JP2016125007A - Epoxy resin composition, cured product, electrical component and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition having excellent heat resistance, low linear expansion, and the like, and provide a cured product and an electrical/electronic component.SOLUTION: An epoxy resin composition comprises a compound represented by the following formula (1) (where R-Rindependently represent a hydrogen atom or a monovalent group represented by the formula (2), where at least one monovalent group represented by the formula (2) is present), and a curing agent.SELECTED DRAWING: None

Description

  The present invention relates to an epoxy resin composition and a cured product excellent in heat resistance and low linear expansion. The present invention also relates to an electrical / electronic component comprising the epoxy resin composition.

Epoxy resins are generally cured with various curing agents, resulting in cured products with excellent mechanical properties, heat resistance, electrical properties, etc., and are used in a wide range of fields such as adhesives, paints, and electronic materials. . Among the fields of electronic materials, for example, cresol novolac type epoxy resins are generally used for semiconductor sealing materials.
With the recent development of the electronics industry, performances such as heat resistance and low linear expansion required for electronic devices have become severe. For example, tetrakisphenolethane type epoxy with improved heat resistance, adhesion and toughness. Resins have been developed (Patent Document 1). However, even if it is the said epoxy resin, it cannot be said that heat resistance and low linear expansion property are enough.

International Publication WO2006 / 001395 Pamphlet

  The subject of this invention is providing the epoxy resin composition excellent in heat resistance, low linear expansion property, etc., hardened | cured material, and an electrical / electronic component.

As a result of intensive studies by the present inventors to solve the above-mentioned problems, it was found that an epoxy resin composition containing an epoxy resin having a specific skeleton and a curing agent solves the above-mentioned problems, and the present invention has been completed. That is, the gist of the present invention is as follows.
[1] The following formula (1):

(Wherein R ^{1 to} R ⁴ are each independently a hydrogen atom or the following formula (2):

The monovalent group represented by Formula (2) is 1 or more. )
An epoxy resin composition comprising a compound represented by: and a curing agent,
[2] The compound represented by the formula (1) is represented by the following formula (3):

The epoxy resin composition according to claim 1, which is a compound obtained by reacting a compound represented by formula (II) with epihalohydrin.
[3] The epoxy resin composition according to [1] or [2], containing 0.01 to 1000 parts by weight of a curing agent with respect to 100 parts by weight of the compound represented by the formula (1).
[4] Any one of [1] to [3], wherein the curing agent is at least one selected from the group consisting of a phenolic curing agent, an amine curing agent, an acid anhydride curing agent, and an amide curing agent. An epoxy resin composition according to claim 1,
[5] The epoxy resin composition according to any one of [1] to [4], further including an epoxy resin different from the compound represented by the formula (1),
[6] The epoxy according to [5], wherein the compound represented by the formula (1) is contained in the epoxy resin composition according to [5] in an amount of 40 wt% to 100 wt% with respect to all epoxy resin components. Resin composition,
[7] The epoxy resin composition according to [6], including 0.01 to 20 parts by weight of a curing agent with respect to 100 parts by weight of all epoxy resin components.
[8] The epoxy resin composition according to any one of [1] to [7], further including an inorganic filler, wherein the content of the inorganic filler in the epoxy resin composition is 65 to 95% by weight,
[9] A cured product obtained by curing the epoxy resin composition according to any one of [1] to [8],
[10] An electrical component obtained by curing the epoxy resin composition according to any one of [1] to [8],
[11] An electronic component obtained by curing the epoxy resin composition according to any one of [1] to [8],
Exist.

  According to the present invention, an epoxy resin composition and a cured product excellent in heat resistance, low linear expansion property, and the like are provided. Moreover, since the epoxy resin composition of this invention has said effect, it can apply especially useful to the field | area of a semiconductor sealing material and a laminated board.

Embodiments of the present invention will be described in detail below, but the following description is an example of the embodiments of the present invention, and the present invention is not limited to the following description unless it exceeds the gist. Absent. In addition, when using the expression “to” in the present specification, it is used as an expression including numerical values or physical property values before and after the expression.
〔Epoxy resin〕
The epoxy resin composition and the cured product of the present invention have the following formula (1):

(Wherein R ^{1 to} R ⁴ are each independently a hydrogen atom or the following formula (2):

(A monovalent group represented by the formula (2) is present, and one or more monovalent groups represented by the formula (2) are present.)
It has an epoxy resin which is a compound represented by.
<Chemical structure>
In the formula (1), R ^{1 to} R ⁴ are each independently a group (epoxy group) represented by the formula (2) or a hydrogen atom. That is, any group may be a hydrogen atom, and the other group may be an epoxy group of the formula (2). However, since Formula (1) is an epoxy resin, at least one group includes an epoxy group as R ^{1 to} R ⁴ in Formula (1). The epoxy resin of formula (1) is usually a mixture of these different molecules of R ^{1 to} R ⁴ . In addition, the number of the epoxy groups in the epoxy resin of Formula (1) is shown as an epoxy equivalent mentioned later.

<Physical properties / characteristics>
[Epoxy equivalent]
The epoxy resin of formula (1) has an epoxy equivalent of 150 g / equivalent or more and 154 g / equivalent or more from the viewpoint of obtaining physical properties such as heat resistance and low linear expansion based on the skeleton of formula (1). On the other hand, from the viewpoint of improving the handleability, it is 300 g / equivalent or less, preferably 250 g / equivalent or less, more preferably 200 g / equivalent or less, and particularly preferably 180 g / equivalent or less. preferable. In the present invention, “epoxy equivalent” is defined as “the mass of an epoxy resin containing one equivalent of an epoxy group” and can be measured according to JIS K7236.

[Method for producing epoxy resin]
Although there is no restriction | limiting in particular about the manufacturing method of the epoxy resin of Formula (1), For example, the manufacturing method by the one-step method demonstrated below, the manufacturing method by a two-step method, the manufacturing method via an allylation reaction, etc. are mentioned. These methods are described in detail below.
[Production method by one-step method]
The epoxy resin according to another embodiment of the present invention has the following formula (3):

It is obtained by reacting a phenol compound represented by the formula with epihalohydrin and has an epoxy equivalent of 150 to 300 g / equivalent.
In addition, when manufacturing the epoxy resin of said Formula (1) by a one-step method, although the phenolic compound and epihalohydrin which are represented by the said Formula (3) are used as a raw material, except a phenolic compound represented by Formula (3) And a phenol represented by the formula (1) and / or the phenol represented by the formula (3), in combination with a polyhydric hydroxy compound (sometimes referred to as “other polyvalent hydroxy compound” in the present invention). You may manufacture as a mixture of a compound and another epoxy resin. However, from the viewpoint of enhancing the effect of the present invention, the ratio of the phenol compound represented by the formula (3) is preferably 30 mol% or more, more preferably 50%, based on the total amount of the entire polyvalent hydroxy compound used as a raw material. It is more than mol%, more preferably more than 80 mol%. Moreover, the upper limit is 100 mol%, Most preferably, it is 100 mol%. The “polyhydric hydroxy compound” in the present invention is a general term for dihydric or higher phenol compounds and dihydric or higher alcohols.

Other polyhydroxy compounds include bisphenol A, bisphenol F, bisphenol S, bisphenol AD, bisphenol AF, hydroquinone, resorcin, methylresorcin, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, thiodiphenols, phenol novolac Resin, cresol novolak resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, terpene phenol resin, dicyclopentadiene phenol resin, bisphenol A novolak resin, naphthol novolak resin, brominated bisphenol A, brominated phenol novolak resin, etc. Polyhydric phenols (however, phenolation represented by the formula (3)) And polyphenol resins obtained by condensation reactions of various phenols with various aldehydes such as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, and glyoxal, and condensation reactions of xylene resins with phenols. Polyphenol resins obtained, various phenol resins such as heavy oil or co-condensation resin of pitches, phenols and formaldehyde, ethylene glycol, trimethylene glycol, propylene glycol, 1,3-butanediol, Chain aliphatic diols such as 1,4-butanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol; cyclohexanediol, cyclodecanediol, etc. Of cycloaliphatic diols; Ether glycol, polyoxyethylene trimethylene ether glycol, polyalkylene ether glycols such as polypropylene ether glycol, and the like. Among these, phenol novolak resin, phenol aralkyl resin, polyhydric phenol resin obtained by condensation reaction of phenol and hydroxybenzaldehyde, biphenyl aralkyl resin, naphthol aralkyl resin, ethylene glycol, trimethylene glycol, propylene glycol, Chain aliphatic diols such as 1,3-butanediol, 1,4-butanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, Cycloaliphatic diols such as cyclohexanediol and cyclodecanediol, and polyalkylene ether glycols such as polyethylene ether glycol, polyoxytrimethylene ether glycol, and polypropylene ether glycol Le, and the like can be mentioned.

  The compound having two or more hydroxyl groups used as a raw material is usually an epihalohydrin in an amount corresponding to 0.8 to 20 equivalents, preferably 0.9 to 15 equivalents, more preferably 1.0 to 10 equivalents per equivalent of the hydroxyl groups. To make a uniform solution. It is preferable that the amount of epihalohydrin is not less than the above lower limit because the high molecular weight reaction can be easily controlled and an appropriate melt viscosity can be obtained. On the other hand, when the amount of epihalohydrin is less than or equal to the above upper limit, production efficiency tends to improve, which is preferable. In addition, as epihalohydrin in this reaction, epichlorohydrin or epibromohydrin is usually used.

  Next, while stirring the solution, it is usually 0.5 to 2.0 equivalents, more preferably 0.7 to 1.8 equivalents, still more preferably 0.9 to 1.6 equivalents per equivalent of hydroxyl group of the raw material. An amount of alkali metal hydroxide corresponding to an equivalent amount is added as a solid or an aqueous solution, and reacted. It is preferable for the amount of the alkali metal hydroxide to be not less than the above lower limit because the unreacted hydroxyl group and the generated epoxy resin are difficult to react and the high molecular weight reaction can be easily controlled. Further, it is preferable that the amount of the alkali metal hydroxide is not more than the above upper limit value because impurities due to side reactions are hardly generated. As the alkali metal hydroxide used here, sodium hydroxide or potassium hydroxide is usually mentioned.

  This reaction can be performed under normal pressure or reduced pressure, and the reaction temperature is preferably 40 to 150 ° C, more preferably 60 to 100 ° C, and still more preferably 80 to 100 ° C. It is preferable for the reaction temperature to be equal to or higher than the above lower limit because the reaction can easily proceed and the reaction can be easily controlled. Further, it is preferable that the reaction temperature is not more than the above upper limit because the side reaction is unlikely to proceed, and in particular, chlorine impurities are easily reduced.

  In the reaction, the reaction liquid is azeotroped while maintaining a predetermined temperature as required, the condensed liquid obtained by cooling the vaporized vapor is separated into oil / water, and the oil component excluding moisture is returned to the reaction system. To dehydrate. The addition of alkali metal hydroxide is preferably 0.1 to 8 hours, more preferably 0.1 to 7 hours, and still more preferably 0.5 to 6 hours in order to suppress a rapid reaction. Add intermittently or continuously. It is preferable for the addition time to be equal to or more than the above lower limit because the reaction can be prevented from proceeding rapidly and the reaction temperature can be easily controlled. It is preferable for the addition time to be less than or equal to the above upper limit because chlorine impurities are less likely to be generated, and from the viewpoint of economy. The total reaction time is usually 1 to 15 hours. After completion of the reaction, the insoluble by-product salt is removed by filtration or removed by washing with water, and then the unreacted epihalohydrin is removed by distillation under reduced pressure to obtain the desired epoxy resin.

In this reaction, quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium bromide; tertiary amines such as benzyldimethylamine and 2,4,6-tris (dimethylaminomethyl) phenol; 2-ethyl Catalysts such as imidazoles such as -4-methylimidazole and 2-phenylimidazole; phosphonium salts such as ethyltriphenylphosphonium iodide; phosphines such as triphenylphosphine may be used.

  Furthermore, in this reaction, alcohols such as ethanol and isopropanol; ketones such as acetone and methyl ethyl ketone; ethers such as dioxane and ethylene glycol dimethyl ether; glycol ethers such as methoxypropanol; aprotic such as dimethyl sulfoxide and dimethylformamide An inert organic solvent such as a polar solvent may be used.

  In addition, when it is necessary to reduce the total chlorine content of the epoxy resin obtained as described above, a purified epoxy resin having a sufficiently reduced total chlorine content can be obtained by reprocessing. That is, the crude epoxy resin is redissolved in an inert organic solvent such as isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, dioxane, methoxypropanol, dimethyl sulfoxide, and the alkali metal hydroxide is added to the solid or aqueous solution. The temperature is preferably 30 to 120 ° C., more preferably 40 to 110 ° C., still more preferably 50 to 100 ° C., preferably 0.1 to 15 hours, more preferably 0.3 to 12 hours, still more preferably 0.00. After re-ringing reaction for 5 to 10 hours, excess alkali metal hydroxide or by-product salt is removed by a method such as washing with water, and further the organic solvent is distilled off under reduced pressure and / or steam distillation to hydrolyze. It is possible to obtain an epoxy resin with a reduced amount of reactive halogen. It is preferable that the reaction temperature is not less than the above lower limit and the reaction time is not less than the above lower limit because the re-ring closure reaction easily proceeds. Moreover, since reaction temperature is below the said upper limit and reaction time is below the said upper limit, since reaction is easy to control, it is preferable.

[Production method by two-stage method]
The epoxy resin of the formula (1) is at least a phenol compound represented by the formula (3) and / or an epoxy resin obtained by producing the phenol compound by the above-mentioned one-step method (for example, other compounds of the present invention). The epoxy resin according to the embodiment can also be obtained by a two-stage method using as a raw material. The two-step method means a method of reacting an epoxy resin and a polyvalent hydroxy compound.

When the epoxy resin of the present invention is produced by a two-stage method, it can be produced using a phenol compound represented by the formula (3) as a raw material and an epoxy resin obtained using the phenol compound.
In the production of the epoxy resin of the formula (1), the use amount of the phenol compound and the polyvalent hydroxy compound represented by the formula (3) is a blending equivalent ratio of (epoxy group equivalent) :( hydroxyl group equivalent) = It is preferable to be 1: 0.90 to 1.10. It is preferable for this equivalent ratio to be in the above range because high molecular weight can be easily promoted.

  A catalyst may be used for the synthesis of the epoxy resin of the present invention, and any catalyst may be used as long as it has a catalytic ability to promote a reaction between an epoxy group and a phenolic hydroxyl group, an alcoholic hydroxyl group or a carboxyl group. Something like that. For example, alkali metal compounds, organic phosphorus compounds, tertiary amines, quaternary ammonium salts, cyclic amines, imidazoles and the like can be mentioned. Of these, quaternary ammonium salts are preferred. Moreover, a catalyst can use only 1 type and can also be used in combination of 2 or more type.

  The amount of the catalyst used is usually 0.001 to 1% by weight in the epoxy resin. However, when an alkali metal compound is used, an alkali metal component remains in the resulting epoxy resin, and insulation of electronic / electrical parts using it. Since there exists a possibility of deteriorating a characteristic, the sum total of lithium, sodium, and potassium atomic content in an epoxy resin is 60 ppm or less normally, Preferably it is 50 ppm or less.

  In addition, when organophosphorus compounds, tertiary amines, quaternary ammonium salts, cyclic amines, imidazoles, etc. are used as catalysts, these remain as catalyst residues in the resulting epoxy resin, and the alkali metal content Since there is a risk of deteriorating the insulating properties of the printed wiring board as well as the residual, the nitrogen content in the epoxy resin is preferably 300 ppm or less, and the phosphorus content in the epoxy resin is preferably 300 ppm or less. is there. More preferably, the content of nitrogen in the epoxy resin is 200 ppm or less, and the content of phosphorus in the epoxy resin is 200 ppm or less.

  The epoxy resin of the formula (1) may use a reaction solvent in the synthesis reaction step at the time of production, and any solvent can be used as long as it dissolves the epoxy resin. . Examples include aromatic solvents, ketone solvents, amide solvents, glycol ether solvents, and the like. The solvent may be used alone or in combination of two or more.

As for the epoxy resin density | concentration in the synthetic reaction at the time of manufacture of an epoxy resin, 35 to 95 weight% is preferable. Further, when a highly viscous product is produced during the reaction, the reaction can be continued by adding an additional solvent. After completion of the reaction, the solvent can be removed or further added as necessary.
In the production of the epoxy resin, the polymerization reaction between the bifunctional epoxy resin and the polyvalent hydroxy compound is carried out at a reaction temperature at which the used catalyst is not decomposed. If the reaction temperature is too high, the produced epoxy resin may be deteriorated. Conversely, if the temperature is too low, the reaction may not proceed sufficiently. For these reasons, the reaction temperature is preferably 50 to 230 ° C, more preferably 120 to 200 ° C. Moreover, reaction time is 1 to 12 hours normally, Preferably it is 3 to 10 hours. When using a low boiling point solvent such as acetone or methyl ethyl ketone, the reaction temperature can be ensured by carrying out the reaction under high pressure using an autoclave.

[Production method by oxidation of allyl compound]
As one method for producing the epoxy resin of the formula (1), an allyl group is introduced into the phenol compound represented by the formula (3) by an allylation reaction to form an allyl compound. And obtaining an epoxy resin of the formula (1) by oxidation reaction. As an example of such a production method, JP2012-213716A, JP2011-225711A, JP2012-092247A, except that the phenol compound represented by the formula (3) is used as a raw material. Can be produced by the methods disclosed in Japanese Unexamined Patent Publication No. 2012-111858.

[Epoxy resin composition]
The epoxy resin composition of the present invention contains at least the above-described epoxy resin of the present invention and a curing agent. Moreover, the epoxy resin composition of this invention can mix | blend suitably another epoxy resin, a hardening accelerator, an inorganic filler, a coupling agent, etc. as needed. The epoxy resin composition of the present invention is excellent in heat resistance, low linear expansion, adhesiveness, and the like, and provides a cured product that sufficiently satisfies various physical properties required for various applications.

<Curing agent>
In the epoxy resin composition of this invention, when other epoxy resins mentioned later are contained, it is preferably 0.1 to 1000 parts by weight with respect to 100 parts by weight of the total epoxy resin component as a solid content. Further, it is more preferably 500 parts by weight or less, and still more preferably 300 parts by weight or less. In the present invention, the “solid content” means a component excluding the solvent, and includes not only a solid epoxy resin but also a semi-solid or viscous liquid material. The “total epoxy resin component” means the total of the epoxy resin of the present invention and other epoxy resins described later.

  In this invention, a hardening | curing agent shows the substance which contributes to the crosslinking reaction and / or chain length extension reaction between the epoxy groups of an epoxy resin. In the present invention, even if what is usually called a “curing accelerator” is a substance that contributes to a crosslinking reaction and / or chain extension reaction between epoxy groups of an epoxy resin, it is regarded as a curing agent. To do.

[Phenolic curing agent]
The epoxy resin composition of the present invention contains a phenolic curing agent. By including the phenolic curing agent, the epoxy resin composition of the present invention can obtain excellent heat resistance, low linear expansion, and adhesiveness.

  The phenolic curing agent used in the present invention is not limited as long as it is a phenolic curing agent. Specific examples include bisphenol A, bisphenol F, bisphenol S, bisphenol AD, hydroquinone, resorcin, methyl resorcin, biphenol, and tetramethyl. Biphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, thiodiphenols, phenol novolac resin, cresol novolac resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, terpene phenol resin, dicyclopentadiene phenol resin, bisphenol A novolak resin, naphthol novolak Various polyphenols such as resin, brominated bisphenol A, brominated phenol novolac resin, Polyphenols obtained by condensation reaction of various phenols with various aldehydes such as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, and glyoxal, polyhydric phenol resins obtained by condensation reaction of xylene resin and phenols , Co-condensation resin of heavy oil or pitches, phenols and formaldehyde, phenol / benzaldehyde / xylylene dimethoxide polycondensate, phenol / benzaldehyde / xylylene dihalide polycondensate, phenol / benzaldehyde 4,4 ' -Various phenol resins such as dimethoxide biphenyl polycondensate and phenol / benzaldehyde / 4,4′-dihalide biphenyl polycondensate. These phenol compounds may be used alone or in combination of two or more.

(However, in the above formulas (4) to (9), k _{1 to} k ₆ each represents a number of 0 or more.)

(However, in the above formulas (10) and (11), k ₇ , k ₈ , l ₁ , and l ₂ each represent a number of 1 or more.)
The phenolic curing agent is preferably 0.1 to 1000 parts by weight with respect to 100 parts by weight of the total epoxy resin component as a solid content. Further, it is more preferably 500 parts by weight or less, and still more preferably 300 parts by weight or less. Each component of the phenolic curing agent listed above may be used after mixing in advance to prepare a mixed curing agent, or when mixing each component of the epoxy resin composition, each component of the curing agent may be used. They may be added separately and mixed at the same time.

[Amine curing agent]
Examples of amine curing agents (excluding tertiary amines) include aliphatic amines, polyether amines, alicyclic amines, aromatic amines and the like. Aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis ( Hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra (hydroxyethyl) ethylenediamine and the like are exemplified. Examples of polyether amines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene triamines, and the like. Cycloaliphatic amines include isophorone diamine, metacene diamine, N-aminoethylpiperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9-bis (3-amino). Propyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, norbornenediamine and the like. Aromatic amines include tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4 -Toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-dimethylaminomethyl) phenol, triethanolamine, methylbenzylamine, α- (m-aminophenyl) ethylamine, α- (p-aminophenyl) ethylamine Diaminodiethyldi Examples thereof include methyldiphenylmethane and α, α′-bis (4-aminophenyl) -p-diisopropylbenzene.

  The amine curing agents mentioned above may be used alone or in combination of two or more in any combination and mixing ratio. Moreover, it is preferable to use an amine hardening | curing agent so that it may become the range of 0.8-1.5 by the equivalent ratio of the functional group in a hardening | curing agent with respect to the epoxy group in an epoxy resin. Within this range, unreacted epoxy groups and functional groups of the curing agent are unlikely to remain, which is preferable.

Examples of the tertiary amine include 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol. .
The tertiary amines mentioned above may be used alone or in combination of two or more in any combination and blending ratio. Moreover, it is preferable to use a tertiary amine so that it may become the range of 0.8-1.5 in the equivalent ratio of the functional group in the hardening | curing agent with respect to the epoxy group in an epoxy resin. Within this range, unreacted epoxy groups and functional groups of the curing agent are unlikely to remain, which is preferable.

[Acid anhydride curing agent]
The epoxy resin composition of the present invention preferably uses an acid anhydride curing agent from the viewpoint of heat resistance. Examples of the acid anhydride curing agent include acid anhydrides and modified acid anhydrides.
Examples of acid anhydrides include phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, dodecenyl succinic acid anhydride, polyadipic acid anhydride, polyazelinic acid anhydride, polysebacic acid Anhydride, poly (ethyloctadecanedioic acid) anhydride, poly (phenylhexadecanedioic acid) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride , Methyl hymic acid anhydride, tetrahydrophthalic acid anhydride, trialkyltetrahydrophthalic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, methylcyclohexene tetracarboxylic acid anhydride, ethylene glycol bis trimellitate dianhydride, het acid anhydride , Najit Acid anhydride, methyl nadic acid anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic acid anhydride, 3,4-dicarboxy- Examples include 1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, and the like.

  Examples of modified acid anhydrides include those obtained by modifying the above acid anhydride with glycol. Examples of glycols that can be used for modification include alkylene glycols such as ethylene glycol, propylene glycol, and neopentyl glycol; polyether glycols such as polyethylene glycol, polypropylene glycol, and potassium tetramethylene ether glycol. Is mentioned. Further, a copolymer polyether recall of two or more kinds of these and / or polyether glycol can also be used.

In the modified product of acid anhydride, it is preferable to modify with 0.4 mol or less of glycol with respect to 1 mol of acid anhydride. When the modification amount is not more than the above upper limit, the viscosity of the epoxy resin composition does not become too high, the workability tends to be good, and the rate of the curing reaction with the epoxy resin also tends to be good. .
The acid anhydride curing agents listed above may be used alone or in combination of two or more in any combination and blending amount. When an acid anhydride curing agent is used, it is preferably used so that the equivalent ratio of the functional group in the curing agent to the epoxy group in the epoxy resin is in the range of 0.8 to 1.5. Within this range, unreacted epoxy groups and functional groups of the curing agent are unlikely to remain, which is preferable.

[Amide-based curing agent]
It is preferable to use an amide-based curing agent as the curing agent from the viewpoint of improving heat resistance and the like. Use of an amide type epoxy resin curing agent as the epoxy resin curing agent is preferable from the viewpoint of improving the heat resistance of the resulting epoxy resin composition. Examples of the amide-based curing agent include dicyandiamide and derivatives thereof, and polyamide resins.

  The phenolic curing agents listed above may be used alone or in a combination of two or more in any combination and ratio. Moreover, it is preferable to use an amide type hardening | curing agent in 0.1-20 weight% with respect to the sum total of all the epoxy resin components and amide type hardening | curing agents as solid content in an epoxy resin composition.

[Imidazoles]
It is preferable to use imidazoles as the curing agent from the viewpoint of sufficiently proceeding the curing reaction and improving the heat resistance. Examples of imidazoles include 2-phenylimidazole, 2-ethyl-4 (5) -methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1 -Cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino- 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s -Triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-tri Azine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and an epoxy resin and the above imidazoles Examples include adducts. In addition, since imidazoles have catalytic ability, they can generally be classified as curing accelerators described later, but in the present invention, they are classified as curing agents.

  The imidazoles listed above may be used alone or in combination of two or more in any combination and ratio. Moreover, it is preferable to use imidazole in 0.1-20 weight% with respect to the sum total of all the epoxy resin components and imidazoles as solid content in an epoxy resin composition.

[Other curing agents]
In the epoxy resin composition of the present invention, other curing agents can be used in addition to the curing agent. Other curing agents that can be used in the epoxy resin composition of the present invention are not particularly limited, and any of those generally known as curing agents for epoxy resins can be used. These other curing agents may be used alone or in combination of two or more.

<Other epoxy resins>
The epoxy resin composition of the present invention can further contain other epoxy resins in addition to the epoxy resin of the formula (1). By including other epoxy resins, the heat resistance, stress resistance, moisture absorption resistance, flame retardancy, and the like of the epoxy resin composition of the present invention can be improved.
Other epoxy resins that can be used in the epoxy resin composition of the present invention include all epoxy resins other than the epoxy resin of the formula (1), and specific examples include bisphenol A type epoxy resin and bisphenol F type. Epoxy resin, bisphenol AD type epoxy resin, hydroquinone type epoxy resin, methyl hydroquinone type epoxy resin, dibutyl hydroquinone type epoxy resin, resorcin type epoxy resin, methyl resorcin type epoxy resin, biphenol type epoxy resin, tetramethyl biphenol type epoxy resin, tetra Methyl bisphenol F type epoxy resin, dihydroxy diphenyl ether type epoxy resin, epoxy resin derived from thiodiphenols, dihydroxy naphthalene type epoxy resin, dihydroxy ant Sen-type epoxy resins, dihydroxydihydroanthracene-type epoxy resins, epoxy resins derived from dihydroxystilbenes, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, naphthol novolak type epoxy resins, phenol aralkyl type Epoxy resin, naphthol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, terpene phenol type epoxy resin, dicyclopentadiene phenol type epoxy resin, epoxy resin derived from phenol / hydroxybenzaldehyde condensate, phenol / crotonaldehyde condensate Epoxy resin derived from phenol, glyoxal condensate, heavy Or epoxy resin derived from co-condensation resin of pitches, phenols and formaldehyde, epoxy resin derived from diaminodiphenylmethane, epoxy resin derived from aminophenol, epoxy resin derived from xylenediamine, methylhexa Examples thereof include an epoxy resin derived from hydrophthalic acid, an epoxy resin derived from dimer acid, and the like. These may be used alone, or two or more may be used in any combination and mixing ratio.

  Among these, from the viewpoint of fluidity of the composition, heat resistance, moisture absorption resistance, flame retardancy, and the like of the cured product, among the above epoxy resins, bisphenol A type epoxy resin, tetramethylbiphenol type epoxy resin and 4 , 4'-biphenol type epoxy resin, biphenyl aralkyl type epoxy resin, phenol aralkyl type epoxy resin and dihydroanthracene type epoxy resin, dicyclopentadiene type epoxy resin, orthocresol novolac type epoxy resin, trisphenol methane type epoxy resin Particularly preferred.

  In the epoxy resin composition of this invention, when other epoxy resins are contained, it is preferably 0.01 to 60 parts by weight with respect to 100 parts by weight of the total epoxy resin component. Further, it is more preferably 40 parts by weight or less, still more preferably 30 parts by weight or less, particularly preferably 20 parts by weight or less, and more preferably 1 part by weight or more.

<Curing accelerator>
The epoxy resin composition of the present invention preferably contains a curing accelerator. By including a curing accelerator, the curing time can be shortened and the curing temperature can be lowered, and a desired cured product can be easily obtained.
The curing accelerator is not particularly limited, and specific examples include organic phosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, and boron halide amine complexes.

  Compounds that can be used as curing accelerators include triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, and tris (dialkylphenyl). ) Phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine Organic phosphines such as alkyldiarylphosphine, complexes of these organic phosphines with organic borons, and organic phosphines Maleic acid, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone And quinone compounds such as 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and compounds formed by adding a compound such as diazophenylmethane.

Of the curing accelerators listed above, organic phosphines and phosphonium salts are preferred, and organic phosphines are most preferred. Moreover, only 1 type may be used for a hardening accelerator among the above-mentioned, and 2 or more types may be mixed and used for them in arbitrary combinations and ratios.
The curing accelerator is preferably used in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the epoxy resin in the epoxy resin composition. More preferably, it is 0.5 parts by weight or more, further preferably 1 part by weight or more, more preferably 15 parts by weight or less, and still more preferably 10 parts by weight or less. When the content of the curing accelerator is not less than the above lower limit value, it is preferable for obtaining a curing accelerating effect.

<Inorganic filler>
An inorganic filler can be blended in the epoxy resin composition of the present invention. Examples of the inorganic filler include fused silica, crystalline silica, glass powder, alumina, calcium carbonate, calcium sulfate, talc, boron nitride and the like. Among these, when used for semiconductor sealing, a crushing type and / or spherical, fused and / or crystalline silica powder filler is preferable. By using an inorganic filler, when the epoxy resin composition is used as a semiconductor encapsulant, the thermal expansion coefficient of the semiconductor encapsulant can be brought close to the internal silicon chip or lead frame, and the semiconductor encapsulant can be used. Since the moisture absorption amount of the entire stopper can be reduced, the solder crack resistance can be improved. When using an inorganic filler for the epoxy resin composition of the present invention, it is preferable to blend 60 to 90% by weight of the entire epoxy resin composition.

When an inorganic filler is used in the epoxy resin composition of the present invention, the average particle size of the inorganic filler is usually 1 to 50 μm, preferably 1.5 to 40 μm, more preferably 2 to 30 μm. When the average particle size is not less than the above lower limit value, the melt viscosity is not excessively high and fluidity is not easily lowered, and when the average particle size is not more than the above upper limit value, a narrow gap in the mold is formed during molding. It is preferable because the filler is not easily clogged and the filling property of the material is easily improved.

<Release agent>
A mold release agent can be mix | blended with the epoxy resin composition containing the epoxy resin of this invention. As the release agent, for example, natural wax such as carnauba wax; synthetic wax such as polyethylene wax; higher fatty acids such as stearic acid and zinc stearate and metal salts thereof; and hydrocarbon release agents such as paraffin are appropriately blended. May be.

  The amount of the release agent used in the epoxy resin composition of the present invention is preferably 0.1 to 5.0 parts by weight, more preferably 0.5 to 3.0 parts per 100 parts by weight of all epoxy resin components. Parts by weight. It is preferable for the amount of the release agent to be in the above range because good release properties can be exhibited while maintaining the curing characteristics of the epoxy resin composition.

<Coupling agent>
A coupling agent is preferably blended in the epoxy resin composition of the present invention. The silane coupling agent is preferably used in combination with an inorganic filler, and the adhesiveness between the epoxy resin as a matrix and the inorganic filler can be improved by blending the coupling agent. Examples of coupling agents include silane coupling agents and titanate coupling agents.

  Examples of the silane coupling agent include epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- Aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxy Aminosilane such as silane, mercaptosilane such as 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysila And vinyl silanes such as γ-methacryloxypropyltrimethoxysilane, and epoxy, amino and vinyl polymer type silanes.

  Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tri (N-aminoethyl / aminoethyl) titanate, diisopropyl bis (dioctyl phosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis ( Ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate It is done.

Any of these coupling agents may be used alone or in a combination of two or more in any combination and ratio. In addition, the compounding quantity of a coupling agent becomes like this. Preferably it is 0.1-3.0 weight part with respect to 100 weight part of all the epoxy resin components. If the blending amount of the coupling agent is equal to or more than the above lower limit value, the effect of improving the adhesion between the epoxy resin as a matrix and the inorganic filler due to the blending of the coupling agent tends to be improved. When the blending amount of the agent is not more than the above upper limit value, the coupling agent is less likely to bleed out from the resulting cured product.

<Other ingredients>
In the epoxy resin composition of the present invention, components other than those described above (may be referred to as “other components” in the present invention) can be blended. Examples of these various additives include flame retardants, plasticizers, reactive diluents, pigments, and the like, which can be appropriately blended as necessary. However, the epoxy resin composition of the present invention does not prevent any compounding other than the components listed above.

  Examples of the flame retardant include halogenated flame retardants such as brominated epoxy resins and brominated phenol resins, antimony compounds such as antimony trioxide, red flame retardants such as red phosphorus, phosphate esters and phosphines, melamine derivatives, etc. Nitrogen-based flame retardants, and inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide. The cured product of the epoxy resin composition of the present invention has excellent flame retardancy without the addition of a flame retardant. Of these, halogenated flame retardants such as brominated epoxy resins and brominated phenolic resins, and antimony compounds such as antimony trioxide, which are of particular concern for the environment, need to be blended with these flame retardants? Can be in small quantities.

[Cured product]
A cured product can be obtained by curing the epoxy resin composition of the present invention (hereinafter sometimes referred to as “cured product of the present invention”). Although it does not specifically limit about the method to harden | cure, Usually, hardened | cured material can be obtained by the thermosetting reaction by heating. The curing temperature is preferably selected as follows depending on the type of the curing agent. The specific temperature is usually 130 to 300 ° C. for a phenolic curing agent. Moreover, the curing temperature can be lowered by adding an accelerator to these curing agents. The reaction time is preferably 1 to 20 hours, more preferably 2 to 18 hours, and further preferably 3 to 15 hours. It is preferable for the reaction time to be not less than the above lower limit value because the curing reaction tends to proceed sufficiently. On the other hand, it is preferable for the reaction time to be less than or equal to the above upper limit value because it is easy to reduce deterioration due to heating and energy loss during heating.

The cured product of the present invention has an effect that is particularly excellent in cured product properties such as heat resistance and low linear expansion. The reason why the cured epoxy resin of the present invention has these effects is not clear, but it is presumed that the excellent heat resistance and low linear expansion have a rigid dibenzochrysene skeleton in the formula (1).
The hardened | cured material of this invention is excellent in the heat resistant, low linear expansion property, and adhesive hardened | cured material characteristic. These measuring methods will be described in the following examples.

〔Heat-resistant〕
The epoxy resin composition of the present invention has a glass transition temperature (Tg) of preferably 200 ° C. or higher. A higher glass transition temperature is preferable because thermal stress is less likely to be applied to the resin sealed when a semiconductor encapsulant is used, and defects such as passivation, chip damage, aluminum wiring slides, and package cracks are less likely to occur.

[Low linear expansion]
The epoxy resin composition of the present invention has low linear expansion (average linear expansion (range of 60 ° C. to 250 ° C.))
However, it is preferably 100 ppm / ° C. or less. A lower linear expansion coefficient is preferred because stress is less likely to be applied to the resin sealed when a semiconductor encapsulant is used, and peeling from the semiconductor chip and wiring and cracking of the semiconductor are less likely to occur.

[Use]
Since the epoxy resin composition of the present invention is excellent in heat resistance, low linear expansion and the like, it can be effectively used for any application as long as these physical properties are required. For this reason, paint fields such as electrodeposition paint for automobiles, heavy duty anti-corrosion paint for ships and bridges, paint for inner surface of beverage cans; laminated electronics, semiconductor encapsulant, insulating powder paint, electric and electronic for coil impregnation, etc. Field: Seismic reinforcement for bridges, concrete reinforcement, flooring for buildings, linings for water supply facilities, drainage / water-permeable pavement, civil / construction / adhesive fields for vehicle and aircraft adhesives, etc. be able to. Among these, it is particularly useful for applications of semiconductor encapsulants and laminates.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited at all by the following example. In addition, the value of various manufacturing conditions and evaluation results in the following examples has a meaning as a preferable value of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used.

〔material〕
The following raw materials were used in the following examples and comparative examples.
Component (A): Epoxy resin A-1 (Epoxy resin of the present invention): [Production Example 1]
In a 3 L four-necked flask equipped with a thermometer, a stirrer, and a cooling tube, a “phenol compound represented by tetrahydroxydibenzochrysene formula (3) (manufactured by Kurokin Kasei Co., Ltd.) (“ DBC (OH) ₄ ”) 29 g, 166 g of epichlorohydrin, 64 g of isopropyl alcohol and 23 g of water were charged, and the mixture was heated to 80 ° C. and dissolved uniformly. Then, 28 g of a 48.5 wt% aqueous sodium hydroxide solution was added dropwise over 90 minutes. After completion of dropping, the reaction was completed by maintaining at 80 ° C. for 30 minutes, and by-product salt and excess sodium hydroxide were removed by washing with water. Subsequently, excess epichlorohydrin and isopropyl alcohol were distilled off from the product under reduced pressure to obtain a crude epoxy resin. This crude epoxy resin was dissolved in 69 g of cyclohexanone, 1 g of a 48.5% by weight aqueous sodium hydroxide solution was added, and the mixture was reacted again at a temperature of 65 ° C. for 1 hour. Thereafter, 38 g of methyl isobutyl ketone was added, and an aqueous sodium dihydrogen phosphate solution was added to the reaction solution to neutralize excess sodium hydroxide, followed by washing with water to remove by-product salts. Next, the solvent was completely removed under reduced pressure to obtain 40 g of the desired epoxy resin (A-1).

About the obtained epoxy resin (A-1), the epoxy equivalent was measured according to JISK7236. The epoxy equivalent was 179 g / equivalent.
a-1 (Other epoxy resin): Tetrakisphenolethane type epoxy resin (trade name jER (registered trademark) 1031S manufactured by Mitsubishi Chemical Corporation (epoxy equivalent: 198 g / equivalent))
a-2 (other epoxy resins): epoxy resins obtained by reacting bisphenolacetophenone with 3,3 ′, 5,5′-tetramethylbiphenol diglycidyl ether (epoxy equivalent 12,000 g / equivalent, weight average) Molecular weight 36,000) 30% by weight
MEK / cyclohexanone mixed solution (weight ratio of MEK to cyclohexanone 1: 1)

-Component (B): Curing agent b-1: Pheno-novolak resin (trade name, Resitop PSM, manufactured by Gunei Chemical Industry Co., Ltd.)
4261 (hydroxyl equivalent: 103 g / equivalent, softening point: 85 ° C.))
b-2: Biphenyl aralkyl resin (trade name MEH7851S manufactured by Meiwa Kasei Co., Ltd. (hydroxyl equivalent: 205 g / equivalent))
b-3: Diaminodiphenylmethane (manufactured by Tokyo Chemical Industry Co., Ltd. (active hydrogen equivalent: 50 g / equivalent))
b-4: 2-Ethyl-4-methylimidazole (Mitsubishi Chemical Corporation, trade name: EMI24)

Curing accelerator c-1: Triphenylphosphine (trade name, triphenylphosphine, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Diluent d-1: cyclohexanone (trade name: cyclohexanone, manufactured by Tokyo Chemical Industry Co., Ltd.)

[Example 1-1 and Comparative Example 1-1]
<Manufacture of epoxy resin composition and cured product>
The raw materials were blended in an aluminum dish as shown in Table-1. Subsequently, the mixture was uniformly mixed at 100 ° C. on a hot plate, and then a cured product was obtained at 120 ° C. for 2 hours and further at 175 ° C. for 6 hours. About the obtained hardened | cured material, the glass transition temperature (heat resistance (1)) and the average linear expansion coefficient were tested with the following method, and the result was shown in Table-1.

<Evaluation of cured product>
(Heat resistance (1): Glass transition temperature (Tg))
The cured product was a cylindrical test piece having a thickness of about 1.6 mm and a diameter of about 7 mm, and thermomechanical analysis was performed in a compression mode using a thermomechanical analyzer (TMA: EXSTAR6000 manufactured by Seiko Instruments Inc.) (measurement) Load: 30 mN, heating rate: 5 ° C./min, measurement temperature range: 30 ° C. to 250 ° C., 250 ° C. to 30 ° C. cycle performed twice).
The glass transition temperature in the second measurement was measured. A higher glass transition temperature is evaluated as being excellent in heat resistance, and is preferably 200 ° C. or higher because thermal deformation is reduced when used as a semiconductor sealing material.

(Low linear expansion: Average linear expansion coefficient (60 to 250 ° C.))
The cured product was a cylindrical test piece having a thickness of about 1.6 mm and a diameter of about 7 mm, and thermomechanical analysis was performed in a compression mode using a thermomechanical analyzer (TMA: EXSTAR6000 manufactured by Seiko Instruments Inc.) (measurement) Load: 30 mN, heating rate: 5 ° C./min, measurement temperature range: 30 ° C. to 250 ° C., 250 ° C. to 30 ° C. cycle performed twice). The average linear expansion coefficient from 60 ° C. to 250 ° C. in the second measurement was measured. A lower average linear expansion coefficient is evaluated as being excellent in low linear expansion and is preferably 100 ppm / ° C. or lower because thermal deformation becomes smaller when used as a semiconductor encapsulant.

[Examples 2-1 and 2-2 and Comparative Examples 2-1 and 2-2]
The raw materials shown in Table-2 were blended in a vial and uniformly mixed by applying ultrasonic waves for 6 hours. Then, using a 100 μm thick applicator, it was applied onto a Teflon (registered trademark) film (trade name: Skived Tape manufactured by Chukoh Kasei Kogyo Co., Ltd.), and then at 120 ° C. for 2 hours and further at 200 ° C. for 2 hours. A cured product (film thickness 0.016 mm) was obtained. About the obtained hardened | cured material, the glass transition temperature (heat resistance (2)) was tested with the following method, and the result was shown in Table-2.

(Heat resistance (2): Glass transition temperature (Tg))
Using DMA (dynamic viscoelasticity analyzer: DMS6100 manufactured by SII), the above cured film sample (length 20 mm, width 5 mm) was heated at 2 ° C./min from 30 ° C. to 250 ° C. under tensile conditions. The peak top of tan δ was measured as the glass transition temperature (Tg). A higher glass transition temperature is evaluated as being excellent in heat resistance, and is preferably 230 ° C. or higher because thermal deformation is reduced when used as a semiconductor sealing material.

[Evaluation of results]
As can be seen from Table 1, Example 1-1 using the epoxy resin composition of the present invention is superior to Comparative Example 1-1 in heat resistance and low linear expansion. Further, as can be seen from Table-2, Examples 2-1 and 2-2 using the epoxy resin composition of the present invention are superior in heat resistance to Comparative Examples 2-1 and 2-2. I understand.

Claims (11)

Following formula (1):

(Wherein R ^{1 to} R ⁴ are each independently a hydrogen atom or the following formula (2):

The monovalent group represented by Formula (2) is 1 or more. )
The epoxy resin composition containing the compound represented by these, and a hardening | curing agent. The compound represented by the formula (1) is represented by the following formula (3):

The epoxy resin composition according to claim 1, which is a compound obtained by reacting a compound represented by formula (II) with epihalohydrin.   The epoxy resin composition of Claim 1 or 2 which contains 0.01-1000 weight part of hardening | curing agents with respect to 100 weight part of compounds represented by said Formula (1).   The epoxy according to any one of claims 1 to 3, wherein the curing agent is at least one selected from the group consisting of a phenolic curing agent, an amine curing agent, an acid anhydride curing agent, and an amide curing agent. Resin composition.   The epoxy resin composition according to any one of claims 1 to 4, further comprising an epoxy resin different from the compound represented by the formula (1). The epoxy resin composition according to claim 5, wherein the compound represented by the formula (1) is contained in an amount of 40 wt% or more and 100 wt% or less with respect to all epoxy resin components in the epoxy resin composition according to claim 5. .   The epoxy resin composition of Claim 6 which contains 0.01-20 weight part of hardening | curing agents with respect to 100 weight part of all the epoxy resin components.   The epoxy resin composition according to any one of claims 1 to 7, further comprising an inorganic filler, wherein the content of the inorganic filler in the epoxy resin composition is 65 to 95% by weight.   Hardened | cured material formed by hardening | curing the epoxy resin composition of any one of Claim 1 to 8.   The electrical component formed by hardening | curing the epoxy resin composition of any one of Claim 1 to 8.   The electronic component formed by hardening | curing the epoxy resin composition of any one of Claim 1 to 8.