WO2012070387A1

WO2012070387A1 - Epoxy resin and resin composition

Info

Publication number: WO2012070387A1
Application number: PCT/JP2011/075864
Authority: WO
Inventors: 建樹清水; 下田　晃義; 弘樹谷口; 雄史新井; 賢三鬼塚
Original assignee: 旭化成イーマテリアルズ株式会社
Priority date: 2010-11-25
Filing date: 2011-11-09
Publication date: 2012-05-31
Also published as: JPWO2012070387A1; TW201226468A

Abstract

[Problem] To provide: an epoxy resin which exhibits low viscosity when used in a resin composition and which exhibits excellent heat resistance when used in a cured product; and a resin composition. [Solution] This resin composition comprises an epoxy resin (A) that has a total chlorine content of 0.01 to 1000ppm and a resin (B) that has a melting or softening point of 50°C or higher, the content of the epoxy resin (A) being 20 to 90% by mass relative to the total amount of all the resins.

Description

Epoxy resin and resin composition

The present invention relates to an epoxy resin and a resin composition.

Epoxy resins are used as binders for various purposes because they are solvent-soluble and have excellent mechanical properties. Epoxy resins are usually obtained by reacting phenolic compounds with epichlorohydrin, and therefore contain a large amount of chlorine such as hydrolyzable chlorine and organic bondable chlorine. When an epoxy resin containing a chlorine content is used for an electronic material, it causes corrosion of wiring and the like, and thus an epoxy resin with a reduced chlorine content is required.

As a method for reducing the amount of chlorine in the epoxy resin, a heating method using an alkali compound is known (for example, see Patent Document 1).

Also, a resin composition in which naphthalene epoxy is added to a phenoxy resin solution is disclosed as a low chlorinated epoxy resin composition (see, for example, Patent Document 2).

Furthermore, as a method of lowering the viscosity of the epoxy resin composition, a method of adding a reactive diluent or an aliphatic epoxy resin can be mentioned (for example, see Patent Document 3).

JP-A-57-031922 JP 2009-242508 A JP 2003-26766 A

Epoxy resins generally tend to crystallize when the chlorine content is reduced. This tendency is particularly strong in resins such as aromatic epoxy resins that have a strong intermolecular force and are easy to work. The crystallized epoxy resin is unsuitable for so-called sealing applications from the viewpoint of handleability.

For example, in the method described in Patent Document 1, high molecular weight of the epoxy resin occurs, and the viscosity of the epoxy resin tends to increase remarkably. Further, depending on the type of epoxy resin, gelation may proceed, and the target compound may not be isolated.

Although the method described in Patent Document 2 can uniformly disperse or dissolve naphthalene epoxy in a solvent, the resulting epoxy resin composition may not be suitable for sealing applications because the solvent needs to be removed. .

Although the method disclosed in Patent Document 3 does not require solvent removal, the heat resistance of the resulting cured product tends to be significantly reduced.

As mentioned above, it is a low chlorinated epoxy resin, low viscosity, good storage stability, and good heat resistance of the cured product when cured, and an epoxy resin suitable for sealing applications and Development of an epoxy resin composition is desired.

The present invention has been made in view of such points, and has an epoxy resin and a resin composition that have low viscosity, good storage stability, and can exhibit excellent heat resistance when used as a cured product. The purpose is to provide.

As a result of intensive studies, the present inventors have found that the above problems can be solved, and have completed the present invention.

That is, the present invention is as follows.

[1]
An epoxy resin (A) having a total chlorine content of 0.01 ppm to 1000 ppm,
A resin (B) having a melting point or softening point of 50 ° C. or higher,
During the total resin content of the epoxy resin (A) is not less than 20% by mass to 90% by mass, the resin composition.

[2]
Resin composition as described in [1] whose content of the said resin (B) is 10 to 80 mass% in all the resins.

[3]
The resin composition according to [1] or [2], wherein the epoxy resin (A) has a melting point or softening point of 30 ° C or higher.

[4]
The resin composition according to any one of [1] to [3], wherein the epoxy resin (A) is an aromatic epoxy resin.

[5]
The resin composition according to [4], wherein the aromatic epoxy resin has an aromatic diglycidyl ether structure.

[6]
[4] The resin composition according to [4], wherein the aromatic epoxy resin is at least one selected from the group consisting of the following general formulas (1) to (3).

(In the formulas (1) to (3), R ₁ to R ₆ each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and x, y, and z represent 0 to 10 Represents an integer.)

[7]
The resin composition according to [4], wherein the aromatic epoxy resin is at least one selected from the group consisting of the following general formulas (1) and (2).

(In the formulas (1) and (2), R ₁ and R ₂ each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and x and y represent an integer of 0 to 5) To express.)

[8]
The resin composition according to any one of [1] to [7], wherein the resin (B) has an aromatic structure or a heterocyclic structure.

[9]
The resin (B) is at least one selected from the group consisting of epoxy resins, phenoxy resins, phenol novolacs, polyamic acids, polyimides, polybenzoxazoles and (meth) acrylate resins, [1] to [8] The resin composition in any one.

[10]
The resin composition according to any one of [1] to [9], wherein the resin (B) is at least one selected from the group consisting of the following general formulas (4) to (8).

(In the formulas (4) to (8), R _8, R ₉ , R ₁₁ and R ₁₂ each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and R ₇ and R ₁₀ Each independently represents a divalent organic group having 1 to 10 carbon atoms.)

[11]
The resin composition according to any one of [1] to [10], wherein the resin (B) is at least one selected from the group consisting of the following general formulas (4) and (5).

(In the formulas (4) and (5), R ₇ each independently represents a divalent organic group having 1 to 10 carbon atoms, and R ₈ each independently represents a hydrogen atom or a carbon atom having 1 to 10 carbon atoms. Represents a monovalent organic group.)

[12]
At least one epoxy resin (A) selected from the group consisting of the following general formulas (1) to (3);
At least one resin (B) selected from the group consisting of the following general formulas (4) to (8);
Containing at least one compound selected from the group consisting of the following general formulas (9) to (11) and / or an alkali metal chloride,
In all the resins, the proportion of the epoxy resin (A) is 20% by mass or more and 90% by mass or less, and the proportion of the resin (B) is 10% by mass or more and 80% by mass or less.
The total concentration of the compounds represented by the following general formulas (9) to (11) contained in the total resin composition and the chlorine concentration derived from the alkali metal chloride is 0.01 ppm or more and 1000 ppm or less. , Resin composition.

(In the formulas (9) to (11), R ₁ to R ₆ each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and x, y, and z are 0 to 10 Rx and Ry each independently represents any structure selected from the following formulas (a) to (e), provided that Rx and Ry are not simultaneously represented by the following formula (a) .)

[13]
Epoxy resin (A), the general formula (1) and at least one selected from the group consisting of (2),
The resin (B) is at least one selected from the group consisting of the general formulas (4) and (5),
The sum total of the concentration of the compound represented by the general formulas (9) and (10) contained in the total resin composition and the chlorine concentration derived from the alkali metal chloride is 0.01 ppm or more and 1000 ppm or less. [12] The resin composition described in [12].

[14]
The epoxy resin (A) is a resin represented by the general formula (1),
The resin (B) is a resin represented by the general formula (4),
The total of the concentration of the compound represented by the general formula (9) and the chlorine concentration derived from sodium chloride and potassium chloride contained in the entire resin composition is 0.01 ppm or more and 1000 ppm or less, [12 ] The resin composition as described in.

[15]
Any of [12] to [14], wherein the proportion of the epoxy resin (A) is 50% by mass or more and 85% by mass or less and the proportion of the resin (B) is 15% by mass or more and 50% by mass or less in the total resin. A resin composition according to claim 1.

[16]
An epoxy resin (A) having a melting point or softening point of 30 ° C. or higher;
A resin (B) having a melting point or softening point of 50 ° C. or higher;
Containing a compound (C) having a dioxane structure;
Hardened | cured material for sealing whose ratio of the compound (C) which has this dioxane structure is 0.01 ppm or more and 5000 ppm or less.

[17]
The epoxy resin (A) is represented by the following general formula (1):
The compound (C) having the dioxane structure is the following general formula (12),
Hardened | cured material for sealing as described in [16] whose ratio of the compound (C) which has a dioxane structure is 0.035 ppm or more and 3450 ppm or less in all the hardened | cured material.

(In Formula (1), R ₁ represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and x represents an integer of 0 to 5)

(In Formula (12), each R ₁ independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and x represents an integer of 0 to 10)

[18]
The epoxy resin (A) is represented by the following general formula (2):
The compound (C) having the dioxane structure is the following general formula (13),
Hardened | cured material for sealing as described in [16] whose ratio of the compound (C) which has a dioxane structure is 0.04 ppm or more and 4000 ppm or less in all the hardened | cured material.

(In Formula (2), R ₂ represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and y represents an integer of 0 to 5)

(In Formula (13), each R ₂ independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and y represents an integer of 0 to 10)

[19]
An epoxy resin represented by the general formula (1),
The epoxy resin whose total chlorine amount contained in the said epoxy resin is 0.01 ppm or more and 1000 ppm or less.

(In Formula (1), each R ₁ independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, x represents an integer of 0 or more and 5 or less, and all represented by Formula (1) (The ratio of the compound represented by x = 0 contained in the resin is 99% by mass or more.)

[20]
An epoxy resin represented by the general formula (2),
The epoxy resin whose total chlorine amount contained in the said epoxy resin is 0.01 ppm or more and 1000 ppm or less.

(In the formula (2), R ₂ each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, y represents an integer of 0 or more and 5 or less, and all represented by the formula (2) (The ratio of the compound represented by y = 0 contained in the resin is 95% by mass or more.)

[21]
[1] to [15] the resin composition according to any one of [19] to [20] and the epoxy resin (a) according to any one of
A curable resin composition containing a curing accelerator (I).

[22]
The curable resin composition according to [21], wherein the curing accelerator (I) is a nitrogen compound or a latent curing accelerator.

[23]
The curable resin composition according to [21] or [22], wherein the curing accelerator (A) is a microencapsulated latent curing accelerator.

[24]
The curable resin composition according to any one of [21] to [23], further containing a curing agent (c).

[25]
The curable resin composition according to [24], wherein the curing agent (c) is at least one selected from the group consisting of an acid anhydride compound, an acid dianhydride compound, an amine compound, and a phenol compound.

[26]
Containing inorganic filler (d) In addition, [21] The curable resin composition according to any one of - [25].

[27]
An underfill material comprising the resin composition according to any one of [1] to [15] or the curable resin composition according to any one of [21] to [26].

[28]
A die attach material comprising the resin composition according to any one of [1] to [15] or the curable resin composition according to any one of [21] to [26].

[29]
A liquid sealing material comprising the resin composition according to any one of [1] to [15] or the curable resin composition according to any one of [21] to [26].

[30]
An electronic component comprising at least one selected from the group consisting of an underfill material according to [27], a die attach material according to [28], and a liquid sealing material according to [29].

According to the present invention, when the resin composition is used, the viscosity is low, the storage stability is good, and when the resin composition is used, excellent heat resistance can be realized.

Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

≪Resin composition≫
The resin composition according to the present embodiment contains an epoxy resin (A) having a total chlorine content of 0.01 ppm to 1000 ppm and a resin (B) having a melting point or a softening point of 50 ° C. or higher, Inside, content of resin (A) is 20 mass% or more and 90 mass% or less.

The low chlorine epoxy resin (A) having a total chlorine content of 0.01 ppm to 1000 ppm is generally solid, and the resin (B) having a melting point or softening point of 50 ° C. or higher is also solid. And it is very difficult to mix resin of solids, The resin composition concerning this embodiment is a liquid state of low viscosity by adjusting content of resin (A) to said range. While maintaining the above, the cured product can exhibit high heat resistance. Generally, when mixing resins between solids, it is known to melt by heating or the like to form a liquid, but when this is returned to room temperature, the obtained liquid resin composition It is common for things to return to a solid state again. However, the resin composition according to the present embodiment can maintain a low-viscosity liquid state even when the temperature is returned to room temperature. The reason for this is not clear, but since the amount of chlorine in the epoxy resin (A) is low, impurities in the resin composition are reduced and the interaction with the resin (B) is strengthened. (B) It is presumed that each intermolecular force has decreased and it has become easier to maintain a liquid state. In general, when a plurality of resins are melt-mixed, it is necessary to heat them to the melting point or more of each resin. And in the case of the heating, the hydroxyl group contained in a hydrolyzable chlorine content etc. will react with an epoxy group, and there exists a subject that a viscosity becomes very high even if a resin composition becomes liquid state. In the resin composition according to the present embodiment, hydrolyzable chlorine is also sufficiently reduced. Therefore, it is presumed that low viscosity can be maintained even after becoming liquid.

<Epoxy resin (A)>
The epoxy resin (A) used in the present embodiment is a low chlorine epoxy resin having a total chlorine content of 0.01 ppm to 1000 ppm. Here, the epoxy resin (A) is not particularly limited as long as the total chlorine amount is in the above range.

The “total chlorine amount” referred to herein means the total amount of chlorine contained in the epoxy resin, and indicates the total amount of organic bondable chlorine, hydrolyzable chlorine, and inorganic chlorine. Unless otherwise specified, ppm, which is the unit of total chlorine, is based on mass. The total chlorine amount was determined by adding a potassium hydroxide solution to an epoxy resin, heating and refluxing, and then adding acetic acid, and using a potentiometric titrator (manufactured by Kyoto Electronics Co., Ltd., automatic potentiometric titrator “AT-510”). It can be measured by precipitation titration.

When the total chlorine content in the epoxy resin (A) is 0.01 ppm or more, crystallization of the epoxy resin can be suppressed, so that a low viscosity can be maintained. High heat resistance (glass transition temperature) can be achieved. The total chlorine content in the epoxy resin (A) is preferably 0.1 ppm or more and 1000 ppm from the viewpoint of further suppressing crystallization and maintaining low viscosity, and has a glass transition temperature (hereinafter also referred to as “Tg”) of the cured product. From the viewpoint, 1 ppm to 650 ppm is more preferable, and from the viewpoint of a balance between the viscosity of the resin composition and the heat resistance of the cured product, 1 ppm to 200 ppm is particularly preferable.

In the total resin, the content of the epoxy resin (A) is 20% by mass or more and 90% by mass or less. If the content of the epoxy resin (A) is 20% by mass or more, the viscosity of the resin composition tends to be sufficiently low, and if it is 90% by mass or less, the heat resistance of the cured product is good. The content of the epoxy resin (A) is preferably 30% by mass or more and 90% by mass or less from the viewpoint of low viscosity of the resin composition, and 30% by mass or more and 85% by mass or less from the viewpoint of heat resistance when a cured product is obtained. From the viewpoint of storage stability, 50% by mass or more and 85% by mass or less is particularly preferable.

The epoxy resin (A) preferably has a melting point or softening point of 30 ° C or higher. If the melting point or softening point of the epoxy resin (A) is 30 ° C. or higher, the heat resistance when cured is likely to be good. The melting point or softening point of the epoxy resin (A) is more preferably 30 to 80 ° C., further preferably 30 to 50 ° C. In the present embodiment, the melting point and the softening point can be measured with a differential scanning calorimeter or the like.

The structure of the epoxy resin (A) is not particularly limited, and examples of such an epoxy resin (A) include an aromatic epoxy resin, an aliphatic epoxy resin, and an alicyclic epoxy resin. In these, an aromatic epoxy resin is preferable from a compatible viewpoint with resin (B). When the aromatic epoxy resin contains an aromatic in the epoxy resin skeleton, it becomes easy to interact with the resin (B), the compatibility is improved, and the resin composition tends to have a low viscosity.

The aromatic epoxy resin is not limited as long as it has an aromatic structure and an epoxy group. Examples of such aromatic epoxy resins include resins having an aromatic glycidyl ether structure, an aromatic glycidyl ester structure, and an aromatic glycidyl amine structure. Among these, a resin having an aromatic glycidyl ether structure and an aromatic glycidyl ester structure is preferable from the viewpoint of low viscosity of the resin composition, and a resin having an aromatic glycidyl ether structure from the viewpoint of heat resistance of the cured product. More preferred is a resin having an aromatic diglycidyl ether structure.

The resin having an aromatic glycidyl ether structure (aromatic glycidyl ether compound) used in the present embodiment is preferably at least one selected from the group consisting of the following general formulas (1) to (3).

(In the formulas (1) to (3), R ₁ to R ₆ each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and x, y, and z are integers of 0 to 10 Represents.)

R ₁ in the general formula (1) are each independently a monovalent organic group hydrogen atom or a C 1-10. Examples of the monovalent organic group having 1 to 10 carbon atoms include hydrocarbon groups such as a methyl group and an ethyl group. The hydrocarbon group may be substituted with a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, or may be unsubstituted. Among these, R ₁ in the general formula (1) is independently preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom, from the viewpoint of heat resistance when a cured product is obtained.

X in the general formula (1) represents an integer of 0 to 10. Among these, x is preferably 0 to 5 from the viewpoint of low viscosity of the epoxy resin.

The bonding position of the glycidyl ether group in the general formula (1) is not particularly limited, but the meta position and the para position are preferable from the viewpoint of heat resistance when the cured product is formed, and the meta position is more preferable from the viewpoint of the viscosity of the epoxy resin. .

As described above, x in the general formula (1) represents an integer of 0 to 10, but may be in a state where compounds having different numerical values of x are mixed. In this case, the compound represented by x = 0 in the general formula (1) is preferably contained in an amount of 95% by mass or more in the compound represented by the general formula (1), and the low viscosity of the resin composition From a viewpoint, 99 mass% or more is more preferable, and 99.9 mass% or more is especially preferable.

R ₂ in the general formula (2) is each independently a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. Examples of the monovalent organic group having 1 to 10 carbon atoms include hydrocarbon groups such as a methyl group and an ethyl group. The hydrocarbon group may be substituted with a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, or may be unsubstituted. Among these, R ₂ in the general formula (2) is preferably independently a hydrogen atom or a methyl group, more preferably a hydrogen atom, from the viewpoint of heat resistance when a cured product is used.

Y in the general formula (2) represents an integer of 0 to 10. Among these, y is preferably 0 to 5 from the viewpoint of low viscosity of the epoxy resin.

The bonding position of the glycidyl ether group in the general formula (2) is not particularly limited, but from the viewpoint of heat resistance when a cured product is obtained, the 1,5-position, 1,6-position, 1,7-position, 1,8-position 2,6 and 2,7 are preferable, and the 1,6th and 1,7th positions are more preferable from the viewpoint of the low viscosity of the epoxy resin.

As described above, y in the general formula (2) represents an integer of 0 to 10, but may be a state in which compounds having different y values are mixed. In this case, the compound represented by y = 0 in the general formula (2) is preferably contained in an amount of 95% by mass or more in the compound represented by the general formula (2), and the low viscosity of the resin composition From a viewpoint, 99 mass% or more is more preferable, and 99.9 mass% or more is especially preferable.

R ₃ and R ₄ in the general formula (3) are each independently a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. Examples of the monovalent organic group having 1 to 10 carbon atoms include hydrocarbon groups such as a methyl group and an ethyl group. The hydrocarbon group may be substituted with a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, or may be unsubstituted.

R ₅ and R ₆ in the general formula (3) are each independently a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. Examples of the monovalent organic group having 1 to 10 carbon atoms include hydrocarbon groups such as a methyl group and an ethyl group. The hydrocarbon group may be substituted with a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, or may be unsubstituted.

Among them, R ₅ and R ₆ in the general formula (3) are preferably each independently a hydrogen atom or a methyl group from the viewpoint of heat resistance of the obtained cured product, and further R ₅ and R _6. Are both methyl groups, R ₅ and R ₆ are both hydrogen atoms, R ₅ is a methyl group, and R ₆ is preferably a hydrogen atom.

Z in the general formula (3) represents an integer of 0 to 10. Among these, z is preferably 0 to 5 from the viewpoint of the low viscosity of the epoxy resin.

The bonding position of the glycidyl ether group in the general formula (3) is not particularly limited, but a meta position and a para position are preferable from the viewpoint of heat resistance when a cured product is used.

As described above, z in the general formula (3) represents an integer of 0 to 10, but may be in a state where compounds having different numerical values of z are mixed. In this case, the compound represented by z = 0 in the general formula (3) is preferably contained in an amount of 95% by mass or more in the compound represented by the general formula (3), and 99% by mass from the viewpoint of melt viscosity. % Or more is more preferable, and 99.9 mass% or more is especially preferable.

In addition, the numerical values of x, y and z in the general formulas (1) to (3) and the content of the compound in which x, y and z in the epoxy resin are 0 are as described in Examples described later. It can be measured by a method by liquid chromatography. Moreover, when a high molecular weight body is included in an epoxy resin, it can measure by the method by a gel permeation chromatography (GPC).

Among the general formulas (1) to (3), the epoxy resin (A) is represented by the general formula (1) or the general formula (2) from the viewpoint of the balance between the viscosity of the resin composition and the heat resistance of the cured product. It is preferable that it is, and more preferably, it is general formula (1). An epoxy resin (A) may be used individually by 1 type, and may be used together 2 or more types.

<Resin (B)>
The resin (B) used in the present embodiment has a melting point or softening point of 50 ° C. or higher. The melting point or softening point of the resin (B) is more preferably 50 to 150 ° C, and further preferably 60 to 130 ° C. If the melting point or softening point of the resin (B) is within the above numerical range, the resin (B) is not particularly limited, but preferably has an aromatic structure or a heterocyclic structure. Such a resin (B) is preferably at least one selected from the group consisting of epoxy resins, phenoxy resins, phenol novolacs, polyamic acids, polyimides, polybenzoxazoles and (meth) acrylate resins. Among these, as the resin (B), epoxy resin, polyamic acid, polyimide, and polybenzoxazole are preferable from the viewpoint of heat resistance of the obtained cured product, and epoxy resin is preferable from the viewpoint of low viscosity of the resin composition. More preferred. Resin (B) may be used individually by 1 type, and may be used together 2 or more types. In the present embodiment, the resin (B) is a resin different from the epoxy resin (A).

The resin (B) is preferably at least one selected from the group consisting of the following general formulas (4) to (8).

R ₇ in the general formula (4) independently represents a divalent organic group having 1 to 10 carbon atoms. Among these, R ₇ in the general formula (4) is independently preferably a divalent organic group having 1 to 5 carbon atoms, from the viewpoint of heat resistance of the cured product to be obtained. A valent organic group is more preferable. An example of the compound when R ₇ is a divalent organic group having 1 carbon atom is triglycidyl isocyanurate.

R ₈ in the general formula (5) independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. Examples of the monovalent organic group having 1 to 10 carbon atoms include hydrocarbon groups such as a methyl group and an ethyl group. The hydrocarbon group may be substituted with a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, or may be unsubstituted. Among these, from the viewpoint of the heat resistance of the resulting cured product, R ₈ is independently preferably a hydrogen atom or a monovalent organic group having 1 to 5 carbon atoms, and preferably a hydrogen atom or 1 to 3 carbon atoms. A monovalent organic group is more preferable.

The bonding position of the glycidyl ether group in the general formula (5) is not particularly limited, but a meta position and a para position are preferable from the viewpoint of heat resistance when a cured product is used.

These compounds include biphenyl type epoxy resins.

R ₉ in the general formula (6) each independently represents a monovalent organic group hydrogen atom or a C 1-10. Examples of the monovalent organic group having 1 to 10 carbon atoms include hydrocarbon groups such as a methyl group and an ethyl group. The hydrocarbon group may be substituted with a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, or may be unsubstituted. Among these, from the viewpoint of the heat resistance of the resulting cured product, each R ₉ is independently preferably a hydrogen atom or a monovalent organic group having 1 to 5 carbon atoms, and is preferably a hydrogen atom or 1 to 3 carbon atoms. A monovalent organic group is more preferable.

_{R 10} in the general formula (6) is not limited as long as a divalent organic group having 1 to 10 carbon atoms. Among these, from the viewpoint of heat resistance of the obtained cured product, a divalent organic group having 1 to 5 carbon atoms is preferable, and a divalent organic group having 1 to 3 carbon atoms is more preferable.

The bonding position of the glycidyl ether group in the general formula (6) is not particularly limited, but from the viewpoint of heat resistance when a cured product is used, the 1,5-position, 1,6-position, 1,7-position, 1,8-position 2,6 and 2,7 are preferable, and the 1,6th and 1,7th positions are more preferable from the viewpoint of the low viscosity of the epoxy resin.

_{R 11} in the general formula (7) each independently represents a monovalent organic group hydrogen atom or a C 1-10. Examples of the monovalent organic group having 1 to 10 carbon atoms include hydrocarbon groups such as a methyl group and an ethyl group. The hydrocarbon group may be substituted with a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, or may be unsubstituted. Among these, from the viewpoint of the heat resistance of the resulting cured product, each R ₁₁ is preferably a hydrogen atom or a monovalent organic group having 1 to 5 carbon atoms, preferably a hydrogen atom or 1 to 3 carbon atoms. A monovalent organic group is more preferable.

The bonding position of the glycidyl ether group in the general formula (7) is not particularly limited, but a meta position and a para position are preferable from the viewpoint of heat resistance when a cured product is obtained.

_{R 12} in the general formula (8) each independently represents a monovalent organic group hydrogen atom or a C 1-10. Examples of the monovalent organic group having 1 to 10 carbon atoms include hydrocarbon groups such as a methyl group and an ethyl group. The hydrocarbon group may be substituted with a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, or may be unsubstituted. Among these, from the viewpoint of the heat resistance of the resulting cured product, R ₁₂ is each independently preferably a hydrogen atom or a monovalent organic group having 1 to 5 carbon atoms, and preferably a hydrogen atom or 1 to 3 carbon atoms. A monovalent organic group is more preferable.

The bonding position of the glycidyl ether group in the general formula (8) is not particularly limited, but a meta position and a para position are preferable from the viewpoint of heat resistance when a cured product is obtained.

Among the above, from the viewpoint of the balance between the viscosity of the resin composition and the heat resistance of the cured product and the storage stability of the resin composition, the resin (B) is selected from the group consisting of the general formulas (4) and (5). It is preferable that it is one.

In the resin composition according to the present embodiment, the content of the resin (B) is not limited, but is preferably 10% by mass or less and 80% by mass or less in the total resin. In this embodiment, when mixing the solid epoxy resin (A) and the solid resin (B), it is important to adjust the content of the epoxy resin (A) to a specific range. By adjusting the content of B) to the above range, when the resin composition is obtained, the viscosity becomes low and the liquid state is maintained, and the heat resistance of the obtained cured product can be achieved. If the content of the resin (B) is 10% by mass or more in the total resin, the resulting cured product tends to have high heat resistance, and if it is 80% by mass or less, the resin composition has a low viscosity. Tend to be. In all the resins, the content of the resin (B) is preferably 15% by mass or more and 70% by mass or less, and particularly preferably 15% by mass or more and 50% by mass or less from the viewpoint of storage stability of the resin composition.

The resin composition of the present embodiment includes at least one epoxy resin (A) selected from the group consisting of general formulas (1) to (3) and at least selected from the group consisting of general formulas (4) to (8). 1 resin (B) and at least one compound selected from the group consisting of the following general formulas (9) to (11) and / or alkali metal chloride, the ratio of the resin (A) in the total resin Is 20% by mass or more and 90% by mass or less, and the ratio of the resin (B) is 10% by mass or more and 80% by mass or less. The following general formulas (9) to (11) included in the total resin composition The total of the concentration of the compound represented and the chlorine concentration derived from the alkali metal chloride is preferably 0.01 ppm or more and 1000 ppm or less. Such a resin composition can achieve high heat resistance when it is made into a cured product while maintaining low viscosity.

In addition, sodium, potassium, lithium etc. are mentioned as an alkali metal in the alkali metal chloride used for this embodiment.

(In the formulas (9) to (11), R ₁ to R ₆ each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and x, y, and z are integers of 0 to 10 Rx and Ry each independently represents any structure selected from the following formulas (a) to (e), provided that Rx and Ry are not simultaneously represented by the following formula (a). )

Here, R ₁ to R ₆ , x, y, and z in formulas (9) to (11) have the same meanings as those in formulas (1) to (3) described above.

The epoxy resin (A) used in the present embodiment is preferably at least one selected from the group consisting of the general formulas (1) and (2) from the viewpoint of the viscosity of the resin composition. 1) is more preferable.

The resin (B) used in the present embodiment is preferably at least one selected from the group consisting of general formulas (4) and (5) from the viewpoint of heat resistance of the cured product. It is more preferable that

In the resin composition of the present embodiment, the epoxy resin (A) is at least one selected from the group consisting of the general formulas (1) and (2), and the resin (B) is represented by the general formulas (4) and (4). 5) The concentration of the compound represented by the general formulas (9) and (10), which is at least one selected from the group consisting of 5) and contained in the total resin composition, and the chlorine concentration derived from the alkali metal chloride Is more preferably 0.01 ppm or more and 1000 ppm or less.

In the resin composition of the present embodiment, the epoxy resin (A) is a resin represented by the general formula (1), and the resin (B) is a resin represented by the general formula (4). More preferably, the sum of the concentration of the compound represented by the general formula (9) contained in the total resin composition and the chlorine concentration derived from sodium chloride and potassium chloride is 0.01 ppm or more and 1000 ppm or less. .

In the present embodiment, the sum of the concentration of the compounds represented by the general formulas (9) to (11) contained in the total resin composition and the chlorine concentration derived from the alkali metal chloride is 0.01 ppm. It is preferable that it is 1000 ppm or less. When the total concentration is 0.01 ppm or more, there is a tendency to suppress crystallization of the resin composition and maintain a low viscosity, and when it is 1000 ppm or less, the heat resistance (glass transition temperature) of the cured product is high. Tend to be. The total concentration is preferably from 0.1 ppm to 1000 ppm from the viewpoint of suppressing crystallization, and more preferably from 1 ppm to 650 ppm from the viewpoint of the glass transition temperature (hereinafter also referred to as “Tg”) of the cured product. From the viewpoint of the balance between the viscosity of the cured product and the heat resistance of the cured product, 1 ppm to 200 ppm is particularly preferable.

In the present embodiment, the concentrations of the compounds represented by the general formulas (9) to (11) and the chlorine concentration derived from the alkali metal chloride can be measured by the methods described in the examples below. .

The ratio of the epoxy resin (A) in the total resin is 20% by mass or more and 90% by mass or less. If the proportion of the epoxy resin (A) is 20% by mass or more, the viscosity of the resin composition tends to be sufficiently low, and if it is 90% by mass or less, the heat resistance of the cured product is good. The proportion of the epoxy resin (A) is preferably 30% by mass or more and 90% by mass or less from the viewpoint of the viscosity of the resin composition, and more preferably 30% by mass or more and 85% by mass or less from the viewpoint of heat resistance when a cured product is obtained. Preferably, from the viewpoint of storage stability of the resin composition, 50% by mass or more and 85% by mass or less is particularly preferable.

The ratio of the resin (B) in the total resin is preferably 10% by mass or less and 80% by mass or less. If the ratio of the resin (B) is 10% by mass or more, the heat resistance of the obtained cured product tends to be high, and if it is 80% by mass or less, the handleability tends to be good and the viscosity tends to be low. The proportion of the resin (B) is more preferably 15% by mass or more and 70% by mass or less, and particularly preferably 15% by mass or more and 50% by mass or less from the viewpoint of the storage stability of the resin composition.

≪Hardened material for sealing≫
The cured product for sealing according to this embodiment includes an epoxy resin (A) having a melting point or softening point of 30 ° C. or higher, a resin (B) having a melting point or softening point of 50 ° C. or higher, and a compound having a dioxane structure. The ratio of the compound (C) containing (C) and having the dioxane structure is 0.01 ppm or more and 5000 ppm or less.

The compound (C) having a dioxane structure used in the present embodiment is not limited as long as it has a dioxane structure in the molecular structure. Examples of the dioxane structure include 1,2-dioxane, 1,3-dioxane, and 1,4-dioxane structure. Among these, 1,3-dioxane and 1,4-dioxane are preferable and 1,4-dioxane is more preferable from the viewpoint of heat resistance of the encapsulated cured product.

The structure of the compound (C) having a dioxane structure used in this embodiment is preferably the following general formula (12) or (13). The following general formula (12) or (13) corresponds to a compound in which Rx and / or Ry in the general formula (9) or (10) are reacted with each other between the compounds represented by the formula (c). In the resin composition, it exists in the state represented by the general formula (9) or (10), but when this is heated to obtain a cured product, an intermolecular reaction proceeds, and the formula (12 Or a compound having a dioxane structure represented by (13).

Therefore, if the ratio of the compound (C) having a dioxane structure is 0.01 ppm or more in the encapsulated cured product, the compound represented by the formula (c) at the end has a dioxane structure. If it is 5000 ppm or less, the crosslink density is high, so that the heat resistance is improved.

In the encapsulated cured product of the present embodiment, the ratio of the compound (C) having a dioxane structure is not limited as long as it is 0.01 ppm or more and 5000 ppm or less, but the epoxy resin (A) is represented by the general formula (1). In the case where the compound (C) having a dioxane structure is a compound represented by the general formula (12), it is preferably 0.035 ppm or more and 3450 ppm or less. In the cured cured product of this embodiment, the proportion of the compound (C) having a dioxane structure is such that the epoxy resin (A) is the general formula (2) and the compound (C) having the dioxane structure is the general formula. In the case of the structure represented by (13), it is preferably 0.04 ppm or more and 4000 ppm or less.

In addition, in this embodiment, the ratio of the compound (C) which has a dioxane structure can be measured by the method as described in the below-mentioned Example.

<Method for producing epoxy resin (A)>
A method for producing an epoxy resin (A) having a total chlorine content of 0.01 ppm or more and 1000 ppm or less will be described below, taking the case where the epoxy resin (A) is a compound represented by the general formula (1) as an example. To do.

In the production of the epoxy resin of the present embodiment, the method for reducing the chlorine content is not particularly limited, and examples thereof include a method of heating in the presence of a basic substance (alkali heating method) and a method of molecular distillation. By these methods, the amount of chlorine can be sufficiently reduced. Among them, molecular distillation alone and a method of performing molecular distillation after alkali treatment are preferable.

The basic substance used in this embodiment is not limited as long as the chlorination of the epoxy resin can be performed without increasing the molecular weight or gelling. These basic substances include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal hydrides such as sodium hydride and lithium hydride, potassium t-butoxide, sodium t-butoxide, potassium iso Examples include alkali metal alkoxides such as propoxide. Among these, alkali metal alkoxides are preferable from the viewpoint of the hue of the epoxy resin described later.

Hereinafter, a method for alkali treatment using an alkali metal alkoxide and a method for molecular distillation will be described as examples.

As a method for producing the epoxy resin (A), for example, (a) a step of treating a crude epoxy resin containing the compound represented by the general formula (1) and a chlorine content with an alkali metal alkoxide in an organic solvent; And (b) performing a purification step (purification method) including a step of distillation to obtain an epoxy resin in which the proportion of the compound of x = 0 in the compound represented by the general formula (1) is 95% by mass or more. The manufacturing method including a process is mentioned. The total chlorine content in the resulting epoxy resin (A) is 0.01 ppm or more and 1000 ppm or less, preferably 0.1 ppm or more and 1000 ppm, from the viewpoint of the glass transition temperature of the cured product (hereinafter also referred to as “Tg”). 1 ppm or more and 650 ppm or less are more preferable, and 1 ppm or more and 200 ppm or less are particularly preferable from the viewpoint of the balance between the viscosity of the resin composition and the heat resistance of the cured product. By performing a purification step (purification method) including these steps (a) and (b), the amount of chlorine in the epoxy resin (A) is sufficiently reduced, and in the compound represented by the general formula (1) The proportion of compounds with x = 0 is improved. As a result, an epoxy resin exhibiting low viscosity and excellent in hue can be obtained.

<Coarse epoxy resin>
The crude epoxy resin used for this embodiment can be obtained by a well-known method, for example, can be obtained by the manufacturing method including the process of making a phenol compound and an epichlorohydrin compound react.

The crude epoxy resin obtained by such a production method contains chlorine as an impurity in addition to the compound represented by the general formula (1). Examples of the chlorine content include hydrolyzable chlorine and organic bond chlorine. The content of chlorine in the crude epoxy resin (hereinafter also referred to as “total chlorine content”) is, for example, 1000 to 8000 ppm.

<Mechanism of low chlorination>
An epoxy resin (A) in which the amount of chlorine is reduced (hereinafter also referred to as “low chlorination”) can be obtained by the production method including the purification step.

Although the reason why the chlorination can be reduced by including the above purification step is not clear, the present inventors presume as follows.

As described above, the crude epoxy resin contains, for example, both hydrolyzable chlorine and organic bond chlorine as the chlorine component. In the present embodiment, hydrolyzable chlorine refers to, for example, chlorine existing in a state as shown in the following formula (1-2), and organic bond chlorine refers to, for example, the following formula (1) -3) Chlorine that exists in the state shown in the figure.

First, in the case of a compound containing hydrolyzable chlorine (for example, chemical formula (1-2)), when it is reacted with an alkali metal alkoxide in an organic solvent, the ring is closed as shown in the following formula (2-2). Is removed.

Next, in the case of a compound containing organic bond chlorine, the mechanism by which the organic bond chlorine is removed is not clear, but the present inventors consider as follows. That is, in the case of a compound containing organic bond chlorine (for example, chemical formula (1-3)), a hydrogen atom is extracted by an alkali metal alkoxide having a high basicity as shown in the following formula (3-2). A site is formed, and organic bond chlorine is considered to be removed.

Generally, a hydrogen atom that is supposed to be extracted by the mechanism shown in the following formula (3-2) has a low acidity and is conventionally considered to be difficult to be extracted. Nevertheless, according to the above-described method for producing the epoxy resin (A), hydrogen atoms are extracted as shown in the following formula (3-2), and organic bond chlorine can be removed.

Further, generally, when the epoxy group in the compound represented by the general formula (1) coexisting is subjected to nucleophilic attack, the gelation of the epoxy resin proceeds. However, according to the above-described method for producing an epoxy resin, in any reaction, by using a highly basic alkali metal alkoxide, the alkoxide acts as a base in preference to a nucleophilic reaction. It is thought that the removal of the chlorine content proceeds without the gelation of.

<About hue>
When the crude epoxy resin containing the compound represented by the general formula (1) and the chlorine content is treated with an alkali, the hue tends to change to yellow, and depending on the reagent used, the hue is improved even in the distillation step. It may not be done. On the other hand, an epoxy resin that has been subjected to a distillation step without performing an alkali treatment tends to be yellowed over time despite being transparent after distillation. The epoxy resin (A) production method described above is an epoxy having an excellent hue by performing the above-mentioned step (a), which is a treatment using an alkali metal alkoxide among alkali treatments, and further combining a distillation step (b). A resin can be obtained. This will be described in detail below.

Generally, since a crude epoxy resin is obtained by reacting a phenol compound with an epichlorohydrin compound, it contains various impurities in addition to the target epoxy compound. By carrying out distillation of the crude epoxy resin, many impurities in the crude epoxy resin tend to be removed, but impurities having a boiling point similar to that of the target epoxy compound cannot be removed. For example, an epoxy compound having a large equivalent among the epoxy compounds represented by the general formula (1) can be separated from impurities by carrying out distillation. On the other hand, about the epoxy compound with a small equivalent, since the impurity which is the cause of coloring has a boiling point comparable as the objective epoxy compound, even if it distills, it cannot isolate | separate with an impurity. Therefore, in the case of a crude epoxy resin containing an epoxy compound with a small equivalent weight, coloring cannot be suppressed only by carrying out distillation. In this regard, when the crude epoxy resin is treated with an alkali metal alkoxide, impurities that cannot be removed by the distillation step are effectively removed or modified. Therefore, an epoxy resin excellent in hue can be obtained by combining (a) the step of treating the crude epoxy resin with an alkali metal alkoxide in an organic solvent and (b) the step of distillation.

In addition, when an alkali metal hydroxide or the like is used instead of the alkali metal alkoxide, the impurity causing the coloring is not effectively removed or modified in the case of the crude epoxy resin containing the compound represented by the general formula (1). Therefore, there is a tendency that coloring after distillation cannot be suppressed.

The manufacturing method of the above-mentioned epoxy resin (A) is an epoxy resin having an excellent hue by performing both (a) a step of treating with an alkali metal alkoxide in an organic solvent and (b) a step of distillation. A) can be obtained.

<Low viscosity>
A crude epoxy resin contains the compound represented by the said General formula (1), for example. In the crude epoxy resin, the content of the compound represented by the general formula (1) is, for example, 90 to 95% by mass.

In the crude epoxy resin, for example, the compound represented by the general formula (1) exists as a mixture containing two or more compounds having different values of x in the formula (1).

In the compound represented by the general formula (1) contained in the crude epoxy resin, the ratio of the compound of x = 0 is, for example, 90% by mass or more and less than 95% by mass.

The manufacturing method of the above-mentioned epoxy resin (A) can improve the ratio of the compound of x = 0 in the compound represented by the said General formula (1) by performing the said refinement | purification process.

In the compound represented by the general formula (1) contained in the obtained epoxy resin (A) after the purification step, the proportion of the compound where x = 0 is 95% by mass or more, preferably 99% by mass or more. More preferably, it is 99.9 mass% or more. Before the (b) distillation step, the compound contains a plurality of compounds having x = 0 or more and 10 or less. However, by performing the (b) distillation step, the compound with x = 0 (hereinafter “single” This is because the ratio of “mer” is also increased. Thereby, the low viscosity of an epoxy resin is realizable.

<Purification process>
The above-mentioned method for producing an epoxy resin includes (a) a step of treating a crude epoxy resin containing a compound represented by the general formula (1) and a chlorine content with an alkali metal alkoxide in an organic solvent, and (b) distillation. A purification process including the process is performed.

The order of the steps (a) and (b) is not limited, but it is more preferable to carry out the step (b) after the step (a) from the viewpoint of the hue of the epoxy resin. Each step will be described below.

<(A) Process of processing with alkali metal alkoxide in organic solvent>
(Organic solvent)
The organic solvent used in the present embodiment is not particularly limited as long as the organic solvent can uniformly dissolve or disperse the crude epoxy resin. Examples of such organic solvents include ethers such as tetrahydrofuran, dioxane, and dibutyl ether; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane and cyclohexane; acetone, methyl ethyl ketone, and isobutyl ketone. Ketones; Esters such as methyl acetate and ethyl acetate; Amides such as dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone; Sulfur compounds such as dimethyl sulfoxide Is mentioned. These may be used alone or in combination of two or more.

(Alkali metal alkoxide)
Since the epoxy group in the compound represented by the general formula (1) has high reactivity with the nucleophile, the alkali metal alkoxide used in this embodiment does not act as a nucleophile on the epoxy group. In addition, it is preferable to use a bulky alkali metal alkoxide having strong basicity and low nucleophilicity. Specific examples of the alkali metal alkoxide include potassium t-butoxide, sodium t-butoxide, potassium isopropoxide, sodium isopropoxide, potassium ethoxide, sodium ethoxide and the like. These may be used alone or in combination of two or more. Of these, potassium t-butoxide, sodium t-butoxide, potassium isopropoxide, and sodium isopropoxide are preferable from the viewpoint of suppression of gelation of the epoxy resin and basicity, and chlorine contained in the epoxy resin. From the viewpoint of reducing the amount, potassium t-butoxide and sodium t-butoxide are more preferable, and potassium t-butoxide is particularly preferable.

(Processing conditions)
The treatment time in step (a) is not limited as long as the epoxy resin does not gel and the chlorine content in the crude epoxy resin is reduced, but is preferably 1 minute to 24 hours, more preferably 5 minutes to 10 hours. 15 minutes to 5 hours is more preferable. It is particularly preferable that the treatment time in the step (a) is within the above range from the viewpoint of achieving both suppression of the progress of gelation of the epoxy resin and reduction of the chlorine content in the crude epoxy resin.

The treatment temperature in the step (a) is not limited as long as the epoxy resin does not gel and the chlorine content in the crude epoxy resin is reduced, but it is preferably −20 ° C. or higher and 90 ° C. or lower, and −10 ° C. or higher and 80 ° C. or lower. The following is more preferable, and 0 ° C. or higher and 60 ° C. or lower is further preferable. It is particularly preferable that the treatment temperature in the step (a) is in the above range from the viewpoint of achieving both suppression of the progress of gelation of the epoxy resin and reduction of the chlorine content in the crude epoxy resin.

(Addition amount of alkali metal alkoxide in step (a))
The addition amount of the alkali metal alkoxide used in the present embodiment is not limited as long as the total chlorine amount in the crude epoxy resin is sufficiently reduced and gelation of the epoxy resin does not occur, but the total amount contained in the crude epoxy resin is not limited. The amount is preferably 1 to 20 molar equivalents relative to the amount of chlorine, more preferably 2 to 15 molar equivalents from the viewpoint of reducing the amount of chlorine in the crude epoxy resin, and 3 to 15 molar equivalents. More preferably, it is 5 to 12 molar equivalents, particularly preferably 5 to 10 molar equivalents.

Generally, hydrogen atoms that are supposed to be extracted by the mechanism of the formula (3-2) have low acidity, and are conventionally considered difficult to be extracted. On the other hand, when the amount of a reagent such as an alkali metal alkoxide is increased, the gelation of the epoxy resin proceeds. Therefore, conventionally, the amount of a reagent such as an alkali metal alkoxide needs to be suppressed to some extent. However, the above-described method for producing an epoxy resin is a low-chlorine resin that does not progress in gelation even when an alkali metal alkoxide is added within the above range in a crude epoxy resin containing a compound represented by the general formula (1). Can be realized.

(Weight of crude epoxy resin and organic solvent in step (a))
In the method for producing the epoxy resin (A), the concentration of the crude epoxy resin used in the step (a) is 10 to 90 when the total amount of the crude epoxy resin and the organic solvent used in the step (a) is 100% by mass. The content is preferably in the range of mass%, more preferably in the range of 15 mass% to 70 mass% from the viewpoint of suppressing side reactions.

The weight of the crude epoxy resin and the organic solvent in the step (a) preferably satisfies 0.1 ≦ (weight of the crude epoxy resin) / (weight of the crude epoxy resin + weight of the organic solvent) ≦ 0.9. It is more preferable that 15 ≦ (weight of crude epoxy resin) / (weight of crude epoxy resin + weight of organic solvent) ≦ 0.7. If the weight of the crude epoxy resin and the organic solvent in the step (a) satisfies the above conditions, the epoxy resin tends to be reduced in the chlorine content efficiently without the gelation of the epoxy resin proceeding.

(Post-processing process)
The method for producing the epoxy resin is not limited as long as the epoxy resin does not gel and the chlorine content in the crude epoxy resin is reduced, but from the viewpoint of separation from the inorganic salt after the step (a). Further, it is preferable to further include a post-processing step. As the post-treatment step, a treatment step with an acid or water and a treatment step with a liquid separation operation are preferable. The acid used in the post-treatment step is not particularly limited. For example, phosphoric acid, sodium phosphate, potassium phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, acetic acid, oxalic acid, hydrochloric acid, sulfuric acid, nitric acid Etc.

<(B) Step of distillation>
(B) The method used in distillation step, the crude epoxy resin is not limited as long as distillation method can be purified. Examples of such distillation methods include simple distillation and thin film distillation. In the above-described method for producing an epoxy resin, the step (b) of distillation is preferably performed at a degree of vacuum of 0.05 kPa to 0.3 kPa and a distillation internal temperature of 150 ° C. to 180 ° C. When the degree of vacuum is 0.05 kPa or more, it is preferable that a compound having a ring-opening as an impurity can be suppressed in addition to the target epoxy compound (for example, resorcinol diglycidyl ether). Further, when the degree of vacuum is 0.3 kPa or less, it is preferable that the heating temperature exceeds 180 ° C., so that the gelation of the epoxy resin proceeds during distillation and the yield can be significantly reduced. . From the viewpoint of the amount of chlorine contained in the resulting epoxy resin and productivity, the degree of vacuum is preferably from 0.1 kPa to 0.2 kPa, and the distillation internal temperature is preferably from 155 ° C. to 175 ° C.

Further, (b) by repeating the distillation step several times, an epoxy resin with further reduced chlorine content can be obtained.

≪Epoxy resin≫
The epoxy resin which concerns on this embodiment is an epoxy resin represented by following General formula (1), Comprising: The total chlorine amount contained in the said epoxy resin is 0.01 ppm or more and 1000 ppm or less.

The epoxy resin which concerns on this embodiment is an epoxy resin represented by following General formula (2), Comprising: The total chlorine amount contained in the said epoxy resin is 0.01 ppm or more and 1000 ppm or less.

≪Curable resin composition≫
The curable resin composition according to this embodiment preferably contains the above-described resin composition or the above-described epoxy resin (A) and the curing accelerator (A).

In the curable resin composition according to the present embodiment, the content of the above-described resin composition or the above-described epoxy resin (A) is preferably 20 to 99% by mass from the viewpoint of heat resistance of the cured product. The content is more preferably -98% by mass, and further preferably 40-96% by mass.

Further, the curable resin composition according to the present embodiment can further contain other epoxy resins within a range that does not adversely affect the performance.

Other epoxy resins include alicyclic epoxy resins having a total chlorine content of 0 ppm, such as 3,4-epoxy-6-methylcyclohexylmethyl carboxylate and 3,4-epoxycyclohexylmethylcarboxylate.

The amount of other epoxy resin added is not limited as long as it does not adversely affect the performance, but it is preferably 30% by mass or less in the total resin.

<Curing accelerator (I)>
As a hardening accelerator (I), what is necessary is just a compound which can accelerate | stimulate hardening of the resin composition mentioned above or the epoxy resin (A) mentioned above, and the kind is not specifically limited. As a hardening accelerator (I), a nitrogen compound, a phosphorus compound, and a latent hardening accelerator are preferable from a compatible viewpoint with the resin composition mentioned above or the epoxy resin (A) mentioned above. As the curing accelerator (I), from the viewpoint of compatibility with the above-described resin composition or the above-described epoxy resin (A), a nitrogen compound and a latent curing accelerator are more preferable, and from the viewpoint of storage stability, latent From the viewpoint of insulation reliability of the resulting cured product, a microencapsulated latent curing accelerator is even more preferable. A hardening accelerator (I) may be used individually by 1 type, and may be used together 2 or more types.

Examples of the nitrogen compound include 1,8-diaza-bicyclo (5,4,0) undecene-7, 1,5-diaza-bicyclo (4,3,0) nonene, 5,6-dibutylamino-1, Cycloamidine compounds such as 8-diaza-bicyclo (5,4,0) undecene-7; tertiary amines such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and their derivatives Imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and derivatives thereof.

Examples of the phosphorus compound include organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, and phenylphosphine. These may be used alone or in combination of two or more.

As latent curing accelerators, dispersion type curing accelerators, thermal decomposition type curing accelerators, photodegradation type curing accelerators, moisture curing type curing accelerators, molecular sieve encapsulated type curing accelerators, and microencapsulated potentials A hardening accelerator etc. are mentioned. The latent curing accelerator is a curing accelerator that can extremely slow the curing reaction rate at room temperature while maintaining the curing reaction rate at the curing temperature of the epoxy resin.

Examples of the dispersion type curing accelerator include dicyandiamide, adipic acid hydrazide, diamino maleonitrile, diallyl melamine, poly (piperidine-sebatic acid) amide, and imidazole / triazine derivatives.

A thermal decomposition type curing agent is a compound that decomposes into an amine compound such as a tertiary amine and a compound such as isocyanate when heated. Examples thereof include amine imide synthesized from carboxylic acid ester, methyl hydrazine and epoxy compound.

A photodegradable curing accelerator is a compound that is decomposed by irradiation with ultraviolet rays or visible light and activated as a curing accelerator. For example, aromatic diazonium salt, diallyl iodonium salt, triallyl sulfonium salt, triallyl selenium salt and the like can be mentioned.

Examples of the moisture curable curing accelerator include ketimine compounds synthesized from aliphatic polyamines and ketone compounds.

Examples of the molecular sieve encapsulated curing accelerator include those obtained by absorbing an aliphatic polyamine in a molecular sieve.

The microencapsulated curing accelerator refers to a curing accelerator having a curing accelerator as a core and a shell structure around it. For example, an amine-epoxy adduct type in which an imidazole compound is arranged in the core structure and an epoxy resin is arranged in the shell structure, and “Novacure (registered trademark)” and the like correspond to this.

In the curable resin composition according to this embodiment, the content of the curing accelerator (A) is more preferably 1 to 50% by mass from the viewpoint of heat resistance of the cured product, and 2 to 40% by mass. More preferably.

<Curing agent (U)>
The curable resin composition according to this embodiment preferably further contains a curing agent.

The curing agent (c) is not particularly limited as long as it is a compound that can cure the above-described resin composition or the above-described epoxy resin (a). As the curing agent (c), an acid anhydride compound, an acid dianhydride compound, an amine compound, a phenol compound, and the like are preferable from the viewpoint of reactivity with the above-described epoxy resin. A hardening | curing agent (c) may be used individually by 1 type, and may be used together 2 or more types.

Examples of the acid anhydride compound include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic acid anhydride, methylnadic acid anhydride, trialkyltetrahydrophthalic anhydride, phthalic anhydride, and trimellitic anhydride. Acid, dodecenyl succinic anhydride and the like.

Examples of the acid dianhydride compound include pyromellitic anhydride, oxydiphthalic dianhydride, biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, and benzophenone-3,3 ′, 4,4. '-Tetracarboxylic dianhydride, diphenylsulfone-3,3', 4,4'-tetracarboxylic dianhydride, 4,4 '-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, Meta-terphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2,2,2] oct-7- Ene-2,3,5,6-tetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 1-carboxymethyl-2,3,5-cyclopentatricarboxylic acid 2, : 3,5-dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 5- (2 , 5-Dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, ethylene glycol bis (trimellitic acid monoester anhydride), p-phenylene bis (trimellitic acid mono Ester acid anhydride), pentanediol bis (trimellitic acid monoester acid anhydride), decanediol bis (trimellitic acid monoester acid anhydride), and the like.

Examples of amine compounds include aromatic amines, aliphatic amines, and alicyclic amines. Examples of the aromatic amine include metaxylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, metaphenylenediamine, and the like. Commercially available products can also be used as aromatic amines, for example, “Epicure W”, “Epicure Z” (all trade names made by Japan Epoxy Resin Co., Ltd.), “Kayahard AA”, “Kayahard A— B ”,“ Kayahard AS ”(all trade names, manufactured by Nippon Kayaku Co., Ltd.),“ Totoamine HM-205 ”(trade names, manufactured by Tohto Kasei Co., Ltd.),“ Adeka Hardener EH-101 ”(Asahi Denka Kogyo) And “Epomic Q-640”, “Epomic Q-643” (both trade names, Mitsui Chemicals), “DETDA80” (trade names, manufactured by Lonza), and the like. Examples of the aliphatic amine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and diethylaminopropylamine. Examples of alicyclic amines include mensendiamine, isophoronediamine, N-aminoethylpiperazine, bis (4-aminocyclohexyl) methane, and the like.

Examples of the phenol compound include phenol compounds such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol; phenols (phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, and phenylphenol). , Aminophenol, etc.) and / or naphthols (α-naphthol, β-naphthol, dihydroxynaphthalene, etc.) and compounds having an aldehyde group (formaldehyde, benzaldehyde, salicylaldehyde, etc.) in the presence of an acidic catalyst. Novolac-type phenolic resin obtained by mixing with phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl Phenol-aralkyl resins synthesized from aralkyl; aralkyl-type phenol resins such as naphthol-aralkyl resins; dichloropentadiene-type phenol novolac resins synthesized by copolymerization from phenols and / or naphthols and cyclopentadiene; naphthol novolaks Examples thereof include dichloropentadiene-type phenol resins such as resins; terpene-modified phenol resins.

Among these, an acid anhydride compound is preferable from the viewpoint of the viscosity of the curable resin composition. Among the acid anhydride compounds, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic acid anhydride, and methyl nadic acid anhydride are more preferable from the viewpoint of heat resistance of the resulting cured product, and particularly nadic acid. An acid anhydride and methyl nadic acid anhydride are more preferable.

In the curable resin composition according to the present embodiment, the content of the curing agent (c) is P, the epoxy equivalent of the resin composition described above or the epoxy resin (a) described above, and the functional group equivalent of the curing agent (c). When Q is Q, 0.7 ≦ Q / P ≦ 1.3 is preferable from the viewpoint of heat resistance of the cured product, 0.8 ≦ Q / P ≦ 1.2 is more preferable, and 0.9 ≦ Q / P ≦ 1.1 is particularly preferred.

<Inorganic filler (d)>
The curable resin composition of the present embodiment may contain an inorganic filler (d) if necessary. Examples of the inorganic filler (d) include fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, zirconia, zircon, fosterite, Examples thereof include powders such as steatite, spinel, mullite, and titania, beads formed by spheroidizing these, and glass fibers. Furthermore, examples of the inorganic filler (d) having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc molybdate. Among these, fused silica, crystalline silica, and alumina are preferable from the viewpoint of chemical resistance of the obtained cured product, and alumina is more preferable from the viewpoint of thermal conductivity. Further, these inorganic fillers (d) are preferably surface-treated with a silane coupling agent or the like from the viewpoint of the viscosity of the curable resin composition.

In the curable resin composition according to this embodiment, the amount of the inorganic filler (d) added is the above-mentioned epoxy resin (A) having a total chlorine content of 0.01 ppm to 1000 ppm, and a melting point or softening point of 50. When the total content of the resin (B) at a temperature equal to or higher than 100 ° C. is 100 parts by mass, it is preferably 0 to 500 parts by mass, more preferably 0 to 300 parts by mass, and 0 to 200 parts by mass. More preferably.

<Other ingredients>
Other components can be added to the curable resin composition of the present embodiment as long as the performance is not adversely affected. Examples of other components include an adhesion aid, a flame retardant, an ion scavenger, conductive particles, a colorant, and a release agent.

Examples of the adhesion assistant include silane coupling agents, titanate coupling agents, aluminum coupling agents, etc. Among them, silane coupling agents are preferable.

Examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, and N-β-aminoethyl. -Γ-aminopropyltrimethoxysilane and the like. The blending amount of the coupling agent is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin composition or the epoxy resin (a), from the effect of addition and heat resistance.

Examples of the flame retardant include phosphorus compounds such as phosphate ester compounds and phosphazene compounds, and nitrogen compounds such as melamine flame retardants.

Examples of the phosphoric acid ester compound include phosphoric acid esters substituted with an aliphatic hydrocarbon group such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, triisobutyl phosphate, tris (2-ethylhexyl) phosphate; tris (butoxyethyl) Phosphate ester substituted with an aliphatic organic group containing an oxygen atom such as phosphate; aromatic organic group such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, resorcinol bis (diphenyl phosphate) as a substituent And phosphoric acid ester compounds.

Examples of the phosphazene compound include “Ravitor (registered trademark) FP-100” and “Ravitor (registered trademark) FP-300” manufactured by Fushimi Pharmaceutical.

Examples of the melamine flame retardant include melamine cyanurate and melamine polyphosphate.

Examples of the ion scavenger include a copper damage preventing agent for preventing copper from being ionized and dissolved, and an inorganic ion adsorbent. For example, when the curable resin composition of the present embodiment is used on various electronic components such as a copper wiring board, the copper component used as a material may be ionized by contact with moisture or the like. In such a case, by using the curable resin composition containing the copper damage inhibitor and the inorganic ion adsorbent described above, it is possible to supplement and adsorb copper ions and the like that are eluted in contact with moisture and the like.

Examples of copper damage inhibitors include triazine thiol compounds and bisphenol reducing agents. These can also use a commercial item, for example, "disnet DB" (trade name, manufactured by Sankyo Pharmaceutical Co., Ltd.) as a copper damage inhibitor containing a triazine thiol compound as a component, and copper damage containing a bisphenol-based reducing agent as a component. Examples of the inhibitor include “Yoshinox BB” (trade name, manufactured by Yoshitomi Pharmaceutical Co., Ltd.).

Examples of the inorganic ion adsorbent include zirconium compounds, antimony bismuth compounds, magnesium aluminum compounds, and the like. Commercially available products can also be used as the inorganic ion adsorbent, and examples thereof include “IXE-100” (trade name, manufactured by Toa Gosei Chemical Co., Ltd.) as a cation exchange type.

Examples of the conductive particles include metal particles such as Au, Ag, Ni, Cu, and solder, and carbon. Further, non-conductive glass, ceramic, plastic or the like may be used as a core, and the core may be coated with the metal particles or carbon. In the case where the conductive particles are made of plastic as a core and the core is coated with the metal particles or carbon, or are hot-melt metal particles, they have deformability due to heat and pressure. This is preferable because the contact area is increased and the connection reliability is improved. The fine particles obtained by further coating the surface of these conductive particles with a polymer resin or the like can suppress short-circuiting due to contact between the particles when the amount of the conductive particles is increased, and can improve the insulation between the electrode circuits. . Therefore, you may use this individually or in mixture with electroconductive particle suitably. The average particle diameter of the conductive particles is preferably 1 to 18 μm from the viewpoint of dispersibility and conductivity. The average particle diameter here is the primary particle diameter and can be measured by a particle size distribution meter or the like.

The amount of the conductive particles used is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition or epoxy resin (a). . When the amount of the conductive particles used is 0.1 parts by mass or more, the conductivity tends to be improved, and when it is 30 parts by mass or less, a short circuit tends to be prevented.

Examples of the colorant include carbon black.

As the mold release agent, a conventionally known mold release agent can be used. Examples of commercially available products include “SH 7020” (trade name, manufactured by Toray Dow Corning).

≪Usage≫
Since the viscosity of the resin composition of the present embodiment is sufficiently low, the workability is good, and high heat resistance can be exhibited when a cured product is obtained. Therefore, the resin composition of the present embodiment and the curable resin composition using the resin composition are preferably used as an underfill material, a die attach material, a liquid sealing material, and a material for an electronic component including them. it can.

<Underfill material, liquid sealing material>
Underfill material and liquid encapsulant of the present embodiment includes the above-mentioned resin composition or the curable resin composition.

The underfill material and liquid sealing material of this embodiment can be manufactured by a known manufacturing method. For example, it can be manufactured by sufficiently mixing the above-described curable resin composition and enclosing it in a container that can be dispensed. Since the resin composition and the curable resin composition described above has good workability, underfill material and liquid encapsulant comprising the resin composition and the curable resin composition, a semiconductor component or the like and the substrate with the It is possible to easily fill the gaps and the like. Moreover, since the above-mentioned resin composition and curable resin composition exhibit high heat resistance when made into a cured product, the underfill material and the liquid sealing material containing the resin composition and the curable resin composition are: Low performance degradation due to thermal history during soldering. It does not specifically limit as a kind of said base material, For example, a silicon wafer etc. are mentioned.

<Die attach material>
The die attach material of this embodiment contains the above-mentioned resin composition or curable resin composition.

The die attach material of this embodiment can be manufactured by a known manufacturing method. For example, it can be produced by applying the above-mentioned resin composition or curable resin composition to a base material and heating it until it loses fluidity at room temperature. It does not specifically limit as a kind of said base material, For example, a silicon wafer etc. are mentioned.

<Electronic parts>
The electronic component of the present embodiment includes at least one selected from the group consisting of the above-described underfill material, die attach material, and liquid sealing material.

Examples of electronic components including the above-described underfill material, die attach material, and liquid sealing material include semiconductor packages, interposers, Si through electrodes, and the like.

After forming at least one selected from the group consisting of an underfill material, a die attach material, and a liquid sealing material containing the above-described resin composition or curable resin composition, It can be formed by including at least one selected from the group consisting of a material, a die attach material and a liquid sealing material.

The resin composition or the curable resin composition according to the present embodiment, specifically, a protective layer formed of a printed wiring board and the circuit board used in the operation panel of various electronic devices and the like in the electronics field, the insulating laminated board Used for film formation for use in layer formation, silicon wafers used in semiconductor devices, semiconductor chips, semiconductor device peripherals, semiconductor mounting substrates, heat sinks, lead pins, semiconductors themselves, insulation and adhesion Is done.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.

<Reagent>
The following reagents were used in Examples and Comparative Examples.

<Epoxy resin>
Resorcinol diglycidyl ether, trade name “ERISYS RDGE-H” manufactured by CVC Specialty Chemicals, hereinafter abbreviated as “RDGE-H”. In RDGE-H, in the general formula (1), all R ₁ are hydrogen atoms, the bonding position of the glycidyl ether and epoxy group ring-opening sites to the benzene ring is the meta position, and the ratio of the compound of x = 0 is It corresponds to a crude epoxy resin containing a mixture of about 80 to 90% by mass and the ratio of the compound of x = 1 to 10 being about 10 to 20% by mass. The total amount of chlorine in RDGE-H was 3254 ppm.

1,6-bis (glycidyloxy) naphthalene DIC Corporation, trade name “EPICLON HP-4032”, hereinafter also abbreviated as “HP-4032”. HP-4032 is a compound of the general formula (2) in which R ₂ is all hydrogen atoms, the bonding position of the ring opening site of the glycidyl ether and epoxy group to the naphthalene ring is the 1,6-position, and y = 0 This corresponds to a crude epoxy resin containing a mixture having a ratio of about 80 to 90% by mass and a ratio of the compound of y = 1 to 10 being about 10 to 20% by mass. The total chlorine content in HP-4032 was 1400 ppm.

-Bisphenol A type epoxy resin manufactured by Asahi Kasei E-Materials, trade name "AER260", hereinafter also abbreviated as "AER260". AER260 is a compound represented by the general formula (3), wherein R ₃ and R ₄ are all hydrogen atoms, R ₅ and R ₆ are methyl groups, and the ratio of the compound with z = 0 is about 80 to 90% by mass; Corresponds to a crude epoxy resin containing a mixture in which the ratio of the compound of z = 1 to 10 is about 10 to 20% by mass. The total chlorine content in AER260 was 1350 ppm.

-Bisphenol A type epoxy resin, trade name “LX-01” manufactured by Daiso Corporation, also abbreviated as “LX-01”. In the general formula (3), LX-01 is such that R ₃ and R ₄ are all hydrogen atoms, R ₅ and R ₆ are methyl groups, and the proportion of the compound with z = 0 is about 95.2% by mass. It corresponds to an epoxy resin containing a mixture in which the ratio of the compound having z = 1 to 10 is about 4.8% by mass. The total chlorine content in LX-01 was 10 ppm.

<Resin (B)>
Triglycidyl isocyanurate, manufactured by Nissan Chemical Industries, Ltd., trade name “TEPIC-S”, hereinafter also abbreviated as “TEPIC-S”. TEPIC-S corresponds to a resin in which R ₇ is a methylene group in the general formula (4). Melting point: 90-125 ° C.

-Tetramethylbiphenol type epoxy resin, manufactured by Mitsubishi Chemical Corporation, trade name “jER YX4000H”, hereinafter also abbreviated as “YX4000H”. YX4000H is a resin in the formula (5) in which two R ₈ out of four R ₈ are methyl groups, the remaining two R ₈ are hydrogen atoms, and the bonding positions of the glycidyl ether groups are each in the para position. Equivalent. Specifically, it corresponds to the following general formula (14). Melting point: 105-110 ° C.

1-Chloro-2,3-epoxypropane, formaldehyde, 2,7-naphthalenediol polycondensate DIC Corporation, trade name “EPICRON HP-4710”, hereinafter also abbreviated as “HP-4710”. HP-4710 corresponds to a resin in formula (6) in which R ₉ is all hydrogen atoms, R ₁₀ is a methylene group, and the bonding positions of glycidyl ether groups are 1 and 4 positions, respectively. Specifically, it corresponds to the following general formula (15). Melting point: 95 ° C.

Tetrakis (hydroxyphenyl) ethane type epoxy resin, trade name “jER 1031S” manufactured by Mitsubishi Chemical Corporation, hereinafter also abbreviated as “1031S”. 1031S corresponds to a resin in which R ₁₁ is all hydrogen atoms and the bonding position of the glycidyl ether group is para-position in formula (7). Specifically, it corresponds to the following general formula (16). Melting point: 90-100 ° C.

Tris (hydroxyphenyl) methane type epoxy resin, trade name “jER 1032H60” manufactured by Mitsubishi Chemical Corporation, hereinafter also abbreviated as “1032H60”. 1032H60 corresponds to a resin in which R ₁₂ is all hydrogen atoms and the bonding position of the glycidyl ether group is para-position in formula (8). Specifically, it corresponds to the following general formula (17). Melting point: 56-62 ° C.

<Curing accelerator>
・ Novacure HX3941-HP (manufactured by Asahi Kasei E-Materials). NovaCure HX3941-HP is a microencapsulated latent cure accelerator.

<Curing agent>
-HNA-100 (manufactured by Shin Nippon Rika). HNA-100 is an acid anhydride compound.

<Inorganic filler>
-Alumina filler AC2500 SXQ (manufactured by Admatechs).

<Alkali metal alkoxide>
Potassium t-butoxide (manufactured by Wako Pure Chemical Industries, Ltd.)

<Organic solvent>
-Toluene (manufactured by Wako Pure Chemical Industries, super dehydrated grade).
N-methyl-2-pyrrolidone (manufactured by Wako Pure Chemical Industries, dehydrated grade).
2-Propanol (made by Wako Pure Chemical Industries, reagent special grade).
-Methyl isobutyl ketone (manufactured by Wako Pure Chemical Industries, special reagent grade).

<Other reagents>
-Potassium hydroxide (made by Wako Pure Chemical Industries).
Acetic acid (manufactured by Wako Pure Chemical Industries).
Propylene glycol (manufactured by Wako Pure Chemical Industries).
-0.01 mol / L silver nitrate aqueous solution (made by Wako Pure Chemical Industries, Ltd.).
2- (2-butoxyethoxy) ethanol (manufactured by Wako Pure Chemical Industries, Ltd.)
-Acetonitrile (manufactured by Wako Pure Chemical Industries).

The above reagents were used without any particular purification.

<Measurement method of total chlorine content>
In a separable flask, 0.3 g of a sample epoxy resin or resin composition was weighed and dissolved in 25 mL of 2- (2-butoxyethoxy) ethanol to obtain a solution. To the solution was added 25 mL of a 1.16 mmol / L potassium hydroxide propylene glycol solution, and the mixture was heated to reflux for 30 minutes. Thereafter, 200 mL of acetic acid was added to the solution after cooling to room temperature. Then, the amount of chlorine was measured by subjecting the solution to precipitation titration using a potentiometric titrator (“AT-510” manufactured by Kyoto Electronics Co., Ltd.). The said chlorine amount was made into the "total chlorine amount" contained in an epoxy resin or a resin composition. A composite silver electrode (for Ag precipitation titration, “C-373” manufactured by Kyoto Electronics Co., Ltd.) was used as an electrode, and titration was performed using a 0.01 mol / L silver nitrate aqueous solution.

<Measurement method of alkali metal chloride>
In a separable flask, 0.3 g of the epoxy resin or resin composition as a sample was weighed and dissolved in 100 mL of toluene and 100 mL of methanol to obtain a solution. Then, the amount of chlorine was measured by subjecting the solution to precipitation titration using a potentiometric titrator (“AT-510” manufactured by Kyoto Electronics Co., Ltd.). The said chlorine amount was made into the "inorganic chlorine amount" contained in an epoxy resin or a resin composition, and was made into the chlorine amount derived from an alkali metal chloride. A composite silver electrode (for Ag precipitation titration, “C-373” manufactured by Kyoto Electronics Co., Ltd.) was used as an electrode, and titration was performed using a 0.01 mol / L silver nitrate aqueous solution.

<Measurement of compounds represented by general formulas (9) to (11)>
The method for measuring the compounds represented by the general formulas (9) to (11) will be described by taking the resin represented by the general formula (9) as an example.

The compounds in which Rx and Ry in the general formula (9) are (a) to (e) were measured by GC-MS (manufactured by Shimadzu Corporation, GC-2010).

Column type: DB-1 (length: 30 m, diameter: 0.25 mm)
Column temperature: 50 ° C. (1 minute hold) → 280 ° C. (temperature increase 10 ° C./minute, 10 minute hold)
Injection temperature: 250 ° C
Ion source temperature: 250 ° C
Interface temperature: 320 ° C

In the above condition, x = 0, the compound represented by Rx = Ry = (a) is 18 minutes, Rx = (a), a compound represented by Ry = (b) 19.6 minutes, Rx = (a), a compound represented by Ry = (c) is 19.8 minutes, Rx = (a), a compound represented by Ry = (d) 22.5 minutes, Rx = (a), Ry = The compound represented by (e) was detected at 22.9 minutes. From the ratio between the total peak area and the peak area, the ratio of each compound in the general formula (9) was calculated. The ratio of the compounds represented by the general formulas (10) and (11) was calculated in the same manner.

<Formula (1), the proportion of such compound of x = 0, y = 0 in the compound represented by (2)>
The ratio of the compound of x = 0 in the compound represented by the general formula (1) was measured by liquid chromatography (HPLC) or gel permeation chromatography (GPC). In the HPLC measurement, specifically, an acetonitrile solution (0.1% by mass) of an epoxy resin as a sample was prepared, and measurement was performed by liquid chromatography (HPLC) under the following conditions using the solution.

Column: TS-gel ODS-100V (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Pump: DP-8020 (manufactured by Tosoh Corporation)
Detector: UV-8020 (manufactured by Tosoh Corporation)
Mobile phase: liquid A; water, liquid B; acetonitrile Mobile phase gradient conditions: 0 minutes; liquid B 30% by volume, 60 minutes; liquid B 100% by volume, 80 minutes; liquid B 30% by volume

When RDGE-H in which R ₁ is a hydrogen atom was measured under the above conditions, the ratio of the compound having x = 0 in the compound represented by the general formula (1) contained in RDGE-H was 89.3 mass. %. The calculation of the ratio of the compound represented by the general formula (2) where R ₂ is y = 0 in the hydrogen atom was performed in the same manner.

In the GPC measurement, specifically, a tetrahydrofuran solution of an epoxy resin as a sample was prepared, and measurement was performed by liquid chromatography (GPC) under the following conditions using the solution.

GPC: HCL-8320GPC (manufactured by Tosoh Corporation)
Column: shodex A-804 (made by Showa Denko)
: Shodex A-803 (Showa Denko)
: Shodex A-802 (made by Showa Denko KK)
: Shodex A-802 (made by Showa Denko KK)
Column temperature: 40 ° C
Mobile phase: tetrahydrofuran

Measurement of HP-4032 in which R ₂ is a hydrogen atom under the above conditions revealed that the ratio of the compound with y = 0 to the compound represented by the general formula (2) contained in HP-4032 was 82.3 masses. %.

<Viscosity measurement>
The viscosity was measured using a viscometer (manufactured by Toki Sangyo Co., Ltd., “VISCOMETER TV-20”). The measurement temperature was 23 ° C. or 40 ° C., and CORD-1 (1 ° 34 ′ × R24) was used as the rotor.

<Storage stability evaluation>
The initial viscosity (measured within 6 hours after adjusting the composition) and the viscosity after standing for 30 days at 23 ° C. were measured for the resin composition by the above viscosity measurement method, and the “viscosity after 30 days / initial viscosity” The storage stability was evaluated based on the calculated viscosity increase rate. The smaller the viscosity increase rate, the better the storage stability.

<Evaluation of heat resistance (glass transition temperature) of cured product>
The glass transition temperature (Tg) was measured using a differential scanning calorimeter (manufactured by Shimadzu Corporation, “DSC-60”). A sample epoxy resin composition (about 20 mg) was placed in an aluminum pan, heated to 250 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, held for 30 minutes, and cured. Then, after cooling the cured product of the epoxy resin composition to room temperature, the Tg of the cured product was measured by further raising the temperature to 280 ° C. at 10 ° C./min.

<Measurement of ratio of compound (C) having dioxane structure in cured product>
The ratio of the compound (C) having a dioxane structure in the cured product was measured using pyrolysis gas chromatography. After the epoxy resin composition was cured (in air atmosphere, the temperature was raised from room temperature to 120 ° C. at 10 ° C./min, held for 30 minutes, then heated to 180 ° C. at 10 ° C./min and held for 30 minutes). The cured product was measured by pyrolysis gas chromatography. The ratio of the compound (C) having a dioxane structure was calculated from the ratio between the total peak area and the peak area derived from the compound (C).

Column type: DB-1 (length: 30 m, diameter: 0.25 mm)
Column temperature: 40 ° C. (held for 5 minutes) → 320 ° C. (temperature raised 20 ° C./minute, held for 21 minutes)
Injection temperature: 320 ° C
Ion source temperature: 250 ° C
Thermal decomposition temperature: 600 ° C

Under the above conditions, a peak derived from the compound (C) having a dioxane structure was detected at 15.2 minutes.

<Melting point or measurement of resin>
The melting point of the resin was measured using a differential scanning calorimeter (“DSC-60” manufactured by Shimadzu Corporation). A sample resin (about 20 mg) was placed in an aluminum pan, heated to 250 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, and the temperature at which an endothermic peak was observed was defined as the melting point or softening point.

Example 1
Resorcinol diglycidyl ether: RDGE-H (386.75 g) was placed in an eggplant-shaped flask, a T-tube, a thermometer and a condenser were attached, and molecular distillation was performed at a reduced pressure of 0.1 kPa. Distillation was started at a system temperature of 137 ° C, and the first distillation was performed until the system temperature increased to 157 ° C. Distillation was started when the system temperature reached 165 ° C. A molecular distillate of resorcinol diglycidyl ether was obtained with a yield of 57.7%. The total amount of chlorine in the obtained molecular distillate was 610 ppm. The total chlorine content of resorcinol diglycidyl ether not subjected to molecular distillation was 3254 ppm, and the viscosity at 40 ° C. was 150 mPa · s. Also, in all the epoxy resins that are molecular distillates obtained, a compound represented by x = 0 (hereinafter also referred to as “monomer”), a compound represented by x = 1 (hereinafter referred to as “dimer”). The content of a compound represented by x = 2 (hereinafter also referred to as “trimer”), a compound represented by x = 4 (hereinafter also referred to as “tetramer”) and the like by liquid chromatography. As a result of the measurement, the detected peak was only the monomer, and no dimer or higher peak was detected, and both were below the detection limit (0.01% by mass or less). The resulting molecular distillate had a melting point of 39-40 ° C.

(Example 2)
Resorcinol diglycidyl ether (168.59 g) obtained in Example 1 and subjected to molecular distillation once was subjected to molecular distillation again in the same manner as in Example 1. In the second molecular distillation, distillation was started at a reduced pressure of 0.2 kPa and an internal temperature of 145 ° C, and the first distillation was performed until the internal temperature increased to 160 ° C. Distillation was started when the system temperature reached 170 ° C. A molecular distillate was obtained with a yield of 58.0%. The total amount of chlorine in the obtained molecular distillate was 420 ppm. Further, when the content of monomers to tetramers in the total epoxy resin as the molecular distillate obtained was measured by liquid chromatography, the detected peak was only the monomer, and the dimer The above peaks were not detected, and all were below the detection limit (0.01% by mass or less). The resulting molecular distillate had a melting point of 39-40 ° C.

(Example 3)
Resorcinol diglycidyl ether (41.04 g) obtained by carrying out the molecular distillation twice obtained in Example 2 was again subjected to molecular distillation in the same manner as in Example 1. In the third molecular distillation, distillation was started at a reduced pressure of 0.11 kPa and an internal temperature of 135 ° C., and the initial distillation was performed until the internal temperature increased to 155 ° C. Distillation was started when the system temperature reached 160 ° C. A molecular distillate was obtained with a yield of 59.8%. The total amount of chlorine in the obtained molecular distillate was 130 ppm. Further, when the content of monomers to tetramers in the total epoxy resin as the molecular distillate obtained was measured by liquid chromatography, the detected peak was only the monomer, and the dimer The above peaks were not detected, and all were below the detection limit (0.01% by mass or less). The resulting molecular distillate had a melting point of 39-40 ° C.

(Example 4)
Under a nitrogen atmosphere, resorcinol diglycidyl ether: RDGE-H (60.0 g), toluene (105.0 g), and N-methyl-2-pyrrolidone (18.0 g) were placed in an eggplant type flask at 35 ° C. After stirring for 5 minutes, a solution of potassium t-butoxide (3.83 g, 5 molar equivalents relative to the total chlorine content) in N-methyl-2-pyrrolidone was added and stirred with heating at 35 ° C. for 10 minutes. Distilled water (50.0 g) and toluene (120.0 g) were added to the solution heated and stirred for 10 minutes, and the mixture was separated to obtain an organic phase. Thereafter, the organic phase was washed with distilled water (50.0) three times and separated to obtain an organic phase. The obtained organic phase was distilled off under reduced pressure to obtain an epoxy resin with a yield of 75.5%. The obtained epoxy resin was distilled at a reduced pressure of 0.12 kPa and an internal temperature of 135 ° C., and the initial distillation was performed until the internal temperature increased to 155 ° C. Distillation was started when the system temperature reached 160 ° C. A molecular distillate was obtained with a two-stage yield of 43.8%. The total amount of chlorine in the obtained molecular distillate was 8 ppm. Further, when the content of monomers to tetramers in the total epoxy resin as the molecular distillate obtained was measured by liquid chromatography, the detected peak was only the monomer, and the dimer The above peaks were not detected, and all were below the detection limit (0.01% by mass or less). The resulting molecular distillate had a melting point of 39-40 ° C.

(Example 5)
In an eggplant-shaped flask, 1,6-bis (glycidyloxy) naphthalene: HP-4032 (15.0 g) was added, toluene (30.0 g) and N-methyl-2-pyrrolidone (30.0 g) were added, and magnetic. The mixture was stirred with a stirrer until uniform. Further, 0.67 g of potassium t-butoxide (10 molar equivalents relative to the total amount of chlorine in HP4032) was added and stirred at 35 ° C. for 30 minutes. Distilled water (15.0 g) was added to the stirred solution and stirred for 10 minutes. The obtained solution was transferred to a separating funnel, and distilled water (15.0 g), 2-propanol (15.0 g) and methyl isobutyl ketone (15.0 g) were added and washed. After washing, the organic phase was obtained by further washing with distilled water (15.0 g) three times. The obtained organic phase was distilled off under reduced pressure to obtain an epoxy resin (1,6-bis (glycidyloxy) naphthalene).

The obtained epoxy resin was distilled at a reduced pressure of 0.08 kPa and an internal temperature of 155 ° C., and the initial distillation was performed until the internal temperature increased to 175 ° C. Distillation was started when the system temperature reached 180 ° C. A molecular distillate was obtained with a two-stage yield of 47.4%. The total amount of chlorine in the obtained molecular distillate was 4 ppm. Further, the epoxy resin, which is the molecular distillate obtained, was subjected to gel permeation chromatography (GPC) measurement to analyze the detected peak. As a result, the monomer ratio was 96.5% by mass. . The obtained molecular distillate had a melting point of 45 to 48 ° C.

(Example 6)
Resorcinol diglycidyl ether (85 parts by mass) obtained in Example 1 and TEPIC-S (15 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX3941-HP (4.0 parts by mass) was added and stirred to prepare a resin composition. The viscosity, Tg and storage stability at 23 ° C. of the composition were measured. The results are shown in Table 1.

(Example 7)
Resorcinol diglycidyl ether (70 parts by mass) obtained in Example 1 and TEPIC-S (30 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX3941-HP (4.0 parts by mass) was added and stirred to prepare a resin composition. The viscosity, Tg and storage stability at 23 ° C. of the composition were measured. The results are shown in Table 1. Moreover, it was 1200 ppm when this resin composition was measured by the measuring method of the ratio of the compound (C) which has a dioxane structure in the above-mentioned hardened | cured material.

(Example 8)
Resorcinol diglycidyl ether (40 parts by mass) obtained in Example 1 and TEPIC-S (60 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX3941-HP (4.0 parts by mass) was added and stirred to prepare a resin composition. The viscosity, Tg and storage stability at 23 ° C. of the composition were measured. The results are shown in Table 1.

Example 9
Resorcinol diglycidyl ether (88 parts by mass) obtained in Example 1 and TEPIC-S (12 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX3941-HP (4.0 parts by mass) was added and stirred to prepare a resin composition. The viscosity, Tg and storage stability at 23 ° C. of the composition were measured. The results are shown in Table 1.

(Example 10)
Resorcinol diglycidyl ether (70 parts by mass) obtained in Example 2 and TEPIC-S (30 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX3941-HP (4.0 parts by mass) was added and stirred to prepare a resin composition. The viscosity, Tg and storage stability at 23 ° C. of the composition were measured. The results are shown in Table 1.

(Example 11)
Resorcinol diglycidyl ether (70 parts by mass) obtained in Example 3 and TEPIC-S (30 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX3941-HP (4.0 parts by mass) was added and stirred to prepare a resin composition. The viscosity, Tg and storage stability at 23 ° C. of the composition were measured. The results are shown in Table 1.

(Example 12)
Resorcinol diglycidyl ether (70 parts by mass) obtained in Example 4 and TEPIC-S (30 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX3941-HP (4.0 parts by mass) was added and stirred to prepare a resin composition. The viscosity, Tg and storage stability at 23 ° C. of the composition were measured. The results are shown in Table 1.

(Example 13)
By mixing 85 parts by weight of resorcinol diglycidyl ether obtained in Example 1 with TEPIC-S (15 parts by weight) and HNA-100 (161.1 parts by weight), heating at 130 ° C. TEPIC-S was dissolved to obtain a solution. After this solution was cooled to 25 ° C., NovaCure HX-3941HP (4 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg and storage stability at 23 ° C. of this epoxy resin composition were measured. The results are shown in Table 1.

(Example 14)
After mixing TEPIC-S (20 parts by mass) and HNA-100 (162 parts by mass) with 80 parts by mass of resorcinol diglycidyl ether obtained in Example 1, the TGIC was heated at 130 ° C. Dissolved to obtain a solution. After this solution was cooled to 25 ° C., NovaCure HX-3941HP (4 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.

(Example 15)
After mixing TEPIC-S (30 parts by mass) and HNA-100 (164 parts by mass) with 70 parts by mass of resorcinol diglycidyl ether obtained in Example 1, TGIC was heated at 130 ° C. Dissolved to obtain a solution. After this solution was cooled to 25 ° C., NovaCure HX-3941HP (4 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.

(Example 16)
After mixing TEPIC-S (30 parts by mass) and HNA-100 (164 parts by mass) with 70 parts by mass of resorcinol diglycidyl ether obtained in Example 1, TGIC was heated at 130 ° C. Dissolved to obtain a solution. After cooling this solution to 25 ° C., NovaCure HX-3941HP (4 parts by mass) and alumina filler (177.4 parts by mass) were mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.

(Example 17)
After mixing YH4000H (15 parts by mass) with 85 parts by mass of resorcinol diglycidyl ether obtained in Example 1, YH4000H was dissolved by heating at 130 ° C. to obtain a solution. After cooling to 0 ° C., NovaCure HX-3941HP (4 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability at 23 ° C. of this epoxy resin composition were measured by the method described above. The results are shown in Table 1.

(Example 18)
YX4000H (15 parts by mass) and HNA-100 (149.1 parts by mass) were mixed with 85 parts by mass of resorcinol diglycidyl ether obtained in Example 1, and then heated at 130 ° C. to obtain YX4000H. Dissolved to obtain a solution. After this solution was cooled to 25 ° C., NovaCure HX-3941HP (4 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability at 23 ° C. of this epoxy resin composition were measured by the method described above. The results are shown in Table 1.

(Example 19)
After mixing HP4710 (15 parts by mass) with 85 parts by mass of resorcinol diglycidyl ether obtained in Example 1, HP4710 was dissolved by heating at 130 ° C. to obtain a solution. After this solution was cooled to 25 ° C., NovaCure HX-3941HP (4 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.

(Example 20)
HP4710 (15 parts by mass) and HNA-100 (150.4 parts by mass) were mixed with 85 parts by mass of resorcinol diglycidyl ether obtained in Example 1, and then heated at 130 ° C. to obtain HP4710. Dissolved to obtain a solution. After this solution was cooled to 25 ° C., NovaCure HX-3941HP (4 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.

(Example 21)
After mixing 1031S (15 parts by mass) with 85 parts by mass of resorcinol diglycidyl ether obtained in Example 1, HP 4710 was dissolved by heating at 130 ° C. to obtain a solution. After this solution was cooled to 25 ° C., NovaCure HX-3941HP (4 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.

(Example 22)
After mixing 1032S (15 parts by mass) with 85 parts by mass of resorcinol diglycidyl ether obtained in Example 1, HP 4710 was dissolved by heating at 130 ° C. to obtain a solution. After this solution was cooled to 25 ° C., NovaCure HX-3941HP (4 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity and Tg at 23 ° C. of this epoxy resin composition were measured. The results are shown in Table 1.

(Example 23)
1,6-bis (glycidyloxy) naphthalene (85 parts by mass) obtained in Example 5 and TEPIC-S (15 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX3941-HP (4.0 parts by mass) was added and stirred to prepare a resin composition. The viscosity, Tg and storage stability at 23 ° C. of the composition were measured. The results are shown in Table 1.

(Example 24)
1,6-Bis (glycidyloxy) naphthalene (70 parts by mass) obtained in Example 5 and TEPIC-S (30 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX3941-HP (4.0 parts by mass) was added and stirred to prepare a resin composition. The viscosity, Tg and storage stability at 23 ° C. of the composition were measured. The results are shown in Table 1. Moreover, it was 1000 ppm when this resin composition was measured by the measuring method of the ratio of the compound (C) which has a dioxane structure in the above-mentioned hardened | cured material.

(Example 25)
1,6-Bis (glycidyloxy) naphthalene (50 parts by mass) obtained in Example 5 and TEPIC-S (50 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX3941-HP (4.0 parts by mass) was added and stirred to prepare a resin composition. The viscosity, Tg and storage stability at 23 ° C. of the composition were measured. The results are shown in Table 1.

(Example 26)
1,6-bis (glycidyloxy) naphthalene obtained in Example 5 (80 parts by mass), TEPIC-S (20 parts by mass) and HNA-100 (138.7 parts by mass) were mixed at 130 ° C. A solution was obtained by heating. After the solution was cooled to room temperature, NovaCure HX-3941HP (4.0 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.

(Example 27)
1,6-bis (glycidyloxy) naphthalene obtained in Example 5 (70 parts by mass), TEPIC-S (30 parts by mass) and HNA-100 (143.4 parts by mass) were mixed, and at 130 ° C. A solution was obtained by heating. After the solution was cooled to room temperature, NovaCure HX-3941HP (4.0 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.

(Example 28)
LX-01 (85 parts by mass) and TEPIC-S (15 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX-3941HP (4.0 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.

(Example 29)
LX-01 (70 parts by mass), TEPIC-S (30 parts by mass) and HNA-100 (124.2 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX-3941HP (4.0 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.

(Comparative Example 1)
Resorcinol diglycidyl ether (92 parts by mass) obtained in Example 1 and TEPIC-S (8 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. When the solution was cooled to room temperature and allowed to stand at room temperature for a while, it crystallized and a liquid composition could not be obtained.

(Comparative Example 2)
Resorcinol diglycidyl ether (15 parts by mass) obtained in Example 1 and TEPIC-S (85 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. When the solution was cooled to room temperature and allowed to stand at room temperature for a while, it crystallized and a liquid composition could not be obtained.

(Comparative Example 3)
Resorcinol diglycidyl ether: RDGE-H (70 parts by mass) and TEPIC-S (30 parts by mass) not subjected to low chlorination treatment by molecular distillation are mixed and heated at 130 ° C. to obtain a solution. It was. After the solution was cooled to room temperature, NovaCure HX-3941HP (4.0 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.

(Comparative Example 4)
Resorcinol diglycidyl ether not subjected to low chlorination treatment by molecular distillation: RDGE-H (total chlorine amount 3254 ppm, the proportion of monomers in the total epoxy resin is 93.6% by mass, 1.74 mass%, trimer 3.54 mass% and tetramer 1.11 mass%) 70 parts by mass) TEPIC-S (30 parts by mass) and HNA-100 (160.8 (Mass parts) was mixed, and then TGIC was dissolved by heating at 130 ° C. to obtain a solution. After this solution was cooled to 25 ° C., Novacure HX-3941HP (4 parts by mass) and alumina filler (176.6 parts by mass) were further mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability at 23 ° C. of the obtained epoxy resin composition were measured. The results are shown in Table 1.

(Comparative Example 5)
1,6-Bis (glycidyloxy) naphthalene (92 parts by mass) obtained in Example 5 and TEPIC-S (8 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. When the solution was cooled to room temperature and allowed to stand at room temperature for a while, it crystallized and a liquid composition could not be obtained.

(Comparative Example 6)
1,6-Bis (glycidyloxy) naphthalene (15 parts by mass) obtained in Example 5 and TEPIC-S (85 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. When the solution was cooled to room temperature and allowed to stand at room temperature for a while, it crystallized and a liquid composition could not be obtained.

(Comparative Example 7)
1,6-bis (glycidyloxy) naphthalene not subjected to low chlorination treatment by molecular distillation: HP-4032 (70 parts by mass) and TEPIC-S (30 parts by mass) are mixed and heated at 130 ° C. A solution was obtained. After the solution was cooled to room temperature, NovaCure HX-3941HP (4.0 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.

(Comparative Example 8)
1,6-bis (glycidyloxy) naphthalene not subjected to low chlorination treatment by molecular distillation: HP-4032 (70 parts by mass), TEPIC-S (30 parts by mass) and HNA-100 (136.8 parts by mass) ) And heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX-3941HP (4.0 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.

(Comparative Example 9)
AER260 (85 parts by mass) and TEPIC-S (15 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX-3941HP (4.0 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.

(Comparative Example 10)
AER260 (70 parts by mass), TEPIC-S (30 parts by mass), and HNA-100 (120.0 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX-3941HP (4.0 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.

From comparison between Examples 6 to 8 and Comparative Examples 1 and 2, it was confirmed that the resin composition in which the content of resorcinol diglycidyl ether reduced in chlorine within a specific range was kept in a liquid state.

Comparison between Examples 22 to 24 and Comparative Examples 5 to 6 confirms that the resin composition in which the content of low-chlorinated 1,6-bis (glycidyloxy) naphthalene is within a specific range remains liquid. It was done.

In comparison with Examples 7, 9, 10 and 11 and Comparative Example 4, the use of resorcinol diglycidyl ether which is less chlorinated by using less chlorinated resorcinol diglycidyl ether, It was found that the composition had a low viscosity and the cured product had a high Tg.

According to the comparison between Example 23 and Comparative Example 7, and the comparison between Example 27 and Comparative Example 8, by using 1,6-bis (glycidyloxy) naphthalene having low chlorination, As compared with the case of using 6-bis (glycidyloxy) naphthalene, it was found that the composition had a low viscosity and the cured product had a high Tg.

By comparing the comparison between Example 28 and Comparative Example 9 and the comparison between Example 29 and Comparative Example 10 with the use of a low chlorinated bisphenol A type epoxy resin, a chlorinated bisphenol A type epoxy resin was used. It was found that the composition had a low viscosity and the Tg of the cured product was high as compared with the case where it was.

This application is based on a Japanese patent application filed on November 25, 2010 (Japanese Patent Application No. 2010-262810) and a Japanese patent application filed on November 7, 2011 (Japanese Patent Application No. 2011-243399). The contents are incorporated herein by reference.

Since the epoxy resin and the resin composition according to the present invention have low viscosity, they are suitably used for adhesives for electronic parts. In addition, the epoxy resin and resin composition according to the present invention have low viscosity and high heat resistance of the cured product after being cured. Therefore, in the underfill material, die attach material, liquid sealing material, and electronics field. Protective layer formation for printed wiring boards and circuit boards used for operation panels of various electronic devices, insulating layer formation for laminated substrates, silicon wafers used in semiconductor devices, semiconductor chips, members around semiconductor devices, and semiconductor mounting It is used to form films on electronic components for use in protecting, insulating and bonding substrates, heat sinks, lead pins, semiconductors, etc.

Claims

An epoxy resin (A) having a total chlorine content of 0.01 ppm to 1000 ppm,
A resin (B) having a melting point or softening point of 50 ° C. or higher,
During the total resin content of the epoxy resin (A) is not less than 20% by mass to 90% by mass, the resin composition.
2. The resin composition according to claim 1, wherein the content of the resin (B) is 10% by mass or more and 80% by mass or less in all resins.
The resin composition according to claim 1 or 2, wherein the melting point or softening point of the epoxy resin (A) is 30 ° C or higher.
The resin composition according to any one of claims 1 to 3, wherein the epoxy resin (A) is an aromatic epoxy resin.
The resin composition according to claim 4, wherein the aromatic epoxy resin has an aromatic diglycidyl ether structure.
The resin composition according to claim 4, wherein the aromatic epoxy resin is at least one selected from the group consisting of the following general formulas (1) to (3).

(In the formulas (1) to (3), R 1 to R 6 each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and x, y, and z represent 0 to 10 Represents an integer.)
The resin composition according to claim 4, wherein the aromatic epoxy resin is at least one selected from the group consisting of the following general formulas (1) and (2).

(In the formulas (1) and (2), R 1 and R 2 each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and x and y represent an integer of 0 to 5) To express.)
The resin composition according to any one of claims 1 to 7, wherein the resin (B) has an aromatic structure or a heterocyclic structure.
The resin (B) is at least one selected from the group consisting of epoxy resin, phenoxy resin, phenol novolac, polyamic acid, polyimide, polybenzoxazole, and (meth) acrylate resin. The resin composition according to one item.
The resin composition according to any one of claims 1 to 9, wherein the resin (B) is at least one selected from the group consisting of the following general formulas (4) to (8).

(In the formulas (4) to (8), R 8, R 9 , R 11 and R 12 each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and R 7 and R 10 Each independently represents a divalent organic group having 1 to 10 carbon atoms.)
The resin composition according to any one of claims 1 to 10, wherein the resin (B) is at least one selected from the group consisting of the following general formulas (4) and (5).

(In the formulas (4) and (5), R 7 each independently represents a divalent organic group having 1 to 10 carbon atoms, and R 8 each independently represents a hydrogen atom or a carbon atom having 1 to 10 carbon atoms. Represents a monovalent organic group.)
At least one epoxy resin (A) selected from the group consisting of the following general formulas (1) to (3);
At least one resin (B) selected from the group consisting of the following general formulas (4) to (8);
Containing at least one compound selected from the group consisting of the following general formulas (9) to (11) and / or an alkali metal chloride,
In all the resins, the proportion of the epoxy resin (A) is 20% by mass or more and 90% by mass or less, and the proportion of the resin (B) is 10% by mass or more and 80% by mass or less.
The total concentration of the compounds represented by the following general formulas (9) to (11) contained in the total resin composition and the chlorine concentration derived from the alkali metal chloride is 0.01 ppm or more and 1000 ppm or less. , Resin composition.

(In the formulas (1) to (3), R 1 to R 6 each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and x, y, and z represent 0 to 10 Represents an integer.)

(In the formulas (4) to (8), R 8, R 9 , R 11 and R 12 each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and R 7 and R 10 Each independently represents a divalent organic group having 1 to 10 carbon atoms.)

(In the formulas (9) to (11), R 1 to R 6 each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and x, y, and z are 0 to 10 Rx and Ry each independently represents any structure selected from the following formulas (a) to (e), provided that Rx and Ry are not simultaneously represented by the following formula (a) .)
Epoxy resin (A), the general formula (1) and at least one selected from the group consisting of (2),
The resin (B) is at least one selected from the group consisting of the general formulas (4) and (5),
The sum total of the concentration of the compound represented by the general formulas (9) and (10) contained in the total resin composition and the chlorine concentration derived from the alkali metal chloride is 0.01 ppm or more and 1000 ppm or less. The resin composition according to claim 12.
The epoxy resin (A) is a resin represented by the general formula (1),
The resin (B) is a resin represented by the general formula (4),
The sum total of the concentration of the compound represented by the general formula (9) contained in the total resin composition and the chlorine concentration derived from sodium chloride and potassium chloride is 0.01 ppm or more and 1000 ppm or less. 12. The resin composition according to 12.
The proportion of the epoxy resin (A) is 50% by mass or more and 85% by mass or less in the total resin, and the proportion of the resin (B) is 15% by mass or more and 50% by mass or less. The resin composition according to item.
An epoxy resin (A) having a melting point or softening point of 30 ° C. or higher;
A resin (B) having a melting point or softening point of 50 ° C. or higher;
Containing a compound (C) having a dioxane structure;
Hardened | cured material for sealing whose ratio of the compound (C) which has this dioxane structure is 0.01 ppm or more and 5000 ppm or less.
The epoxy resin (A) is represented by the following general formula (1):
The compound (C) having the dioxane structure is the following general formula (12),
The hardened | cured material for sealing of Claim 16 whose ratio of the compound (C) which has a dioxane structure is 0.035 ppm or more and 3450 ppm or less in all the hardened | cured materials.

(In Formula (1), R 1 represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and x represents an integer of 0 to 5)

(In Formula (12), each R 1 independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and x represents an integer of 0 to 10)
The epoxy resin (A) is represented by the following general formula (2):
The compound (C) having the dioxane structure is the following general formula (13),
The hardened | cured material for sealing of Claim 16 whose ratio of the compound (C) which has a dioxane structure is 0.04 ppm or more and 4000 ppm or less in all the hardened | cured materials.

(In Formula (2), R 2 represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and y represents an integer of 0 to 5)

(In Formula (13), each R 2 independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and y represents an integer of 0 to 10)
An epoxy resin represented by the general formula (1),
The epoxy resin whose total chlorine amount contained in the said epoxy resin is 0.01 ppm or more and 1000 ppm or less.

(In Formula (1), each R 1 independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, x represents an integer of 0 or more and 5 or less, and all represented by Formula (1) (The ratio of the compound represented by x = 0 contained in the resin is 99% by mass or more.)
An epoxy resin represented by the general formula (2),
The epoxy resin whose total chlorine amount contained in the said epoxy resin is 0.01 ppm or more and 1000 ppm or less.

(In the formula (2), R 2 each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, y represents an integer of 0 or more and 5 or less, and all represented by the formula (2) (The ratio of the compound represented by y = 0 contained in the resin is 95% by mass or more.)
The resin composition according to any one of claims 1 to 15 or the epoxy resin (a) according to any one of claims 19 to 20,
A curable resin composition containing a curing accelerator (I).
The curable resin composition according to claim 21, wherein the curing accelerator (I) is a nitrogen compound or a latent curing accelerator.
The curable resin composition according to claim 21 or 22, wherein the curing accelerator (I) is a microencapsulated latent curing accelerator.
The curable resin composition according to any one of claims 21 to 23, further comprising a curing agent (c).
25. The curable resin composition according to claim 24, wherein the curing agent (c) is at least one selected from the group consisting of an acid anhydride compound, an acid dianhydride compound, an amine compound, and a phenol compound.
The curable resin composition according to any one of claims 21 to 25, further comprising an inorganic filler (D).
An underfill material comprising the resin composition according to any one of claims 1 to 15 or the curable resin composition according to any one of claims 21 to 26.
A die attach material comprising the resin composition according to any one of claims 1 to 15 or the curable resin composition according to any one of claims 21 to 26.
A liquid sealing material comprising the resin composition according to any one of claims 1 to 15 or the curable resin composition according to any one of claims 21 to 26.
An electronic component comprising at least one selected from the group consisting of the underfill material according to claim 27, the die attach material according to claim 28, and the liquid sealing material according to claim 29.