JP6119392B2 - Modified polyarylene ether resin, epoxy resin composition, cured product thereof, prepreg, circuit board, and build-up film - Google Patents

Description

  The present invention has a high industrial utility value due to its excellent solubility in various solvents, a modified polyarylene ether resin excellent in heat resistance and dielectric properties, an epoxy resin composition containing the same, a cured product thereof, a prepreg, The present invention relates to a circuit board and a build-up film.

  Epoxy resin compositions containing an epoxy resin and a curing agent as an essential component exhibit excellent heat resistance and insulation in the cured product, and are widely used in electronic component applications such as semiconductors and multilayer printed boards. . Among the electronic component applications, in the technical field of insulating materials for multilayer printed circuit boards, resin materials having excellent dielectric properties that can cope with the increase in signal speed and frequency in various electronic devices, that is, dielectric constant and dielectric There is a demand for the development of a resin material having a sufficiently low tangent.

  Polyphenylene ether resin with a number average molecular weight (Mn) of 5000 or less is blended into an epoxy resin composition containing an epoxy resin and a cyanate ester resin as a technique for reducing both the dielectric constant and dielectric loss tangent of the cured epoxy resin composition. There is a known method (see Patent Document 1 below). In the method described in Patent Document 1, the dielectric constant and dielectric loss tangent of the cured product are reduced by blending the polyphenylene ether resin with the epoxy resin composition as compared with those not blended. The nature was lowered. In addition, since the conventional polyphenylene ether resin used in Patent Document 1 has very low solubility in various solvents, it is heated to around 90 ° C. and dissolved in an organic solvent such as toluene to cure an epoxy resin or a cured resin. It was necessary to mix with the agent component, and it was difficult to handle for industrial use.

WO2009 / 041137

  Therefore, the problem to be solved by the present invention is a modified polyarylene ether resin having high industrial utility value, excellent heat resistance and dielectric properties because of its excellent solubility in various solvents, and an epoxy resin composition containing the same. It is providing a thing, its hardened | cured material, a prepreg, a circuit board, and a buildup film.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have introduced a glycidyl ether structure of a tetraalkylbiphenol having an aralkyl group on the aromatic nucleus at the molecular end of the polyarylene ether resin, whereby It has been found that the solubility in various solvents is remarkably improved as compared with the arylene ether resin, and the resin is also excellent in heat resistance and dielectric properties, and the present invention has been completed.

  That is, the present invention has a polyarylene ether structure as a main skeleton, and at least one of molecular ends has the following structural formula (i)

（式中、Ｒ^１はそれぞれ独立して炭素原子数１〜６のアルキル基又は炭素原子数１〜６のアルコキシ基の何れかであり、Ｒ^２はそれぞれ独立して水素原子、炭素原子数１〜６のアルキル基、又は炭素原子数１〜６のアルコキシ基の何れかであり、Ａｒはそれぞれ独立してフェニレン基、ナフチレン基、或いはこれらの芳香核上に炭素原子数１〜６のアルキル基又は炭素原子数１〜６のアルコキシ基を１乃至複数個有する構造部位の何れかであり、ｍはそれぞれ独立して１又は２であり、ｎはそれぞれ独立して０〜２の整数であり、かつ、２つのｎのうち少なくとも一方は１又は２である。）
で表される構造部位（ｉ）を有することを特徴とする変性ポリアリーレンエーテル樹脂に関する。

(In the formula, each R ¹ is independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R ² is independently a hydrogen atom or 1 carbon atom. Or an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and Ar is independently a phenylene group, a naphthylene group, or an alkyl group having 1 to 6 carbon atoms on the aromatic nucleus. Or any one of structural parts having 1 to a plurality of alkoxy groups having 1 to 6 carbon atoms, m is each independently 1 or 2, n is each independently an integer of 0 to 2, And at least one of two n is 1 or 2.)
And a modified polyarylene ether resin characterized by having a structural moiety (i) represented by

  The present invention further relates to an epoxy resin composition comprising the modified polyarylene ether resin, epoxy resin, and curing agent as essential components.

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

  The present invention further relates to a prepreg obtained by impregnating a reinforcing substrate with a solution obtained by diluting the epoxy resin composition in an organic solvent and semi-curing the resulting impregnated substrate.

  The present invention further relates to a circuit board obtained by obtaining a varnish obtained by diluting the epoxy resin composition in an organic solvent, and heating and press-molding a varnish shaped into a plate shape and a copper foil.

  The present invention further relates to a build-up film obtained by applying a solution obtained by diluting the epoxy resin composition in an organic solvent on a base film and drying it.

  According to the present invention, a modified polyarylene ether resin having high industrial utility value due to excellent solubility in various solvents, excellent heat resistance and dielectric properties, an epoxy resin composition containing the same, a cured product thereof, A prepreg, a circuit board, and a buildup film can be provided.

FIG. 1 is a GPC chart of the aralkyl-modified biphenol compound (c1) obtained in Production Example 1. FIG. 2 is a GPC chart of the epoxy compound (B1) obtained in Production Example 2. FIG. 3 is a GPC chart of the modified polyarylene ether resin (1) obtained in Example 1.

Hereinafter, the present invention will be described in detail.
The modified polyarylene ether resin of the present invention has a polyarylene ether structure as a main skeleton, and at least one of molecular ends has the following structural formula (i)

（式中、Ｒ^１はそれぞれ独立して炭素原子数１〜６のアルキル基又は炭素原子数１〜６のアルコキシ基の何れかであり、Ｒ^２はそれぞれ独立して水素原子、炭素原子数１〜６のアルキル基、又は炭素原子数１〜６のアルコキシ基の何れかであり、Ａｒはそれぞれ独立してフェニレン基、ナフチレン基、或いはこれらの芳香核上に炭素原子数１〜６のアルキル基又は炭素原子数１〜６のアルコキシ基を１乃至複数個有する構造部位の何れかであり、ｍはそれぞれ独立して１又は２であり、ｎはそれぞれ独立して０〜２の整数であり、かつ、２つのｎのうち少なくとも一方は１又は２である。）
で表される構造部位（ｉ）を有することを特徴とする。

(In the formula, each R ¹ is independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R ² is independently a hydrogen atom or 1 carbon atom. Or an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and Ar is independently a phenylene group, a naphthylene group, or an alkyl group having 1 to 6 carbon atoms on the aromatic nucleus. Or any one of structural parts having 1 to a plurality of alkoxy groups having 1 to 6 carbon atoms, m is each independently 1 or 2, n is each independently an integer of 0 to 2, And at least one of two n is 1 or 2.)
It has the structure site | part (i) represented by these, It is characterized by the above-mentioned.

  As mentioned above, polyarylene ether resins are known to have the effect of reducing the dielectric constant and dielectric loss tangent in cured products when used in an epoxy resin composition, etc., but are soluble in various solvents. Since the property is very low, it is difficult to handle, and the heat resistance of the cured product is lowered by blending the polyarylene ether resin. In contrast, in the modified polyarylene ether resin of the present invention, the crystallinity of the polyarylene ether is relaxed by introducing the structural site (i) represented by the structural formula (i) into at least one of the molecular ends. The solubility in various solvents is improved and the heat resistance and dielectric properties are excellent. In general, a resin having a sterically bulky substituent skeleton is excellent in solvent solubility, but tends to decrease in dielectric properties and heat resistance as crystallinity decreases, but the modified polyarylene ether resin of the present invention is a solvent. Combines solubility, dielectric properties, and heat resistance.

  Examples of the arylene group in the modified polyarylene ether resin of the present invention include a phenylene group, a naphthylene group, and a structural site having a substituent such as an alkyl group, an alkoxy group, an aryl group, and an aralkyl group on the aromatic nucleus. Among these, since it becomes a modified polyarylene ether resin having an excellent balance between solvent solubility, dielectric properties, and heat resistance, the polyarylene ether structure is represented by the following structural formula (ii):

（式中Ｒ^２はそれぞれ独立に水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基、アラルキル基の何れかであり、ｌは繰り返し単位数を表す整数である。）
で表される構造部位であることが好ましい。

(In the formula, each R ² is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group, and l represents the number of repeating units. (It is an integer.)
It is preferable that it is a structure site | part represented by these.

  The modified polyarylene ether resin of the present invention having such a polyarylene ether structure is specifically represented by the following general formula (I):

［前記一般式（Ｉ）中、（ｉ）は前記構造式（ｉ）で表される構造部位であり、（ｉｉｉ）は下記構造式（ｉｉｉ）

[In the general formula (I), (i) is a structural moiety represented by the structural formula (i), and (iii) is the following structural formula (iii)

｛式中Ｒ^３はそれぞれ独立に水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基、アラルキル基の何れかであり、ｐ及びｑはそれぞれ独立に０以上の整数であり、ｐとｑとの和は４以上である。また、式中Ｙは下記構造式（ｙ−１）〜（ｙ−９）

{Wherein R ³ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group, and p and q are each independently It is an integer of 0 or more, and the sum of p and q is 4 or more. In the formula, Y represents the following structural formulas (y-1) to (y-9).

（式中、Ｒ^４はそれぞれ独立に水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基、アラルキル基の何れかであり、Ｒ^５はそれぞれ独立に炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基の何れかであり、ｋは０〜４の整数である。）
の何れかで表される構造部位である。｝
で表される構造部位であり、（ｉｖ）は下記構造式（ｉｖ）

(In the formula, each R ⁴ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group, and each R ⁵ is independently (It is any one of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a phenyl group, and k is an integer of 0 to 4).
It is a structural part represented by either. }
Wherein (iv) is the following structural formula (iv)

（式中、Ｒ^１はそれぞれ独立して炭素原子数１〜６のアルキル基又は炭素原子数１〜６のアルコキシ基の何れかであり、Ｒ^２はそれぞれ独立して水素原子、炭素原子数１〜６のアルキル基、又は炭素原子数１〜６のアルコキシ基の何れかであり、Ａｒはそれぞれ独立してフェニレン基、ナフチレン基、或いはこれらの芳香核上に炭素原子数１〜６のアルキル基又は炭素原子数１〜６のアルコキシ基を１乃至複数個有する構造部位の何れかであり、ｍはそれぞれ独立して１又は２であり、ｎはそれぞれ独立して０〜２の整数であり、かつ、２つのｎのうち少なくとも一方は１又は２である。）
で表される構造部位であり、Ｘは水素原子又は前記構造式（ｉ）で表される構造部位であり、ｒは０〜２の整数である。］
で表される分子構造を有するものが挙げられる。

(In the formula, each R ¹ is independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R ² is independently a hydrogen atom or 1 carbon atom. Or an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and Ar is independently a phenylene group, a naphthylene group, or an alkyl group having 1 to 6 carbon atoms on the aromatic nucleus. Or any one of structural parts having 1 to a plurality of alkoxy groups having 1 to 6 carbon atoms, m is each independently 1 or 2, n is each independently an integer of 0 to 2, And at least one of two n is 1 or 2.)
X is a hydrogen atom or a structural moiety represented by the structural formula (i), and r is an integer of 0-2. ]
The thing which has the molecular structure represented by these is mentioned.

R ¹ in the structural formulas (i) and (iv) is independently any one of an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. Especially, since it becomes a modified polyarylene ether resin having low dielectric constant and dielectric loss tangent and excellent heat resistance, it is preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group.

R ² in the structural formulas (i) and (iv) is each independently any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Among them, since it becomes a modified polyarylene ether resin having a low dielectric constant and dielectric loss tangent and excellent heat resistance, it is preferably all hydrogen atoms.

  Ar in the structural formula (i) or (iv) is each independently a phenylene group, a naphthylene group, or an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms on the aromatic nucleus. One of the structural parts having one or more alkoxy groups. Among them, since it becomes a modified polyphenylene ether resin having better solvent solubility, 1 to 6 alkyl groups having 1 to 6 carbon atoms or 1 to 6 alkoxy groups having 1 to 6 carbon atoms on the aromatic nucleus of the phenylene group or phenylene group. It is preferably any one of a plurality of structural sites, and more preferably a phenylene group.

R ³ in the structural formula (iii) is independently any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, and an aralkyl group. Especially, since it becomes a modified polyarylene ether resin having low dielectric constant and dielectric loss tangent and excellent heat resistance, it is preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group. The bonding position of R ³ is preferably ortho with respect to the bonding position of the ether bond oxygen, that is, preferably a 2,6-xylylene ether structure.

Y in the structural formula (iii) is a structural portion represented by any one of the structural formulas (y-1) to (y-9). Among them, since it becomes a modified polyarylene ether resin having a lower dielectric constant and dielectric loss tangent and excellent dielectric properties, the structural site represented by the structural formula (y-9) is preferable. It is more preferable that all ^four R ⁴ in the formula (I) are methyl groups, and two R ⁵ are both methyl groups. In addition, the bonding position of R ⁴ is preferably ortho-position relative to the bonding position of the ether bond oxygen, that is, has a 4,4′-isopropylidenebis (2,6-dimethyl-phenylene) structure. Is preferred.

  In the general formula (I), r is an integer of 0 to 2, but since the modified polyarylene ether resin is excellent in solvent solubility and high in heat resistance, the value of r is 0. preferable. Further, X in the general formula (I) is a hydrogen atom or a structural moiety represented by the structural formula (i), but is a modified polyarylene ether resin having high solvent solubility and excellent heat resistance and dielectric properties. Therefore, X is preferably a structural site represented by the structural formula (i).

  From the above, a more preferred form of the modified polyarylene ether resin of the present invention is the following structural formula (II)

［式中Ｘは下記構造式（ｖ）

[Wherein X represents the following structural formula (v)

（式中ｍはそれぞれ独立して１又は２であり、ｎはそれぞれ独立して０〜２の整数であり、かつ、２つのｎのうち少なくとも一方は１又は２である。）
で表される構造部位である。］
で表される分子構造を有するものである。

(In the formula, m is each independently 1 or 2, n is each independently an integer of 0 to 2, and at least one of the two n is 1 or 2.)
It is a structural site represented by ]
It has the molecular structure represented by these.

  The epoxy equivalent of the modified polyarylene ether resin of the present invention is preferably in the range of 800 to 3,000 g / equivalent because it has high solvent solubility and is excellent in heat resistance and dielectric properties.

  The modified polyarylene ether resin of the present invention includes, for example, a polyarylene ether resin (A) having a polyarylene ether structure in the molecular structure and a hydroxyl group equivalent in the range of 500 to 1,500 g / equivalent, and the following structural formula ( III)

（式中、Ｒ^１はそれぞれ独立して炭素原子数１〜６のアルキル基又は炭素原子数１〜６のアルコキシ基の何れかであり、Ｒ^２はそれぞれ独立して水素原子、炭素原子数１〜６のアルキル基、又は炭素原子数１〜６のアルコキシ基の何れかであり、Ａｒはそれぞれ独立してフェニレン基、ナフチレン基、或いはこれらの芳香核上に炭素原子数１〜６のアルキル基又は炭素原子数１〜６のアルコキシ基を１乃至複数個有する構造部位の何れかであり、Ｇはグリシジル基を表し、ｍはそれぞれ独立して１又は２であり、ｎはそれぞれ独立して０〜２の整数であり、かつ、２つのｎのうち少なくとも一方は１又は２である。）
で表されるエポキシ化合物（Ｂ）とを、ポリアリーレンエーテル樹脂（Ａ）が有する水酸基１モルに対し、前記エポキシ化合物（Ｂ）が有するエポキシ基が０．５〜４モルの範囲となる割合で両者を反応させる方法により製造することが出来る。

(In the formula, each R ¹ is independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R ² is independently a hydrogen atom or 1 carbon atom. Or an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and Ar is independently a phenylene group, a naphthylene group, or an alkyl group having 1 to 6 carbon atoms on the aromatic nucleus. Or any one of structural parts having one or more alkoxy groups having 1 to 6 carbon atoms, G represents a glycidyl group, m is each independently 1 or 2, and n is each independently 0 And an integer of ˜2, and at least one of the two n is 1 or 2.)
The epoxy compound (B) represented by the formula (B) is a ratio in which the epoxy group of the epoxy compound (B) is in the range of 0.5 to 4 mol with respect to 1 mol of the hydroxyl group of the polyarylene ether resin (A). It can manufacture by the method of making both react.

  Examples of the arylene group in the polyarylene ether resin (A) used in the production method include a phenylene group, a naphthylene group, and a structural site having a substituent such as an alkyl group, an alkoxy group, or an aryl group on the aromatic nucleus. . Among them, since it becomes a modified polyarylene ether resin having an excellent balance between solvent solubility and dielectric properties and heat resistance, the polyarylene ether structure is preferably a structural portion represented by the structural formula (ii). Specifically, such a polyarylene ether resin (A) has the following structural formula (IV):

［式中Ｒ^３はそれぞれ独立に水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基、アラルキル基の何れかであり、ｐ及びｑはそれぞれ独立に０以上の整数であり、ｐとｑとの和は４以上である。また、式中Ｙは下記構造式（ｙ−１）〜（ｙ−９）

[Wherein R ³ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group, and p and q are each independently It is an integer of 0 or more, and the sum of p and q is 4 or more. In the formula, Y represents the following structural formulas (y-1) to (y-9).

（式中、Ｒ^４はそれぞれ独立に水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基、アラルキル基の何れかであり、Ｒ^５はそれぞれ独立に炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基の何れかであり、ｋは０〜４の整数である。）
の何れかで表される構造部位である。］
で表される分子構造を有するものが挙げられる。

(In the formula, each R ⁴ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group, and each R ⁵ is independently (It is any one of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a phenyl group, and k is an integer of 0 to 4).
It is a structural part represented by either. ]
The thing which has the molecular structure represented by these is mentioned.

R ³ in the structural formula (IV) has the same meaning as R ³ in the structural formula (iii), and as described above, a modified polyarylene ether resin having a low dielectric constant and dielectric loss tangent and excellent heat resistance; Therefore, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is particularly preferable. The bonding position of R ³ is preferably ortho with respect to the bonding position of ether-bonded oxygen, that is, preferably a 2,6-xylylene ether structure.

Y in the structural formula (IV) is synonymous with Y in the structural formula (iii), and as described above, a modified polyarylene ether resin having a lower dielectric constant and dielectric loss tangent and excellent dielectric properties, It is preferable that it is a structural site represented by the structural formula (y-9), in which 4 R ^{4 in} the structural formula (y-9) are all methyl groups, and 2 R ⁵ are both methyl. What is a group is more preferable. In addition, the bonding position of R ⁴ is preferably ortho-position relative to the bonding position of the ether bond oxygen, that is, has a 4,4′-isopropylidenebis (2,6-dimethyl-phenylene) structure. Is preferred.

  The hydroxyl equivalent of the polyarylene ether resin (A) used here is in the range of 500 to 1500 g / equivalent because a modified polyarylene ether resin having excellent solvent solubility and dielectric properties and excellent heat resistance can be obtained. It is preferable that the range is 600 to 1000 g / equivalent.

  Next, the epoxy compound (B) to be reacted with the polyarylene ether resin (A) has the following structural formula (III)

（式中、Ｒ^１はそれぞれ独立して炭素原子数１〜６のアルキル基又は炭素原子数１〜６のアルコキシ基の何れかであり、Ｒ^２はそれぞれ独立して水素原子、炭素原子数１〜６のアルキル基、又は炭素原子数１〜６のアルコキシ基の何れかであり、Ａｒはそれぞれ独立してフェニレン基、ナフチレン基、或いはこれらの芳香核上に炭素原子数１〜６のアルキル基又は炭素原子数１〜６のアルコキシ基を１乃至複数個有する構造部位の何れかであり、Ｇはグリシジル基を表し、ｍはそれぞれ独立して１又は２であり、ｎはそれぞれ独立して０〜２の整数であり、かつ、２つのｎのうち少なくとも一方は１又は２である。）
で表される化合物であり、このような化合物は、例えば下記構造式（ａ）

(In the formula, each R ¹ is independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R ² is independently a hydrogen atom or 1 carbon atom. Or an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and Ar is independently a phenylene group, a naphthylene group, or an alkyl group having 1 to 6 carbon atoms on the aromatic nucleus. Or any one of structural parts having one or more alkoxy groups having 1 to 6 carbon atoms, G represents a glycidyl group, m is each independently 1 or 2, and n is each independently 0 And an integer of ˜2, and at least one of the two n is 1 or 2.)
Such a compound is represented by the following structural formula (a), for example.

（式中、Ｒ^１はそれぞれ独立して炭素原子数１〜６のアルキル基又は炭素原子数１〜６のアルコキシ基の何れかである。）
で表されるビフェノール化合物（ａ）とアラルキル化剤（ｂ）とを反応させて得られるアラルキル変性ビフェノール化合物（ｃ）をグリシジルエーテル化する方法等により得ることが出来る。

(In the formula, each R ¹ is independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.)
The aralkyl modified biphenol compound (c) obtained by reacting the biphenol compound (a) and the aralkylating agent (b) can be obtained by a method such as glycidyl etherification.

Examples of the biphenol compound (a) include 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol, 3,3 ′, 5,5′-tetraethyl-4,4′-biphenol, 3 , 3 ′, 5,5′-tetraisopropyl-4,4′-biphenol and the like. These may be used alone or in combination of two or more. R ¹ in the structural formula (a) is synonymous with R ¹ in the structural formula (i), and is a modified polyarylene ether resin having a low dielectric constant and dielectric loss tangent and excellent heat resistance. An alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is particularly preferable.

  Examples of the aralkylating agent (b) include a phenylmethanol compound, a phenylmethyl halide compound, a naphthylmethanol compound, a naphthylmethyl halide compound, and a styrene compound. Specifically, benzyl chloride, benzyl bromide, benzyl iodide, o-methylbenzyl chloride, m-methylbenzyl chloride, p-methylbenzyl chloride, p-ethylbenzyl chloride, p-isopropylbenzyl chloride, p-tert-butyl Benzyl chloride, p-phenylbenzyl chloride, 5-chloromethylacenaphthylene, 2-naphthylmethyl chloride, 1-chloromethyl-2-naphthalene and their nuclear substituted isomers, α-methylbenzyl chloride, α, α-dimethyl Benzyl chloride, benzyl methyl ether, o-methyl benzyl methyl ether, m-methyl benzyl methyl ether, p-methyl benzyl methyl ether, p-ethyl benzyl methyl ether and their nuclear substitution isomerism , Benzyl ethyl ether, benzyl propyl ether, benzyl isobutyl ether, benzyl n-butyl ether, p-methylbenzyl methyl ether and their nuclear substitution isomers, benzyl alcohol, o-methylbenzyl alcohol, m-methylbenzyl alcohol, p-methyl Benzyl alcohol, p-ethylbenzyl alcohol, p-isopropylbenzyl alcohol, ptert-butylbenzyl alcohol, p-phenylbenzyl alcohol, α-naphthylmethanol and their nuclear substituted isomers, α-methylbenzyl alcohol, α, α-dimethyl Examples include benzyl alcohol, styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, β-methyl styrene and the like. These may be used alone or in combination of two or more.

  Among these, benzyl chloride, benzyl bromide, or benzyl alcohol is preferable because it becomes a modified polyarylene ether resin having better solvent solubility.

  Examples of the reaction of the biphenol compound (a) and the aralkylating agent (b) include a method of reacting at a temperature of 100 to 180 ° C. for 3 to 10 hours in the presence of an acid catalyst.

  Since the reaction ratio between the biphenol compound (a) and the aralkylating agent (b) can easily adjust the values of m and n in the structural formula (III), the biphenol compound (a) It is preferable that it is the ratio from which the said aralkylation agent (b) becomes the range of 1-4 mol with respect to 1 mol. Especially, since it becomes polyarylene ether resin excellent in solvent solubility, it is a ratio that the aralkylating agent (b) is in the range of 1.5 to 2.5 mol with respect to 1 mol of the biphenol compound (a). It is preferable.

  Examples of the acid catalyst used when the biphenol compound (a) is reacted with the aralkylating agent (b) include inorganic acids such as phosphoric acid, sulfuric acid, hydrochloric acid, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, Examples thereof include 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 these acid catalysts used can be appropriately selected depending on the desired aralkylation rate and the like, but when using an inorganic acid or an organic acid, 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the reaction raw material. When using the Friedel-Crafts catalyst in the range, it is preferably used in the range of 0.2 to 3.0 mol with respect to 1 mol of the aralkylating agent (b).

  The reaction between the biphenol compound (a) and the aralkylating agent (b) may be performed in an organic solvent as necessary. Examples of the organic solvent used herein include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, cellosolve, butyl carbitol, and the like. Examples thereof include carbitol solvents, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.

  After completion of the reaction, the product aralkyl-modified biphenol compound (c) is obtained by a method of neutralizing the reaction mixture and washing with water.

  Next, the method of diglycidyl etherifying the obtained aralkyl-modified biphenol compound (c) is, for example, the above aralkyl-modified biphenol compound (c) and epihalohydrin at a temperature of 20 to 120 ° C. in the presence of a basic catalyst. And reacting for 0.5 to 10 hours.

  The epihalohydrin used here is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and the like. Of these, epichlorohydrin is preferred because it is easily available industrially. Moreover, these reaction ratios at the time of making the said aralkyl modification biphenol compound (c) and epichlorohydrin react are 2-10 mol of epihalohydrin with respect to 1 mol of the phenolic hydroxyl group which the said aralkyl modification biphenol compound (c) has. The ratio is preferably

  Examples of the basic catalyst used in the reaction of the aralkyl-modified biphenol compound (c) with epihalohydrin include alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydroxides, and the like, and are particularly excellent in catalytic activity. Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferred. These may be used in a solid form or in the form of an aqueous solution of about 10 to 55% by mass. The amount of the basic catalyst used is in the range of 0.9 to 2.0 mol with respect to 1 mol of the phenolic hydroxyl group, and may be added all at once, or may be added or gradually added. When the basic catalyst is used as an aqueous solution, it is continuously added, and water and epihalohydrin are continuously distilled from the reaction mixture under reduced pressure or normal pressure, and further separated to remove water and the epihalohydrin is removed. A method of continuously returning to the reaction mixture may also be used.

  In industrial production, the epihalohydrin used in the initial batch of diglycidyl ether production is all new, but the subsequent batch is consumed by the reaction with epihalohydrins recovered from the crude reaction product. It is preferable to use in combination with new epihalohydrins corresponding to the amount disappeared.

  The reaction rate of the aralkyl-modified biphenol compound (c) and epihalohydrin can be increased by performing the reaction in an organic solvent. The organic solvent used here is not particularly limited. For example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aromatic hydrocarbon solvents such as toluene and xylene, methanol, ethanol, 1-propyl alcohol, and isopropyl alcohol. Alcohol solvents such as 1-butanol, secondary butanol and tertiary butanol, cellosolve solvents such as methyl cellosolve and ethyl cellosolve, ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, acetonitrile And aprotic polar solvents such as dimethyl sulfoxide and dimethylformamide. These organic solvents may be used alone or in combination of two or more kinds in order to adjust the polarity.

  After completion of the reaction, the reaction product is washed with water, and unreacted epihalohydrin and the combined organic solvent are distilled off by distillation under heating and reduced pressure. Further, in order to obtain an epoxy compound with less hydrolyzable halogen, unreacted epihalohydrin and the organic solvent used in combination are distilled off before the water washing step, and the resulting crude product is toluene, methyl isobutyl ketone, It can be redissolved in an organic solvent such as methyl ethyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide can be added for further reaction. 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 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the crude epoxy product used. After completion of the post-reaction, the produced salt is removed by a method such as filtration or washing with water, and further, the target epoxy compound (B) is obtained by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure. Can be obtained.

  The reaction of the polyarylene ether resin (A) and the epoxy compound (B) can be performed, for example, by a method of reacting at a temperature of 50 to 150 ° C. for 5 to 30 hours in the presence of a catalyst.

  Since the reaction ratio of the polyarylene ether resin (A) and the epoxy compound (B) is high in solvent solubility, a modified polyarylene ether resin having excellent heat resistance and dielectric properties can be obtained. The ratio of the epoxy group of the epoxy compound (B) in the range of 0.5 to 4 mol is preferable with respect to 1 mol of the hydroxyl group of the resin (A), and the ratio in the range of 1 to 3 mol. More preferably.

  The catalyst used for the reaction of the polyarylene ether resin (A) and the epoxy compound (B) can be any catalyst that is usually used for the reaction of an epoxy group and a phenolic hydroxyl group. Metallic compounds, organic phosphorus compounds such as triphenylphosphine, tertiary amines such as 1,8-diazabicyclo- [5.4.0] -undecene (DBU), 2-methylimidazole, 2-ethyl-4-methylimidazole Imidazole compounds such as 2-phenylimidazole, Lewis acids, amine complex salts and the like. Among them, an imidazole compound having high catalytic activity and not containing an alkali metal atom is preferable, and the amount of the catalyst used is 50 ppm to 1000 ppm with respect to the total mass of the polyarylene ether resin (A) and the epoxy compound (B). A range is preferable.

  The reaction between the polyarylene ether resin (A) and the epoxy compound (B) may be carried out in the presence of an organic solvent, and is preferably carried out in the presence of an organic solvent because the reactivity is increased. At this time, the amount of the organic solvent used is preferably in the range where the non-volatile content is 50 to 90%.

  Examples of the organic solvent used here include aromatic compounds such as benzene, toluene, xylene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, Amide solvents such as N-methylacetamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol mono Ethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n- Chirueteru, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol mono -n- butyl ether, etc. glycol ethers solvents such as propylene glycol monomethyl ether acetate. Of these, ketone solvents are preferred because of the excellent solubility of the resulting modified polyarylene ether resin.

  The epoxy resin composition of the present invention contains the aforementioned modified polyarylene ether resin, epoxy resin, and curing agent as essential components.

  Examples of the epoxy resin used in the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, polyhydroxynaphthalene type epoxy resin, phenol novolac type epoxy resin, and 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 Condensed novolac epoxy resin, naphthol-cresol co-condensed novolac epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic tree Type epoxy resins, biphenyl-modified novolak type epoxy resins. Among these epoxy resins, tetramethylbiphenol type epoxy resin, biphenyl aralkyl type epoxy resin, polyhydroxynaphthalene type epoxy resin, and novolac type epoxy resin are used in that a cured product having excellent flame retardancy can be obtained. A dicyclopentadiene-phenol addition reaction type epoxy resin is preferable in that a cured product having excellent dielectric properties is obtained.

Examples of the curing agent used in the present invention include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, guanidine derivatives and other amine compounds: dicyandiamide, linolenic acid Amide compounds such as polyamide resin synthesized from the product and ethylenediamine: phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydro Acid anhydrides such as phthalic anhydride and methylhexahydrophthalic anhydride: phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadi Phenol addition resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin ( Polyphenolic compounds in which phenol nuclei are linked by bismethylene groups), biphenyl-modified naphthol resins (polyvalent naphthol compounds in which phenol nuclei are linked by bismethylene groups), aminotriazine-modified phenolic resins (phenolic nuclei are linked by melamine, benzoguanamine, etc.) Polyhydric phenol compounds).

  Among these, those containing a large amount of an aromatic skeleton in the molecular structure are preferable because of their excellent dielectric properties. Specifically, phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, and phenol aralkyl resins. A naphthol aralkyl resin, a naphthol novolak resin, a naphthol-phenol co-condensed novolak resin, a naphthol-cresol co-condensed novolak resin, a biphenyl-modified phenol resin, a biphenyl-modified naphthol resin, and an aminotriazine-modified phenol resin are preferable.

  The content of the modified polyarylene ether resin in the epoxy resin composition of the present invention is not particularly limited and can be blended at an arbitrary ratio, but has a low dielectric constant and dielectric loss tangent, and excellent heat resistance. Since a cured product is obtained, the proportion of the modified polyarylene ether resin is preferably in the range of 10 to 80 parts by mass with respect to 100 parts by mass in total of the epoxy resin and the curing agent. Moreover, since the mixture ratio of an epoxy resin and a hardening | curing agent becomes an epoxy resin composition excellent in sclerosis | hardenability and a hardened | cured material with high heat resistance is obtained, with respect to 1 mol of epoxy groups in an epoxy resin, in a hardening | curing agent. It is preferable that the total number of active groups is 0.7 to 1.5 mol.

  The epoxy resin composition of the present invention may contain a curing accelerator as necessary. Examples of the curing accelerator used here include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like. In particular, when the epoxy resin composition of the present invention is used as a build-up material application or a circuit board application, dimethylaminopyridine and imidazole are preferable because of excellent heat resistance, dielectric characteristics, solder resistance, and the like.

  As described above, the modified polyarylene ether resin of the present invention has characteristics that are superior in solvent solubility as compared with conventional polyarylene ether resins, and the epoxy resin composition of the present invention is used for build-up materials and circuit boards. When used as an application, it can be varnished using various organic solvents such as ketone solvents, alcohol solvents, and ester solvents in addition to conventionally used solvents such as toluene. Organic solvents that can be used as the solvent of the epoxy resin composition of the present invention include, for example, aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, Examples include acetate solvents such as propylene glycol monomethyl ether acetate and carbitol acetate; alcohol solvents such as ethanol, propanol and butanol; carbitol solvents such as cellosolve and butyl carbitol; dimethylformamide, dimethylacetamide and N-methylpyrrolidone. .

  When the epoxy resin composition of the present invention is used for printed wiring board applications, it is preferably a polar solvent having a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, 1-methoxy-2-propanol, etc., and has a nonvolatile content of 40 to 80 It is preferable to use at a ratio of mass%. On the other hand, for use in build-up adhesive film applications, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, etc., acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, ethanol, propanol It is preferable to use an alcohol solvent such as butanol, a carbitol solvent such as cellosolve or butyl carbitol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., and a non-volatile content of 30 to 60% by mass. preferable.

  Moreover, the epoxy resin composition of this invention may use together other thermosetting resin suitably as needed. Examples of other thermosetting resins that can be used here include cyanate ester compounds, vinylbenzyl compounds, acrylic compounds, maleimide compounds, and copolymers of styrene and maleic anhydride. When other thermosetting resins described above are used in combination, the amount used is not particularly limited as long as the effect of the present invention is not impaired, but is in the range of 1 to 50 parts by weight in 100 parts by weight of the epoxy resin composition. It is preferable.

  When the epoxy resin composition of the present invention is used for applications requiring higher flame retardancy than for printed wiring boards, a non-halogen flame retardant containing substantially no halogen atoms may be blended.

  Examples of the non-halogen flame retardant include a phosphorus flame retardant, a nitrogen flame retardant, a silicone flame retardant, an inorganic flame retardant, an organic metal salt flame retardant, and the like. It is not intended to be used alone, and a plurality of the same type of flame retardants may be used, or different types of flame retardants 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-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7- Examples thereof include cyclic organic phosphorus compounds such as dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

  For example, in the case where red phosphorus is used in 100 parts by mass of the epoxy resin composition, the amount of these phosphorus-based flame retardants is preferably 0.1 to 2.0 parts by mass. When using, it is preferable to mix | blend in the range of 0.1-10.0 mass part, and it is more preferable to mix | blend in the range of 0.5-6.0 mass part.

  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, and 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, sulfuric acid such as guanylmelamine sulfate, melem sulfate, and melam sulfate. Examples thereof include aminotriazine compounds, aminotriazine-modified phenol resins, and aminotriazine-modified phenol resins that are further modified with tung oil, isomerized linseed oil, and the like.

  Examples of the cyanuric acid compound include cyanuric acid and cyanuric acid melamine.

  The blending amount of the nitrogen-based flame retardant is preferably blended in the range of 0.05 to 10 parts by weight, for example, in the range of 0.1 to 5 parts by weight in 100 parts by weight of the epoxy resin composition. Is more preferable.

  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.

  It is preferable to mix | blend the compounding quantity of the said silicone type flame retardant in the range of 0.05-20 mass parts in 100 mass parts of epoxy resin compositions, for example. 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.

  Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and zirconium hydroxide.

  Examples of the metal oxide include zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, Examples thereof include chromium oxide, nickel oxide, copper oxide, and tungsten oxide.

  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.

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

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

Examples of the low-melting-point glass include Sheepley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, and P ₂ O. Glass forms such as _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. A compound can be mentioned.

  The blending amount of the inorganic flame retardant is, for example, preferably in the range of 0.05 to 20 parts by mass and in the range of 0.5 to 15 parts by mass in 100 parts by mass of the epoxy resin composition. Is more preferable.

  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. And the like.

  It is preferable to mix | blend the compounding quantity of the said organometallic salt type flame retardant in the range of 0.005-10 mass parts in 100 mass parts of epoxy resin compositions, for example.

  The epoxy resin composition of this invention can mix | blend an inorganic filler as needed. 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 20% by mass or more with respect to the total amount of the thermosetting resin composition. Moreover, when using for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can be used.

  In addition to the above, the epoxy resin composition of the present invention may contain various compounding agents such as a silane coupling agent, a release agent, a pigment, and an emulsifier, if necessary.

  The epoxy resin composition of the present invention is obtained by uniformly mixing the above-described components, and can be easily made into a cured product by a method similar to the curing of conventionally known epoxy resin compositions. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

  Since the epoxy resin composition of the present invention has a low dielectric constant and dielectric loss tangent of the cured product, circuit boards such as hard printed wiring board materials, resin compositions for flexible wiring boards, interlayer insulation materials for build-up boards, etc. It can be suitably used for various electronic materials such as insulating materials for semiconductors, semiconductor sealing materials, conductive pastes, build-up adhesive films, resin casting materials, adhesives and the like. Above all, taking advantage of both the high solubility in various solvents and the dielectric properties of the modified polyarylene ether resin of the present invention, rigid printed wiring board materials, resin compositions for flexible wiring boards, and interlayers for build-up boards It can be particularly preferably used for circuit board materials such as insulating materials.

  Of these, when applied to circuit board applications, a varnish obtained by diluting the epoxy resin composition of the present invention in an organic solvent is obtained, and this is formed into a plate shape, laminated with copper foil, and heated and pressed. Can be manufactured. In addition, when applying to hard printed circuit board applications, a prepreg is obtained by impregnating a reinforcing base material with a varnish-like epoxy resin composition containing an organic solvent and semi-curing it, and copper foil is laminated on it and heated. It can be manufactured by a method of pressure bonding. Examples of the reinforcing substrate that can be used here include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. More specifically, the varnish-like epoxy resin composition described above is first heated at a heating temperature corresponding to the solvent type used, preferably 50 to 170 ° C. to obtain a prepreg that is a cured product. . Under the present circumstances, although the mass ratio of the thermosetting resin composition to be used and a reinforcement base material is not specifically limited, Usually, it is preferable to prepare so that the resin content in a prepreg may be 20-60 mass%. Next, the prepreg obtained as described above is laminated by a conventional method, and a copper foil is appropriately stacked, and then subjected to thermocompression bonding at a pressure of 1 to 10 MPa at 170 to 250 ° C. for 10 minutes to 3 hours, A target circuit board can be obtained.

  In order to produce a flexible wiring board from the epoxy resin composition of the present invention, an epoxy resin composition containing an organic solvent is applied to an electrically insulating film using a coating machine such as a reverse roll coater or a comma coater. Subsequently, it heats for 1 to 15 minutes at 60-170 degreeC using a heater, volatilizes a solvent, and makes an epoxy resin composition B-stage. Next, the metal foil is thermocompression bonded to the resin composition layer using a heating roll or the like. At that time, the pressure is preferably 2 to 200 N / cm and the pressure is preferably 40 to 200 ° C. If sufficient adhesive performance can be obtained, the process may be completed here. However, when complete curing is required, it is preferably post-cured at 100 to 200 ° C. for 1 to 24 hours. The thickness of the resin composition layer after finally curing is preferably in the range of 5 to 100 μm.

  In order to produce an interlayer insulating material for a build-up board from the epoxy resin composition of the present invention, for example, an epoxy resin composition appropriately blended with rubber, filler, etc. After applying using a method or the like, it is 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. Also, a copper foil with resin obtained by semi-curing the resin composition on the copper foil is heat-pressed at 170 to 250 ° C. on a wiring board on which a circuit is formed, thereby forming a roughened surface and a plating process. It is also possible to produce a build-up board without the above.

  The method for producing an adhesive film for buildup from the epoxy resin composition of the present invention is, for example, an adhesive for multilayer printed wiring boards by applying the epoxy resin composition of the present invention on a support film to form a resin composition layer. The method of using a film is mentioned.

  When the epoxy resin composition of the present invention is used for a build-up adhesive film, the adhesive film is softened under the lamination temperature condition (usually 70 ° C. to 140 ° C.) in the vacuum laminating method, and at the same time as laminating the circuit board, It is important to show fluidity (resin flow) capable of filling the via hole or through hole in the substrate, and it is preferable to blend the above-described components so as to exhibit such characteristics.

  Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. It is usually preferable to allow resin filling in this range. When laminating both surfaces of the circuit board, it is desirable to fill about 1/2 of the through hole.

  Specifically, the method for producing the adhesive film described above is, after preparing the varnish-like epoxy resin composition of the present invention, coating the varnish-like composition on the surface of the support film and further heating, or It can manufacture by drying an organic solvent by hot air spraying etc. and forming the layer ((alpha)) of an epoxy resin composition.

  The thickness of the formed layer (α) is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

  In addition, the said layer ((alpha)) may be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches.

  The above-mentioned support film and protective film are made of polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples thereof include metal foil such as pattern paper, copper foil, and aluminum foil. In addition, the support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.

  Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in 25-50 micrometers. Moreover, it is preferable that the thickness of a protective film shall be 1-40 micrometers.

  The above support film is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film is peeled after the adhesive film is heat-cured, adhesion of dust and the like in the curing process can be prevented. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.

  Next, the method for producing a multilayer printed wiring board using the adhesive film obtained as described above is, for example, when the layer (α) is protected with a protective film, Lamination is performed on one or both sides of the circuit board by, for example, vacuum laminating so that α) is in direct contact with the circuit board. The laminating method may be a batch method or a continuous method using a roll. Further, the adhesive film and the circuit board may be heated (preheated) as necessary before lamination.

The laminating conditions are preferably a pressure bonding temperature (laminating temperature) of 70 to 140 ° C., a pressure bonding pressure of preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m 2), Lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.

  When the epoxy resin composition of the present invention is used as a conductive paste, for example, a method in which fine conductive particles are dispersed in an epoxy resin composition to form a composition for an anisotropic conductive film, a circuit that is liquid at room temperature Examples thereof include a paste resin composition for connection and an anisotropic conductive adhesive.

  The epoxy resin composition of the present invention can also be 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 are blended in the epoxy resin composition, and further a pigment, talc, and filler are added to obtain a resist ink composition. Then, after apply | coating on a printed circuit board by a screen printing system, the method of setting it as a resist ink hardened | cured material is mentioned.

  As described above, the modified polyarylene ether resin of the present invention has higher solvent solubility and superior dielectric properties and heat resistance compared to conventional polyarylene ether resins. In addition to contributing to the realization, it can be easily varnished when applied to various electronic material applications. Therefore, it has been replaced with organic solvents with high environmental impact such as toluene, which has been the mainstream in the past. Alcohol solvents and ester solvents can be used.

  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. The softening point and GPC were measured under the following conditions.

Softening point measurement method: compliant with JIS K7234.

GPC: Measured under the following conditions.
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.

(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

Production Example 1 Production of aralkyl-modified biphenol compound (c1) 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol 300 was added to a flask equipped with a thermometer, a condenser tube, a fractionating tube, and a stirrer. 0.08 g (1.24 mol) and 267.8 g (2.48 mol) of benzyl alcohol were charged, the inside of the system was purged with nitrogen, the nitrogen was slowly flowed, the temperature was raised to 120 ° C. with stirring, and then 15 minutes. Stir. Next, 5.53 g of paratoluenesulfonic acid was charged, and the temperature was raised to 150 ° C. while distilling off the generated water to the outside of the system, followed by stirring for 5 hours. Next, the mixture was cooled to 120 ° C., added with 2.5 g of a 49% aqueous sodium hydroxide solution, cooled to 80 ° C. with stirring, added with 1135 g of methyl isobutyl ketone and 284 g of water, stirred at 80 ° C. for 5 minutes, and then allowed to stand for 10 minutes. And the aqueous layer was separated. After confirming that the aqueous layer was almost neutral, 284 g of water was further added, followed by liquid separation in the same manner. Thereafter, water was removed by decanter dehydration, and subsequently MIBK was removed under reduced pressure to obtain 479 g of a brown solid aralkyl-modified biphenol compound (c1). The resulting aralkyl-modified biphenol compound (c1) had a hydroxyl group equivalent of 216 g / equivalent. A GPC chart of the aralkyl-modified biphenol compound (c1) is shown in FIG.

Production Example 2 Production of Epoxy Compound (B1) 203.0 g (0.47 mol) of biphenol compound (A) obtained in Production Example 1 and epichlorohydrin were placed in a flask equipped with a thermometer, a condenser tube, a fractionating tube, and a stirrer. 105.2 g (3.76 mol) and 60.0 g of butanol were charged, the inside of the system was purged with nitrogen, nitrogen was slowly flowed, and 18.8 g (0.094 mol) of 20% NaOH aqueous solution was charged, and the temperature was raised to 40 ° C. After warming, the mixture was stirred for 2 hours. Then, it heated up to 60 degreeC and stirred for 30 minutes. Next, 188.0 g (0.94 mol) of a 20% NaOH aqueous solution was charged with stirring at 60 ° C. over 30 minutes, and then stirred for 90 minutes. Next, 57.4 g of water was added, and the mixture was stirred at 60 ° C. for 5 minutes and then allowed to stand for 10 minutes to separate the aqueous layer. Next, excess epichlorohydrin was distilled off under reduced pressure, and 430.1 g of methyl isobutyl ketone and 10.3 g of 5% NaOH aqueous solution were charged with stirring at 80 ° C. and stirred for 1 hour. Subsequently, 126.5g of 1% NaOH aqueous solution was prepared, and it stirred at 80 degreeC for 1 hour, Then, it left still for 10 minutes, and the water layer was liquid-separated. Next, the oil layer was washed 3 times with 126.5 g of water. Water was removed by decanter dehydration, and filtered while hot at 120 ° C., and the solvent was distilled off under reduced pressure to obtain 205.3 g of a brown solid epoxy compound (B1). The epoxy equivalent of the obtained epoxy compound (B1) was 290 g / equivalent. A GPC chart of the epoxy compound (B1) is shown in FIG.

Example 1 Production of Modified Polyarylene Ether Resin (1) 78.4 g of epoxy compound (B1) obtained in Production Example 2 (epoxy group content 0.27 mol) in a flask equipped with a thermometer, condenser and stirrer ), Polyphenylene ether resin [“MX-90” manufactured by SABIC, having a hydroxyl group equivalent of 880 g / equivalent, and a molecular structure represented by the following structural formula (1). ] 121.3 g (hydroxyl group content 0.14 mol) and cyclohexanone 200.0 g were charged, the inside of the system was purged with nitrogen, nitrogen was slowly flowed, the temperature was raised to 100 ° C. with stirring, and 2-ethyl-4- 80 mg of methylimidazole was added, and the temperature was raised to 150 ° C. and reacted for 10 hours. After cooling to 80 ° C., 41.5 g of methyl ethyl ketone was added and stirred for 30 minutes to obtain a modified polyarylene ether resin (1) solution. The epoxy equivalent of the resin solid content of the resulting modified polyarylene ether resin (1) solution was 1,778 g / equivalent. A GPC chart of the modified polyarylene ether resin (1) is shown in FIG.

Evaluation of Solvent Solubility Modified polyarylene ether resin (1) obtained in Example 1 and polyphenylene ether resin (“MX-90” manufactured by SABIC: hydroxyl group equivalent 880 g / equivalent, represented by the above structural formula (1) as a comparative sample. And dried at 150 ° C. under vacuum under reduced pressure for 12 hours to obtain a dried solid resin. This solid resin was subjected to toluene, methyl ethyl ketone (hereinafter abbreviated as “MEK”), methyl isobutyl ketone (hereinafter abbreviated as “MIBK”), N, N′-dimethylformamide (hereinafter “DMF”) at 25 ° C. ), Cyclohexanone, 1-methoxy-2-propanol (hereinafter abbreviated as “MP”), propylene glycol monomethyl ether acetate (hereinafter abbreviated as “PGMAC”), N-methylpyrrolidone (hereinafter “NMP”). ”, Normal butanol (hereinafter abbreviated as“ BuOH ”), and ethyl acetate, and the amount (g) of solid content dissolved in 100 g of each solvent was evaluated. The results are shown in Table 1.

Example 2 and Comparative Examples 1 and 2
An epoxy resin composition and a laminate were prepared in the following manner, and the laminate was evaluated for heat resistance, copper foil peel strength, delamination strength, and dielectric properties by the following methods. The results are shown in Table 2.

<Preparation of epoxy resin composition and evaluation of physical properties>
Cresol novolak type epoxy resin (“EPICLON N-680-75M” epoxy group equivalent 214 g / equivalent) manufactured by DIC Corporation as an epoxy resin and phenol novolak resin (“PHENOLITE TD-2090-60M” hydroxyl group manufactured by DIC Corporation) as a curing agent Equivalent to 105 g / equivalent) as the polyarylene ether resin, the modified polyarylene ether resin (1) or the polyarylene ether resin before modification [“MX-90” hydroxyl group equivalent of 880 g / equivalent, SABIC, structural formula (1) It has a molecular structure represented by Were blended in the proportions shown in Table 2 below using 2-ethyl-4-methylimidazole as a curing catalyst. Furthermore, it adjusted so that the non volatile matter (NV) of each composition might be 58 mass% using methyl ethyl ketone, and the epoxy resin composition was obtained.

<Production of laminated plate>
Using the epoxy resin composition obtained above, a laminate was prepared under the following conditions.
Base material: Glass cloth “# 2116” (210 × 280 mm) manufactured by Nitto Boseki Co., Ltd.
Number of plies: 6 Condition of prepreg: 160 ° C
Curing conditions: 200 ° C., 40 kg / cm ² for 1.5 hours, post-molding plate thickness: 0.8 mm

<Evaluation of heat resistance>
The laminated board obtained above is etched and the copper foil is removed, and then a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device RSAII manufactured by Rheometric, rectangular tension method; frequency 1 Hz, heating rate 3 ° C./min) Was used to measure the viscoelasticity, and the temperature at which the change in elastic modulus was maximum (the largest change in tan δ) was evaluated as the glass transition temperature.

<Measurement of copper foil peel strength>
The peel strength of the copper foil was measured in accordance with JIS-K6481 for the laminate obtained above.

<Measurement of delamination strength>
The laminate obtained above was measured for delamination strength according to JIS-K6481.

<Measurement of dielectric constant and dissipation factor>
After the laminated board obtained in advance is stored in an indoor room at 23 ° C. and a humidity of 50% for 24 hours using an impedance material analyzer “HP4291B” manufactured by Agilent Technologies, in accordance with JIS-C-6481. The dielectric constant and dielectric loss tangent at 1 GHz or 10 GHz were measured.

Claims (9)

The polyarylene ether structure is the main skeleton, and at least one of the molecular ends has the following structural formula (i)

(In the formula, each R ¹ is independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R ² is independently a hydrogen atom or 1 carbon atom. Or an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and Ar is independently a phenylene group, a naphthylene group, or an alkyl group having 1 to 6 carbon atoms on the aromatic nucleus. Or any one of structural parts having 1 to a plurality of alkoxy groups having 1 to 6 carbon atoms, m is each independently 1 or 2, n is each independently an integer of 0 to 2, And at least one of two n is 1 or 2.)
A modified polyarylene ether resin characterized by having a structural moiety (i) represented by: The following general formula (I)

[In the general formula (I), (i) is a structural moiety represented by the structural formula (i), and (iii) is the following structural formula (iii)

{Wherein R ³ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group, and p and q are each independently It is an integer of 0 or more, and the sum of p and q is 4 or more. In the formula, Y represents the following structural formulas (y-1) to (y-9).

(In the formula, each R ⁴ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group, and each R ⁵ is independently (It is any one of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a phenyl group, and k is an integer of 0 to 4).
It is a structural part represented by either. }
Wherein (iv) is the following structural formula (iv)

(In the formula, each R ¹ is independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R ² is independently a hydrogen atom or 1 carbon atom. Or an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and Ar is independently a phenylene group, a naphthylene group, or an alkyl group having 1 to 6 carbon atoms on the aromatic nucleus. Or any one of structural parts having 1 to a plurality of alkoxy groups having 1 to 6 carbon atoms, m is each independently 1 or 2, n is each independently an integer of 0 to 2, And at least one of two n is 1 or 2.)
X is a hydrogen atom or a structural moiety represented by the structural formula (i), and r is an integer of 0-2. ]
The modified polyarylene ether resin according to claim 1, which has a molecular structure represented by: A polyarylene ether resin (A) having a polyarylene ether structure in the molecular structure and a hydroxyl group equivalent of 500 to 1,500 g / equivalent, and the following structural formula (III)

(In the formula, each R ¹ is independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R ² is independently a hydrogen atom or 1 carbon atom. Or an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and Ar is independently a phenylene group, a naphthylene group, or an alkyl group having 1 to 6 carbon atoms on the aromatic nucleus. Or any one of structural parts having one or more alkoxy groups having 1 to 6 carbon atoms, G represents a glycidyl group, m is each independently 1 or 2, and n is each independently 0 And an integer of ˜2, and at least one of the two n is 1 or 2.)
The epoxy compound (B) represented by the formula (B) is a ratio in which the epoxy group of the epoxy compound (B) is in the range of 0.5 to 4 mol with respect to 1 mol of the hydroxyl group of the polyarylene ether resin (A). A process for producing a modified polyarylene ether resin, characterized by reacting both. The polyarylene ether resin (A) is represented by the following structural formula (IV)

[Wherein R ² is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group, and p and q are each independently It is an integer of 0 or more, and the sum of p and q is 4 or more. In the formula, Y represents the following structural formulas (y-1) to (y-9).

(In the formula, each R ⁴ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group, and each R ⁵ is independently (It is any one of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a phenyl group, and k is an integer of 0 to 4).
It is a structural part represented by either. ]
The method for producing a modified polyarylene ether resin according to claim 3, which has a molecular structure represented by: According to claim 1 or 2 modified polyarylene ether resins, epoxy resins, and curing agent of the epoxy resin composition as an essential component. A cured product of the epoxy resin composition according to claim 5 . A prepreg that is semi-cured of an impregnated substrate having the epoxy resin composition according to claim 5 and a reinforcing substrate . A circuit board comprising a plate-shaped shaped product of the epoxy resin composition according to claim 5 and a copper foil . A build-up film comprising a cured product of the epoxy resin composition according to claim 5 and a base film.

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