JP2018087322A - Epoxy resin, epoxy resin composition, cured product and electric/electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin having excellent electric characteristics and productivity, an epoxy resin composition having excellent blocking resistance, resistance to thermal weight loss, and electric characteristics, a cured product, and an electric/electronic component.SOLUTION: The present invention provides an epoxy resin obtained by making a phenolic resin represented by the formula (1) (where n is an average value and 0.3-1.7) into an epoxy resin. Suitably, the epoxy resin has an epoxy equivalent of 160-180 g/eq, a melt viscosity at 150°C of 6.0 Pa s or less, hydrolyzable chlorine of 700 ppm or less, and a softening point of 63-77°C.SELECTED DRAWING: None

Description

The present invention relates to an epoxy resin excellent in electrical characteristics and productivity, an epoxy resin composition excellent in electrical resistance, blocking resistance, heat-resistant weight reduction rate, and electrical characteristics, a cured product, and electrical / electronic parts.

Epoxy resins are generally cured with various curing agents, so that mechanical properties, heat resistance,
The cured product has excellent electrical properties and is used in a wide range of fields such as adhesives, paints, and electrical / electronic materials. In the field of electrical / electronic materials, for example, cresol novolac type epoxy resins are generally used for semiconductor sealing materials.
With the remarkable development of the electronic industry in recent years, the requirements for heat resistance and water absorption required for electronic devices have become increasingly severe. Patent Document 1 discloses an epoxy resin having a skeleton of biphenylene and dihydroxybenzenes, with the object of providing an epoxy resin that gives a cured product having excellent heat resistance, water resistance, and mechanical strength. However, in recent years, next-generation power devices such as silicon carbide have been required to be driven in a high-temperature environment such as 250 ° C., and conventional epoxy resins have not been sufficient in terms of heat decomposition resistance.

Japanese Patent Laid-Open No. 7-292066

An object of the present invention is to provide an epoxy resin excellent in productivity, an epoxy resin that gives a cured product excellent in blocking resistance, heat-resistant weight loss rate, and electrical properties, and an epoxy resin composition. Provide cured products and electrical / electronic components.

As a result of intensive studies to solve the above problems, the present inventors have found that an epoxy resin obtained from a phenol resin having a specific n number of a specific skeleton and an epoxy resin composition containing the epoxy resin and a curing agent have the above problems. It was found that the problem was solved and the invention was completed. That is, the gist of the present invention resides in the following [1] to [10].
[1] The following formula (1)

(In the formula, n represents an average value and is a value of 0.3 to 1.7.)
An epoxy resin obtained by converting a phenol resin represented by
[2] The epoxy resin according to [1], wherein the epoxy equivalent is 160 to 180 g / equivalent.
[3] The epoxy resin according to [1] or [2], which has a melt viscosity at 150 ° C. of 0.6 Pa · s or less.
[4] The epoxy resin according to any one of [1] to [3], wherein the hydrolyzable chlorine is 700 ppm or less.
[5] The epoxy resin according to any one of [1] to [4], which has a softening point of 63 to 77 ° C.
[6] With respect to 100 parts by weight of the epoxy resin according to any one of [1] to [5], a curing agent is added in an amount of 0.00.
An epoxy resin composition containing 01 to 1000 parts by weight.
[7] The epoxy resin according to [6], 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, an amide curing agent, and imidazoles. Composition.
[8] Including an epoxy resin different from the epoxy resin according to any one of [1] to [5] [6]
Or the epoxy resin composition as described in [7].
[9] A cured product obtained by curing the epoxy resin composition according to any one of [6] to [8].
[10] An electrical / electronic component obtained by curing the epoxy resin composition according to any one of [6] to [8].

According to the present invention, an epoxy resin excellent in productivity and an epoxy resin composition, a cured product, and an electrical
Electronic components 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.

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 of the present invention is obtained by converting a phenol resin of the following formula (1) into an epoxy resin. The epoxy resin of the present invention has an effect that the hydrolyzable chlorine is low and the electrical characteristics are particularly excellent, and the amount of polymer at the time of synthesis is small and the productivity is excellent.
The reason why the epoxy resin of the present invention exhibits these effects is not clear, but the reason why the hydrolyzable chlorine is low is presumed that the n number of the raw material phenol of the epoxy resin represented by the following formula (1) is appropriate. To do. If n is high, it is presumed that the hydrolyzable chlorine is increased because the polymer component is inhibited during alkali treatment by the hydrolyzable chlorine reduction reaction. If n is low, the amount of resorcin used as a raw material for synthesizing the phenol resin increases, so it is estimated that residual resorcin is increased and hydrolyzable chlorine is increased. The reason for the small amount of polymer at the time of synthesis is presumed that the higher the n number, the more polymer components are polymerized during the alkali treatment to produce more polymer.

(In the formula, n represents an average value and is a value of 0.3 to 1.7.)
<Chemical structure>
In said Formula (1), n shows an average value and is a value of 0.3-1.7. When the value of n is less than 0.3, when the epoxy resin cured product is used, the blocking resistance is deteriorated and the use thereof becomes difficult, which is not preferable. On the other hand, if the value of n exceeds 1.7, the melt viscosity at 150 ° C. is increased, which is not preferable from the viewpoint of handleability. In addition, the content of hydrolyzable chlorine is increased and the electrical characteristics are deteriorated.

The value of n is more preferably 0.5 to 1.5, particularly preferably 0.7 to 1.3. A person skilled in the art can produce the epoxy resin of the present invention so as to fall within this range without requiring undue trial and error. For example, the following methods can be mentioned.
The compound represented by the formula (1) can be obtained, for example, by reacting the compound represented by the formula (2) with resorcin in the presence of an acid catalyst (condensation reaction).

(In the formula, X represents a halogen atom, a hydroxyl group or a lower alkoxy group.)
In the formula (2), examples of the halogen atom include a chlorine atom and a bromine atom, and the lower alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and examples thereof include a methoxy group and an ethoxy group. .
When performing the above condensation reaction, the amount of resorcin used is 2.5 to 6 with respect to 1 mol of the compound represented by formula (2) in order to make n fall within the range of 0.3 to 1.7. It can be carried out by setting the molar range. In the above condensation reaction, it is preferable to use an acid catalyst, and various acid catalysts can be used, such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous aluminum chloride, zinc chloride and the like. Particularly preferred are p-toluenesulfonic acid, sulfuric acid and hydrochloric acid. The amount of these acid catalysts used is not particularly limited, but the formula (
It is preferable to use 0.1 to 30% by weight of the compound represented by 2). The condensation reaction can be performed in the absence of a solvent or in the presence of an organic solvent. Specific examples in the case of using an organic solvent include toluene, xylene, methyl isobutyl ketone and the like. The amount of the organic solvent used is preferably 50 to 300% by weight, particularly 100 to 25%, based on the total weight of the charged raw materials.
0% by weight is preferred. The reaction temperature is preferably in the range of 40 to 180 ° C., and the reaction time is preferably 1 to 8 hours.

After completion of the reaction, neutralization treatment or water washing treatment is performed to adjust the pH value to 3-7, preferably 5-7. When performing the water washing treatment, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide,
Various basic substances such as ammonia, sodium dihydrogen phosphate, and organic amines such as diethylenetriamine, triethylenetetramine, aniline, and phenylenediamine may be used as a neutralizing agent. Moreover, what is necessary is just to perform according to a conventional method in the case of a washing process. For example, water in which the neutralizing agent is dissolved is added to the reaction mixture, and the liquid separation extraction operation is repeated. After the neutralization treatment, the unreacted dihydroxybenzenes and the solvent are distilled off under heating under reduced pressure to concentrate the product, whereby the compound represented by the formula (1) can be obtained.

<Physical properties / characteristics>
[Epoxy equivalent]
The epoxy resin of the present invention has an epoxy equivalent of 160 from the viewpoint of increasing blocking resistance.
It is preferable to set it as the range of -180g / equivalent. 167 to 176 g / equivalent is more 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.

[Hydrolyzable chlorine content]
The epoxy resin of the present invention preferably has a hydrolyzable chlorine content (hereinafter sometimes referred to as “hydrolyzable chlorine content”) of 700 ppm or less. Moreover, it is more preferable that it is 500 ppm or less from a viewpoint of making an electrical property more favorable.

As a method for measuring the amount of hydrolyzable chlorine, for example, about 0.5 g of epoxy resin is dissolved in 20 ml of dioxane, refluxed with 5 ml of 1N KOH / ethanol solution for 30 minutes, 0.0%
The method of quantifying by titrating with a 1N silver nitrate solution is mentioned.
In order to reduce the amount of hydrolyzable chlorine in the epoxy resin, the epoxy resin may be purified by a reaction between the epoxy resin and the alkali metal hydroxide in the epoxy resin production method described later.

[Melt viscosity]
From the viewpoint of handleability, the epoxy resin of the present invention has a melt viscosity at 150 ° C. of 0.6 Pa ·
The melt viscosity is preferably s or less, and from the viewpoint of improving the handleability, the melt viscosity is particularly preferably 0.4 Pa · s or less.
In the present invention, “melt viscosity” refers to a cone plate viscometer (adjusted to 150 ° C.)
The viscosity is measured at a rotational speed of 750 rpm after melting an epoxy resin on a hot plate of Tokai Yagami Co., Ltd.

[Softening point]
The epoxy resin of the present invention preferably has a softening point in the range of 63 to 77 ° C. from the viewpoint of handleability. From the viewpoint of improving the handleability, the softening point is 64 to 70.
It is more preferable that it is ° C. In the present invention, the “softening point” can be measured according to JIS K7234.

[Method for producing epoxy resin]
Although there is no restriction | limiting in particular about the manufacturing method of an epoxy resin, 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 of the present invention is obtained by reacting a phenol compound represented by the following formula (1) with epihalohydrin.

(In the formula, n represents an average value and is a value of 0.3 to 1.7.)
In addition, when manufacturing the epoxy resin of this invention by a one-step method, although the phenolic compound and epihalohydrin represented by the said Formula (1) are used as a raw material at least, polyvalents other than the phenolic compound represented by Formula (1) are used. Hydroxy compounds (sometimes referred to as “other polyvalent hydroxy compounds” in the present invention) may be used in combination. However, from the viewpoint of enhancing the effect of the present invention, the proportion of the phenol compound represented by the formula (1) is preferably 30 mol% or more, more preferably 50 mol, 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%.
And particularly preferably 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 novolac resin, phenol aralkyl resin, biphenyl aralkyl resin,
Various polyhydric phenols such as naphthol aralkyl resin, terpene phenol resin, dicyclopentadiene phenol resin, bisphenol A novolak resin, naphthol novolak resin, brominated bisphenol A, brominated phenol novolak resin (in the formula (1)) And the polyhydric phenol resins obtained by condensation reaction of various phenols with various aldehydes such as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, and glyoxal, and xylene resins and phenols. Various phenol resins such as polyhydric phenol resins obtained by condensation reaction, heavy oil or pitch, co-condensation resin of phenols and formaldehyde, ethylene glycol, trimethylene glycol, propylene Chain aliphatics such as ethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, etc. Diols; cycloaliphatic diols such as cyclohexanediol and cyclodecanediol; polyethylene ether glycol,
Examples include polyalkylene ether glycols such as polyoxytrimethylene ether glycol and polypropylene ether glycol. 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 other polyvalent hydroxy compounds mentioned above may be used alone or in combination of two or more in any combination and any mixing ratio.
A compound having two or more hydroxyl groups used as a raw material is usually 0 per equivalent of the hydroxyl groups.
. A uniform solution is obtained by dissolving in 8 to 20 equivalents, preferably 0.9 to 15 equivalents, more preferably 1.0 to 10 equivalents of epihalohydrin. 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 an epihalohydrin in this reaction,
Epichlorohydrin or epibromohydrin is used.

Next, while stirring the solution, it is usually 0.5 to 2 per equivalent of the hydroxyl group of the raw material.
. An amount of alkali metal hydroxide corresponding to 0 equivalent, more preferably 0.7 to 1.8 equivalent, and still more preferably 0.9 to 1.6 equivalent, is added as a solid or an aqueous solution to be 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 60-100 ° C, still more preferably 80-100 ° 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 in order to suppress a rapid reaction.
Small portions are added intermittently or continuously over a period of time, more preferably 0.1 to 7 hours, still more preferably 0.5 to 6 hours. 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, insoluble by-product salts are filtered off or removed by washing with water, and unreacted epihalohydrin is distilled off under reduced pressure.
The target epoxy resin can be obtained.

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. Preferably 30 to 120 ° C, more preferably 40 to 110 ° C, still more preferably 5
Preferably at a temperature of 0-100 ° C. for 0.1-15 hours, more preferably 0.3-12 hours,
More preferably, after re-ringing reaction for 0.5 to 10 hours, excess alkali metal hydroxide or secondary salt is removed by a method such as washing with water, and the organic solvent is distilled off under reduced pressure and / or steam distillation. When performed, an epoxy resin having a reduced amount of hydrolyzable halogen can be obtained. 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 oxidation of allyl compound]
As one of the manufacturing methods of the epoxy resin of this invention, an allyl group is introduce | transduced by the allylation reaction with respect to the phenol compound represented by said Formula (1), and it is made an allyl compound, and also oxidation reaction with respect to this allyl group The method of obtaining an epoxy resin by doing is mentioned. As an example of such a production method, JP2012-213716A, JP2011-225711A, JP2012-092247A, except that the phenol compound represented by the formula (1) 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, water absorption, and thermal elastic modulus, 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 200 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 100 parts by weight or less, and still more preferably 80 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 ' -Dimethoxide biphenyl polycondensate, phenol benzaldehyde
Examples include various phenol resins such as 4,4′-dihalide biphenyl polycondensate.
These phenol compounds may be used alone or in combination of two or more.

(In the above formulas (2) to (7), k _{1 to} k ₆ each represents a number of 0 or more.)

(In the above formulas (8) and (9), 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 200 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 100 parts by weight or less, and still more preferably 80 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)
Examples include ethylenediamine. Examples of polyether amines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene triamines, and the like. Alicyclic amines include isophorone diamine, metacene diamine, N-aminoethylpiperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (
Aminomethyl) cyclohexane, 3,9-bis (3-aminopropyl) -2,4,8,1
Examples include 0-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)
Examples include ethylamine, diaminodiethyldimethyldiphenylmethane, α, α′-bis (4-aminophenyl) -p-diisopropylbenzene, and the like.

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- 1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-
And naphthalene succinic dianhydride.

Examples of modified acid anhydrides include those obtained by modifying the above acid anhydride with glycol. Here, 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 pothitetramethylene ether glycol. It is done. 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. In addition, the amide-based curing agent is 0.1 to 20% by weight based on the total of all epoxy resin components and amide-based curing agent as a solid content in the epoxy resin composition.
It is preferable to use in the range.

[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-triazine isocyanuric acid adduct, 2-phenyl Examples include an imidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and an adduct of an epoxy resin and the imidazoles. 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, the curing agent may be used alone or in combination of two or more in any combination and in any ratio, but other curing agents may be used besides them. it can. 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 present invention. 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 are all epoxy resins other than the epoxy resin of the present invention. Specific examples include bisphenol A type epoxy resins, bisphenol F type epoxy resins, 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, tetramethyl bisphenol F type epoxy resin, dihydroxy diphenyl ether Type epoxy resin,
Epoxy resins derived from thiodiphenols, dihydroxynaphthalene type epoxy resins, dihydroxyanthracene type epoxy resins, dihydroxydihydroanthracene type epoxy resins, epoxy resins derived from dihydroxystilbenes, phenol novolac type epoxy resins, cresol novolac type epoxy Resin, bisphenol A novolac epoxy resin, naphthol novolac epoxy resin, phenol aralkyl epoxy resin, naphthol aralkyl epoxy resin, biphenyl aralkyl epoxy resin, terpene phenol epoxy resin, dicyclopentadiene phenol epoxy resin, phenol hydroxy Epoxy resin derived from the condensation product of benzaldehyde, phenol crotonaldehyde Epoxy resin derived from condensate, epoxy resin derived from phenol / glyoxal condensate, epoxy resin derived from co-condensation resin of heavy oil or pitches with phenols and formaldehyde, derived from diaminodiphenylmethane Epoxy resin derived from aminophenol, epoxy resin derived from xylenediamine, epoxy resin derived from methylhexahydrophthalic acid, 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 mentioned later 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, tris (
Dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine,
Organic phosphines such as tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, etc., complexes of these organic phosphines with organic borons, and these organic phosphines Maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4- Benzoquinone, 2,3-dimethoxy-
Examples thereof include quinone compounds such as 1,4-benzoquinone and phenyl-1,4-benzoquinone, and compounds obtained 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 0.5 parts by weight or more,
More preferably, it is 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. On the other hand, when the content is not more than the above upper limit value, desired cured physical properties are easily obtained.

<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 in the epoxy resin composition of the present invention, it is preferable to blend 60 to 95% by weight of the entire epoxy resin composition.

When using an inorganic filler in the epoxy resin composition of the present invention, the average particle size of the inorganic filler is:
Usually, it is 1-50 micrometers, Preferably it is 1.5-40 micrometers, More preferably, it is 2-30 micrometers. 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 the total epoxy resin component 1
Preferably it is 0.1-5.0 weight part with respect to 00 weight part, More preferably, it is 0.5-3.0 weight part. 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 Aminosilanes such as silane, mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane,
Vinyl trichlorosilane, vinyl tris (β-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and other vinyl silanes, as well as epoxy, amino and vinyl polymer types Silane etc. are mentioned.

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. It is preferable for the amount of coupling agent to be greater than or equal to the above lower limit because the effect of improving the adhesion between the epoxy resin, which is a matrix resulting from the incorporation of the coupling agent, and the inorganic filler tends to be improved.
On the other hand, when the blending amount of the coupling 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 other components include:
Examples 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.

[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 200 ° 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 hardened | cured material of this invention is excellent in blocking resistance, a heat-resistant weight reduction rate, and an electrical property. These measuring methods will be described in the following examples.

[Blocking resistance]
The epoxy resin composition of the present invention is excellent in blocking resistance, and preferably satisfies the test described below. Even if the material with the problem of blocking resistance is excellent in other properties,
It is an important characteristic that is difficult to use. Moreover, since the handling property of a composition improves and production efficiency improves, it is preferable that blocking resistance is high.

[Heat-resistant weight reduction rate]
The cured epoxy resin product of the present invention has a thermal weight loss rate after 50 hours at 250 ° C., preferably 0.
9% or less. Since the thermal decomposition of the cured product is suppressed as the thermal weight reduction rate is lower, the material is less likely to be embrittled.

[Electrical characteristics]
The cured epoxy resin of the present invention is excellent in electrical characteristics. Preferably, the amount of chlorine in the extracted water is 300
ppm or less. The lower the amount of chlorine in the water extracted from the cured epoxy resin, the better the electrical and electronic parts can be prevented from being insulated even in a high temperature and high humidity environment.

[Use]
The epoxy resin composition of the present invention is excellent in blocking resistance, and the cured epoxy resin is excellent in heat-resistant weight loss rate and electrical characteristics. Therefore, the epoxy resin composition should be used effectively for any application that requires these physical properties. Can do. For this reason, paint fields such as automotive electrodeposition paints, heavy-duty anti-corrosion paints for ships and bridges, paints for the inner surface of beverage cans; laminates, semiconductor encapsulants, insulating powder paints,
Electrical and electronic fields for coil impregnation, etc .; Seismic reinforcement of bridges, concrete reinforcement, flooring of buildings, lining of water supply facilities, drainage / water-permeable pavement, civil engineering / architecture / adhesive fields for adhesives for vehicles and aircraft Any of the above can be suitably used. Among these, it is particularly useful for the application of a semiconductor sealing material.

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.

<Manufacture of epoxy resin>
[Production Example 1]
In a flask equipped with a thermometer, dropping funnel, condenser, and stirrer, 251 parts of 4,4′-bis (chloromethyl) biphenyl, 330 parts of resorcin, and 500 m of methyl isobutyl ketone
L was charged and stirred at room temperature while blowing nitrogen. 2.8 parts of p-toluenesulfonic acid (monohydrate) is added so that the liquid temperature does not exceed 50 ° C, and then heated to 110 ° C.
Reacted for hours. After completion of the reaction, 500 mL of methyl isobutyl ketone was further added, transferred to a separatory funnel and washed with water. After washing with water until the aqueous layer becomes neutral, the solvent is distilled off from the organic layer, and unreacted substances are removed by heating under reduced pressure to obtain a phenol resin represented by the formula (10) (n = 0.9). It was. The calculation method of n number was shown below.

[N number]
Using “HLC-8320GPC EcoSEC (registered trademark)” manufactured by Tosoh Corporation, measurement was performed under the following conditions. The n number (average value) was calculated from the ratio of the obtained area%.
Column: “TSKGEL SuperHM-H + H5000 + H400” manufactured by Tosoh Corporation
0 + H3000 + H2000 "
Eluent: Tetrahydrofuran Flow rate: 0.5 ml / min
Detection: UV (wavelength 254 nm)
Temperature: 40 ° C
Sample concentration: 0.1% by weight
Ink injection volume: 10 μl

[Production Example 2]
In the same manner as in Production Example 1 except that resorcin was changed to 660 parts in Production Example 1, the formula (11
) (N = 0.2) was obtained.

[Production Example 3]
Except for using 275 parts of resorcin in Production Example 1, the formula (12
) (N = 1.8) phenol resin was obtained.

[Example 1]
65 g of phenol resin (formula (10) (n = 0.9)) obtained in Production Example 1, 378 g of epichlorohydrin, 221 g of isopropyl alcohol, water After charging 60 g, the temperature was raised to 65 ° C. and dissolved uniformly.
60 g of an 8.5 wt% aqueous sodium hydroxide solution was added dropwise over 90 minutes. After dropping, 6
The reaction was completed by maintaining at 5 ° 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 150 g of methyl isobutyl ketone, 2 g of a 48.5 wt% sodium hydroxide aqueous solution was added, and reacted again at a temperature of 65 ° C. for 1 hour. Thereafter, an aqueous sodium dihydrogen phosphate solution was added to the reaction solution to neutralize excess sodium hydroxide and washed with water to remove by-product salts. Next, methyl isobutyl ketone was completely removed under reduced pressure to obtain the desired epoxy resin.

[Comparative Example 1]
Example 1 Example 1 except that the phenol resin obtained in Production Example 1 (the phenol resin obtained in Production Example 2 (Formula (11) (n = 0.2)) was used instead of Formula (10). The objective epoxy resin was obtained by the same method.

[Comparative Example 2]
Example 1 Example 1 except that the phenol resin obtained in Production Example 1 (the phenol resin obtained in Production Example 3 (Formula (12) (n = 1.8)) was used instead of Formula (10). The objective epoxy resin was obtained by the same method.
Epoxy equivalent of the epoxy resin obtained in Example 1, Comparative Example 1 and Comparative Example 2, melt viscosity (
150 ° C.), the amount of hydrolyzable chlorine, the softening point, and the amount of polymer produced during synthesis were measured by the methods described above, and the results are shown in Table 1.

[Production and evaluation of epoxy resin composition]
[Example 2 and Comparative Examples 3 and 4]
The epoxy resin and the curing agent were blended in the proportions shown in Table 2, heated to 100 ° C. and stirred until uniform. Then, it cooled to 80 degreeC, the hardening accelerator was added in the ratio shown in Table 2, and it stirred until it became uniform, and prepared the epoxy resin composition. In Table 2, “part” represents “part by weight”.

The used curing agents and curing accelerators are as follows.
Curing agent: phenol novolac resin (trade name PSM6200 manufactured by Gunei Chemical Co., Ltd. (hydroxyl equivalent: 103 g / equivalent))
Curing accelerator: Triphenylphosphine (trade name, triphenylphosphine, manufactured by Tokyo Chemical Industry Co., Ltd.)
Two glass plates each having a release pet film laminated thereon were prepared on one side, and these glass plates were provided with the release pet film side as an inner surface, and a glass plate interval was adjusted to 5 mm to prepare a casting plate.
An epoxy resin composition is cast on this casting plate, and it is heated at 120 ° C. for 2 hours and then at 175 ° C. for 6 hours.
A cured product was obtained by heating and curing for a period of time.
The obtained cured product was evaluated as follows, and the results are shown in Table 2.

[Blocking test of composition]
Heat the epoxy resin and curing agent to 100 ° C with the formulation shown in Table 2 and stir until uniform.
The composition was obtained by cooling at 0 ° C. for 30 minutes. Thereafter, the product crushed with a hammer and passed through a 5 mm square mesh was put into a cylinder having a diameter of 5 cm and a length of 15 cm and left at 20 ° C. for 72 hours.

Then, what passed 50 weight% or more of 1 cm square mesh was set as "(circle)" as the composition which did not block, and what passed 1 cm square mesh less than 50 weight% was set as the blocked composition. It was set as “x”. The blocking test is an indicator of ease of fusion (handling property).

[Weight reduction rate of cured product at 250 ° C for 50 hours]
The cured product was cut into a length of 5 cm, a width of 1 cm, and a thickness of 5 mm to obtain a test piece. It was allowed to stand in an air atmosphere at 250 ° C. in an air atmosphere for 50 hours, and the weight reduction rate was measured from the weight before charging and the weight after charging.

[Chlorine content of extracted water]
The obtained cured product was pulverized with a wonder blender (manufactured by Osaka Chemical Co., Ltd.) and 20 mesh pass
20 g of the powder was prepared. 8 g of this was weighed into a polyethylene bottle, 80 mL of ultrapure water was added, the lid was closed, and this was kept in a dryer at 95 ° C. for 20 hours. Then, it cooled to room temperature and filtered extraction water with the filter paper 5A, and obtained extraction water. 1 g of the extracted water obtained was put into a beaker and acetone 10
0 mL and 25 mL of acetic acid were added, and the amount of chlorine was measured by potentiometric titration using a 0.002 mol / L silver nitrate solution.

[Evaluation of results]
From Table 1, Example 1 which is an epoxy resin of the present invention manufactured using a phenol resin in which the n number of the formula (1) is within the specified range of the present invention is compared with the epoxy resins of Comparative Examples 1 and 2. It can be seen that the amount of hydrolyzable chlorine is excellent. Moreover, it turns out that it is excellent in productivity from the epoxy resin of the comparative example 2 because melt viscosity is low and the polymer amount at the time of epoxy manufacture is small.

From Table 2, the cured epoxy resin of Example 2 using the epoxy resin of Example 1 is
Compared to the cured epoxy resin of Comparative Example 3, it can be seen that it has excellent blocking resistance, heat-resistant weight reduction property, and electrical characteristics.
In summary, the epoxy resin of Example 1 and the epoxy resin composition of Example 2 are superior to the epoxy resins of Comparative Examples 1 and 2 and Comparative Examples 3 and 4. I understand.

Claims (10)

Following formula (1)

(In the formula, n represents an average value and is a value of 0.3 to 1.7.)
An epoxy resin obtained by converting a phenol resin represented by   The epoxy resin according to claim 1, which has an epoxy equivalent of 160 to 180 g / equivalent. The epoxy resin according to claim 1, wherein the melt viscosity at 150 ° C. is 0.6 Pa · s or less. The epoxy resin according to any one of claims 1 to 3, wherein the hydrolyzable chlorine is 700 ppm or less.   The epoxy resin according to any one of claims 1 to 4, which has a softening point of 63 to 77 ° C. The curing agent is 0 with respect to 100 parts by weight of the epoxy resin according to any one of claims 1 to 5.
. An epoxy resin composition containing 01 to 1000 parts by weight. The epoxy resin composition according to claim 6, 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, an amide curing agent, and imidazoles. The epoxy resin composition according to claim 6 or 7, comprising an epoxy resin different from the epoxy resin according to any one of claims 1 to 5.   Hardened | cured material formed by hardening | curing the epoxy resin composition of any one of Claim 6 to 8. An electrical / electronic component obtained by curing the epoxy resin composition according to any one of claims 6 to 8.