)

In Synthesis Example 5, "o-cresol novolac (softening point 138 ° C 2 nucleus 2.2 area% 3 nucleus 3.6 area% hydroxyl equivalent 120 g / eq.) 120 parts" was changed to "o-cresol novolac (softening The synthesis was carried out in the same manner except that the nucleus of 8.2% of the nucleus, 8.2% of the nucleus, and the hydroxy group equivalent of 120 g/eq.

The obtained epoxy resin (EP-C) had an epoxy equivalent of 196 g/eq., a softening point of 61 ° C, and an ICI melt viscosity of 150 ° C of 0.1 Pa ‧ (EOCN-1020-62). Further, the average molecular weight Mw was 1,526.

Examples 1, 2, and 3 Comparative Examples 1 to 3

<various hardening property test>

The epoxy resin obtained above was blended in the ratio (parts by weight) of the following Table 1, and uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition of the present invention and a comparative example. The epoxy resin composition was pulverized by a mixer and further slabized by a tablet press. The plated epoxy resin composition was transferred (175 ° C × 60 sec), and further cured at 160 ° C × 2 hours + 180 ° C × 6 hours after demolding to obtain a test piece for evaluation.

The evaluation method for each evaluation is described below. Further, the evaluation results are shown in Table 1 below.

‧ Heat resistance (TMA): Measured in accordance with JIS K 7244.

‧ Flame retardancy: According to UL94. Among them, the sample size was set to have a width of 12.5 mm × a length of 150 mm and a thickness of 0.8 mm.

‧lingering flame time: the total of the residual flame time after five flames of one set of samples in contact with the flame

‧heat resistance (DMA)

Dynamic viscoelasticity measuring device: TA-instruments, DMA-2980

Measuring temperature range: -30~280°C

Heating rate: 2 ° C / min

Test piece size: use cut to 5mm × 50mm (thickness about 800μm)

Tg: set the peak point of Tan-δ to Tg

*EP5: Trisphenol methane type epoxy resin (EPPN 501H, softening point (according to JIS K-7234) 52 ° C)

From the above results, it was confirmed that the epoxy resin composition of the present invention can obtain a cured product having both high heat resistance and flame retardancy.

The present invention has been described in detail above with reference to the specific embodiments thereof, and it is understood that various changes and modifications may be made without departing from the spirit and scope of the invention.

In addition, the present application is based on a Japanese patent application filed on Feb. 7, 2014 (Japanese Patent Application No. Hei. Further, all references cited herein are incorporated herein by reference in their entirety.

[Industrial availability]

Since the epoxy resin composition of the present invention is excellent in heat resistance and flame retardancy, it is useful as an electrical and electronic material, particularly a semiconductor sealing agent or a film substrate material.

Claims (3)

An epoxy resin composition containing an epoxy resin having an epoxy resin represented by the formula (1) and an epoxy compound represented by the following formula (2) at a softening point (according to ASTM D 3104) of 100 to 120 ° C a mixture, a biphenyl aralkyl type phenol resin and an inorganic filler, wherein the epoxy resin represented by the formula (1) is an epoxy resin obtained by reacting epihalohydrin with an o-cresol novolak. The total content of the 2 nucleus and the 3 nucleus in the o-cresol novolac is 10% by area or less based on the area ratio of the gel permeation chromatography (GPC). (In the formula (1), n represents the average value of 5 to 20) A hardened material obtained by hardening an epoxy resin composition of the first application of the patent scope. A semiconductor device which covers a semiconductor wafer with an epoxy resin composition of the first application of the invention in the form of a pellet or a plate, and is molded at 175 to 250 °C.