JP6407580B2 - Epoxy resin, composition thereof, and compound - Google Patents

Description

  The present invention relates to an epoxy resin, a composition containing the epoxy resin, a cured product thereof, and a compound.

  Epoxy resins are cured with various curing agents, and generally become cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., so adhesives, paints, laminates It is used in a wide range of fields such as molding materials and casting materials. Conventionally, a bisphenol A type epoxy resin obtained by reacting bisphenol A with epichlorohydrin is known as an epoxy resin most used industrially. However, the industrial application range of this bisphenol A type epoxy resin may be limited due to insufficient toughness and adhesiveness.

  Patent Document 1 proposes an epoxy resin having a structure in which a propyleneoxy group is introduced between bisphenol A and an epoxy group as an epoxy resin that enhances toughness.

  In Non-Patent Document 1, Ortiz et al. Report that an epoxy resin having a methylstilbene skeleton exhibits high fracture toughness. On the other hand, in Non-Patent Document 2, Jahomi et al. Report an epoxy resin in which an oxyethylene structure is introduced between a mesogenic structure and an epoxy group.

JP-A-8-333357

C. Ortiz, et al., “Deformation of Polydomain, Liquid Crystalline Epoxy-Based Thermoset”, Macromolecules, 31, 1998, p. 4074-4088 S. JAHROMIandW. J. et al. MIJS, “Liquid Crystalline Epoxide Thermosets”, Mol. Cryst. Liq. Cryst. Vol. 250, 1994, p. 209-222

  Although the epoxy resin described in Patent Document 1 is a flexible cured product, sufficient strength cannot be obtained.

  In addition, since the epoxy resins described in Non-Patent Document 1 and Non-Patent Document 2 have a high melting point, the curing reaction proceeds at the stage where the epoxy resin is mixed with a curing agent widely used industrially, and uniform. There exists a subject that a hardened | cured material cannot be obtained. Further, even when the purpose is to prepare a liquid curable resin composition, the resin composition may not be liquid due to strong crystallinity of the epoxy resin, or may be liquid immediately after compounding. During storage, the resin composition becomes solid due to crystallization of the epoxy resin.

  The present invention has been made in view of the above-described problems of the prior art, and an object of the present invention is to provide an epoxy resin that can exhibit excellent toughness and adhesiveness while ensuring sufficient curability and heat resistance. It is to provide.

  As a result of intensive studies to solve the problems of the prior art, the present inventors have found that a compound or epoxy resin having a specific structure can solve the above-described problems of the prior art, and completed the present invention. I came to let you.

（式（１）中、ＭＳは置換又は無置換の２つ以下のフェニレン基から構成されるメソゲン構造を表し、ＳＰ１及びＳＰ２はそれぞれ独立に下記一般式（２）で示される構造を表し、Ｇはそれぞれ独立に水素原子又は下記一般式（４）で示される１価の有機基を表す。）

（式（２）中Ｒ₁は、下記一般式（３）で示される構造を含む炭素数２から１０の炭化水素基を表す。）

（式（３）中Ｒ₂及びＲ₃はそれぞれ独立に水素原子又は炭素数３以下の炭化水素基であり、Ｒ₂及びＲ₃のいずれかは水素原子以外の構造を示す。）

（式（４）中、Ｒ₄は水素原子又は炭素数１以上３以下の炭化水素基を表す。）
［２］
前記式（１）中におけるＭＳが下記一般式（５）又は（６）で示されるいずれかの構造である、［１］に記載のエポキシ樹脂。

（式（５）中、Ｒ₅及びＲ₆はそれぞれ独立に水素原子又は炭素数１以上４以下の飽和若しくは不飽和の炭化水素基を示す。）

（式（６）中、Ｒ₇及びＲ₈はそれぞれ独立に水素原子又は炭素数１以上４以下の飽和若しくは不飽和の炭化水素基を表し、ｐ及びｑはそれぞれ独立に４以下の整数を表す。）
［３］
前記式（１）中におけるＭＳが下記式（９）で示される構造である、［１］又は［２］に記載のエポキシ樹脂。

［４］
前記式（１）中におけるＳＰ１及びＳＰ２がそれぞれ独立に下記式（１１）又は式（１２）で示される構造である、［１］〜［３］のいずれか記載のエポキシ樹脂。

［５］
エポキシ化率が８０％以上である、［１］〜［４］のいずれか記載のエポキシ樹脂。
［６］
［１］〜［５］のいずれか記載のエポキシ樹脂及び硬化剤を含有する、エポキシ樹脂組成物。
［７］
無機フィラーをさらに含有する、［６］に記載のエポキシ樹脂組成物。
［８］
室温で液状である、［６］又は［７］に記載のエポキシ樹脂組成物。
［９］
［１］〜［５］のいずれか記載のエポキシ樹脂を含有し、かつ、固形又は液状である、半導体封止材。
［１０］
［１］〜［５］のいずれか記載のエポキシ樹脂を含有する、熱伝導材料。
［１１］
［１］〜［５］のいずれか記載のエポキシ樹脂を含有する、フィルム状接着剤。
［１２］
［６］〜［８］のいずれか記載のエポキシ樹脂組成物を硬化して得られる、エポキシ樹脂硬化物。
［１３］
下記一般式（１）で表される、化合物。

（式（１）中、ＭＳは２つ以下の置換又は無置換のフェニレン基から構成されるメソゲン構造を表し、ＳＰ１及びＳＰ２はそれぞれ独立に下記一般式（２）で示される構造を表し、Ｇはそれぞれ独立に水素原子又は下記一般式（４）で示される１価の有機基を表す。）

（式（２）中Ｒ₁は、下記一般式（３）で示される構造を含む炭素数２から１０の炭化水素基を表す。）

（式（３）中Ｒ₂及びＲ₃はそれぞれ独立に水素原子又は炭素数３以下の炭化水素基であり、Ｒ₂及びＲ₃のいずれかは水素原子以外の構造を示す。）

（式（４）中、Ｒ₄は水素原子又は炭素数１以上３以下の炭化水素基を表す。） That is, the gist of the present invention for achieving the above object is as follows.
[1]
An epoxy resin containing a compound represented by the following general formula (1).

(In formula (1), MS represents a mesogenic structure composed of two or less substituted or unsubstituted phenylene groups, SP1 and SP2 each independently represent a structure represented by the following general formula (2), G Each independently represents a hydrogen atom or a monovalent organic group represented by the following general formula (4).)

(In formula (2), R ₁ represents a hydrocarbon group having 2 to 10 carbon atoms including the structure represented by the following general formula (3).)

(In Formula (3), R ₂ and R ₃ are each independently a hydrogen atom or a hydrocarbon group having 3 or less carbon atoms, and either R ₂ or R ₃ represents a structure other than a hydrogen atom.)

(In formula (4), R ₄ represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.)
[2]
The epoxy resin according to [1], wherein MS in the formula (1) is any structure represented by the following general formula (5) or (6).

(In Formula (5), R ₅ and R ₆ each independently represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.)

(In Formula (6), R ₇ and R ₈ each independently represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms, and p and q each independently represent an integer of 4 or less. .)
[3]
The epoxy resin according to [1] or [2], wherein MS in the formula (1) is a structure represented by the following formula (9).

[4]
The epoxy resin according to any one of [1] to [3], wherein SP1 and SP2 in the formula (1) are each independently a structure represented by the following formula (11) or formula (12).

[5]
Epoxy resin in any one of [1]-[4] whose epoxidation rate is 80% or more.
[6]
An epoxy resin composition comprising the epoxy resin according to any one of [1] to [5] and a curing agent.
[7]
The epoxy resin composition according to [6], further containing an inorganic filler.
[8]
The epoxy resin composition according to [6] or [7], which is liquid at room temperature.
[9]
The semiconductor sealing material which contains the epoxy resin in any one of [1]-[5], and is solid or liquid.
[10]
The heat conductive material containing the epoxy resin in any one of [1]-[5].
[11]
The film adhesive containing the epoxy resin in any one of [1]-[5].
[12]
A cured epoxy resin obtained by curing the epoxy resin composition according to any one of [6] to [8].
[13]
A compound represented by the following general formula (1).

(In the formula (1), MS represents a mesogenic structure composed of 2 or less substituted or unsubstituted phenylene groups, SP1 and SP2 each independently represents a structure represented by the following general formula (2), G Each independently represents a hydrogen atom or a monovalent organic group represented by the following general formula (4).)

(In formula (2), R ₁ represents a hydrocarbon group having 2 to 10 carbon atoms including the structure represented by the following general formula (3).)

(In Formula (3), R ₂ and R ₃ are each independently a hydrogen atom or a hydrocarbon group having 3 or less carbon atoms, and either R ₂ or R ₃ represents a structure other than a hydrogen atom.)

(In formula (4), R ₄ represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.)

  The present invention can provide an epoxy resin that exhibits excellent toughness and adhesiveness while ensuring sufficient curability and heat resistance, and further provides a stable liquid epoxy resin composition. Can do.

2 is a ¹ H-NMR chart of Compound A obtained in Synthesis Example 1. FIG. 2 is a ¹ H-NMR chart of glycidylated product B obtained in Synthesis Example 2. FIG. 2 is a ¹ H-NMR chart of Compound C obtained in Synthesis Reference Example 3. 3 is a ¹ H-NMR chart of glycidylated product D obtained in Synthesis Reference Example 4.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the present embodiment described below, and can be implemented with various modifications within the scope of the gist.

<< Compound Represented by Formula (1) and Epoxy Resin Containing This >>
The compound of this embodiment is represented by the following general formula (1). Moreover, the epoxy resin of this embodiment contains the compound of this embodiment. In the present specification, when G in the following general formula (1) is a hydrogen atom, the compound is particularly referred to as an “alcoholic compound”.

（式（１）中、ＭＳは置換又は無置換の２つ以下のフェニレン基から構成されるメソゲン構造を表し、ＳＰ１及びＳＰ２はそれぞれ独立に下記一般式（２）で示される構造を表し、Ｇはそれぞれ独立に水素原子又は下記一般式（４）で示される１価の有機基を表す。）

(In formula (1), MS represents a mesogenic structure composed of two or less substituted or unsubstituted phenylene groups, SP1 and SP2 each independently represent a structure represented by the following general formula (2), G Each independently represents a hydrogen atom or a monovalent organic group represented by the following general formula (4).)

（式（２）中Ｒ₁は、下記一般式（３）で示される構造を含む炭素数２から１０の炭化水素基を表す。）

(In formula (2), R ₁ represents a hydrocarbon group having 2 to 10 carbon atoms including the structure represented by the following general formula (3).)

（式（３）中Ｒ₂及びＲ₃はそれぞれ独立に水素原子又は炭素数３以下の炭化水素基であり、Ｒ₂及びＲ₃のいずれかは水素原子以外の構造を示す。）

(In Formula (3), R ₂ and R ₃ are each independently a hydrogen atom or a hydrocarbon group having 3 or less carbon atoms, and either R ₂ or R ₃ represents a structure other than a hydrogen atom.)

（式（４）中、Ｒ₄は水素原子又は炭素数１以上３以下の炭化水素基を表す。）

(In formula (4), R ₄ represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.)

  Since the compound or epoxy resin of the present embodiment is configured as described above, an epoxy resin excellent in toughness and adhesiveness can be provided, and a stable liquid epoxy resin composition is provided. be able to.

<Mesogenic structure>
In the present embodiment, MS represents a mesogenic structure composed of two or less substituted or unsubstituted phenylene groups. The mesogenic structure is a rigid structure necessary for the molecular structure to exhibit liquid crystallinity, and the specific structure of the mesogenic structure is not particularly limited. For example, the Journal of Adhesion Society of Japan, Vol. 40, No. 1 ( (2004) from page 14 to page 15. Hereinafter, it is also simply referred to as “mesogen”.

  Since the mesogen structure has a rigid structure, when an epoxy resin containing the mesogen structure is cured, it tends to be a tough network structure.

<Identification of mesogenic structure>
However, since the mesogen structure has a relatively planar structure, the melting point of the epoxy resin containing the normal mesogen structure is generally high. When the melting point is high, the epoxy resin is usually placed in a pre-molten state at a high temperature in order to uniformly mix with the curing agent. However, since the epoxy resin previously melted at a high temperature is high in temperature, the reaction starts simultaneously with the addition of the curing agent, and as a result, a uniform cured product often cannot be obtained. There are industrial problems.

  In addition, conventionally, in order to prepare a uniform resin composition, an epoxy resin and a curing agent are often dissolved in an organic solvent to make it uniform. However, an epoxy resin containing a mesogenic structure usually tends to have low solubility in an organic solvent, and it is difficult to prepare a uniform resin composition even by the above method.

  Therefore, in order to solve the above problem, the mesogenic structure contained in the epoxy resin of this embodiment is assumed to be “the number of phenylene groups contained is 2 or less”.

  That is, by specifying that the number of phenylene contained is 2 or less, the melting point can be lowered without impairing the original characteristics of the mesogen-containing epoxy resin, and the solubility in organic solvents can be increased.

  Examples of such MS include, but are not limited to, the structures represented by the following general formulas (5) to (8), and when MS has such a structure, an epoxy as compared with other mesogenic structures is used. The melting point of the resin is low, the organic solubility is high, and the toughness when cured is excellent.

（式（５）中、Ｒ₅及びＲ₆はそれぞれ独立に水素原子又は炭素数１以上４以下の飽和若しくは不飽和の炭化水素基を示す。）

(In Formula (5), R ₅ and R ₆ each independently represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.)

（式（６）中、Ｒ₇及びＲ₈はそれぞれ独立に水素原子又は炭素数１以上４以下の飽和若しくは不飽和の炭化水素基を表し、ｐ及びｑはそれぞれ独立に４以下の整数を表す。）

（式（７）中、Ｒ₉及びＲ₁₀はそれぞれ独立に水素原子又は炭素数１以上４以下の飽和若しくは不飽和の炭化水素基を示す。）

(In Formula (6), R ₇ and R ₈ each independently represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms, and p and q each independently represent an integer of 4 or less. .)

(In Formula (7), R ₉ and R ₁₀ each independently represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.)

（式（８）中、Ｒ₆及びＲ₇はそれぞれ独立に水素原子又は炭素数１以上４以下の飽和若しくは不飽和の炭化水素基を示す。）

(In formula (8), R ₆ and R ₇ each independently represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.)

  The MS in the formula (1) is more preferably a structure represented by the above general formulas (5) and (6) in that it is chemically stable and can be easily synthesized, and the following formulas (9), (10 ) Is more preferable in that it can be easily synthesized industrially, and among them, the compound represented by the following formula (9) is more preferable because the melting point tends to be low.

<SP1, SP2>
The epoxy resin of this embodiment has a structure in which SP1 and SP2 (a divalent organic group represented by the above general formula (2)) are bonded to MS (mesogenic structure) as represented by the above formula (1).

<R ₁ carbon number>
R ₁ is a hydrocarbon group having 2 to 10 carbon atoms. The larger the carbon number, the lower the melting point of the epoxy resin. However, when the carbon number is greater than 10, the concentration of mesogen is lowered, and the toughness of the mesogenic skeleton is not sufficiently exhibited. From such a viewpoint, the preferable carbon number is 2 to 5, more preferably 3 carbon atoms.

<Branched structure (formula (3), R ₂ , R ₃ )>
When the branched structure represented by the formula (3) is bonded to both ends of the mesogen, the melting point of the epoxy resin can be lowered and the organic solubility can be increased. Moreover, the toughness and adhesive strength of hardened | cured material can be improved because the branched structure shown by Formula (3) is couple | bonded with the both ends of a mesogen. In a network formed by reaction of an epoxy resin containing a mesogen with a curing agent, the mobility of molecular chains forming the network is remarkably suppressed when the mesogen is extremely oriented. As a result, the phenomenon of relaxation of molecular chains that occurs during the curing process and during the cooling process after curing is less likely to occur, resulting in a cured product having a high internal stress. Therefore, when the branched structure represented by the formula (3) is bonded to both ends of the mesogen, the internal stress of the cured product is reduced, and the high adhesion functioning based on the high toughness of the mesogen group-containing epoxy resin is effective. It can be expressed in an experimental manner.

When R ₁ contains even one structure of the formula (3), a sufficient effect of improving the adhesive strength is exhibited. The larger the content, the lower the melting point of the epoxy resin, and the smaller the content. The heat resistance tends to be higher. From such a viewpoint, the preferred number of the formula (3) in R ₁ is 1 to 3, more preferably 1.

The organic group other than the hydrogen atom of R ₂ and R ₃ is a hydrocarbon group having 3 or less carbon atoms, and the preferred carbon number of R ₂ and R ₃ is 1 from the viewpoint that the smaller the number, the higher the heat resistance. is there.

  From such a viewpoint, the following formulas (11) and (12) are exemplified as the most preferable structure of the general formula (2).

<Epoxy group>
G in the general formula (1) independently represents a hydrogen atom or a monovalent organic group represented by the general formula (4).

R ₁ is a hydrocarbon group as described above, and as the carbon number of the hydrocarbon group increases, the water resistance of the cured product obtained by curing the epoxy resin is improved, but the melting point of the epoxy resin is relatively increased. Tend to. From such a viewpoint, R ₄ in the formula (4) is preferably a hydrogen atom or a hydrocarbon group having 1 carbon atom, more preferably a hydrogen atom.

<Melting point>
The epoxy resin of the present embodiment is not limited depending on the melting point, but the lower the melting point, the lower the melting point, it becomes possible to mix at a low temperature when mixing with a curing agent, and since the reaction during the mixing can be suppressed, uniform curing is possible. There is a tendency to obtain things. From such a viewpoint, the melting point of the epoxy resin of the present embodiment is preferably 150 ° C. or less, more preferably 130 ° C. or less, further preferably 110 ° C. or less, still more preferably 80 ° C. or less, and particularly preferably 60 ° C. or less. Further, it is particularly preferably 40 ° C. or lower. Moreover, the minimum of melting | fusing point of the epoxy resin of this embodiment is not specifically limited, For example, it is -100 degreeC or more. The epoxy resin of this embodiment is preferably liquid at room temperature. The melting point of the epoxy resin of this embodiment can be measured by the method described in the examples described later.

<Synthesis method>
Hereinafter, the method for synthesizing the epoxy resin of the present embodiment is not particularly limited, and examples thereof include the following synthesis methods.

  The epoxy resin of the present embodiment can be synthesized by, for example, polycondensation of an alcoholic hydroxyl group of a compound represented by the following general formula (13) with an epihalohydrin such as epichlorohydrin under alkaline conditions.

（式（１３）中、ＭＳ、ＳＰ１及びＳＰ２は上記式（１）中のＭＳ、ＳＰ１及びＳＰ２と同義である。なお、式（１３）で示される化合物において、アルコール性水酸基とは、末端のＨ（水素原子）とＳＰ１中のＯ（酸素原子）とが結合した部分の−ＯＨ（水酸基）、及びもう一方の末端のＨ（水素原子）とＳＰ２中のＯ（酸素原子）とが結合した部分の−ＯＨ（水酸基）を意味する。）

(In the formula (13), MS, SP1 and SP2 have the same meanings as MS, SP1 and SP2 in the formula (1). In the compound represented by the formula (13), an alcoholic hydroxyl group means a terminal. The part of —OH (hydroxyl group) where H (hydrogen atom) and O (oxygen atom) in SP1 are bonded, and the other terminal H (hydrogen atom) and O (oxygen atom) in SP2 are bonded. (It means -OH (hydroxyl group) of the part)

Although the manufacturing method of the compound shown by following General formula (13) is not specifically limited, The following general formula (XX):
HO-MS-OH (XX)
(In formula (XX), MS has the same meaning as MS in general formula (1).)
And a compound represented by the general formula (XXX):
X—R ₁ —OH (XXX)
(In formula (XXX), R ₁ has the same meaning as R ₁ in formula (2).)
It can obtain by making it react with the compound represented by alkali in presence of an alkali. Alternatively, it can also be synthesized by reacting the compound represented by the general formula (XX) with propylene carbonate in the absence of a catalyst or in the presence of a catalyst such as an alkali.

  Moreover, the epoxy resin of this embodiment is reacted with an alkenyl bromide having a double bond with an alcoholic hydroxyl group of the compound represented by the general formula (13), for example, allyl bromide under alkaline conditions, and then metachloroperbenzoic acid. It can also be synthesized by oxidizing the double bond by, for example.

  The epoxy resin of the present embodiment can be synthesized by any of the above-described methods, but may be obtained as a sequential polymer, and in that case, usually has a molecular weight distribution.

  The epoxy resin of this embodiment may have a molecular weight distribution when used industrially. Moreover, the epoxy resin of this embodiment can also be refine | purified by crystallization using a solvent etc. and can also be used as a monomer.

  The epoxy resin of the present embodiment tends to have a lower melt viscosity and better workability as the number average molecular weight is smaller. From such a viewpoint, the number average molecular weight of the epoxy resin of the present embodiment is preferably 5000 or less, more preferably 1000 or less, and further preferably 500 or less. Although the minimum of the number average molecular weight of the epoxy resin of this embodiment is not specifically limited, For example, it is 200 or more. The number average molecular weight of the epoxy resin of the present embodiment can be measured by the method described in Examples described later.

<Chlorine content>
The epoxy resin of the present embodiment is preferable because the reactivity of the epoxy group tends to be higher as the chlorine content is lower, and the effects of the present embodiment tend to be more noticeable. From such a viewpoint, the chlorine content in the epoxy resin of the present embodiment is preferably as low as possible, preferably 5000 ppm or less, more preferably 1000 ppm or less, and even more preferably 500 ppm or less. The chlorine content in the epoxy resin of this embodiment can be measured by the method described in the examples described later.

<Epoxidation rate>
The epoxy resin of this embodiment tends to exhibit the effect of this embodiment sufficiently, so that the epoxy group content rate (epoxidation rate) is high. The epoxidation rate in the epoxy resin of this embodiment is defined as a percentage of the theoretical epoxy value calculated from the chemical structural formula of the epoxy resin. The epoxy value is the content of epoxy groups per 100 g of the epoxy resin, and is measured by the measurement method described in the examples. The epoxy resin of this embodiment tends to increase the degree of orientation of the epoxy resin structure as the epoxidation rate is closer to 100%. From such a viewpoint, the epoxidation rate in the epoxy resin of the present embodiment is preferably 60% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 95% or more.

≪Epoxy resin composition≫
The epoxy resin composition of this embodiment contains the above-mentioned epoxy resin and a curing agent. Moreover, the epoxy resin composition of this embodiment may further contain a curing accelerator.

<Curing agent, curing accelerator>
Although the above-mentioned epoxy resin is not limited to the following, it can be normally hardened | cured by mix | blending with the hardening | curing agent for epoxy resins, a hardening accelerator, etc.

  Although it does not specifically limit as a hardening | curing agent used for this embodiment, For example, an amine type hardening | curing agent, a phenol type hardening | curing agent, an acid anhydride type hardening | curing agent, a catalyst type hardening | curing agent, a photocatalyst type hardening | curing agent etc. are mentioned.

a) Amine-based curing agent The amine-based curing agent is preferably an amine compound. Although it does not specifically limit as an amine compound, For example, an aliphatic amine and an aromatic amine are mentioned. Aliphatic amines are more preferred because they are highly reactive and can be cured at low temperatures to obtain cured products with high orientation.

  Examples of the aliphatic amine include, but are not limited to, ethylenediamine, diaminopropane, diaminobutane, diaminopentane, hexamethylenediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, Examples include ethylenetetramine, o-xylylenediamine, m-xylylenediamine, and p-xylylenediamine. As the aliphatic amine, diaminopropane, 1,4-cyclohexanediamine, hexamethylenediamine, and p-xylylenediamine are preferable because they are highly compatible with the above-described epoxy resin and give a uniform cured product. Among them, diaminopropane and 1,4-cyclohexanediamine are preferable because they have high orientation strength and as a result, a cured product having high mechanical strength and high thermal conductivity tends to be obtained.

  Although it does not specifically limit as an aromatic amine, For example, o-xylenediamine, m-xylenediamine, p-xylenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Examples include ethane, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ester, monoallyldiaminodiphenylmethane, diallyldiaminodiphenylmethane, and sulfanilamide. Among them, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, p-xylylenediamine, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine are compatible with the above epoxy resin. Therefore, 4,4′-diaminodiphenylethane is more preferable because it has a tendency to obtain a cured product having higher toughness and adhesiveness as well as higher heat resistance. .

  In the epoxy resin composition of the present embodiment, the content of these amine-based curing agents is not particularly limited, but the ratio of active hydrogen bonded to nitrogen atoms is 0.7 to 1 with respect to 1 mol of epoxy groups in the epoxy resin. 0.5 mol is preferable, and 0.9 to 1.2 mol is more preferable.

b) Phenolic curing agent The phenolic curing agent is not particularly limited, and examples thereof include phenol novolac, cresol novolac, catechol novolac, pyrogallol and pyrogallol derivatives.

  Among these, catechol novolak, pyrogallol, and pyrogallol derivatives having an adjacent hydroxyl group are preferred because they tend to give a cured product having higher heat resistance.

  In the epoxy resin composition of the present embodiment, the content of the phenolic curing agent is such that the phenolic hydroxyl group is 0.8 per mol of the epoxy group in the epoxy resin from the viewpoint of improving heat resistance. It is preferable that it is -1.3 mol, More preferably, it is 0.9-1.2 mol, More preferably, it is 1.0-1.1 mol.

c) Acid anhydride type curing agent The acid anhydride type curing agent is not particularly limited. For example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride An acid etc. are mentioned.

  As the acid anhydride curing agent, methyltetrahydrophthalic anhydride is particularly preferable from the viewpoint of obtaining a stable liquid composition and obtaining a cured product having high heat resistance.

  In the epoxy resin composition of the present embodiment, the content of the acid anhydride-based curing agent is such that the acid anhydride is 0 with respect to 1 mol of the epoxy group in the epoxy resin from the viewpoint of high heat resistance and low water absorption. It is preferable that it is 0.7-1.2 mol, More preferably, it is 0.75-1.1 mol, More preferably, it is 0.8-1.0 mol.

d) Catalyst-based curing agent The catalyst-based curing agent is not particularly limited. For example, cations such as boron trifluoride, boron trifluoride-amine complex, aromatic sulfonium salt, diazonium salt, aromatic iodonium salt, etc. System curing catalyst, imidazole catalysts such as 1-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, diazabicycloundecene (DBU), diazabicyclooctane (DABCO), quinuclidine, tributylamine, Tertiary amine compounds such as benzyldimethylamine and dimethylaminopyridine are listed.

  In the epoxy resin composition of the present embodiment, the content of these catalyst-based curing agents is preferably 0.0001 to 10 parts by mass, and 0.01 to 1 part by mass with respect to 100 parts by mass of the epoxy resin. More preferably.

e) Curing Accelerator The epoxy resin composition of the present embodiment may further contain a curing accelerator in addition to the above-mentioned curing agents such as amine curing agents, phenol curing agents, and acid anhydride curing agents. it can. Such a curing accelerator is not particularly limited, and examples thereof include compounds exemplified above as catalyst-based curing agents, phosphines such as triphenylphosphine, tributylphosphine and triethylphosphine, and n-butyltriphenylphosphonium bromide. A phosphonium salt is mentioned.

  Moreover, in the epoxy resin composition of this embodiment, it is preferable that content of a hardening accelerator is 0.01-10 mass parts with respect to 100 mass parts of epoxy resins, and is 0.05-6 mass parts. It is more preferable.

<Fillers etc.>
The epoxy resin composition of the present embodiment is optionally provided with an inorganic filler, a thixotropic agent such as fine silica powder, a defoaming agent, a flame retardant such as a phosphorus compound or a halogen compound, and a flame retardant aid such as antimony trioxide. Agents, colorants such as carbon black and iron oxide, elastomers such as modified nitrile rubber and modified polybutadiene, mold release agents, leveling agents, anti-repellent agents, antifoaming agents, etc. Glass fiber, glass cloth, carbon fiber and the like can be contained.

  The inorganic filler is not particularly limited. For example, spherical or crushed fused silica, silica powder such as crystalline silica, alumina powder, or mica, talc, calcium carbonate, aluminum, alumina, hydrated alumina, asbestos, magnesium oxide. Diatomaceous earth, graphite, boron nitride, aluminum nitride, silicon carbide, silicon nitride and the like.

  When the epoxy resin composition of the present embodiment contains an inorganic filler having a high thermal conductivity such as boron nitride or aluminum nitride, a cured epoxy resin having a higher thermal conductivity than the conventional one tends to be obtained.

<Other epoxy resins>
The epoxy resin composition of the present embodiment can contain other epoxy resins or epoxy compounds other than the above-described epoxy resins as necessary within a range that does not impair the purpose.

  Such other epoxy resin or epoxy compound is not particularly limited. For example, divalent phenols such as bisphenol A, bisphenol S, bisphenol F, hydroquinone, and resorcin; tris- (4-hydroxyphenyl) ethane, Trivalent or higher phenols such as 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak; halogenated bisphenols such as tetrabromobisphenol A, or divalent or trivalent Cyclic aliphatic epoxides such as alicyclic diepoxy carboxylates, alicyclic diepoxy acetals, alicyclic diepoxy adipates, vinylcyclohexene diepoxides, etc. derived from the above phenols Shi resins; polyglycidyl compound of glycerol, aliphatic epoxy compound of polyglycidyl compounds such as trimethylol propane.

  Furthermore, monoglycidyl compounds such as phenyl glycidyl ether, cresyl glycidyl ether, p-tert-butylphenol glycidyl ether, o-tert-butylphenol glycidyl ether, m-tert-butylphenol glycidyl ether, o-bromophenyl glycidyl ether, etc. Can be mentioned.

  In particular, when the epoxy resin composition of the present embodiment contains an epoxy resin having a mesogenic structure in the molecule, the effects of the present embodiment tend to be more effectively expressed. Such an epoxy resin is not particularly limited, and examples thereof include a twin mesogen type epoxy resin as exemplified in Journal of Material Science (1997, Vol. 32, page 4039).

<Method for producing epoxy resin composition>
The epoxy resin composition of the present embodiment can be produced, for example, by thoroughly mixing and kneading the above-described components according to a conventional method and then degassing under reduced pressure.

  Melting | fusing point of the epoxy resin composition of this embodiment can be measured by the method as described in the below-mentioned Example.

≪Hardened epoxy resin≫
The cured epoxy resin of this embodiment is obtained by curing the above-described epoxy resin composition.

≪Usage≫
Although the alcoholic compound or epoxy resin of this embodiment is not limited to the following, for example, a solid or liquid curable resin composition is provided by selecting a curing agent, etc., and a semiconductor sealing material, a heat conductive material, a structural adhesive It can be used as various films (for example, a film adhesive). Thus, it is preferable that the epoxy resin composition of this embodiment is liquid. In particular, in applications used as a liquid epoxy resin composition, the liquid state can be kept stable for a long period of time.

  The present embodiment will be described in more detail with reference to the following examples, but the present embodiment is not limited to the following examples. “Part” or “%” in Examples and Comparative Examples is based on mass unless otherwise specified.

  In addition, various physical properties in each example and comparative example were evaluated by the following methods.

1) Epoxy value An epoxy resin (sample) was dissolved in benzyl alcohol and 1-propanol to obtain a solution. After adding an aqueous potassium iodide solution and a bromophenol blue indicator to this solution, the solution was titrated with 1 N hydrochloric acid. The point where the reaction system in the solution turned from blue to yellow was defined as the equivalent point. From this equivalent point, the epoxy value of the epoxy resin was calculated according to the following formula.

Epoxy value (equivalent / 100 g) = (V × N × F) / (10 × W)
W: Weight of sample (g)
V: titration to the equivalent point (mL)
N: Normality of hydrochloric acid used for titration (N)
F: Factor of hydrochloric acid used for titration

2) Chlorine content Samples 0.1 to 3 g were dissolved in 25 mL of ethylene glycol monobutyl ether to obtain a solution. To this solution was added 20 mL of 1N KOH-propylene glycol solution, and the solution was boiled for 20 minutes. Thereafter, 100 mL of acetic acid was added to this solution, and potentiometric titration was performed on this solution using an aqueous silver nitrate solution. From the inflection point detected by this potentiometric titration, the number of moles of the compound to be titrated was determined, and the chlorine content in the sample was calculated based on the number of moles of the compound to be titrated, assuming that the total amount of the compound to be titrated was chlorine.

3) Melting | fusing point of epoxy resin Melting | fusing point of epoxy resin was measured on the conditions of the temperature increase rate of 5 degree-C / min using the differential scanning calorimetry apparatus (7020 by SII nanotechnology company). In this measurement, the peak temperature of the endothermic peak was taken as the melting point, and when there were a plurality of endothermic peaks, the endothermic peak temperature in the highest temperature region was taken as the melting point.

4) Number average molecular weight The number average molecular weight was measured by gel permeation chromatography (GPC). For the measurement, LC-10AD manufactured by Shimadzu Corporation was used, and a differential refractometer was used as the detector. The measurement sample used was tetrahydrofuran adjusted to a concentration of 0.5 wt / vol% using tetrahydrofuran as a solvent.

  As the column, a column made by connecting two Shodex LF-804 manufactured by Showa Denko KK in series was used, and tetrahydrofuran was used as the mobile phase. The measurement sample was introduced into the measurement apparatus at a flow rate of 1 mL / min at 40 ° C. and analyzed.

  A calibration curve was prepared using polystyrene having number average molecular weights of 1160, 2810, 6020, and 16000 as standard substances, and the number average molecular weight was determined in terms of polystyrene.

5) Tensile property test The tensile property test was conducted under the following conditions in accordance with JIS-K-7161-1994 and JIS-K-7162-1994.

Test apparatus: Instron type tensile tester (AGS-J, manufactured by Shimadzu Corporation)
Crosshead speed: 2 mm / min, maximum load: 100 kgf
Test piece: 5B type, full length: 30 mm, width: 4 mm, thickness: 2 mm
Length of parallel part: 12 mm, width of parallel part: 2 mm, radius of roundness: 12 mm
Distance between grippers: 24 mm, distance between marked lines: 10 mm

  The fracture energy was determined from the descending area of the stress-strain curve obtained in the tensile property test.

σ = F × 9.8 / A
(Σ: tensile stress (MPa), F: load (kgf), 9.8: gravitational acceleration (m / s ² ), A: cross-sectional area (mm ² ))

ε = (δL / L0) × 100
(Ε: strain (%), δL: elongation at break (mm), L0: distance between marked lines (mm) = 10)

6) Shear bond strength Measured according to JIS K6850 under the following conditions.

Test apparatus: Instron type tensile tester (AG-20 / 50KINIS MO, manufactured by Shimadzu Corporation)
Substrate: mild steel sheet, size (25mmX100mmX3.2mm)
Bonding area: 12.5mmX25.0mm
Crosshead speed: 50mm / min, maximum load: 1t

  The fracture energy was determined from the lower area of the Stress-Strain diagram.

7) Water absorption rate The following test piece was evaluated by the increase in mass before and after being immersed in boiling water for 5 hours.
Test piece: 10mmX10mmX0.5mm

8) Glass transition temperature (Tg)
The glass transition temperature of the cured product was measured by dynamic viscoelasticity measurement under the following conditions. The measurement was performed in a tensile mode using a non-resonant forced vibration type viscoelasticity measurement analyzer (Rheogel-E4000, manufactured by UBM). In this measurement, the peak temperature of tan δ was defined as the glass transition temperature (Tg) of the cured product.

〔Measurement condition〕
Sample size: 30mm x 4.0mm x 0.4mm
Waveform: Sine wave Frequency: 10Hz
Displacement amplitude: 5 μm
Measurement temperature: -150 to 250 ° C
Temperature increase rate: 2 ° C / min

9) NMR measurement NMR measurement was performed using JNM-EX400 manufactured by JEOL.

(Synthesis Example 1)
A mixture obtained by adding 11.3 parts of 4,4′-dihydroxy-α-methylstilbene and 11 parts of propylene carbonate to a glass reactor equipped with a stirring blade made of Teflon (registered trademark), a glass condenser, and a thermometer. Was heated to 120 ° C. After adding 0.3 part of 50 mass% potassium carbonate aqueous solution to the said glass reactor, the obtained mixture was heated to 170 degreeC and was further reacted for 2 hours. After completion of the reaction, the obtained resin was dispensed and crystallized from a mixed solvent of 15 parts of dimethylformamide and 85 parts of methanol, and 10.3 parts of compound A (a compound represented by the following formula (14)) (yield 60%). Got.

The obtained compound A had a melting point of 143 ° C. A ¹ H-NMR chart of the resulting compound A is shown in FIG.

The NMR analysis results (solvent: DMSOd6) were as follows.
7.5ppm (2H), 7.3ppm (2H), 7.0ppm (4H), 6.9ppm (1H), 4.9ppm (2H), 3.8-4.0ppm (6H), 2.2ppm ( 3H), 1.2 ppm (6H)

(Synthesis Example 2)
4 parts of Compound A, 13 parts of epichlorohydrin and 9 parts of dimethyl sulfoxide were added to a glass reactor equipped with a stirring blade made of Teflon (registered trademark), a glass condenser, and a thermometer, and the resulting mixture was heated and stirred at 50 ° C. To the glass reactor, 4.7 parts of a 50% by mass aqueous sodium hydroxide solution was added over 1 hour, and the resulting mixture was stirred for 1 hour to carry out the reaction. Thereafter, 40 parts of toluene was added to the glass reactor, and after washing 6 times with 10 parts of water, excess epichlorohydrin and toluene were distilled off, and 5.2 parts of glycidylated product b (epoxy value 0.308 [equivalent / 100 g], an epoxidation rate of 70%).

  Subsequently, 4.8 parts of glycidylated product B (yield 90%) (compound represented by the following formula (15)) was performed by using the same operation as described above using 4 parts of glycidylated product b instead of Compound A. Got.

The obtained glycidylated product B had an epoxy value of 0.420 [equivalent / 100 g] and an epoxidation rate of 95%. Moreover, the number average molecular weight of the obtained compound B was 470, and chlorine content was 420 ppm. Compound B was liquid at room temperature. A portion of Compound B crystallized after 3 months at room temperature, and the melting point was measured by separating the crystal. A ¹ H-NMR chart of the resulting glycidylated product B is shown in FIG.

The NMR analysis result (solvent: CDCl ₃ ) was as follows.
7.5ppm (2H), 7.3ppm (2H), 6.9ppm (4H), 6.8ppm (1H), 3.5-4.3ppm (10H), 3.2ppm (2H), 2.8ppm ( 2H), 2.6 ppm (2H), 2.2 ppm (3H), 1.3 ppm (6H)

(Synthesis Reference Example 3)
Teflon stirring blade, a glass condenser, DMF19 parts in a glass reactor equipped with a thermometer, 4,4'-dihydroxybiphenyl 9.3 parts and heated to 100 ° C. carbonate added propylene emissions 15.3 parts Then, 2.7 parts of 50% by mass aqueous potassium carbonate solution was added, and the mixture was reacted at 140 ° C. for 8 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, the solid content in the reaction system was filtered off, washed with 50 parts of water and 100 parts of methanol, and then dried under reduced pressure at 120 ° C. for 2 hours to give compound C (formula (16) below) Compound (3.5 parts) (yield 23%).

The obtained compound C had a melting point of 189 ° C. A ¹ H-NMR chart of the obtained compound C is shown in FIG.

The NMR analysis results (solvent: DMSOd6) were as follows.
7.5ppm (4H), 7.0ppm (4H), 4.9ppm (2H), 3.8-4.0ppm (6H), 1.1ppm (6H)

(Synthesis Reference Example 4)
To a glass reactor equipped with a Teflon (registered trademark) stirring blade, glass condenser and thermometer, 3.0 parts of Compound C, 11 parts of epichlorohydrin and 7.8 parts of dimethyl sulfoxide were added, and the resulting mixture was heated at 50 ° C. Stir. To the glass reactor, 4.0 parts of a 50% by mass aqueous sodium hydroxide solution was added over 1 hour, and the resulting mixture was stirred for 1 hour to carry out the reaction. Thereafter, 25 parts of toluene was added to the glass reactor and washed 6 times with 10 parts of water, and then excess epichlorohydrin and toluene were distilled off. 4.2 parts of glycidyl compound d (epoxy value 0.377 equivalent / 100 g, Epoxidation rate 78%) was obtained.

  Subsequently, the same operation as described above was carried out using 4.2 parts of glycidylated product d instead of Compound C, whereby 4.0 parts of glycidylated product D (yield 96%, epoxy value 0.454 equivalent / 100 g, epoxy 94%) (compound represented by the following formula (17)) was obtained.

The number average molecular weight of the obtained compound D was 420, and the chlorine content was 480 ppm. A ¹ H-NMR chart of the resulting glycidylated product D is shown in FIG.

The NMR analysis result (solvent: CDCl ₃ ) was as follows.
7.5ppm (4H), 7.0ppm (4H), 4.2ppm (0.3H), 3.9-4.1ppm (7.5H), 3.6ppm (1.8H), 3.1ppm (1 .7H), 2.8 ppm (1.7 H), 2.6 ppm (1.7 H), 1.2 ppm (6H)

  Next, glycidylation product D was crystallized from methyl isobutyl ketone to obtain glycidylation product DF. The melting point of glycidylated product DF was 81 ° C., and the epoxy value was 0.473 equivalent / 100 g (epoxidation rate 98%).

(Synthesis Comparative Example 1)
70.7 parts of 4,4′-dihydroxy-α-methylstilbene and 59 parts of ethylene carbonate were added to a glass reactor equipped with a stirring blade made of Teflon (registered trademark), a glass condenser, and a thermometer, and the resulting mixture was obtained. Was heated to 120 ° C. After adding 2 parts of 50% by weight aqueous potassium carbonate solution to the glass reactor, the resulting mixture was heated to 170 ° C. and further reacted for 1 hour. After completion of the reaction, the obtained resin was discharged and crystallized using methyl ethyl ketone to obtain 64 parts (yield 65%) of Compound E (compound represented by the following formula (18)). The obtained compound E had a melting point of 163 ° C.

(Synthesis Comparative Example 2)
50 parts of Compound E, 178 parts of epichlorohydrin and 124 parts of dimethyl sulfoxide were added to a glass reactor equipped with a stirring blade made of Teflon (registered trademark), a glass condenser, and a thermometer, and the resulting mixture was heated and stirred at 50 ° C. To the glass reactor, 128 parts of 50% by weight aqueous sodium hydroxide solution was added over 1 hour, and the resulting mixture was stirred for 1 hour to carry out the reaction. Thereafter, 250 parts of toluene was added to the glass reactor to obtain a reaction product. The obtained reaction product was washed 6 times with 250 parts of water, and excess epichlorohydrin and toluene were distilled off. The obtained residue was crystallized using methyl isobutyl ketone to obtain glycidylated product F (compound represented by the following formula (19)) in a yield of 70%.

(Application Example 1)
Diaminodiphenylethane is blended so that the active amine is a chemical equivalent with respect to the epoxy group of glycidylated product B, heated at 120 ° C. for 1 hour, and further heated at 150 ° C. for 2 hours to obtain a cured product. It was. The evaluation results of the obtained cured product are shown in Table 1.

(Application Examples 2 and 3)
Evaluation was conducted in the same manner as in Application Example 1 except that glycidylated products b and D were used instead of glycidylated product B. The evaluation results are shown in Table 1.

(Application comparison example 1)
Table 1 shows the results of evaluation in the same manner as in Application Example 1 except that glycidylated product E was used in place of glycidylated product B and cured under the following conditions.
Curing conditions: heated at 170 ° C. for 1.5 hours.

(Application Example 4)
A liquid composition P was prepared by blending methyltetrahydrophthalic anhydride equivalent to the epoxy group of glycidylated product B and 1 part of 2-ethyl-4-methylimidazole with 100 parts of glycidylated product B. The composition P was still in a liquid state after one week at room temperature, and was found to be useful as a semiconductor liquid encapsulant.

  Further, when the composition P was cured at 120 ° C. for 1 hour, further at 150 ° C. for 2 hours, and then at 180 ° C. for 2 hours, the Tg was 80 ° C. and the water absorption was 0.3%.

(Application comparison example 2)
A liquid composition Q was prepared in the same manner as in Application Example 4 except that glycidylated product E was used instead of glycidylated product B. It was found that the composition P became solid after 2 days at room temperature and could not be used as a semiconductor liquid encapsulant.

  Table 1 shows the results of evaluation performed in Application Examples 1 to 3 and Application Comparative Example 1.

  The epoxy resin of the present invention is cured by various blending and curing methods to obtain a cured product excellent in high toughness, adhesion, thermal conductivity, heat resistance, gas barrier properties, hygroscopicity, mechanical strength, chemical resistance, etc. provide. Due to these characteristics, the epoxy resin of the present invention is an insulating material such as an electric / electronic component represented by a semiconductor element, a conductive material, a sealing material or a casting material, a laminated material, various heat dissipation materials, and an organic EL sealing. It can be suitably used for materials, various paints, adhesives and the like.

Claims (13)

An epoxy resin containing a compound represented by the following general formula (1).

(In formula (1), MS represents a structure represented by the following general formula (5), (7) or (8), SP1 and SP2 each independently represents a structure represented by the following general formula (2), G represents each independently a monovalent organic group represented by the following general formula (4).)

(In formula (2), R ₁ represents a hydrocarbon group having 2 to 10 carbon atoms including the structure represented by the following general formula (3).)

(In Formula (3), R ₂ and R ₃ are each independently a hydrogen atom or a hydrocarbon group having 3 or less carbon atoms, and either R ₂ or R ₃ represents a structure other than a hydrogen atom.)

(In formula (4), R ₄ represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.)

(In Formula (5), R ₅ and R ₆ each independently represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.)

(In Formula (7), R ₉ and R ₁₀ each independently represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.)

(In formula (8), R ₆ and R ₇ each independently represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.) The epoxy resin according to claim 1, wherein MS in the formula (1) has a structure represented by the following general formula (5).

(In Formula (5), R ₅ and R ₆ each independently represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.) The epoxy resin according to claim 1 or 2, wherein MS in the formula (1) has a structure represented by the following formula (9).

The epoxy resin according to any one of claims 1 to 3, wherein SP1 and SP2 in the formula (1) are each independently a structure represented by the following formula (11) or formula (12).

The epoxy resin as described in any one of Claims 1-4 whose epoxidation rate computed according to following formula ((alpha)) is 80% or more:
Epoxidation rate = 100 × epoxy value theoretical value / epoxy value measured value (α)
(In the above formula (α), the theoretical value of the epoxy value is a value calculated from the chemical structural formula of the epoxy resin. The measured value of the epoxy value is obtained by dissolving the epoxy resin as a sample in benzyl alcohol and 1-propanol. After adding potassium iodide aqueous solution and bromophenol blue indicator to the obtained solution, the solution was titrated with 1N hydrochloric acid, and the reaction system in the solution turned from blue to yellow. And is calculated from the equivalent point according to the following formula (β).)
Epoxy value measured value (equivalent / 100 g) = (V × N × F) / (10 × W) (β)
(In the above formula (β), W is the weight (g) of the sample, V is the titration amount (mL) up to the equivalence point, and N is the normality (N) of hydrochloric acid used for titration. Yes, F is the factor of hydrochloric acid used for titration.)   The epoxy resin composition containing the epoxy resin and hardening | curing agent as described in any one of Claims 1-5.   The epoxy resin composition according to claim 6, further comprising an inorganic filler.   The epoxy resin composition according to claim 6 or 7, which is liquid at room temperature.   The semiconductor sealing material which contains the epoxy resin as described in any one of Claims 1-5, and is solid or liquid at room temperature.   The heat conductive material containing the epoxy resin as described in any one of Claims 1-5.   The film adhesive containing the epoxy resin as described in any one of Claims 1-5.   The epoxy resin hardened | cured material obtained by hardening | curing the epoxy resin composition as described in any one of Claims 6-8. A compound represented by the following general formula (1).

(In formula (1), MS represents a structure represented by the following general formula (5), (7) or (8) , SP1 and SP2 each independently represents a structure represented by the following general formula (2), G represents a hydrogen atom or a monovalent organic group represented by the following general formula (4).

(In formula (2), R ₁ represents a hydrocarbon group having 2 to 10 carbon atoms including the structure represented by the following general formula (3).)

(In Formula (3), R ₂ and R ₃ are each independently a hydrogen atom or a hydrocarbon group having 3 or less carbon atoms, and either R ₂ or R ₃ represents a structure other than a hydrogen atom.)

(In formula (4), R ₄ represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.)

(In Formula (5), R ₅ and R ₆ each independently represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.)

(In Formula (7), R ₉ and R ₁₀ each independently represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.)

(In formula (8), R ₆ and R ₇ each independently represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.)

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