JP5245199B2 - Epoxy resin composition, cured product thereof, novel epoxy resin, production method thereof, and novel phenol resin - Google Patents

Description

INDUSTRIAL APPLICABILITY The present invention can be suitably used as a resin composition for a semiconductor device, a circuit board device or the like that exhibits an excellent cured product without using an additive-based flame retardant in the cured product and also has excellent dielectric characteristics. The present invention relates to an epoxy resin composition, a cured product thereof, a novel epoxy resin used therefor, a method for producing the same, and a resin having a novel phenolic hydroxyl group which is an intermediate of the epoxy resin.

  Epoxy resins are widely used in the fields of electronics, high-performance paints, and the like from the viewpoint of providing a cured product excellent in low shrinkage during curing, dimensional stability of the cured product, electrical insulation and chemical resistance. However, in the electronics field such as semiconductor encapsulating materials, for example, the surface mounting of semiconductors for the purpose of increasing the density of electronic components in recent years, the moisture resistance to the encapsulating materials with the miniaturization of the semiconductor itself, especially after moisture resistance The demand for solder crack resistance is becoming extremely high. Therefore, in order to meet such demands, a technique for increasing the number of aromatic nuclei in the resin and reducing the amount of secondary hydroxyl groups that appear during the curing reaction to improve the moisture resistance and lower the stress of the cured product is known. For example, an epoxy resin composition using a solid novolak resin having a reduced functional group concentration as a curing agent for an epoxy resin by reaction of monostyrenated phenol with formaldehyde or paraformaldehyde (see, for example, Patent Document 1). An epoxy resin composition using the polyglycidyl ether of the solid novolac resin (for example, see Patent Document 2) has been proposed. Similarly, by modifying polyphenol with a benzylating agent, the functional group concentration was reduced to improve the moisture resistance of the cured product, and in particular, improved the package crack resistance as a surface mount semiconductor encapsulation material. An epoxy resin composition using benzylated polyphenol and its polyglycidyl ether has been proposed (see, for example, Patent Document 3).

  Such novolak resins, polyphenols, and epoxidized products thereof have a sufficiently low functional group concentration and good moisture resistance of the cured product, and exhibit good solder crack resistance in the electronics field and the high-performance paint field. Therefore, it becomes a material that can meet the demand for a low dielectric constant accompanying the increase in the frequency of electronic equipment in recent years.

  However, materials used in the electronics and high-performance paint fields are indispensable to cope with environmental problems such as the dioxin problem, and in recent years, without using halogenated flame retardants of additive systems, There is a growing demand for so-called halogen-free flame retardant systems having a flame retardant effect. However, the above-mentioned novolak resins, polyphenols, and epoxidized products thereof have good dielectric properties, but contain many pendant aromatic hydrocarbon groups that easily burn in the molecular structure. It was inferior in the flame retardance of a thing, and the above-mentioned halogen-free flame retardant system could not be constructed.

  Therefore, the present situation is that an epoxy resin having excellent dielectric properties and imparting excellent flame retardancy to a cured product has not been obtained.

JP 05-132544 A (page 3-4) Japanese Patent Laid-Open No. 05-140265 (page 3-5) JP 08-120039 (page 4-6)

The problems to be solved by the present invention include an epoxy resin composition capable of imparting extremely excellent flame retardancy and dielectric properties to a cured product, a novel epoxy resin and a resin having a novel phenolic hydroxyl group, and the performance described above. Another object is to provide a cured epoxy resin and a method for producing the epoxy resin.

  As a result of intensive studies to solve the above problems, the present inventors have introduced a polyaryleneoxy structure into the main skeleton of the resin structure, and further introduced an aralkyl structure into the polyaryleneoxy structure, thereby providing dielectric properties. It has been found that flame retardancy can be drastically improved without lowering, and the present invention has been completed.

That is, the present invention has a polyaryleneoxy structure as a main skeleton, and an aromatic ring of the structure includes a ( β- methyl) glycidyloxy group and the following structural formula (1).

［式（１）中、Ｒ_１及びＲ_２は各々独立して、メチル基又は水素原子であり、Ａｒは、フェニレン基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたフェニレン基、ナフチレン基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたナフチレン基、ｎは繰り返し数の平均値で０．１〜４である。］
で表される構造部位が結合した分子構造を有するエポキシ樹脂（Ａ）、並びに硬化剤（Ｂ）を必須成分とすることを特徴とするエポキシ樹脂組成物に関する（以下、このエポキシ樹脂組成物を「エポキシ樹脂組成物（I）」と略記する）。

[In Formula (1), R ₁ and R ₂ are each independently a methyl group or a hydrogen atom, and Ar is substituted with 1 to 3 of a phenylene group or an alkyl group having 1 to 4 carbon atoms. A phenylene group, a naphthylene group, a naphthylene group that is nucleus-substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms, and n is an average number of repetitions of 0.1 to 4. ]
The epoxy resin (A) having a molecular structure in which the structural sites represented by the formula (I) and the curing agent (B) are essential components, and the epoxy resin composition (hereinafter, this epoxy resin composition is referred to as “ Epoxy resin composition (I) ”.

  The present invention also relates to a cured product obtained by curing the epoxy resin composition.

The present invention further includes a polyaryleneoxy structure as a main skeleton, and an aromatic ring of the structure includes a ( β- methyl) glycidyloxy group and the following structural formula (1).

［式（１）中、Ｒ_１及びＲ_２は各々独立して、メチル基又は水素原子であり、Ａｒは、フェニレン基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたフェニレン基、ナフチレン基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたナフチレン基、ｎは繰り返し数の平均値で０．１〜４である。］
で表される構造部位が結合した分子構造を有し、かつ、「ＡＳＴＭ Ｄ４２８７」に準拠して測定される１５０℃における溶融粘度が０．１〜３．０ｄＰａ・ｓであることを特徴とする新規エポキシ樹脂に関する。

[In Formula (1), R ₁ and R ₂ are each independently a methyl group or a hydrogen atom, and Ar is substituted with 1 to 3 of a phenylene group or an alkyl group having 1 to 4 carbon atoms. A phenylene group, a naphthylene group, a naphthylene group that is nucleus-substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms, and n is an average number of repetitions of 0.1 to 4. ]
And a melt viscosity at 150 ° C. measured in accordance with “ASTM D4287” is 0.1 to 3.0 dPa · s. It relates to a new epoxy resin.

  The present invention further includes a dihydroxy aromatic compound (a1) and the following structural formula (2):

〔式中、Ｒ_１、Ｒ_２は各々独立して、メチル基又は水素原子であり、Ａｒは、フェニレン基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたフェニレン基、ナフチレン基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたナフチレン基を、Ｙはハロゲン原子、アルコキシ基、又は水酸基を表す。〕で表される化合物

[Wherein R ₁ and R ₂ are each independently a methyl group or a hydrogen atom, and Ar is a phenylene group or a phenylene group that is nucleus-substituted with 1 to 3 of a C 1-4 alkyl group. Y represents a halogen atom, an alkoxy group, or a hydroxyl group, a naphthylene group that is nucleus-substituted with 1 to 3 of a naphthylene group or an alkyl group having 1 to 4 carbon atoms. The compound represented by

To obtain a resin having a phenolic hydroxyl group by reacting an aralkylating agent (a2) selected from the following with an acid catalyst, and then obtaining the resin having a phenolic hydroxyl group and an epihalohydrin (a3). It is related with the manufacturing method of the epoxy resin characterized by making it react.

  The present invention also has a polyaryleneoxy structure as a main skeleton, and the aromatic ring of the structure has a phenolic hydroxyl group and the following structural formula (1).

［式（１）中、Ｒ_１及びＲ_２は各々独立して、メチル基又は水素原子であり、Ａｒは、フェニレン基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたフェニレン基、ナフチレン基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたナフチレン基、ｎは繰り返し数の平均値で０．１〜４である。］
で表される構造部位を結合させた分子構造を有するフェノール性水酸基を有する樹脂（Ｂ’）、及びエポキシ樹脂（Ａ’）を必須成分とすることを特徴とするエポキシ樹脂組成物（以下、このエポキシ樹脂組成物を「エポキシ樹脂組成物（II）」と略記する）に関する。

[In Formula (1), R ₁ and R ₂ are each independently a methyl group or a hydrogen atom, and Ar is substituted with 1 to 3 of a phenylene group or an alkyl group having 1 to 4 carbon atoms. A phenylene group, a naphthylene group, a naphthylene group that is nucleus-substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms, and n is an average number of repetitions of 0.1 to 4. ]
An epoxy resin composition (hereinafter referred to as this resin) having an essential component of a resin (B ′) having a phenolic hydroxyl group having a molecular structure to which a structural site represented by the formula is bonded, and an epoxy resin (A ′) The epoxy resin composition is abbreviated as “epoxy resin composition (II)”.

  The present invention further has a polyaryleneoxy structure as a main skeleton, and the aromatic ring of the structure has a phenolic hydroxyl group and the following structural formula (1).

［式（１）中、Ｒ_１及びＲ_２は各々独立して、メチル基又は水素原子であり、Ａｒは、フェニレン基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたフェニレン基、ナフチレン基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたナフチレン基、ｎは繰り返し数の平均値で０．１〜４である。］
で表される構造部位を結合させた分子構造を有し、かつ、「ＡＳＴＭ Ｄ４２８７」に準拠して測定される１５０℃における溶融粘度が０．１〜４．０ｄＰａ・ｓであることを特徴とする新規フェノール性水酸基を有する樹脂に関する。

[In Formula (1), R ₁ and R ₂ are each independently a methyl group or a hydrogen atom, and Ar is substituted with 1 to 3 of a phenylene group or an alkyl group having 1 to 4 carbon atoms. A phenylene group, a naphthylene group, a naphthylene group that is nucleus-substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms, and n is an average number of repetitions of 0.1 to 4. ]
And the melt viscosity at 150 ° C. measured according to “ASTM D4287” is 0.1 to 4.0 dPa · s. The present invention relates to a resin having a novel phenolic hydroxyl group .

According to the present invention, an epoxy resin composition capable of imparting extremely excellent flame retardancy and dielectric properties to a cured product, a novel epoxy resin , a resin having a novel phenolic hydroxyl group, and an epoxy resin having the above-mentioned performance A cured product and a method for producing the epoxy resin can be provided.

Hereinafter, the present invention will be described in detail.
The epoxy resin (A) used in the epoxy resin composition (I) of the present invention has a polyaryleneoxy structure as the main skeleton, and the aromatic ring of the structure has a ( β- methyl) glycidyloxy group and the following structural formula. (1)

［式（１）中、Ｒ_１及びＲ_２は各々独立して、メチル基又は水素原子であり、Ａｒは、フェニレン基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたフェニレン基、ナフチレン基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたナフチレン基、ｎは繰り返し数の平均値で０．１〜４である。］
で表される構造部位を結合させた分子構造を有するものである。

[In Formula (1), R ₁ and R ₂ are each independently a methyl group or a hydrogen atom, and Ar is substituted with 1 to 3 of a phenylene group or an alkyl group having 1 to 4 carbon atoms. A phenylene group, a naphthylene group, a naphthylene group that is nucleus-substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms, and n is an average number of repetitions of 0.1 to 4. ]
It has a molecular structure in which structural parts represented by

That is, since the epoxy resin (A) has a polyarylene oxide structure as a main skeleton in the molecular structure, char is formed by the arylene group in the structure and the aralkyl group represented by the structural formula (1) during combustion. It forms quickly and exhibits excellent flame retardancy. As described above, in general, when a pendant aralkyl group is present in an epoxy resin structure, it is difficult to express a flame retardant effect, and in the present invention, an excellent difficulty is achieved by introducing an aralkyl group into the resin structure. It should be noted that flammability is manifested. Furthermore, the epoxy resin (A) of the present invention introduces the structure represented by the structural formula (1), so that the concentration of ( β- methyl) glycidyloxy group is lowered and the low dielectric constant of the cured product is lowered. Become. Therefore, the epoxy resin (A) can have both excellent dielectric properties and a flame retardant effect.

  The polyarylene oxide structure constituting the basic skeleton of the epoxy resin (A) includes a polynaphthylene oxide structure and a naphthylene oxide structure such as a polynaphthylene oxide structure substituted with an alkyl group having 1 to 4 carbon atoms, In addition, a phenylene oxide structure such as a polyphenylene oxide structure and a polyphenylene oxide structure substituted with an alkyl group having 1 to 4 carbon atoms can be given. Among these, those having a naphthylene oxide structure are particularly preferred in the present invention because the flame retardant effect becomes more remarkable and the dielectric loss tangent is also lowered. Furthermore, among these, a polynaphthylene oxide structure or a methyl group-containing polynaphthylene oxycide structure is preferable, and a polynaphthylene oxide structure is particularly preferable.

  Next, the following structural formula (1) in the molecular structure of the epoxy resin (A)

で表される構造部位において、Ｒ_１及びＲ_２は各々独立してメチル基又は水素原子であり、Ａｒは、フェニレン基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたフェニレン基、ナフチレン基、及び、炭素原子数１〜４のアルキル基の１〜３つで核置換されたナフチレン基からなる群から選択される二価の芳香族系炭化水素基である。また、炭素原子数１〜４のアルキル基の１〜３つで核置換されたフェニレン基とは、メチルフェニレン基、エチルフェニレン基、ｉ−プロピルフェニレン基、又はｔ−ブチルフェニレン基等が挙げられ、炭素原子数１〜４のアルキル基の１〜３つで核置換されたナフチレン基とは、メチルナフチレン基、エチルナフチレン基、ｉ−プロピルナフチレン基、及びｔ−ブチルナフチレン基等が挙げられる。また、ｎは繰り返し数の平均値で０．１〜４である。

R ₁ and R ₂ are each independently a methyl group or a hydrogen atom, and Ar is nucleus-substituted with 1 to 3 of a phenylene group or an alkyl group having 1 to 4 carbon atoms. A divalent aromatic hydrocarbon group selected from the group consisting of a phenylene group, a naphthylene group, and a naphthylene group nucleus-substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms. Examples of the phenylene group nucleus-substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms include methylphenylene group, ethylphenylene group, i-propylphenylene group, and t-butylphenylene group. Examples of the naphthylene group nucleus-substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms include methyl naphthylene group, ethyl naphthylene group, i-propyl naphthylene group, and t-butyl naphthylene group. Moreover, n is an average value of the number of repetitions and is 0.1-4.

Among these, it is preferable that R ₁ and R ₂ are both hydrogen atoms from the viewpoint of easy availability of raw materials in industrial production, excellent flame retardancy of the resulting cured product, and excellent dielectric properties. . The value of n is particularly preferably 0.1 to 2 from the viewpoints of flame retardancy and dielectric properties, and Ar is a phenylene group from the viewpoint of easy availability of raw materials and low viscosity of the epoxy resin (A). It is preferable that

  Furthermore, in the present invention, the divalent aromatic hydrocarbon group represented by “Ar” in the general formula (1) is added at a ratio of 0.1 to 4 per molecule of the epoxy resin (A). It is preferable from the viewpoint that the improvement of the flame retardant effect becomes remarkable.

The ( β- methyl) glycidyloxy group in the molecular structure of the epoxy resin (A) is specifically a glycidyloxy group and a β-methylglycidyloxy group. From the viewpoint of flame retardancy and easy availability of raw materials for industrial production of the epoxy resin (A), a glycidyloxy group is preferred.

  In addition, the epoxy resin (A) used in the present invention has a melt viscosity at 150 ° C. measured in accordance with “ASTM D4287” of 0.1 to 3.0 dPa · s. From the viewpoint of sex. When the epoxy resin (A) satisfies the requirements, it becomes a novel epoxy resin of the present invention. Here, when the epoxy resin (A) satisfies the above-mentioned melt viscosity condition, the resin itself has good fluidity, and the epoxy resin composition of the present invention including this is used for electronic parts such as semiconductor sealing materials and underfill materials. Application to is easy. Here, it should be noted that in general, when a dihydroxy aromatic compound is reacted in the presence of an acid catalyst to form a polyether, the molecular weight is easily increased, making it difficult to apply to an electronic component. Can realize resin viscosity applicable to electronic components such as semiconductor sealing materials and underfill materials by using a aralkylating agent in combination when polyetherizing dihydroxy aromatic compounds. In the point. Among the melt viscosity ranges, the melt viscosity is particularly 0.1 to 2.0 dPa · s, more preferably 0.1 to 1.5 dPa from the point that the balance between the fluidity and the flame retardancy is good. -It is preferable that it is the range of s.

Furthermore, the epoxy resin (A) preferably forms a polyarylene oxide structure using a dihydroxy aromatic compound as a raw material in the production of a resin having a phenolic hydroxyl group which is a precursor thereof. Appears at both ends of the linear molecular structure, and is thus mainly obtained as a bifunctional epoxy resin. However, in the resin component, a resin having a polyfunctional phenolic hydroxyl group having a molecular structure in which another hydroxynaphthalene ring is bonded to the naphthalene ring in the polynaphthylene oxide structure by a direct bond is partially epoxidized. Since those are also included, the epoxy resin (A) is usually obtained as a polyfunctional epoxy resin. Here, when the epoxy resin (A) is applied to an electronic component, it is preferable to further reduce the functional group concentration in the epoxy resin to improve the dielectric properties and moisture resistance after curing. And when the molecular weight in the said epoxy resin (A) becomes large too much, a fluid fall will be caused. Therefore, the epoxy resin (A) has an epoxy equivalent of 200 to 1,000 g / eq. In particular, 200 to 400 g / eq. Those within the range are preferred.

  As described above, the epoxy resin (A) described in detail above preferably has a polynaphthyleneoxy structure as the polyarylene oxide structure, and can be specifically represented by the following general formula (1).

  Here, in said general formula (1), q is an integer of 1-7 and p is an integer of 0-4 each independently. However, the value of p is in the range of 1 to 4 for at least one of R in the general formula (1). R ′ is a hydrogen atom or a methyl group, R is independently the following general formula (2),

（一般式（２）中、ｎは繰り返しの平均値で０．１〜４である。）
又は、下記一般式（３）

(In general formula (2), n is an average value of repetition and is 0.1 to 4.)
Or the following general formula (3)

（一般式（３）中、ｎは繰り返しの平均値で０．１〜４である。）
を表す。

(In general formula (3), n is an average value of 0.1 to 4)
Represents.

  Q in the general formula (1) is preferably an integer of 1 to 3 from the viewpoint that the flowability of the epoxy resin (A) is good, and also the flame retardancy and the ease of production of the epoxy resin. From this point, R ′ is preferably a hydrogen atom. In the general formula (1), the bonding position to the naphthalene skeleton may be any of the two rings constituting the naphthalene ring.

  Here, specific examples of the epoxy resin represented by the general formula (1) include those represented by the following structural formula.

  Here, in the above structural formulas (A-1) to (A-5), G represents a glycidyl group, and the methylene bond bonded to the naphthalene skeleton is bonded to any of the two rings constituting the naphthalene ring. May be.

  As described above, in the present invention, as shown in the above structural formula (A-4), another naphthalene ring is directly bonded to the naphthalene ring in the polynaphthylene oxide structure to form a branched structure. Furthermore, a structure in which an aralkyl group is introduced into the naphthalene ring introduced by this direct bond may be employed.

  As described above, among the compounds represented by the general formula (1), in the present invention, an effective amount of the aralkyl group corresponding to the structural formula (1) needs to be present, but if it is too much, it is difficult. There exists a tendency for the improvement effect of flammability to fall. On the other hand, if the value of q becomes too high, the fluidity becomes low. Therefore, the compound represented by the general formula (1) has a divalent aromatic hydrocarbon group represented by “Ar” in the general formula (1) per molecule of the epoxy resin (A). It is preferable from the point which is excellent in these performance balances that it has the ratio of 0.1-4 pieces, and the value of q is 1-4.

  In the epoxy resin (A) detailed above, for example, after dehydrating etherification reaction using a dihydroxynaphthalene compound in advance to extend the molecular chain, the aralkylating agent described below is reacted to introduce a substituent into the naphthalene ring. It can be produced by a method of post-glycidyl etherification. However, in this case, as described above, since the melt viscosity of the epoxy resin (A) itself is increased, the production of the epoxy resin of the present invention described below from the viewpoint of securing an appropriate melt viscosity of the epoxy resin (A). It is preferable to manufacture by a method.

Hereinafter, the manufacturing method of the epoxy resin of this invention is explained in full detail.
The method for producing an epoxy resin of the present invention comprises a dihydroxy aromatic compound (a1) and the following structural formula (2).

〔式中、Ｒ_１、Ｒ_２は各々独立して、メチル基又は水素原子であり、Ａｒは、フェニレン基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたフェニレン基、ナフチレン基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたナフチレン基を、Ｙはハロゲン原子、アルコキシ基、又は水酸基を表す。〕で表される化合物

[Wherein R ₁ and R ₂ are each independently a methyl group or a hydrogen atom, and Ar is a phenylene group or a phenylene group that is nucleus-substituted with 1 to 3 of a C 1-4 alkyl group. Y represents a halogen atom, an alkoxy group, or a hydroxyl group, a naphthylene group that is nucleus-substituted with 1 to 3 of a naphthylene group or an alkyl group having 1 to 4 carbon atoms. The compound represented by

A step of obtaining a resin having a phenolic hydroxyl group by reacting with an aralkylating agent (a2) selected from the compounds represented by the formula (hereinafter referred to as “Step 1”). ), And then a step of reacting the obtained resin having a phenolic hydroxyl group with epihalohydrins (a3) (hereinafter, this step is abbreviated as “step 2”). Is.

That is, in the present invention, first, in step 1, the dihydroxy aromatic compound (a1) and the aralkylating agent (a2) are reacted with the presence of an acid catalyst to form a polyarylene structure as a main skeleton at both ends. A resin having a phenolic hydroxyl group having a phenolic hydroxyl group and a structure in which an aralkyl group is bonded in a pendant form on the aromatic nucleus of the polyarylene structure can be obtained. Here, it should be noted that, in general, when the dihydroxy aromatic compound (a1) is arylene-etherified under an acid catalyst, as described above, it is extremely difficult to adjust the molecular weight, and it becomes a high molecular weight polyarylene oxide. On the other hand, in the present invention, by using the aralkylating agent (a2) in combination, such high molecular weight can be suppressed, and a resin applicable to a semiconductor sealing material can be obtained.

Furthermore, in this invention, in addition to being able to adjust the content rate of the aralkyl group in the resin which has the target phenolic hydroxyl group by adjusting the usage-amount of the said aralkylating agent (a2), resin which has a phenolic hydroxyl group The melt viscosity itself can be adjusted. That is, the reaction ratio between the dihydroxy aromatic compound (a1) and the aralkylating agent (a2) is usually the reaction ratio between the dihydroxy aromatic compound (a1) and the aralkylating agent (a2) on a molar basis ( a1) / (a2) can be selected from a range of 1 / 0.1 to 1/10. In the present invention, the amount of the polyarylene oxide structure portion is reduced as the amount of the aralkylating agent (a2) is decreased. As a result of the increase in mass, the flame retardancy of the resin having a phenolic hydroxyl group becomes better. Accordingly, the reaction ratio (a1) / (a2) between the dihydroxy aromatic compound (a1) and the aralkylating agent (a2) on a molar basis is within a range of 1 / 0.1 to 1 / 1.0. Preferably there is. Moreover, the melt viscosity in 150 degreeC measured based on "ASTM D4287" of resin which has a phenolic hydroxyl group at the time of making it react in this range will be 0.1-4.0 dPa * s.

Examples of the dihydroxy aromatic compound (a1) that can be used here include dihydric phenols such as catechol, resorcinol, and hydroquinone, and 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxy. Naphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene And dihydroxynaphthalene. Among these, the flame retardancy of the cured resin of the phenolic hydroxyl group or the epoxidized epoxy resin obtained in particular is further improved, and the dielectric loss tangent of the cured product is also lowered and the dielectric properties are improved. In view of the above, dihydroxynaphthalene, particularly 1,6-dihydroxynaphthalene or 2,7-dihydroxynaphthalene is preferable, and 2,7-dihydroxynaphthalene is particularly preferable.

  Next, among the aralkylating agent (a2), the following structural formula (2)

〔式中、Ｒ_１、Ｒ_２は各々独立して、メチル基又は水素原子であり、Ａｒは、フェニレン基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたフェニレン基、ナフチレン基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたナフチレン基を表す。〕で表される化合物としては、例えば、Ｙがハロゲン原子の場合、ベンジルクロライド、ベンジルブロマイド、ベンジルアイオダイト、ｏ−メチルベンジルクロライド、ｍ−メチルベンジルクロライド、ｐ−メチルベンジルクロライド、ｐ−エチルベンジルクロライド、ｐ−イソプロピルベンジルクロライド、ｐ−ｔｅｒｔ−ブチルベンジルクロライド、ｐ−フェニルベンジルクロライド、５−クロロメチルアセナフチレン、２−ナフチルメチルクロライド、１−クロロメチル−２−ナフタレン及びこれらの核置換異性体、α−メチルベンジルクロライド、並びにα，α−ジメチルベンジルクロライド等が挙げられる。

[Wherein R ₁ and R ₂ are each independently a methyl group or a hydrogen atom, and Ar is a phenylene group or a phenylene group that is nucleus-substituted with 1 to 3 of a C 1-4 alkyl group. , A naphthylene group substituted with 1 to 3 of a naphthylene group or an alkyl group having 1 to 4 carbon atoms. For example, when Y is a halogen atom, the compound represented by the above formula is benzyl chloride, benzyl bromide, benzyl iodide, o-methylbenzyl chloride, m-methylbenzyl chloride, p-methylbenzyl chloride, p-ethylbenzyl. Chloride, p-isopropylbenzyl chloride, p-tert-butylbenzyl chloride, p-phenylbenzyl chloride, 5-chloromethylacenaphthylene, 2-naphthylmethyl chloride, 1-chloromethyl-2-naphthalene and their nuclear substitution isomerism Body, α-methylbenzyl chloride, and α, α-dimethylbenzyl chloride.

  When Y is an alkoxy group, the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms. The compound represented by the structural formula (2) is, for example, benzyl methyl ether or o-methylbenzyl methyl ether. M-methylbenzyl methyl ether, p-methylbenzyl methyl ether, p-ethylbenzyl methyl ether and their nuclear substitution isomers, benzyl ethyl ether, benzylpropyl ether, benzylisobutyl ether, benzyl n-butyl ether, p-methylbenzyl And methyl ether and its nucleus-substituted isomers.

  When Y is a hydroxyl group, examples of the compound represented by the structural formula (2) include benzyl alcohol, o-methylbenzyl alcohol, m-methylbenzyl alcohol, p-methylbenzyl alcohol, p-ethylbenzyl alcohol, p- Examples include isopropyl benzyl alcohol, p-tert-butyl benzyl alcohol, p-phenyl benzyl alcohol, α-naphthyl carbinol and their nuclear substitution isomers, α-methyl benzyl alcohol, and α, α-dimethyl benzyl alcohol.

Among these, the aralkylating agent represented by the structural formula (2) is particularly preferable from the viewpoint of flame retardancy, and benzyl chloride, benzyl bromide, and benzyl alcohol are the epoxy resin or phenolic hydroxyl group finally obtained. It is preferable from the point that the flame retardant effect becomes more prominent in the cured product of the resin .

  Examples of the acid catalyst that can be used in the reaction of the dihydroxy aromatic compound (a1) and the aralkylating agent (a2) in Step 1 include inorganic acids such as phosphoric acid, sulfuric acid, and hydrochloric acid, oxalic acid, benzenesulfonic acid, and toluenesulfone. Examples include acids, organic acids such as methanesulfonic acid and fluoromethanesulfonic acid, and Friedel-Crafts catalysts such as aluminum chloride, zinc chloride, stannic chloride, ferric chloride, and diethylsulfuric acid.

  The amount of the acid catalyst used can be appropriately selected depending on the target modification rate and the like. For example, in the case of an inorganic acid or an organic acid, the amount of the acid catalyst is 0.1% relative to 100 parts by mass of the dihydroxy aromatic compound (a1). The range is 001 to 5.0 parts by mass, preferably 0.01 to 3.0 parts by mass, and in the case of a Friedel-Crafts catalyst, 0.2 to 3.0 with respect to 1 mol of the dihydroxy aromatic compound (a1). It is preferable that the amount be in the range of 0.5 to 2.0 mol.

  The reaction of the dihydroxy aromatic compound (a1) and the aralkylating agent (a2) in the step 1 may be performed in the absence of a solvent, but may be performed in a solvent from the viewpoint of improving the uniformity in the reaction system. . Examples of such solvents include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether. Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether and other ethylene glycol and diethylene glycol mono or diether, aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide, Fine chlorobenzene and the like.

  A specific method for carrying out the reaction of Step 1 is to dissolve the dihydroxy aromatic compound (a1), the aralkylating agent (a2), and the acid catalyst in the absence of a solvent or in the presence of the solvent, Preferably, it can be performed under a temperature condition of about 80 to 160 ° C. The reaction time is not particularly limited, but is preferably 1 to 10 hours. Therefore, specifically, the reaction can be performed by maintaining the temperature for 1 to 10 hours. In addition, it is preferable that hydrogen halide, water, alcohols, and the like generated during the reaction are distilled out of the system by using a fractionating tube or the like from the viewpoint that the reaction proceeds rapidly and productivity is improved.

  Further, when the resulting dihydroxynaphthalene compound is highly colored, an antioxidant or a reducing agent may be added to the reaction system in order to suppress it. Examples of the antioxidant include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite compounds containing trivalent phosphorus atoms. Examples of the reducing agent include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, and salts thereof.

  After completion of the reaction, the acid catalyst is removed by neutralization treatment, water washing treatment or decomposition, and the desired resin having a phenolic hydroxyl group can be separated by general operations such as extraction and distillation. The neutralization treatment and the water washing treatment may be performed according to a conventional method. For example, basic substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, triethylenetetramine, aniline can be used as the neutralizing agent.

  Next, as step 2, the target epoxy resin can be obtained by reacting the resin having a phenolic hydroxyl group obtained in step 1 with epihalohydrin (a3). The reaction in step 2 is performed by adding 2 to 10 mol of epihalohydrins (a3) to 1 mol of phenolic hydroxyl group in the resin having a phenolic hydroxyl group, and further phenolic hydroxyl group in the resin having the phenolic hydroxyl group. The method of making it react at the temperature of 20-120 degreeC for 0.5 to 10 hours, adding 0.9-2.0 mol of basic catalysts with respect to 1 mol collectively or gradually is mentioned.

  The basic catalyst used here can be used as a solid or as an aqueous solution thereof. When the basic catalyst is used as an aqueous solution, it is continuously added, and water and epihalohydrins (a3) are continuously distilled from the reaction mixture under reduced pressure or normal pressure. May be removed and the epihalohydrins (a3) may be continuously returned to the reaction mixture.

  Examples of the epihalohydrins (a3) include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin and the like. Among them, epichlorohydrin is preferable because it is easily industrially available. In addition, when performing industrial production, in the reaction after the next batch after completion of the reaction in the first batch of epoxy resin production, the epihalohydrin (a3) recovered from the crude reaction product and the amount consumed in the reaction disappear. It is preferable to use together with a new epihalohydrin (a3) corresponding to the amount to be used.

  Specific examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity of the epoxy resin synthesis reaction, and examples thereof include sodium hydroxide and potassium hydroxide. In use, these basic catalysts may be used in the form of an aqueous solution of about 10 to 55% by mass, or in the form of a solid. Moreover, the reaction rate in the synthesis | combination of an epoxy resin can be raised by using an organic solvent together. Examples of such organic solvents include, but are not limited to, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, and tertiary butanol, methyl Examples include cellosolves such as cellosolve and ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide and dimethylformamide. These organic solvents may be used alone or in combination of two or more as appropriate in order to adjust the polarity.

  After the reaction product of the epoxidation reaction is washed with water, unreacted epihalohydrin and the organic solvent to be used in combination are distilled off by distillation under heating and reduced pressure. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is again dissolved in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, and alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Further reaction can be carried out by adding an aqueous solution of the product. At this time, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present for the purpose of improving the reaction rate. When the phase transfer catalyst is used, the amount used is preferably in the range of 0.1 to 3.0% by mass with respect to the epoxy resin used. After completion of the reaction, the generated salt is removed by filtration, washing with water, and a high-purity epoxy resin can be obtained by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure.

  Moreover, in the epoxy resin composition (I) of the present invention, the epoxy resin (A) may be used alone as an epoxy resin component, and the epoxy resin (A) and the epoxy resin (A) may be used as long as the effects of the present invention are not impaired. You may use together with another epoxy resin. When other epoxy resins are used in combination, the proportion of these used is preferably in the range where the proportion of the epoxy resin (A) in the total mass of the epoxy resin component is 30% by mass or more, particularly 40% by mass or more. .

  As the other epoxy resins that can be used in combination here, various epoxy resins can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolac Type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type Epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, naphthol-cresol co-condensed novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin-modified phenol Lumpur resin type epoxy resins, biphenyl-modified novolak type epoxy resins. Among these epoxy resins, it is preferable to use a tetramethyl biphenol type epoxy resin, a biphenyl aralkyl type epoxy resin, or a novolac type epoxy resin from the viewpoint that a cured product having excellent flame retardancy can be obtained.

The curing agent (B) used in the epoxy resin composition (I) of the present invention is a known various curing agent for epoxy resins, such as amine compounds, amide compounds, acid anhydride compounds, phenol compounds, and the like. A curing agent can be used. Specifically, examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, and guanidine derivative. Examples of the amide compound include dicyandiamide. And polyamide resins synthesized from dimer of linolenic acid and ethylenediamine. Examples of acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, and tetrahydrophthalic anhydride. Acid, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc., and phenolic compounds include phenol novolac resin, cresol novolac resin Aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol -Cresol-condensed novolak resin, biphenyl-modified phenolic resin (polyhydric phenol compound in which phenol nucleus is linked by bismethylene group), biphenyl-modified naphthol resin (polyvalent naphthol compound in which phenol nucleus is linked by bismethylene group), aminotriazine modified Examples thereof include polyhydric phenol compounds such as phenol resins (polyhydric phenol compounds in which phenol nuclei are linked with melamine or benzoguanamine).

  Among these, those containing a large amount of an aromatic skeleton in the molecular structure are preferable from the viewpoint of flame retardancy, and specifically, phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, phenol aralkyls. Resins, naphthol aralkyl resins, naphthol novolak resins, naphthol-phenol co-condensed novolak resins, naphthol-cresol co-condensed novolak resins, biphenyl-modified phenol resins, biphenyl-modified naphthol resins, and aminotriazine-modified phenol resins are preferred because of their excellent flame retardancy. .

  However, in the present invention, the flame retardancy is remarkably improved, and the phenolic aralkyl resin, particularly, the following structural formula (i)

で表される構造を結節基として複数のフェノール類が結節した構造を有するフェノール性水酸基を有する樹脂であることが好ましい。なお、ここで構造式（ｉ）中、Ｘは、炭素原子数１〜４のアルキル基又は水素原子、ｍは０〜３の整数である。

A resin having a phenolic hydroxyl group having a structure in which a plurality of phenols are knotted with the structure represented by In the structural formula (i), X is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and m is an integer of 0 to 3.

  The amount of the epoxy resin (A) and the curing agent (B) in the epoxy resin composition (I) of the present invention is such that the resulting cured product has good mechanical properties and the like. The amount of active groups in the curing agent (B) is preferably in the range of 0.7 to 1.5 equivalents with respect to a total of 1 equivalent of epoxy groups in the epoxy resin containing (A).

  Next, another epoxy resin composition (II) of the present invention has a polyaryleneoxy structure as the main skeleton, and the aromatic ring of the structure has a phenolic hydroxyl group and the following structural formula (1).

［式（１）中、Ｒ_１及びＲ_２は各々独立して、メチル基又は水素原子であり、Ａｒは、フェニレン基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたフェニレン基、ナフチレン基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたナフチレン基、ｎは繰り返し数の平均値で０．１〜４の数である。］
で表される構造部位が結合した分子構造を有するフェノール性水酸基を有する樹脂（Ｂ’）及びエポキシ樹脂（Ａ’）を必須成分とするものである。

[In Formula (1), R ₁ and R ₂ are each independently a methyl group or a hydrogen atom, and Ar is substituted with 1 to 3 of a phenylene group or an alkyl group having 1 to 4 carbon atoms. A phenylene group, a naphthylene group, a naphthylene group nucleus-substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms, and n is an average number of repetitions of 0.1 to 4. ]
A resin (B ′) and a epoxy resin (A ′) having a phenolic hydroxyl group having a molecular structure in which a structural moiety represented by the formula is bonded are essential components.

Here, the resin (B ′) having a phenolic hydroxyl group has the same structure as the resin having a phenolic hydroxyl group which is a precursor of the epoxy resin (A) in the epoxy resin composition (I). Further, the resin having a phenolic hydroxyl group (B ′) has a melt viscosity at 150 ° C. measured in accordance with “ASTM D4287” in the range of 0.1 to 4.0 dPa · s. In this case, the resin (B ′) having a phenolic hydroxyl group is a resin having a novel phenolic hydroxyl group of the present invention. Further, the resin (B ′) having a phenolic hydroxyl group has a melt viscosity at 150 ° C. measured in accordance with “ASTM D4287”, particularly from the viewpoint of the balance between flame retardancy and fluidity. It is preferably 3.0 dPa · s, particularly 0.1 to 2.0 dPa · s.

Further, in the resin (B ′) having the phenolic hydroxyl group, the functional number of the phenolic hydroxyl group forms a polyarylene oxide structure using a dihydroxy aromatic compound as a raw material, as in the case of the epoxy resin (A). In this case, since the phenolic hydroxyl groups appear at both ends of the linear molecular structure, the resin is mainly obtained as a resin having a bifunctional phenolic hydroxyl group. Resins having a polyfunctional phenolic hydroxyl group having a molecular structure in which another hydroxynaphthalene ring is directly bonded to the naphthalene ring in the polynaphthylene oxide structure are also included. Therefore, the resin (B ′) having a phenolic hydroxyl group is usually obtained as a resin having a polyfunctional phenolic hydroxyl group , and is excellent in the effect of improving the dielectric properties and moisture resistance after curing, and is fluid. The hydroxyl equivalent of the phenolic hydroxyl group-containing resin (B ′) is 130 to 800 g / eq. , Especially 130-300 g / eq. Those within the range are preferred.

Among the resins having a phenolic hydroxyl group (B ′) described above , those having a polynaphthyleneoxy structure as the polyarylene oxide structure exhibit an excellent flame retardant effect, and are also preferable in terms of a low dielectric loss tangent, Specifically, it can be represented by the following general formula (4).

  Here, in the said General formula (4), q is an integer of 1-7, p is an integer of 0-4 each independently. However, the value of p is in the range of 1 to 4 for at least one of R in the general formula (1). And R is respectively independently the following general formula (5),

（一般式（５）中、ｎは繰り返しの平均値で０．１〜４である。）
又は、下記一般式（６）

(In general formula (5), n is an average value of 0.1 to 4)
Or the following general formula (6)

（一般式（６）中、ｎは繰り返しの平均値で０．１〜４である。）
を表す。

(In general formula (6), n is an average value of repetitions of 0.1 to 4.)
Represents.

  Q in the general formula (4) is preferably an integer of 1 to 3 from the viewpoint of good fluidity of the epoxy resin (A). In the general formula (4), the bonding position to the naphthalene skeleton may be any of the two rings constituting the naphthalene ring.

Here, specific examples of the resin having a phenolic hydroxyl group represented by the general formula (4) include those represented by the following structural formula.

  Here, in the above structural formulas (P-1) to (P-5), the methylene bond bonded to the naphthalene skeleton may be bonded to any of the two rings constituting the naphthalene ring. Further, as described above, in the present invention, as shown in the above structural formula (P-4), another naphthalene ring is directly bonded to the naphthalene ring in the polynaphthylene oxide structure to form a branched structure. Further, it may have a molecular structure in which an aralkyl group is introduced into the naphthalene ring introduced by this direct bond.

  Among the compounds represented by the general formula (2), when the number of aralkyl groups corresponding to the structural formula (1) is too large, the effect of improving flame retardancy tends to decrease. On the other hand, the higher the q value, the better the flame retardancy but the lower the fluidity. Therefore, the compound represented by the general formula (4) has a divalent aromatic hydrocarbon group represented by “Ar” in the general formula (4) per molecule of the epoxy resin (A). It is preferable that it has a ratio of 0.1 to 4 and the value of q is in the range of 1 to 4 from the viewpoint of excellent performance balance.

The resin (B ′) having a phenolic hydroxyl group described in detail above is, for example, preliminarily subjected to dehydration etherification reaction using a dihydroxynaphthalene compound to extend the molecular chain, and then reacted with an aralkylating agent described later to form a naphthalene ring. It can be produced by a method of introducing a substituent. However, as described above, in this method, the dehydration etherification reaction causes an excessive increase in the molecular weight and causes a thickening. Therefore, it is preferable that the method is manufactured by Step 1 in the manufacturing method of the epoxy resin of the present invention described above. .

In the epoxy resin composition (II) of the present invention, the resin (B ′) having a phenolic hydroxyl group may be used alone as a curing agent for the epoxy resin (A ′), but within a range not impairing the effects of the present invention. Other curing agents may be used in combination. Specifically, other curing agents can be used in combination so that the resin having the phenolic hydroxyl group is 30% by mass or more, preferably 40% by mass or more with respect to the total mass of the curing agent.

Other curing agents that can be used in combination with the resin (B ′) having a phenolic hydroxyl group of the present invention are not particularly limited, and examples thereof include amine compounds, amide compounds, acid anhydride compounds, and the above-described phenols. Phenolic compounds other than the resin (B ′) having a functional hydroxyl group, and polyhydric phenol compounds of aminotriazine-modified phenol resins (polyhydric phenol compounds in which phenol nuclei are linked by melamine, benzoguanamine, etc.).

  Among these, phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, phenol aralkyl resin, naphthol aralkyl resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, Biphenyl-modified phenolic resin, biphenyl-modified naphthol resin, aminotriazine-modified phenolic resin are preferred because of excellent flame retardancy, especially high aromaticity such as phenol aralkyl resin, naphthol aralkyl resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, Using a compound such as a phenolic resin having a high hydroxyl equivalent or an aminotriazine-modified phenolic resin containing a nitrogen atom, From the viewpoint of retardancy and dielectric properties superior.

Next, as the epoxy resin (A ′) used in the epoxy resin composition (II) of the present invention, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, Phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, Naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic Hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin, a biphenyl novolak type epoxy resins. Moreover, these epoxy resins may be used independently and may mix 2 or more types.

  Of these, biphenyl type epoxy resins, naphthalene type epoxy resins, phenol aralkyl type epoxy resins, biphenyl novolac type epoxy resins and xanthene type epoxy resins are particularly preferred because of their excellent flame retardancy and dielectric properties.

The compounding amount of the epoxy resin (A ′) and the resin (B ′) having a phenolic hydroxyl group in the epoxy resin composition (II) of the present invention is not particularly limited, but the obtained cured product has good characteristics. Therefore, the active group in the curing agent containing the resin (B ′) having a phenolic hydroxyl group is 0.7 to 1.5 equivalents with respect to a total of 1 equivalent of the epoxy groups of the epoxy resin (A ′). The amount to be is preferred.

  Further, if necessary, a curing accelerator can be appropriately used in combination with the epoxy resin composition (II) of the present invention. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. In particular, when used as a semiconductor encapsulating material, it is excellent in curability, heat resistance, electrical characteristics, moisture resistance reliability, etc., so that triphenylphosphine is used for phosphorus compounds and 1,8-diazabicyclo is used for tertiary amines. -[5.4.0] -undecene (DBU) is preferred.

  The epoxy resin compositions (I) and (II) of the present invention described in detail above have an excellent flame retardancy imparting effect depending on the selection of the molecular structure of the epoxy resin or its curing agent. Therefore, even if a conventionally used flame retardant is not blended, the cured product has good flame retardancy. However, in order to exert a higher degree of flame retardancy, for example, in the field of semiconductor sealing materials, it contains substantially halogen atoms in a range that does not reduce the moldability in the sealing process and the reliability of the semiconductor device. A non-halogen flame retardant (C) may be added.

  The epoxy resin composition containing such a non-halogen flame retardant (C) is substantially free of halogen atoms. For example, halogen atoms due to trace amounts of impurities of about 5000 ppm or less derived from epihalohydrin contained in the epoxy resin. May be included.

  Examples of the non-halogen flame retardant (C) include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants. The flame retardant is not limited and may be used alone, or a plurality of flame retardants of the same system may be used, or flame retardants of different systems may be used in combination.

  As the phosphorus flame retardant, either inorganic or organic can be used. Examples of the inorganic compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. .

  The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like. Examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide; and A method of coating with a mixture of a thermosetting resin such as a phenol resin, (iii) thermosetting of a phenol resin or the like on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide For example, a method of double coating with a resin may be used.

  The organic phosphorus compounds include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, and 9,10-dihydro -9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,7-dihydro Examples thereof include cyclic organic phosphorus compounds such as oxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

  The blending amount thereof is appropriately selected depending on the type of the phosphorus-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, epoxy resin, curing agent, non-halogen type When using red phosphorus as a non-halogen flame retardant in 100 parts by mass of the epoxy resin composition (I) or (II) containing all of the flame retardant and other fillers and additives, 0.1-2. It is preferable to mix | blend in the range of 0 mass part, and when using an organophosphorus compound, it is preferable to mix | blend in the range of 0.1-10.0 mass part similarly, Especially 0.5-6.0 mass part It is preferable to mix in the range.

  In addition, when using the phosphorous flame retardant, the phosphorous flame retardant may be used in combination with hydrotalcite, magnesium hydroxide, boric compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. Good.

  Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, among which triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.

  Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, (i) guanylmelamine sulfate, melem sulfate, melam sulfate (Iii) co-condensates of phenols such as phenol, cresol, xylenol, butylphenol, nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine, formguanamine, and formaldehyde, (iii) (Ii) a mixture of a co-condensate and a phenol resin such as a phenol formaldehyde condensate, (iv) the above (ii), (iii) further modified with paulownia oil, isomerized linseed oil, etc.

  Specific examples of the cyanuric acid compound include cyanuric acid and cyanuric acid melamine.

  The amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. The epoxy resin composition (I) or (II) in which all of the agent, non-halogen flame retardant and other fillers and additives are blended may be blended in the range of 0.05 to 10 parts by mass in 100 parts by mass. It is particularly preferable to blend in the range of 0.1 to 5 parts by mass.

  Moreover, when using the said nitrogen-type flame retardant, you may use together a metal hydroxide, a molybdenum compound, etc.

  The silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.

  The amount of the silicone flame retardant is appropriately selected according to the type of the silicone flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. The epoxy resin composition (I) or (II) in which all of the agent, non-halogen flame retardant and other fillers and additives are blended may be blended in the range of 0.05 to 20 parts by mass. preferable. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

  Examples of the inorganic flame retardant include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low melting point glass.

  Specific examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide and the like.

  Specific examples of the metal oxide include, for example, zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, and cobalt oxide. Bismuth oxide, chromium oxide, nickel oxide, copper oxide, tungsten oxide and the like.

  Specific examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.

  Specific examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

  Specific examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

Specific examples of the low-melting-point glass include, for example, Ceeley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, P ₂ O ₅ —B ₂ O ₃ —PbO—MgO, P—Sn—O—F, PbO—V ₂ O ₅ —TeO ₂ , Al ₂ O ₃ —H ₂ O, lead borosilicate, etc. The glassy compound can be mentioned.

  The blending amount of the inorganic flame retardant is appropriately selected according to the type of the inorganic flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, epoxy resin, cured The epoxy resin composition (I) or (II) in which all of the agent, non-halogen flame retardant and other fillers and additives are blended may be blended in the range of 0.05 to 20 parts by mass. It is particularly preferable to blend in the range of 0.5 to 15 parts by mass.

  Examples of the organic metal salt flame retardant include ferrocene, acetylacetonate metal complex, organic metal carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound or an ionic bond or Examples thereof include a coordinated compound.

  The amount of the organometallic salt-based flame retardant is appropriately selected depending on the type of the organometallic salt-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. In the range of 0.005 to 10 parts by mass in 100 parts by mass of the epoxy resin composition (I) or (II) containing all of the epoxy resin, curing agent, non-halogen flame retardant and other fillers and additives. It is preferable to mix.

  The epoxy resin composition (I) or (II) of the present invention can contain an inorganic filler as necessary. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When particularly increasing the blending amount of the inorganic filler, it is preferable to use fused silica. The fused silica can be used in either a crushed shape or a spherical shape. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably higher in consideration of flame retardancy, and particularly preferably 65% by mass or more with respect to the total amount of the epoxy resin composition (I) or (II). Moreover, when using for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can be used.

  Various compounding agents, such as a silane coupling agent, a mold release agent, a pigment, an emulsifier, can be added to the epoxy resin composition (I) or (II) of the present invention as necessary.

  The epoxy resin composition (I) or (II) of the present invention can be obtained by uniformly mixing the above-described components. The epoxy resin composition of the present invention, in which the epoxy resin of the present invention, a curing agent and, if necessary, a curing accelerator are blended, can be easily made into a cured product by a method similar to a conventionally known method. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

  Applications for which the epoxy resin composition (I) or (II) of the present invention is used include, for example, semiconductor sealing materials, underfill materials, conductive pastes, resin compositions used for laminated boards, electronic circuit boards, and resin casting Materials, adhesives, interlayer insulating materials for build-up substrates, coating materials such as insulating paints, etc., among these, semiconductor sealing materials and underfill materials for electronic component applications, particularly suitable for semiconductor sealing materials Can be used.

  In order to produce the epoxy resin composition (I) or (II) prepared for a semiconductor encapsulant, an epoxy resin and a compounding agent such as a curing agent and a filler may be used as necessary. A melt-mixed epoxy resin composition may be obtained by mixing thoroughly until uniform using a roll, roll or the like. At that time, silica is usually used as the filler, and the filling ratio is preferably in the range of 30 to 95% by mass per 100 parts by mass of the epoxy resin composition. In order to improve moisture resistance and solder crack resistance, and to reduce the linear expansion coefficient, it is particularly preferably 70 parts by mass or more, and in order to significantly increase these effects, 80 parts by mass or more further enhances the effect. be able to. For semiconductor package molding, the composition is molded by casting, using a transfer molding machine, an injection molding machine or the like, and further heated at 50 to 200 ° C. for 2 to 10 hours to form a semiconductor device which is a molded product. There is a way to get it.

  In order to process the epoxy resin composition (I) or (II) of the present invention into a printed circuit board composition, for example, a resin composition for prepreg can be used. Although it can be used without a solvent depending on the viscosity of the epoxy resin composition, it is preferable to obtain a resin composition for prepreg by varnishing using an organic solvent. As the organic solvent, it is preferable to use a polar solvent having a boiling point of 160 ° C. or lower such as methyl ethyl ketone, acetone, dimethylformamide, etc., and it can be used alone or as a mixed solvent of two or more kinds. The obtained varnish is impregnated into various reinforcing substrates such as paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth, and the heating temperature according to the solvent type used, preferably 50 By heating at ˜170 ° C., a prepreg that is a cured product can be obtained. The mass ratio of the resin composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable that the resin content in the prepreg is 20 to 60% by mass. Moreover, when manufacturing a copper clad laminated board using this epoxy resin composition, the prepreg obtained as mentioned above is laminated | stacked by a conventional method, copper foil is laminated | stacked suitably, and it is under pressure of 1-10 MPa. A copper-clad laminate can be obtained by thermocompression bonding at 170 to 250 ° C. for 10 minutes to 3 hours.

  When the epoxy resin composition (I) or (II) of the present invention is used as a conductive paste, for example, fine conductive particles are dispersed in the epoxy resin composition to form an anisotropic conductive film composition. And a paste resin composition for circuit connection that is liquid at room temperature and an anisotropic conductive adhesive.

  As a method for obtaining an interlayer insulating material for a build-up substrate from the epoxy resin composition (I) or (II) of the present invention, for example, a wiring in which a circuit is formed from the curable resin composition appropriately blended with rubber, filler, etc. The substrate is applied using a spray coating method, a curtain coating method, or the like, and then cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. As the plating method, electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. Such operations are sequentially repeated as desired, and a build-up base can be obtained by alternately building up and forming the resin insulating layer and the conductor layer having a predetermined circuit pattern. However, the through-hole portion is formed after the outermost resin insulating layer is formed. In addition, a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil is thermocompression-bonded at 170 to 250 ° C. on a circuit board on which a circuit is formed, thereby forming a roughened surface and plating treatment. It is also possible to produce a build-up substrate by omitting the process.

  Moreover, the epoxy resin composition (I) of the present invention can be further used as a resist ink. In this case, a vinyl monomer having an ethylenically unsaturated double bond and a cationic polymerization catalyst as a curing agent (B) are blended with the epoxy resin (A), and a pigment, talc and filler are further added to form a resist. A method for forming a resist ink cured product after coating on a printed circuit board by a screen printing method after an ink composition is used.

  The method for obtaining the cured product of the present invention may be based on a general method for curing an epoxy resin composition. For example, the heating temperature condition may be appropriately selected depending on the type and use of the curing agent to be combined. What is necessary is just to heat the composition obtained by the said method in the temperature range about 20-250 degreeC. As the molding method and the like, a general method of the epoxy resin composition is used, and a condition specific to the epoxy resin composition of the present invention is not particularly required.

Therefore, by using the epoxy resin (A) or the resin (B ′) having a phenolic hydroxyl group, an epoxy resin composition excellent in environmental properties that exhibits high flame retardancy without using a halogen-based flame retardant. Can be obtained. In addition, the excellent dielectric properties of these cured products can realize high-speed operation speed of high-frequency devices. In addition, the resin having a phenolic hydroxyl group can be easily and efficiently produced by the production method of the present invention, and the molecular design according to the intended level of performance described above becomes possible.

  Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on mass unless otherwise specified. In addition, the melt viscosity and softening point measurement in 150 degreeC, GPC measurement, NMR, and MS spectrum were measured on condition of the following.

1) Melt viscosity at 150 ° C .: Conforms to ASTM D4287.
2) Softening point measurement method: compliant with JIS K7234.
3) GPC:
Apparatus: Measured under the following conditions using “HLC-8220 GPC” manufactured by Tosoh Corporation.
Column: TSK-GEL G2000HXL + G2000HXL manufactured by Tosoh Corporation
+ G3000HXL + G4000HXL
Solvent: Tetrahydrofuran Flow rate: 1 ml / min
Detector: RI
4) NMR: Measured with “NMR GSX270” manufactured by JEOL Ltd.
5) MS: Measured with a double-focusing mass spectrometer “AX505H (FD505H)” manufactured by JEOL Ltd.

Example 1 (Synthesis of aralkyl group-containing dihydroxy (polyoxynaphthalylene))
In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, the following formula

で表される２，７−ジヒドロキシナフタレン１６０ｇ（１．０モル）、ベンジルアルコール１０８ｇ（１．０モル）を仕込み、室温下、窒素を吹き込みながら撹拌した。パラトルエンスルホン酸・１水和物 ２．７ｇを添加した。その後、油浴中で発熱に注意しながら１５０℃まで加熱し、分留管を用いて生成する水を抜き出した後、更に５時間反応させた。反応終了後、更にメチルイソブチルケトン１０００ｇを加え、溶解後、分液ロートに移した。次いで洗浄水が中性を示すまで水洗後、有機層から溶媒を加熱減圧下に除去し、アラルキル基含有ジヒドロキシ（ポリオキシナフタレチレン）２４０ｇを得た（以下、これを「化合物（１）」とする）。得られた化合物（１）は褐色固体であり、水酸基当量は１６０ｇ／ｅｑ、軟化点は７７℃、ＩＣＩ粘度は０．９ｄＰａ・ｓであった。

160 g (1.0 mol) of 2,7-dihydroxynaphthalene represented by the following formula and 108 g (1.0 mol) of benzyl alcohol were charged and stirred at room temperature while blowing nitrogen. 2.7 g of paratoluenesulfonic acid monohydrate was added. Thereafter, the mixture was heated to 150 ° C. while paying attention to heat generation in an oil bath, and water produced using a fractionating tube was extracted, followed by further reaction for 5 hours. After completion of the reaction, 1000 g of methyl isobutyl ketone was further added, dissolved, and transferred to a separatory funnel. Subsequently, after washing with water until the washing water shows neutrality, the solvent was removed from the organic layer under heating and reduced pressure to obtain 240 g of aralkyl group-containing dihydroxy (polyoxynaphthalylene) (hereinafter referred to as “compound (1)”). And). The obtained compound (1) was a brown solid, the hydroxyl group equivalent was 160 g / eq, the softening point was 77 ° C., and the ICI viscosity was 0.9 dPa · s.

From the results of the FT-IR chart, the absorption derived from a hydroxyl group (3700 to 3400 cm ⁻¹ ) is small compared to the raw material (2,7-dihydroxynaphthalene), and the absorption derived from an aromatic ether (1250 cm ⁻¹ ). It was confirmed that it was newly generated. From this result, it was estimated that the hydroxyl groups were subjected to dehydration etherification reaction.

^From the result of ¹³ C-NMR chart, the methylene bond resulting from the introduction of the benzyl group was confirmed. Of the 1.0 mol of benzyl alcohol charged, about 0.55 mol of the benzyl group introduced into the naphthalene ring ( That is, about 55% of the added benzyl alcohol was bonded to the naphthalene ring), and the remaining about 0.45 mol (that is, about 45% of the added benzyl alcohol) was further bonded as a benzyl group to the formed benzyl. It was analyzed that.

From the results of the FD-MS chart, the molecular weight (Mw: 90) of the benzyl group is 1 (M ⁺ = 250), 2 (M ⁺ ), and the molecular weight (Mw: 160) of 2,7-dihydroxynaphthalene. = 340), 3 peaks (M ⁺ = 430), 4 peaks (M ⁺ = 520) were confirmed, and 2,7-dihydroxynaphthalene was dehydrated between two molecules and produced 2 , 7-dihydroxynaphthalene dimer ether structure (Mw: 302), molecular weight (Mw: 90) of benzyl group is 1 (M ⁺ = 392), 2 (M ⁺ = 482), 3 (M ⁺ = 572), 4 peaks (M ⁺ = 662) with confirmed peaks, and 2,7-dihydroxynaphthalene trimer formed by dehydration of 3,7-dihydroxynaphthalene between three molecules. Ether structure (Mw: 444) Peaks with molecular weight (Mw: 90) of 1 group (M ⁺ = 534), 2 (M ⁺ = 624), 3 (M ⁺ = 714), 4 (M ⁺ = 804) It was also confirmed that it was confirmed. Therefore, among the average 6p + 6 vacant sites present in the above chemical formula, a benzyl group is bonded to 0.55 and 0.45 (q = 0.45) is further introduced into the benzyl group. It was analyzed.

Example 2 (Synthesis of aralkyl-modified poly (oxynaphthalene) type epoxy resin)
While a nitrogen gas purge was performed on a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer, 160 g of the compound (1) obtained in Example 1, 463 g of epichlorohydrin (5.0 mol), 139 g of n-butanol, 2 g of tetraethylbenzylammonium chloride was charged and dissolved. After raising the temperature to 65 ° C., the pressure was reduced to an azeotropic pressure, and 90 g (1.1 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Thereafter, stirring was continued for 0.5 hours under the same conditions. During this time, the distillate distilled by azeotropic distillation was separated with a Dean-Stark trap, the water layer was removed, and the reaction was carried out while returning the oil layer to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. 432 g of methyl isobutyl ketone and 130 g of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 10 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours, and then washing with water 150 g was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after passing through microfiltration, the solvent was distilled off under reduced pressure to have a polynaphthylene oxide structure as the main skeleton, having glycidyloxy groups at both molecular ends, and There were obtained 210 g of an epoxy resin having an aralkyl group bonded to an aromatic nucleus in the polynaphthylene oxide structure (hereinafter abbreviated as “epoxy resin (A-1)”). The resulting epoxy resin had a softening point of 47 ° C., a melt viscosity at 150 ° C. of 0.5 dPa · s, and an epoxy equivalent of 231 g / eq.

Example 3 (Synthesis of aralkyl group-containing dihydroxy (polyoxynaphthalylene))
In Example 1, 330 g of aralkyl group-containing dihydroxy (polyoxynaphthalylene) was obtained in the same manner as in Example 1 except that 108 g of benzyl alcohol was changed to 216 g (2.0 mol) (hereinafter referred to as “ Compound (2) ”). The obtained compound (2) was a brown solid, the hydroxyl group equivalent was 180 g / eq, the softening point was 67 ° C., and the melt viscosity at 150 ° C. was 0.5 dPa · s.

Example 4 (Synthesis of aralkyl-modified poly (oxynaphthalene) type epoxy resin)
In Example 2, a polynaphthylene oxide structure is used as the main skeleton in the same manner as in Example 1 except that 180 g of the compound (2) obtained in Example 3 is used instead of 160 g of the compound (1) used as a raw material. 228 g of an epoxy resin having glycidyloxy groups at both molecular ends and having an aralkyl group bonded to the aromatic nucleus in the polynaphthylene oxide structure was obtained (hereinafter referred to as “epoxy resin (A-2)”). Abbreviated). The resulting epoxy resin had a softening point of 40 ° C., a melt viscosity at 150 ° C. of 0.4 dPa · s, and an epoxy equivalent of 244 g / eq.

Example 5 (Synthesis of aralkyl group-containing dihydroxy (polyoxynaphthalylene))
In Example 1, 230 g of aralkyl group-containing dihydroxy (polyoxynaphthalylene) was obtained in the same manner as in Example 1 except that 108 g of benzyl alcohol was changed to 92 g (0.85 mol) (hereinafter referred to as “ Compound (3) ”). The compound (3) obtained was a brown solid, the hydroxyl group equivalent was 164 g / eq, the softening point was 80 ° C., and the melt viscosity at 150 ° C. was 1.2 dPa · s.
The structure of the compound (3) was analyzed by FD-MS and ¹³ C-NMR, and further, the compound (3) was trimethylsilylated for use in the measurement of FD-MS by the trimethylsilylation method. A. And b. The peak of was confirmed.
a. One benzyl group (molecular weight Mw: 90) was added to 2,7-dihydroxynaphthalene trimer (Mw: 444) (Mw: 534), and two more trimethylsilyl groups (molecular weight Mw: 72) were added thereto. Added peak (M ⁺ = 678) and three added peaks (M ⁺ = 751).
b. Two benzyl groups (molecular weight Mw: 90) were added to 2,7-dihydroxynaphthalene trimer (Mw: 444) (Mw: 624), and further trimethylsilyl group (molecular weight Mw: 72) was 2 One added peak (M ⁺ = 768) and three added peaks (M ⁺ = 841).
Therefore, the compound (3) is a compound having a structure in which 1 mol of a benzyl group is bonded to 1 mol of 2,7-dihydroxynaphthalene trimer ether compound,
2,7-dihydroxynaphthalene trimer ether compound having a structure in which 2 moles of benzyl group are bonded per mole,
A compound having a structure in which 1 mol of a benzyl group is bonded to 1 mol of a trimer compound formed by nuclear dehydration of 1 mol of 2,7-dihydroxynaphthalene to 1 mol of 2,7-dihydroxynaphthalene dimer ether; and ,
It is a compound having a structure in which 2 mol of a benzyl group is bonded to 1 mol of a trimer compound formed by nuclear dehydration of 1 mol of 2,7-dihydroxynaphthalene to 1 mol of 2,7-dihydroxynaphthalene dimer ether. I was able to confirm.

Example 6 (Synthesis of aralkyl-modified poly (oxynaphthalene) type epoxy resin)
In Example 2, a polynaphthylene oxide structure is used as the main skeleton in the same manner as in Example 2 except that 164 g of the compound (3) obtained in Example 5 is used instead of 160 g of the compound (1) used as a raw material. 210 g of an epoxy resin having glycidyloxy groups at both molecular ends and having an aralkyl group bonded to the aromatic nucleus in the polynaphthylene oxide structure was obtained (hereinafter referred to as “epoxy resin (A-3)”). Abbreviated). The resulting epoxy resin had a softening point of 54 ° C., a melt viscosity at 150 ° C. of 0.7 dPa · s, and an epoxy equivalent of 235 g / eq.

Example 7 (Synthesis of aralkyl group-containing dihydroxy (polyoxynaphthalylene))
In Example 1, 210 g of aralkyl group-containing dihydroxy (polyoxynaphthalylene) was obtained in the same manner as in Example 1 except that 108 g of benzyl alcohol was changed to 76 g (0.7 mol) (hereinafter referred to as “ Compound (4) ”). The obtained compound (4) was a brown solid, the hydroxyl group equivalent was 156 g / eq, the softening point was 83 ° C., and the melt viscosity at 150 ° C. was 1.9 dPa · s.
Subsequently, in order to use for the measurement of FD-MS by the trimethylsilylation method similarly to Example 5, the compound (3) was trimethylsilylated.

Example 8 (Synthesis of aralkyl-modified poly (oxynaphthalene) type epoxy resin)
In Example 2, a polynaphthylene oxide structure was mainly used in the same manner as in Example 2 except that 156 g of the compound (4) obtained in Example 7 was used instead of 160 g of the modified dihydroxynaphthalene compound (1) used as a raw material. 200 g of an epoxy resin having a skeleton, having glycidyloxy groups at both ends of the molecule, and having an aralkyl group bonded to the aromatic nucleus in the polynaphthylene oxide structure was obtained (hereinafter referred to as “epoxy resin (A-4)”. ) "). The resulting epoxy resin had a softening point of 66 ° C., a melt viscosity at 150 ° C. of 1.3 dPa · s, and an epoxy equivalent of 255 g / eq.

Example 9 (Synthesis of aralkyl group-containing dihydroxy (polyoxynaphthalylene))
In Example 1, 242 g of aralkyl group-containing dihydroxy (polyoxynaphthalylene) was obtained in the same manner as in Example 1 except that 160 g of 2,7-dihydroxynaphthalene was changed to 160 g of 1,6-dihydroxynaphthalene (hereinafter referred to as “aralkyl group-containing dihydroxy (polyoxynaphthalylene)”). This is referred to as “compound (5)”). The obtained compound (5) was a brown solid, the hydroxyl group equivalent was 147 g / eq, the softening point was 67 ° C., and the ICI viscosity was 0.5 dPa · s.

Example 10 (Synthesis of aralkyl-modified poly (oxynaphthalene) type epoxy resin)
In Example 2, a polynaphthylene oxide structure is used as the main skeleton in the same manner as in Example 2 except that 147 g of the compound (5) obtained in Example 9 is used instead of 160 g of the compound (1) used as a raw material. 211 g of an epoxy resin having a glycidyloxy group at both molecular ends and having an aralkyl group bonded to the aromatic nucleus in the polynaphthylene oxide structure was obtained (hereinafter referred to as “epoxy resin (A-5)”). Abbreviated). The resulting epoxy resin had a softening point of 43 ° C., a melt viscosity at 150 ° C. of 0.5 dPa · s, and an epoxy equivalent of 211 g / eq.

Comparative Example 1 (Synthesis of benzylated novolak resin and its epoxy resinization)
In Example 1, 160 g (1.0 mol) of 2,7-dihydroxynaphthalene was added to a phenol novolak oligomer (manufactured by Showa Polymer Co., Ltd., trade name: BRG-555, softening point 69 ° C., hydroxyl group equivalent; 103 g / eq ICI viscosity was 0) 0.7 dPa · s) 103 g (1.0 equivalent), and benzyl alcohol 432 g (4.0 mol) was changed to benzyl alcohol 75.6 g (0.7 mol). As a result, 146 g of a polybenzylated phenol novolac oligomer compound for comparison (hereinafter abbreviated as “benzylated novolak resin”) was obtained. The obtained benzylated novolak resin was a brown solid, the hydroxyl group equivalent was 166 g / eq, the softening point was 70 ° C., and the ICI viscosity was 0.7 dPa · s. Further, 215 g of a comparative epoxy resin was obtained in the same manner as in Example 1 except that 166 g of the benzylated novolak resin was used instead of 160 g of compound (1) in Example 1 (hereinafter referred to as “epoxy resin”). (A'-1) "). The resulting epoxy resin had a softening point of 40 ° C., a melt viscosity at 150 ° C. of 0.5 dPa · s, and an epoxy equivalent of 245 g / eq.

Examples 11-19 and Comparative Examples 2-4
Epoxy resins (A-1) to (A-5) obtained in Examples as the epoxy resin, epoxy resin (A′-1), and “YX-4000H” (tetramethylbiphenol type epoxy manufactured by Japan Epoxy Resin Co., Ltd.) Resin, epoxy equivalent: 195 g / eq), Nippon Kayaku Co., Ltd. “NC-3000” (biphenyl aralkyl type epoxy resin, epoxy equivalent: 277 g / eq), Dainippon Ink & Chemicals, Inc. “N-665-EXP” (Cresol novolac type epoxy resin, epoxy equivalent: 203 g / eq), “Mirex XLC-LL” (phenol aralkyl resin hydroxyl equivalent: 176 g / eq) manufactured by Mitsui Chemicals, Ltd. as a curing agent phenol resin, and as a curing accelerator Triphenylphosphine (TPP), condensed phosphate ester ( “PX-200” manufactured by Hachi Chemical Industry Co., Ltd.), magnesium hydroxide (“Echo Mug Z-10” manufactured by Air Water Co., Ltd.), spherical silica (“S-COL” manufactured by Micron Co., Ltd.) as an inorganic filler, silane As a coupling agent, γ-glycidoxytriethoxyxysilane (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.), carnauba wax (“PEARL WAX No. 1-P” manufactured by Celalica Noda Co., Ltd.), carbon black is used. Were blended in the composition shown in Table 1 and melt kneaded for 5 minutes at 85 ° C. using two rolls to obtain the desired composition. Regarding the physical properties of the cured product, an evaluation sample was prepared by the following method using the above composition, the flame retardancy and dielectric properties were measured by the following method, and the results are shown in Table 1.

[Geltime]
Place 0.15 g of epoxy resin composition on a cure plate (made by THERMO ELECTRIC) heated to 175 ° C., start timing with a stopwatch, stir the sample uniformly at the tip of the rod, and cut the sample into a string I stopped the stopwatch when it left the plate. The time until this sample was cut and remained on the plate was defined as the gel time.

[Flame retardance]
A sample for evaluation having a width of 12.7 mm, a length of 127 mm, and a thickness of 1.6 mm was formed by molding at a temperature of 175 ° C. for 90 seconds using a transfer molding machine and then post-curing at a temperature of 175 ° C. for 5 hours. A combustion test was performed using five test pieces having a thickness of 1.6 mm in accordance with the UL-94 test method using the prepared test pieces.

[Measurement of dielectric properties]
A sample for evaluation having a width of 25 mm, a length of 75 mm, and a thickness of 2.0 mm was formed by molding at a temperature of 175 ° C. for 90 seconds using a transfer molding machine and then post-curing at a temperature of 175 ° C. for 5 hours. Using the prepared test piece, it was stored in an indoor room at 23 ° C and 50% humidity for 24 hours using the impedance material analyzer "HP4291B" manufactured by Agilent Technologies Co., Ltd., in accordance with JIS-C-6481. Then, the dielectric constant and dielectric loss tangent of the cured product at a frequency of 100 MHz were measured.

Footnotes in Table 1:
* 1: Maximum combustion time (seconds) in one flame contact
* 2: Total burning time of 5 test pieces (seconds)
In Table 1, “Compound (1)” is aralkyl group-containing dihydroxy (polyoxynaphthalene) obtained in Example 1, and the evaluation result shown as “self-extinguishing” is required for V-1. The flame retardancy (ΣF ≦ 250 seconds and F _max ≦ 30 seconds) is not satisfied, but the fire extinguishes without reaching combustion (flame clamp arrival).

3 is a ¹³ C-NMR spectrum of aralkyl group-containing dihydroxy (polyoxynaphthylene) obtained in Example 1. FIG. 2 is a mass spectrum of aralkyl group-containing dihydroxy (polyoxynaphthylene) obtained in Example 1. FIG. 3 is a ¹³ C-NMR spectrum of an aralkyl-modified poly (oxynaphthalene) type epoxy resin obtained in Example 2. FIG. 2 is a mass spectrum of an aralkyl-modified poly (oxynaphthalene) type epoxy resin obtained in Example 2. FIG. 6 is a mass spectrum of aralkyl group-containing dihydroxy (polyoxynaphthylene) obtained in Example 5. FIG. 6 is an FD-MS spectrum obtained by trimethylsilylation of aralkyl group-containing dihydroxy (polyoxynaphthylene) obtained in Example 5. 2 is a mass spectrum of aralkyl group-containing dihydroxy (polyoxynaphthylene) obtained in Example 7. FIG. 4 is an FD-MS spectrum obtained by trimethylsilylation of aralkyl group-containing dihydroxy (polyoxynaphthylene) obtained in Example 7. 4 is a ¹³ C-NMR spectrum of aralkyl group-containing dihydroxy (polyoxynaphthylene) obtained in Example 9. 4 is a mass spectrum of aralkyl group-containing dihydroxy (polyoxynaphthylene) obtained in Example 9. 3 is a ¹³ C-NMR spectrum of an aralkyl-modified poly (oxynaphthalene) type epoxy resin obtained in Example 10. 2 is a mass spectrum of an aralkyl-modified poly (oxynaphthalene) type epoxy resin obtained in Example 10. FIG.

Claims (17)

The polyaryleneoxy structure is the main skeleton, and the aromatic ring of the structure has a ( β- methyl) glycidyloxy group and the following structural formula (1)

[In Formula (1), R ₁ and R ₂ are each independently a methyl group or a hydrogen atom, and Ar is substituted with 1 to 3 of a phenylene group or an alkyl group having 1 to 4 carbon atoms. A phenylene group, a naphthylene group, a naphthylene group that is nucleus-substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms, and n is an average number of repetitions of 0.1 to 4. ]
An epoxy resin composition comprising an epoxy resin (A) having a molecular structure in which structural parts represented by formula (I) and a curing agent (B) are essential components. 2. The epoxy resin composition according to claim 1, wherein the epoxy resin (A) has a melt viscosity of 0.1 to 3.0 dPa · s at 150 ° C. measured in accordance with “ASTM D4287”. The epoxy resin (A) has an epoxy equivalent of 200 to 1,000 g / eq. The epoxy resin composition according to claim 1 or 2, wherein the epoxy resin composition is in the range of. The epoxy resin composition according to claim 1, wherein R ₁ and R ₂ in the general formula (1) are both hydrogen atoms. The epoxy resin (A) has the following structural formula (1)

Here, in said general formula (1), q is an integer of 1-7 and p is an integer of 0-4 each independently. However, the value of p is in the range of 1 to 4 for at least one of R in the general formula (1). R ′ is a hydrogen atom or a methyl group, R is independently the following general formula (2),

(In general formula (2), n is an average value of repetition and is 0.1 to 4.)
Or the following general formula (3)

(In general formula (3), n is an average value of 0.1 to 4)
It is. )
The epoxy resin composition according to claim 1, which is represented by: The curing agent (B) has the following structural formula (i)

[In Structural Formula (i), X is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and m is an integer of 0 to 3. ]
The epoxy resin composition according to claim 1, which is a phenol resin having a structure in which a plurality of phenols are knotted with a structure represented by the formula: In addition to the epoxy resin (A) and the curing agent (B), has been an essential component charge Hamazai and scope filling rate of the filler is 30 to 95 mass% per 100 parts by weight of the epoxy resin composition The epoxy resin composition for semiconductor sealing materials which consists of an epoxy resin composition of Claim 1 . Hardened | cured material obtained by hardening the epoxy resin composition of any one of Claims 1-7. The polyaryleneoxy structure is the main skeleton, and the aromatic ring of the structure has a ( β- methyl) glycidyloxy group and the following structural formula (1)

[In Formula (1), R ₁ and R ₂ are each independently a methyl group or a hydrogen atom, and Ar is substituted with 1 to 3 of a phenylene group or an alkyl group having 1 to 4 carbon atoms. A phenylene group, a naphthylene group, a naphthylene group that is nucleus-substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms, and n is an average number of repetitions of 0.1 to 4. ]
And the melt viscosity at 150 ° C. measured according to “ASTM D4287” is 0.1 to 3.0 dPa · s. New epoxy resin. Dihydroxy aromatic compound (a1) and the following structural formula (2)

[Wherein R ₁ and R ₂ are each independently a methyl group or a hydrogen atom, and Ar is a phenylene group or a phenylene group that is nucleus-substituted with 1 to 3 of a C 1-4 alkyl group. Y represents a halogen atom, an alkoxy group, or a hydroxyl group, a naphthylene group that is nucleus-substituted with 1 to 3 of a naphthylene group or an alkyl group having 1 to 4 carbon atoms. And an aralkylating agent (a2) selected from the compounds represented by formula (I) in the presence of an acid catalyst to obtain a resin having a phenolic hydroxyl group, and then the obtained resin and epihalohydrins (a3) The manufacturing method of the epoxy resin characterized by making react. The reaction ratio (a1) / (a2) between the dihydroxy aromatic compound (a1) and the aralkylating agent (a2) is in a range where the molar ratio is 1 / 0.1 to 1/10. Production method. The reaction ratio (a1) / (a2) between the dihydroxy aromatic compound (a1) and the aralkylating agent (a2) is in a range where the molar ratio is 1 / 0.1 to 1 / 1.0. The manufacturing method as described. The polyaryleneoxy structure is the main skeleton, and the aromatic ring of the structure has a phenolic hydroxyl group and the following structural formula (1)

[In Formula (1), R ₁ and R ₂ are each independently a methyl group or a hydrogen atom, and Ar is substituted with 1 to 3 of a phenylene group or an alkyl group having 1 to 4 carbon atoms. A phenylene group, a naphthylene group, a naphthylene group that is nucleus-substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms, and n is an average number of repetitions of 0.1 to 4. ]
An epoxy resin composition comprising, as essential components, a resin (B ′) having a phenolic hydroxyl group having a molecular structure to which a structural moiety represented by formula (I) is bonded, and an epoxy resin (A ′). The resin (B ′) having a phenolic hydroxyl group is represented by the following general formula (4):

Here, in the said General formula (4), q is an integer of 1-7, p is an integer of 0-4 each independently. However, the value of p is in the range of 1 to 4 for at least one of R in the general formula (1). And R is respectively independently the following general formula (5),

(In general formula (5), n is an average value of 0.1 to 4)
Or the following general formula (6)

(In general formula (6), n is an average value of repetitions of 0.1 to 4.)
Represents. )
The epoxy resin composition according to claim 13, which is represented by: In addition to the resin (B ') and the epoxy resin (A') having a phenolic hydroxyl group, has been an essential component charge Hamazai and filling rate of the filler epoxy resin composition per 100 parts by weight 30 It is the range of -95 mass%, The epoxy resin composition for semiconductor sealing materials which consists of an epoxy resin composition of Claim 14 . A cured product obtained by curing the epoxy resin composition according to claim 14. The polyaryleneoxy structure is the main skeleton, and the aromatic ring of the structure has a phenolic hydroxyl group and the following structural formula (1)

[In the formula (1), R1 and R2 are each independently a methyl group or a hydrogen atom, and Ar is a phenylene that is nucleus-substituted by 1 to 3 of a phenylene group or an alkyl group having 1 to 4 carbon atoms. A group, a naphthylene group, a naphthylene group nucleus-substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms, and n is an average number of repetitions of 0.1 to 4. ]
And the melt viscosity at 150 ° C. measured according to “ASTM D4287” is 0.1 to 3.0 dPa · s. A resin having a novel phenolic hydroxyl group.

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