JP5380763B2 - Epoxy resin composition, cured product thereof, semiconductor encapsulating material, novel phenol resin, novel epoxy resin, novel phenol resin production method, and novel epoxy resin production method - Google Patents

Description

  The present invention is excellent in heat resistance and dielectric properties of the obtained cured product, curability at the time of curing reaction, epoxy resin composition that can be suitably used for semiconductor encapsulant, printed circuit board, paint, casting application, The present invention relates to a cured product, a novel phenol resin and a production method thereof, and a novel epoxy resin and a production method thereof.

  Epoxy resin compositions containing an epoxy resin and its curing agent as essential components have excellent physical properties such as high heat resistance, physical properties, and low viscosity, and are used for electronic components such as semiconductor sealing materials and printed circuit boards, and electronic component fields. It is widely used in conductive adhesives such as conductive pastes, other adhesives, matrix for composite materials, paints, photoresist materials, developer materials, and the like.

  In recent years, in these various applications, particularly in advanced material applications, further improvements in performance typified by high heat resistance and high humidity resistance have been demanded. For example, in the field of semiconductor encapsulating materials, the transition to surface mount packages such as BGA and CSP, as well as support for lead-free solder, led to higher reflow processing temperatures, thus increasing moisture resistance and solder resistance. There is a demand for an electronic component encapsulating resin material that is excellent in performance.

As an electronic component sealing material that meets such required characteristics, for example, a methoxy group-containing phenol resin obtained by methoxylation of a phenolic hydroxyl group in a resole resin and then converting the methoxylation resole resin into a novolak resin under an acid catalyst Is known for improving fluidity and imparting appropriate flexibility to the cured product, and improving the moisture resistance and impact resistance of the cured product itself. (For example, refer to Patent Document 1).
However, such a curing agent for epoxy resins has a low number of functional groups per molecule and is inferior in reactivity during the curing reaction.

  In recent years, in the field of electronic components, it has been urgently necessary to cope with the high frequency of high frequency devices. For this reason, materials related to electronic components such as semiconductor encapsulating materials have low dielectric constants, and the dielectric loss tangent has also been increased so far. A low material is required. In general, the cause of high dielectric constant and dielectric loss tangent in cured epoxy resin is the secondary hydroxyl group that appears during the curing reaction. Therefore, it is advantageous for the dielectric properties to have a lower functional group concentration as a crosslinking point. become. In this regard, although the epoxy resin curing agent has a reduced hydroxyl group concentration, it has not yet achieved the low dielectric constant and low dielectric loss tangent levels required in recent years.

  On the other hand, as an epoxy resin exhibiting excellent heat resistance, for example, as an epoxy resin used in a composite matrix, a reaction intermediate is obtained by reacting an aromatic compound such as anthracene with an excess of a crosslinking agent such as p-xylene glycol. There is known a technique of producing a phenol resin in which an aralkyl structure and an aromatic compound are alternately positioned by reacting with a phenol compound and epoxidizing it with epichlorohydrin. (For example, refer to Patent Document 2).

  Such an epoxy resin has a high content of the aromatic structure portion in the polymer structure and certainly exhibits excellent heat resistance. However, when this epoxy resin is used as an electronic component sealing material, it cannot realize the required levels of low dielectric constant and low dielectric loss tangent. Therefore, for example, if it is intended to reduce the dielectric constant and dielectric loss tangent in the epoxy resin, it may be possible to further reduce the functional group concentration by further introducing an aromatic structure into the polymer chain of the epoxy resin. Then, a marked decrease in curability is unavoidable due to an extremely low functional group concentration.

  As described above, in the field of electronic component-related materials, an epoxy resin composition having a dielectric property that can cope with a recent increase in frequency without causing a curing obstacle has not been obtained.

JP 2004-10700 A JP-A-8-301980

  Therefore, the problem to be solved by the present invention is an epoxy resin composition that realizes a low dielectric constant and a low dielectric loss tangent suitable for recent high-frequency type electronic component-related materials without reducing the curability during the curing reaction, and An object of the present invention is to provide a cured product, a novel phenol resin and a novel epoxy resin that can provide these performances, and a method for producing them.

  As a result of intensive studies to solve the above problems, the present inventors have determined that an aralkyl structural unit and an alkoxy group-substituted aromatic structural unit have a predetermined bond in the molecular skeleton of an epoxy resin or a phenol resin. By introducing it so as to form it, the inventors have found that it exhibits extremely low dielectric constant and dielectric loss tangent even though it exhibits good curability, and has completed the present invention.

That is, the present invention is an epoxy resin composition comprising an epoxy resin and a curing agent as essential components, and the curing agent is
Phenolic hydroxyl group-containing aromatic hydrocarbon group (P),
Each of the structural parts of the alkoxy group-containing aromatic hydrocarbon group (B) and the divalent aralkyl group (X) in the molecular structure; and
A structure in which the phenolic hydroxyl group-containing aromatic hydrocarbon group (P) and the alkoxy group-containing aromatic hydrocarbon group (B) are bonded via the divalent aralkyl group (X),
A structure in which the phenolic hydroxyl group-containing aromatic hydrocarbon group (P) is bonded to the other phenolic hydroxyl group-containing aromatic hydrocarbon group (P) via the divalent aralkyl group (X);
Or
A phenol having a structure in which the alkoxy group-containing aromatic hydrocarbon group (B) is bonded to the other alkoxy group-containing aromatic hydrocarbon group (B) via the divalent aralkyl group (X) in the molecular structure The present invention relates to an epoxy resin composition characterized by being a resin (hereinafter, this epoxy resin composition is abbreviated as “epoxy resin composition (I)”).

  Furthermore, the present invention relates to a cured epoxy resin obtained by curing the epoxy resin composition (I).

Furthermore, this invention has each structure of a phenolic hydroxyl group containing aromatic hydrocarbon group (P), an alkoxy group-containing aromatic hydrocarbon group (B), and a bivalent aralkyl group (X) in the molecular structure. And
A structure in which the phenolic hydroxyl group-containing aromatic hydrocarbon group (P) and the alkoxy group-containing aromatic hydrocarbon group (B) are bonded via the divalent aralkyl group (X),
A structure in which the phenolic hydroxyl group-containing aromatic hydrocarbon group (P) is bonded to the other phenolic hydroxyl group-containing aromatic hydrocarbon group (P) via the divalent aralkyl group (X);
Or
In the molecular structure, the alkoxy group-containing aromatic hydrocarbon group (B) is bonded to the other alkoxy group-containing aromatic hydrocarbon group (B) through the divalent aralkyl group (X). In addition, the present invention relates to a novel phenol resin having a melt viscosity of 0.3 to 5.0 dPa · s at 150 ° C. and a hydroxyl group equivalent of 150 to 500 g / eq measured with an ICI viscometer.

Furthermore, the present invention is an epoxy resin composition comprising an epoxy resin and a curing agent as essential components, wherein the epoxy resin is
Glycidyloxy group-containing aromatic hydrocarbon group (E),
A divalent aromatic hydrocarbon group (B) containing an alkoxy group, and a divalent aralkyl group (X)
In the molecular structure, and
A structure in which the glycidyloxy group-containing aromatic hydrocarbon group (E) and the alkoxy group-containing aromatic hydrocarbon group (B) are bonded via the divalent aralkyl group (X),
A structure in which the glycidyloxy group-containing aromatic hydrocarbon group (E) is bonded to another glycidyloxy group-containing aromatic hydrocarbon group (E) via the divalent aralkyl group (X);
Or
In the molecular structure, the alkoxy group-containing aromatic hydrocarbon group (B) is bonded to the other alkoxy group-containing aromatic hydrocarbon group (B) via the divalent aralkyl group (X). (Hereinafter, this epoxy resin composition is abbreviated as “epoxy resin composition (II)”).

Furthermore, the present invention has each structure of a glycidyloxy group-containing aromatic hydrocarbon group (E), an alkoxy group-containing aromatic hydrocarbon group (B), and a divalent aralkyl group (X) in the molecular structure. And
A structure in which the glycidyloxy group-containing aromatic hydrocarbon group (E) and the alkoxy group-containing aromatic hydrocarbon group (B) are bonded via the divalent aralkyl group (X),
A structure in which the glycidyloxy group-containing aromatic hydrocarbon group (E) is bonded to another glycidyloxy group-containing aromatic hydrocarbon group (E) via the divalent aralkyl group (X);
Or
In the molecular structure, the alkoxy group-containing aromatic hydrocarbon group (B) is bonded to the other alkoxy group-containing aromatic hydrocarbon group (B) through the divalent aralkyl group (X). In addition, the present invention relates to a novel epoxy resin having a melt viscosity at 150 ° C. of 0.3 to 5.0 dPa · s and an epoxy equivalent of 200 to 700 g / eq measured with an ICI viscometer.

  Furthermore, this invention is the said epoxy resin composition (I) or (II), Comprising: In addition to the said epoxy resin and the said hardening | curing agent, it further contains an inorganic filler in the ratio of 70-95 mass% in a composition. The present invention relates to a semiconductor sealing material comprising the epoxy resin composition (I) or (II).

  Furthermore, the present invention relates to a hydroxy group-containing aromatic compound (a1), an alkoxy group-containing aromatic compound (a2), the following structural formula (a3-a), (a3-b) or (a3-c).

（上記式（ａ３−ｂ）中、Ｒ_２は水素原子、又は炭素原子数１〜６の炭化水素基である。）で表される化合物（ａ３）とを、一段階で反応させることを特徴とする、新規フェノール樹脂の製造方法。

(In the above formula (a3-b), R ₂ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.) The compound (a3) represented by the above is reacted in one step. And a method for producing a novel phenol resin.

  Furthermore, this invention relates to the manufacturing method of the novel epoxy resin characterized by making epichlorohydrin react with the novel phenol resin obtained by the said manufacturing method.

  ADVANTAGE OF THE INVENTION According to this invention, it is excellent in the sclerosis | hardenability at the time of hardening reaction, and the epoxy resin composition and its hardened | cured material which implement | achieve the low dielectric constant and low dielectric loss tangent suitable for a recent high frequency type electronic component related material, and these performance A novel epoxy resin, a novel phenol resin, and a production method capable of industrially producing these by a simple method can be provided.

Hereinafter, the present invention will be described in detail.
The epoxy resin composition (I) of the present invention is an epoxy resin composition having an epoxy resin and a curing agent as essential components, and the curing agent is
Phenolic hydroxyl group-containing aromatic hydrocarbon group (P),
Alkoxy group-containing aromatic hydrocarbon group (B) and divalent aralkyl group (X)
Each structural site in the molecular structure, and
A structure in which the phenolic hydroxyl group-containing aromatic hydrocarbon group (P) and the alkoxy group-containing aromatic hydrocarbon group (B) are bonded via the divalent aralkyl group (X),
A structure in which the phenolic hydroxyl group-containing aromatic hydrocarbon group (P) is bonded to the other phenolic hydroxyl group-containing aromatic hydrocarbon group (P) via the divalent aralkyl group (X);
Or
A phenol having a structure in which the alkoxy group-containing aromatic hydrocarbon group (B) is bonded to the other alkoxy group-containing aromatic hydrocarbon group (B) via the divalent aralkyl group (X) in the molecular structure It is characterized by being a resin.

  That is, the phenol resin contains structural units of a phenolic hydroxyl group-containing aromatic hydrocarbon group (P), an alkoxy group-containing aromatic hydrocarbon group (B), and a divalent aralkyl group (X). ”,“ B ”,“ X ”, the following structural sites A1 to A3

の何れかの構造部位を必須として分子構造内に含むものである。

These structural sites are essential and included in the molecular structure.

  In this invention, since the said phenol resin has such a characteristic chemical structure, the aromatic content rate in molecular structure becomes high, and the outstanding heat resistance is expressed. Further, in addition to being able to moderately reduce the hydroxyl group concentration, by introducing an alkoxy group into the molecular structure, the dielectric constant and dielectric loss tangent can be reduced without extremely reducing the hydroxyl group concentration. Therefore, when the phenol resin is used as a curing agent for epoxy resin, the curability does not decrease. It is also worth mentioning that excellent dielectric properties are exhibited while introducing a relatively polar functional group called an alkoxy group.

Here, the molecular structure of the phenol resin may take various structures depending on the valence of the “P” and “B”. For example, 1) The following structural formula A4

で表される構造を繰り返し単位とする直鎖型交互共重合体、或いは、
２） 下記構造式Ａ５〜Ａ７

A linear alternating copolymer having a structure represented by the repeating unit, or
2) The following structural formulas A5 to A7

を繰り返し単位とする、分岐状交互共重合体、
３）前記構造部位Ａ１〜Ａ３の全てを含む直鎖又は分岐状のランダム重合体、
４）構造単位Ｐと構造単位Ｘとが交互に結合した重合体ブロックと、複数の該重合体ブロック中の構造単位Ｐが構造単位Ｘを介して構造単位Ｂと結節した構造の重合体、
５）構造単位Ｐと構造単位Ｘとが交互に結合した重合体ブロックと、構造単位Ｂと構造単位Ｘとが交互に結合した重合体ブロックとを有する重合体、
６）構造単位Ｐと構造単位Ｘとが交互に結合した重合体の末端に構造単位Ｂが結合した重合体、及び
７）構造単位Ｂと構造単位Ｘとが交互に結合した重合体の両末端に構造単位Ｐが結合した重合体
以上の１）〜７）の構造が挙げられる。

A branched alternating copolymer having a repeating unit,
3) A linear or branched random polymer containing all of the structural sites A1 to A3,
4) a polymer block in which the structural unit P and the structural unit X are alternately bonded, and a polymer having a structure in which the structural unit P in the plurality of polymer blocks is connected to the structural unit B via the structural unit X.
5) a polymer having a polymer block in which the structural unit P and the structural unit X are alternately bonded, and a polymer block in which the structural unit B and the structural unit X are alternately bonded;
6) Polymer in which structural unit B is bonded to the end of the polymer in which structural unit P and structural unit X are alternately bonded, and 7) Both ends of the polymer in which structural unit B and structural unit X are alternately bonded The polymer of which the structural unit P couple | bonded with is the structure of the above 1) -7).

  Among such structures, in view of the heat resistance and dielectric properties described above, the phenol resin preferably has an A1 structure as an essential structure and an A2 and A3 as an essential structure. In particular, those having the structure of A1 as an essential structure are particularly preferable.

  Next, the phenolic hydroxyl group-containing aromatic hydrocarbon group (P) can have various structures, specifically, phenol, naphthol represented by the following structural formulas of P1 to P16, and An aromatic hydrocarbon group formed from a compound having an alkyl group as a substituent on these aromatic nuclei is preferable from the viewpoint of excellent dielectric performance.

ここで、前記各構造は、該構造が分子末端に位置する場合には、１価の芳香族炭化水素基となる。また、上掲した構造のうちナフタレン骨格上に他の構造部位との結合位置を二つ以上有するものは、それらの結合位置は同一核上であってもよいし、或いは、それぞれ異核上にあってもよい。

Here, each structure becomes a monovalent aromatic hydrocarbon group when the structure is located at the molecular end. In addition, among the structures listed above, those having two or more bonding positions with other structural sites on the naphthalene skeleton may be on the same nucleus or on different nuclei. There may be.

  Among the phenolic hydroxyl group-containing aromatic hydrocarbon groups (P) described in detail above, in particular, the epoxy resin cured product itself can be imparted with excellent flame retardancy, and in recent years, a halogen-free material that is highly demanded in the field of electronic components. In view of the possibility of design, it is formed from a molecular structure selected from phenol, naphthol, and compounds having a methyl group as a substituent on the aromatic nucleus, represented by the structural formulas P1 to P15. A valent or trivalent aromatic hydrocarbon group is preferred.

  In this invention, when it has the structure represented by following Structural formula (2) or (3), it is preferable from the point which can provide the flame retardance excellent in epoxy resin hardened | cured material itself.

ここで、式（２）及び（３）中、Ｒ_３は水素原子又はメチル基、ｏは１〜３の整数を表す。
該構造式（２）で表される具体的構造としては、前記構造式Ｐ１、Ｐ６〜Ｐ９で表されるものが挙げられる。また、該構造式（３）で表される具体的構造としては、構造式Ｐ１０及びＰ１１で表されるものが挙げられる。

Here, in formulas (2) and (3), R ₃ represents a hydrogen atom or a methyl group, and o represents an integer of 1 to 3.
Specific examples of the structure represented by the structural formula (2) include those represented by the structural formulas P1 and P6 to P9. Specific examples of the structure represented by the structural formula (3) include those represented by the structural formulas P10 and P11.

  Next, the alkoxy group-containing aromatic hydrocarbon group (B) contained in the phenol resin structure is a monovalent or polyvalent aromatic hydrocarbon group having an alkoxy group as a substituent on the aromatic nucleus. Specifically, an alkoxybenzene type structure represented by the following structural formulas B1 to B18 and an alkoxyquinephthalene type structure represented by B19 to B33 can be given.

ここで、前記各構造は、該構造が分子末端に位置する場合には、１価の芳香族炭化水素基となる。また、上掲した構造のうちナフタレン骨格上に他の構造部位との結合位置を二つ以上有するものは、それらの結合位置は同一核上であってもよいし、或いは、それぞれ異核上にあってもよい。

Here, each structure becomes a monovalent aromatic hydrocarbon group when the structure is located at the molecular end. In addition, among the structures listed above, those having two or more bonding positions with other structural sites on the naphthalene skeleton may be on the same nucleus or on different nuclei. There may be.

  Among the alkoxy group-containing aromatic hydrocarbon groups (B) described in detail above, in particular, the epoxy resin cured product itself can be imparted with excellent flame retardancy, and in recent years, a halogen-free material that is highly demanded in the field of electronic components. From the point that design is possible, methoxybenzene, methoxynaphthalene, ethoxybenzene, ethoxynaphthalene, and substituents on these aromatic nuclei represented by the structural formulas B1 to B14 and the structural formulas B19 to B31. It is preferably a monovalent or polyvalent aromatic hydrocarbon group formed from a molecular structure selected from a compound having a methyl group, and particularly preferably a divalent or trivalent aromatic hydrocarbon group. And from the viewpoint of dielectric properties.

  Further, among them, the epoxy resin cured product is a divalent or trivalent aromatic hydrocarbon group formed from a molecular structure selected from a compound having a methyl group with a methoxy group as a substituent on the aromatic nucleus. It is preferable from the point that the effect of imparting flame retardancy to is remarkable, and a structure represented by the following general formula (4) is particularly preferable from the point that the fluidity of the composition is good.

ここで、上記構造式（４）中、Ｒ_４は、水素原子又はメチル基、Ｐｈは、ベンゼン環又はナフタレン環を表し、ｎは１又は２の整数、ｍは１〜３の整数である。かかる構造式（４）で示される構造の具体例としては、前記構造式Ｂ１、Ｂ３、Ｂ５、Ｂ８、Ｂ９、Ｂ１０、Ｂ１１、Ｂ１２、Ｂ１３、Ｂ１９、Ｂ２０、Ｂ２１、Ｂ２３、Ｂ２４、Ｂ２５、Ｂ２６、Ｂ２７、及びＢ３１で表される構造が挙げられる。更に、上記構造式（４）中、Ｐｈで表される構造部位がナフタレン環のものが、誘電特性に極めて優れたものとなる点から好ましい。

Here, in the above structural formula (4), R ₄ is a hydrogen atom or a methyl group, Ph refers to a represents a benzene ring or a naphthalene ring, n represents an integer of 1 or 2, m is an integer of 1 to 3. Specific examples of the structure represented by the structural formula (4) include the structural formulas B1, B3, B5, B8, B9, B10, B11, B12, B13, B19, B20, B21, B23, B24, B25, B26. , B27, and B31. Furthermore, in the above structural formula (4), the structural site represented by Ph is preferably a naphthalene ring from the viewpoint of extremely excellent dielectric properties.

  Next, specific examples of the divalent aralkyl group (X) in the phenol resin structure include those represented by the following structural formulas X1 to X12.

  Among these, the divalent aralkyl group (X) is preferably represented by the following structural formula (1) because of its excellent flame retardant effect.

ここで、Ｒ_１は、水素原子又はメチル基を、Ａｒはフェニレン基、ビフェニレン基、ジフェニルエーテル−４，４’−ジイル基、ナフチレン基、或いはこれらの芳香核上の置換基としてメチル基を有する構造を表す。この構造式（１）の具体例は、上記構造Ｘ１〜Ｘ９、及びＸ１２の構造が挙げられる。また、難燃性の点からは、構造式（１）中、Ｒ_１は特に水素原子であることが好ましい。

Here, R ₁ is a hydrogen atom or a methyl group, Ar is a phenylene group, a biphenylene group, a diphenyl ether-4,4′-diyl group, a naphthylene group, or a structure having a methyl group as a substituent on these aromatic nuclei. Represents. Specific examples of the structural formula (1) include the structures of the above structures X1 to X9 and X12. From the viewpoint of flame retardancy, R ₁ in the structural formula (1) is particularly preferably a hydrogen atom.

  The phenol resin used in the present invention can take any combination of the structures shown in the specific examples of the structural sites (P), (B), and (X).

Here, in the field of use of epoxy resin compositions, in recent years, due to the dioxin problem, there is a high demand for a halogen-free flame retardant system. Sexually improves. In particular,
The alkoxy group-containing aromatic hydrocarbon group (B) is formed from a molecular structure selected from methoxybenzene, methoxynaphthalene, ethoxybenzene, ethoxynaphthalene, and compounds having a methyl group as a substituent on the aromatic nucleus. A monovalent or polyvalent aromatic hydrocarbon group,
The divalent aralkyl group (X) is represented by the following structural formula (1)

（Ｒ_１は、水素原子又はメチル基を、Ａｒはフェニレン基、ビフェニレン基、ジフェニルエーテル−４，４’−ジイル基、ナフチレン基を表す。）
で表される構造を有する２価の炭化水素基であり、かつ、
前記フェノール性水酸基含有芳香族炭化水素基（Ｐ）が、フェノール、ナフトール、及び、これらの芳香核上の置換基としてメチル基を有する化合物から選択される分子構造から形成される２価又は３価の芳香族炭化水素基
である場合、当該フェノール樹脂自体の難燃性が飛躍的に向上し、電子部品関連材としてハロゲンフリーの材料を調整することが可能となる。また、前記アルコキシ基含有芳香族炭化水素基（Ｂ）は、更に、２価又は３価の芳香族炭化水素基であることが、硬化性や誘電特性の点から特に好ましい。

(R ₁ represents a hydrogen atom or a methyl group, and Ar represents a phenylene group, a biphenylene group, a diphenyl ether-4,4′-diyl group or a naphthylene group.)
A divalent hydrocarbon group having a structure represented by:
The phenolic hydroxyl group-containing aromatic hydrocarbon group (P) is formed from a molecular structure selected from phenol, naphthol, and a compound having a methyl group as a substituent on these aromatic nuclei. In the case of the aromatic hydrocarbon group, the flame retardancy of the phenol resin itself is dramatically improved, and it becomes possible to adjust a halogen-free material as an electronic component-related material. The alkoxy group-containing aromatic hydrocarbon group (B) is particularly preferably a divalent or trivalent aromatic hydrocarbon group from the viewpoint of curability and dielectric properties.

  The phenol resin has a hydroxyl equivalent weight of 150 to 500 g / eq. Those in the range are preferable from the viewpoint of further improving the flame retardancy and dielectric properties of the cured product. Further, those having a melt viscosity at 150 ° C. in the range of 0.3 to 5.0 dPa · s measured with an ICI viscometer are preferable in terms of excellent fluidity during molding, heat resistance of the cured product, and the like. Here, in this invention, what comprises the conditions of such a hydroxyl equivalent and melt viscosity becomes the novel phenol resin of this invention. The hydroxyl equivalent is particularly 200 to 350 g / eq. Within this range, the balance between the dielectric properties of the cured product and the curability of the composition is particularly excellent.

  Further, the phenol resin has an abundance ratio of a monovalent or divalent aromatic hydrocarbon group (P) containing a phenolic hydroxyl group and a divalent aromatic hydrocarbon group (B) containing the alkoxy group. The former / the latter is preferably in the range of 30/70 to 98/2 from the viewpoint of further improving the flame retardancy and dielectric properties of the cured product.

  The said phenol resin can be manufactured by the method explained in full detail below as the manufacturing method. Hereinafter, the manufacturing method of a phenol resin is explained in full detail.

  That is, the phenol resin includes a hydroxy group-containing aromatic compound (a1), an alkoxy group-containing aromatic compound (a2), the following structural formula (a3-a), (a3-b), or (a3-c).

（上記式（ａ３−ｂ）中、Ｒ_２は水素原子、又は炭素原子数１〜６の炭化水素基である。）で表される化合物（ａ３）とを、反応させることによって製造することができる。

(In the above formula (a3-b), R ₂ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms) and can be produced by reacting with the compound (a3). it can.

  What should be noted here is that the reaction proceeds without any hydrolysis while using the hydroxy group-containing aromatic compound (a1) as a raw material. Usually, an alkoxy group obtained by alkoxylation of a phenolic hydroxyl group is easily hydrolyzed in a strongly acidic environment, as widely used as a protection technique for the phenolic hydroxyl group. Then, an alkoxy group can be introduced into the phenol resin structure without causing such hydrolysis.

Specific examples of the hydroxy group-containing aromatic compound (a1) used in the above production method include unsubstituted phenols such as phenol, resorcinol and hydroquinone, cresol, phenylphenol, ethylphenol, n-propylphenol, and iso-propyl. Monosubstituted phenols such as phenol and t-butylphenol, disubstituted phenols such as xylenol, methylpropylphenol, methylbutylphenol, methylhexylphenol, dipropylphenol and dibutylphenol, mesitol, 2,3,5-trimethylphenol, 2 , 3,6-trimethylphenol and the like, and naphthols such as 1-naphthol, 2-naphthol and methylnaphthol.
Two or more of these may be used in combination.

  Among these, as described above, 1-naphthol, 2-naphthol, cresol, and phenol are particularly preferable from the viewpoint of the dielectric properties and flame retardancy of the cured product.

  Next, the alkoxy group-containing aromatic compound (a2) specifically includes monoalkoxybenzenes such as anisole and ethoxybenzene, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,4-dimethoxybenzene. Dialkoxybenzenes such as 1,4-diethoxybenzene and 1-methoxy-2-isopropoxybenzene, monoalkoxynaphthalenes such as 1-methoxynaphthalene and 2-methoxynaphthalene, 1,4-dimethoxynaphthalene, 2, Dialkoxynaphthalenes such as 6-dimethoxynaphthalene and 2,7-dimethoxynaphthalene, 1-methoxy-4-propylbenzene, 1- (4-methoxyphenyl) -1-propane, 1-propyl-2-methoxy-4- Substituted alkoxybenzenes such as methylbenzene, anisal Hydrate, and the like.

Two or more of these may be used in combination. Among these, dimethoxybenzene, anisole, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,4-dimethoxybenzene, 1-methoxynaphthalene, from the viewpoint of particularly excellent flame retardancy of the obtained cured product, 2-methoxynaphthalene is particularly preferred.
In addition, anisole, 1-methoxynaphthalene, and 2-methoxynaphthalene are particularly preferable in that a cured product having particularly excellent dielectric characteristics can be obtained.

Next, the compound represented by the structural formula (a3-a) functioning as a crosslinking agent specifically includes 1,2-di (chloromethyl) benzene, 1,2-di (bromomethyl) benzene, 1, 3-di (chloromethyl) benzene, 1,3-di (fluoromethyl) benzene, 1,4-di (chloromethyl) benzene, 1,4-di (bromomethyl) benzene, 1,4-di (fluoromethyl) Benzene, 1,4-di (chloromethyl) -2,5-dimethylbenzene, 1,3-di (chloromethyl) -4,6-dimethylbenzene, 1,3-di (chloromethyl) -2,4- Dimethylbenzene, 4,4′-bis (chloromethyl) biphenyl, 2,2′-bis (chloromethyl) biphenyl, 2,4′-bis (chloromethyl) biphenyl, 2,3′-bis (chloromethyl) biphenyl , 4,4'- S (bromomethyl) biphenyl, 4,4′-bis (chloromethyl) diphenyl ether, 2,7-di (chloromethyl) naphthalene and the like, and the compound represented by the structural formula (a3-b) is specifically Are p-xylylene glycol, m-xylene glycol, 1,4-di (2-hydroxy-2-ethyl) benzene,
4,4′-bis (dimethylol) biphenyl, 2,4′-bis (dimethylol) biphenyl, 4,4′-bis (2-hydroxy-2-propyl) biphenyl, 2,4′-bis (2-hydroxy-) 2-propyl) biphenyl, 1,4′-di (methoxymethyl) benzene, 1,4′-di (ethoxymethyl) benzene, 1,4′-di (isopropoxy) benzene, 1,4′-di (butoxy) ) Benzene, 1,3′-di (methoxymethyl) benzene, 1,3′-di (ethoxymethyl) benzene, 1,3′-di (isopropoxy) benzene, 1,3′-di (butoxy) benzene, 1,4-di (2-methoxy-2-ethyl) benzene,
1,4-di (2-hydroxy-2-ethyl) benzene, 1,4-di (2-ethoxy-2-ethyl) benzene, 4,4′-bis (methoxymethyl) biphenyl, 2,4′-bis (Methoxymethyl) biphenyl, 2,2′-bis (methoxymethyl) biphenyl, 2,3′-bis (methoxymethyl) biphenyl, 3,3′-bis (methoxymethyl) biphenyl, 3,4′-bis (methoxy) Methyl) biphenyl, 4,4′-bis (ethoxymethyl) biphenyl, 2,4′-bis (ethoxymethyl) biphenyl, 4,4′-bis (isopropoxy) methylbiphenyl, 2,4′-bis (isopropoxy) ) Methylbiphenyl, bis (1-methoxy-1-ethyl) biphenyl, bis (1-methoxy-1-ethyl) biphenyl, bis (1-isopropoxy-1-ethyl) biph And bis (2-hydroxy-2-propyl) biphenyl, bis (2-methoxy-2-propyl) biphenyl, bis (2-isopropoxy-2-propyl) biphenyl, etc.

  Examples of the compound represented by the structural formula (a3-c) include bis (vinyl) biphenyl such as p-divinylbenzene, m-divinylbenzene, and 4,4′-bis (vinyl) biphenyl.

The hydroxy group-containing aromatic compound (a1), the alkoxy group-containing aromatic compound (a2), and the compound (a3) represented by the structural formula (a3-a), (a3-b) or (a3-c) ) (Hereinafter, the compound is simply abbreviated as “compound (a3)”), the following method 1 and method 2 may be mentioned.
Method 1: A method of reacting the alkoxy group-containing aromatic compound (a2) and the compound (a3) in advance, and then reacting the obtained intermediate reaction product with the hydroxy group-containing aromatic compound (a1).
Method 2: A method in which the hydroxy group-containing aromatic compound (a1), the alkoxy group-containing aromatic compound (a2), and the compound (a3) are reacted in a single step.

  In the above methods 1 and 2, the desired phenol resin can be obtained by heating and stirring in the presence of an appropriate polymerization catalyst. The polymerization catalyst is preferably an acid catalyst, specifically, an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid, an organic acid such as methanesulfonic acid, p-toluenesulfonic acid or oxalic acid, boron trifluoride or anhydrous chloride. Examples include Lewis acids such as aluminum and zinc chloride. The amount used is preferably in the range of 0.1 to 5% by weight with respect to the total weight of the charged raw materials.

  In the method 1, specifically, 2 to 30 mol of the compound (a3) is reacted with 1 mol of the alkoxy group-containing aromatic compound (a2), and then the hydroxy group-containing aromatic compound (a1) is reacted. A method of charging and reacting is preferable. Here, the charging ratio of the hydroxy group-containing aromatic compound (a1) is the total number of moles of the hydroxy group-containing aromatic compound (a1) and the alkoxy group-containing aromatic compound (a2) and the number of moles of the compound (a3). The ratio {(a1) + (a2)} / (a3) is preferably in the range of 51/49 to 97/3. According to this method, the molecular structure of the target phenol resin can be made into an alternating copolymer, and an alkoxy group can be more efficiently introduced into the molecular structure.

  In the method 2, the reaction charge ratio of the hydroxy group-containing aromatic compound (a1), the alkoxy group-containing aromatic compound (a2), and the compound (a3) is set such that the hydroxy group-containing aromatic compound (a1) and the alkoxy group-containing aromatic The molar ratio (a1) / (a2) to the aromatic compound (a2) is 30/70 to 98/2, and the hydroxy group-containing aromatic compound (a1) and the alkoxy group-containing aromatic compound (a2) The ratio {(a1) + (a2)} / (a3) of the total number of moles to the number of moles of compound (a3) is preferably in the range of 51/49 to 97/3. By satisfying this condition, it is possible to obtain a cured product that is further excellent in flame retardancy and dielectric properties. The single-stage reaction in Method 2 is specifically a method in which all raw materials are charged until the reaction is accelerated by heating.

  In the present invention, since the reactivity of the alkoxy group-containing aromatic compound (a2) is very good, the alkoxy structure can be easily introduced into the phenol resin structure by the method 2. Therefore, Method 2 is preferable from the viewpoint of simplicity of the manufacturing method.

When carrying out the reaction of Method 1 or Method 2, an organic solvent can be used as necessary. Specific examples of the organic solvent that can be used include methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. The amount of the organic solvent used is usually 10 to 500% by weight, preferably 30 to 250% by weight, based on the total weight of the charged raw materials.
Moreover, as reaction temperature, it is 40-250 degreeC normally, and the range of 100-200 degreeC is more preferable. The reaction time is usually 1 to 10 hours.

When the compound represented by the structural formula (a3-a) is used as the compound (a3), the reaction becomes a condensation reaction system, and hydrogen halide gas such as hydrochloric acid is generated as the reaction proceeds. Therefore, it is preferable to quickly discharge out of the system and trap outside the system by alkali treatment or the like.
In addition, when the compound represented by the structural formula (a3-b) is used, a condensation system is formed, and water, methanol, and the like are generated as the reaction proceeds. This is preferable from the viewpoint of increasing the speed.
In addition, when the compound represented by the structural formula (a3-c) is used, an addition reaction system is used, so that no by-product treatment is particularly necessary.

  Moreover, when the coloring of the phenol resin obtained is large, in order to suppress it, you may add antioxidant and a reducing agent. Examples of the antioxidant include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite compounds containing trivalent phosphorus atoms. Although it does not specifically limit as said reducing agent, For example, hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, these salts, zinc, etc. are mentioned.

  After completion of the reaction, the reaction mixture is neutralized or washed with water until the pH value of the reaction mixture becomes 3 to 7, preferably 4 to 7. Such neutralization treatment and washing treatment may be carried out in accordance with conventional methods. For example, when an acid catalyst is used, basic substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, triethylenetetramine, aniline are neutralized. It can be used as an agent. In addition, when neutralizing, phosphoric acid or the like may be added as a buffer in advance, and once the system is made basic, the pH value is adjusted to 3 to 7 with oxalic acid or the like. May be. After neutralization or washing with water, unreacted raw materials, organic solvents and by-products mainly containing hydroxy group-containing aromatic compound (a1) and alkoxy group-containing aromatic compound (a2) are distilled off under reduced pressure heating. The target product can be obtained by concentrating the product. The unreacted raw material recovered here can be reused. It is more preferable to introduce a microfiltration step into the processing operation after the reaction, since inorganic salts and foreign substances can be purified and removed.

  In the epoxy resin composition (I) of the present invention, the phenol resin may be used alone, or another curing agent may be used as long as the effects of the present invention are not impaired. Specifically, other curing agents can be used in combination so that the phenol resin is 30% by weight or more, preferably 40% by weight or more based on the total mass of the curing agent.

  The other curing agent that can be used in combination with the phenol resin of the present invention is not particularly limited, and examples thereof include amine compounds, amide compounds, acid anhydride compounds, and phenol compounds other than the above-described phenol resins. And polyphenolic compounds of aminotriazine-modified phenolic resins (polyhydric phenolic compounds in which phenolic nuclei are linked with melamine, benzoguanamine or the like).

  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 (B) used in the epoxy resin composition (I) 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 epoxy resin, naphthol aralkyl epoxy resin,
Examples thereof include naphthol-phenol co-condensed novolac type epoxy resins, naphthol-cresol co-condensed novolak type epoxy resins, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resins, biphenyl novolac type epoxy resins and the like. 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.

  Although it does not restrict | limit especially as a compounding quantity of the epoxy resin (B) and hardening | curing agent in the epoxy resin composition (I) of this invention, From the point that the hardened | cured material characteristic obtained is favorable, an epoxy resin (B The amount of the active group in the curing agent containing the phenol resin (A) is preferably 0.7 to 1.5 equivalents with respect to a total of 1 equivalent of the epoxy groups.

  Moreover, a hardening accelerator can also be used together suitably with the epoxy resin composition (I) of this invention as needed. 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.

Another epoxy resin composition (II) of the present invention is an epoxy resin composition containing an epoxy resin and a curing agent as essential components, and the epoxy resin is
Glycidyloxy group-containing aromatic hydrocarbon group (E),
A divalent aromatic hydrocarbon group (B) containing an alkoxy group, and a divalent aralkyl group (X)
Each structure, and
A structure in which the glycidyloxy group-containing aromatic hydrocarbon group (E) and the alkoxy group-containing aromatic hydrocarbon group (B) are bonded via the divalent aralkyl group (X),
A structure in which the glycidyloxy group-containing aromatic hydrocarbon group (E) is bonded to another glycidyloxy group-containing aromatic hydrocarbon group (E) via the divalent aralkyl group (X);
Or
In the molecular structure, the alkoxy group-containing aromatic hydrocarbon group (B) is bonded to the other alkoxy group-containing aromatic hydrocarbon group (B) via the divalent aralkyl group (X). It is characterized by being.

  That is, the epoxy resin in the epoxy resin composition (II) is an epoxy resin obtained by reacting the phenol resin constituting the epoxy resin composition (I) with epihalohydrin, and has a basic skeleton common to the phenol resin. Is. Therefore, as in the case of the phenol resin, the aromatic content in the molecular structure is increased to give excellent heat resistance to the cured product, and the epoxy group concentration can be appropriately reduced and the alkoxy group in the molecular structure. Therefore, the dielectric constant and dielectric loss tangent of the cured product can be lowered without impairing the curability.

  Further, as in the case of the phenol resin, the epoxy resin contains a glycidyloxy group-containing aromatic hydrocarbon group (E), an alkoxy group-containing aromatic hydrocarbon group (B), and a divalent aralkyl group (X). When each structural unit is represented by “E”, “B”, “X”, the following structural sites Y1 to Y3

の何れかの構造部位を必須として分子構造内に含むものである。

These structural sites are essential and included in the molecular structure.

  In this invention, since it has such a characteristic chemical structure, the aromatic content rate in a molecular structure becomes high, and the outstanding heat resistance is expressed. Further, in addition to being able to moderately reduce the hydroxyl group concentration, by introducing an alkoxy group into the molecular structure, the dielectric constant and dielectric loss tangent can be reduced without extremely reducing the hydroxyl group concentration. Therefore, when the phenol resin is used as a curing agent for epoxy resin, the curability does not decrease. It is also worth mentioning that excellent dielectric properties are exhibited while introducing a relatively polar functional group called an alkoxy group.

Here, the molecular structure of the epoxy resin may take various structures depending on the valence of the “E” and “B”. For example, 1) The following structural formula Y4

で表される構造を繰り返し単位とする直鎖型交互共重合体、或いは、
２） 下記構造式Ｙ５〜Ｙ７

A linear alternating copolymer having a structure represented by the repeating unit, or
2) The following structural formulas Y5 to Y7

を繰り返し単位とする、分岐状交互共重合体、
３）前記構造部位Ｙ１〜Ｙ３の全てを含む直鎖又は分岐状のランダム重合体、
４）構造単位Ｅと構造単位Ｘとが交互に結合した重合体ブロックと、複数の該重合体ブロック中の構造単位Ｅが構造単位Ｘを介して構造単位Ｂと結節した構造の重合体、
５）構造単位Ｅと構造単位Ｘとが交互に結合した重合体ブロックと、構造単位Ｂと構造単位Ｘとが交互に結合した重合体ブロックとを有する重合体、
６）構造単位Ｅと構造単位Ｘとが交互に結合した重合体の末端に構造単位Ｂが結合した重合体、及び
７）構造単位Ｂと構造単位Ｘとが交互に結合した重合体の両末端に構造単位Ｅが結合した重合体
以上の１）〜７）の構造が挙げられる。

A branched alternating copolymer having a repeating unit,
3) A linear or branched random polymer containing all of the structural sites Y1 to Y3,
4) a polymer block in which the structural unit E and the structural unit X are alternately bonded, and a polymer having a structure in which the structural unit E in the plurality of polymer blocks is connected to the structural unit B via the structural unit X.
5) a polymer having a polymer block in which the structural unit E and the structural unit X are alternately bonded, and a polymer block in which the structural unit B and the structural unit X are alternately bonded;
6) Polymer in which structural unit B is bonded to the end of the polymer in which structural unit E and structural unit X are alternately bonded, and 7) Both ends of the polymer in which structural unit B and structural unit X are alternately bonded The polymer of which the structural unit E couple | bonded with is the structure of the above 1) -7).

  Among such structures, in view of the heat resistance and dielectric properties described above, the phenol resin preferably has a structure of Y1 as an essential structure and a resin having Y2 and Y3 as an essential structure. In particular, those having the structure of A1 as an essential structure are particularly preferable.

  Next, the glycidyloxy group-containing aromatic hydrocarbon group (E) is not particularly limited, and in particular, the glycidyloxy group-containing aromatic hydrocarbon group (E) is preferably an aromatic hydrocarbon group represented by the following structural formulas E1 to E16. It is preferable from the viewpoint of excellent performance.

ここで、前記各構造は、該構造が分子末端に位置する場合には、１価の芳香族炭化水素基となる。また、上掲した構造のうちナフタレン骨格上に他の構造部位との結合位置を二つ以上有するものは、それらの結合位置は同一核上であってもよいし、或いは、それぞれ異核上にあってもよい。

Here, each structure becomes a monovalent aromatic hydrocarbon group when the structure is located at the molecular end. In addition, among the structures listed above, those having two or more bonding positions with other structural sites on the naphthalene skeleton may be on the same nucleus or on different nuclei. There may be.

  The glycidyloxy group-containing aromatic hydrocarbon group (E) described in detail above can give excellent flame retardancy to the cured epoxy resin itself, among others, and in recent years, halogen-free which is highly demanded in the field of electronic components. Molecules selected from glycidyloxybenzene, glycidyloxynaphthalene, and compounds having a methyl group as a substituent on these aromatic nuclei, represented by the structural formulas E1 to E15, from the point that materials can be designed A divalent or trivalent aromatic hydrocarbon group formed from the structure is preferable.

  In this invention, when it has the structure represented by following Structural formula (5) or (6), it is preferable from the point which can provide the flame retardance excellent in epoxy resin hardened | cured material itself.

（式（５）及び（６）中、Ｒ_５は水素原子又はメチル基、ｏは１〜３の整数を表す。
該構造式（５）で表される具体的構造としては、前記構造Ｅ１、Ｅ６〜Ｅ９で表されるものが挙げられる。また、該構造（６）で表される具体的構造としては、構造Ｅ１０及びＥ１１で表されるものが挙げられる。

(In formulas (5) and (6), R ₅ represents a hydrogen atom or a methyl group, and o represents an integer of 1 to 3.
Specific examples of the structure represented by the structural formula (5) include those represented by the structures E1 and E6 to E9. Specific examples of the structure represented by the structure (6) include those represented by the structures E10 and E11.

  Next, the divalent aromatic hydrocarbon group (B) containing the alkoxy group contained in the epoxy resin structure is specifically the same as that in the phenol resin of the epoxy resin composition (I) described above. is there.

  Next, the divalent aralkyl group (X) contained in the epoxy resin structure is specifically the same as that in the phenol resin of the epoxy resin composition (I) described above.

  The epoxy resin used in the present invention can take any combination of the structures shown in the specific examples of the structural portions (E), (B), and (X).

Here, as described above, also in the epoxy resin composition (II), the flame retardancy of the cured product is dramatically improved depending on the selection of the structure of the epoxy resin.
Specifically, the alkoxy group-containing aromatic hydrocarbon group (B) is selected from methoxybenzene, methoxynaphthalene, ethoxybenzene, ethoxynaphthalene, and compounds having a methyl group as a substituent on the aromatic nucleus. A monovalent or polyvalent aromatic hydrocarbon group formed from the molecular structure
The divalent aralkyl group (X) is represented by the following structural formula (1)

（Ｒ_１は、水素原子又はメチル基を、Ａｒはフェニレン基、ビフェニレン基、ジフェニルエーテル−４，４’−ジイル基、ナフチレン基を表す。）
で表される構造を有する２価の炭化水素基であり、かつ、
前記グリシジルオキシ基含有芳香族炭化水素基（Ｅ）が、グリシジルオキシベンゼン、グリシジルオキシナフタレン、及び、これらの芳香核上の置換基としてメチル基を有する化合物から選択される分子構造から形成される２価又は３価の芳香族炭化水素基
である場合、当該エポキシ樹脂自体の難燃性が飛躍的に向上し、電子部品関連材としてハロゲンフリーの材料を調整することが可能となる。
なかでも、前記アルコキシ基含有芳香族炭化水素基（Ｂ）は、２価又は３価の芳香族炭化水素基であることが硬化性及び誘電特性に優れる点から好ましい。

(R ₁ represents a hydrogen atom or a methyl group, and Ar represents a phenylene group, a biphenylene group, a diphenyl ether-4,4′-diyl group or a naphthylene group.)
A divalent hydrocarbon group having a structure represented by:
The glycidyloxy group-containing aromatic hydrocarbon group (E) is formed from a molecular structure selected from glycidyloxybenzene, glycidyloxynaphthalene, and compounds having a methyl group as a substituent on the aromatic nucleus 2 In the case of a trivalent or trivalent aromatic hydrocarbon group, the flame retardancy of the epoxy resin itself is dramatically improved, and it becomes possible to adjust a halogen-free material as an electronic component-related material.
Of these, the alkoxy group-containing aromatic hydrocarbon group (B) is preferably a divalent or trivalent aromatic hydrocarbon group from the viewpoint of excellent curability and dielectric properties.

  The epoxy resin has an epoxy equivalent of 200 to 700 g / eq. Those in the range are preferable from the viewpoint of further improving the flame retardancy and dielectric properties of the cured product. Further, those having a melt viscosity at 150 ° C. in the range of 0.3 to 5.0 dPa · s measured with an ICI viscometer are preferable in terms of excellent fluidity during molding, heat resistance of the cured product, and the like. Here, when it has the conditions of the said epoxy equivalent and melt viscosity, it becomes a novel epoxy resin of this invention. The epoxy equivalent is particularly in the range of 260 to 420 g / eq. Within this range, the balance between the dielectric properties of the cured product and the curability of the composition is particularly excellent.

  Further, the epoxy resin has an abundance ratio between the glycidyloxy group-containing aromatic hydrocarbon group (E) and the divalent aromatic hydrocarbon group (B) containing the alkoxy group, wherein the former / the latter = 30 / The range of 70 to 98/2 is preferable from the viewpoint of further improving the flame retardancy and dielectric properties of the cured product.

The epoxy resin can be produced by the method described in detail below.
Specifically, after the phenol resin in the epoxy resin composition (I) is produced by the above-described method, the objective epoxy resin can be produced by reacting it with epihalohydrin. For example, 2 to 10 mol of epihalohydrin is added to 1 mol of phenolic hydroxyl group in the phenol resin, and 0.9 to 2.0 mol of basic catalyst is added all at once or gradually to 1 mol of phenolic hydroxyl group. The method of making it react for 0.5 to 10 hours at the temperature of 20-120 degreeC, adding is mentioned. The basic catalyst may be solid or an aqueous solution thereof. When an aqueous solution is used, it is continuously added and water and epihalohydrins are continuously distilled from the reaction mixture under reduced pressure or normal pressure. The solution may be taken out and further separated to remove water and the epihalohydrins are continuously returned to the reaction mixture.

  In the first batch of epoxy resin production, all of the epihalohydrins used for preparation are new in industrial production, but the subsequent batches are 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. At this time, the epihalohydrin used 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.

  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 weight 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 weight based on 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.

  In the epoxy resin composition (II) of the present invention, the epoxy resin (A) obtained by the production method of the present invention is used alone or in combination with other epoxy resins as long as the effects of the present invention are not impaired. Can do. When used in combination, the proportion of the epoxy resin of the present invention in the entire epoxy resin is preferably 30% by weight or more, particularly preferably 40% by weight or more.

  As other epoxy resins that can be used in combination with the epoxy resin of the present invention, 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, bisphenol A 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 novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensate Type epoxy resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin, a biphenyl novolak type epoxy resins. Among these, phenol aralkyl type epoxy resins, biphenyl novolak type epoxy resins, naphthol novolak type epoxy resins containing a naphthalene skeleton, naphthol aralkyl type epoxy resins, naphthol-phenol co-condensed novolac type epoxy resins, naphthol-cresol co-condensed novolacs. Type epoxy resin, crystalline biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, and the following structural formula

で表されるキサンテン型エポキシ樹脂が、難燃性や誘電特性に優れる硬化物が得られる点から特に好ましい。

Is particularly preferable from the viewpoint of obtaining a cured product having excellent flame retardancy and dielectric properties.

As the curing agent used for the epoxy resin composition (II) of the present invention, known curing agents for various epoxy resins, for example, curing agents such as amine compounds, amide compounds, acid anhydride compounds, phenol compounds, etc. 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 phenolic resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (commonly known as zylock resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol Co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyhydric phenol compound in which phenol nucleus is linked by bismethylene group), biphenyl-modified naphthol resin (polyvalent naphthol in which phenol nucleus is linked by bismethylene group) Compound), and polyphenol compounds such as aminotriazine-modified phenolic resins (polyphenol compounds in which phenol nuclei are linked with melamine, benzoguanamine, etc.) Can be mentioned.

  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 phenol resin used as an essential component in the above-described epoxy resin composition (I), particularly the present invention, particularly from the point that the effect of reducing the dielectric constant and dielectric loss tangent becomes remarkable. New phenolic resins are preferred. Further, the phenol resin includes an aromatic hydrocarbon group (B) containing an alkoxy group represented by the structural formula (1 ′), and a divalent aralkyl group represented by the structural formula (2 ′) ( X) and the phenolic hydroxyl group-containing aromatic hydrocarbon group (P) represented by the formula (3) or (4), in particular, from the viewpoint of exhibiting an excellent flame retardant effect. preferable.

  The blending amount of the epoxy resin and the curing agent in the epoxy resin composition (II) of the present invention is not particularly limited, but an epoxy resin containing an epoxy resin is preferable because the properties of the resulting cured product are good. The amount by which the active groups in the curing agent are 0.7 to 1.5 equivalents relative to a total of 1 equivalent of epoxy groups in the resin 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, the flame retardancy of the cured product is good without blending a conventionally used flame retardant. 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, organometallic salt flame retardants, etc., are not limited in any way, and even if used alone A plurality of flame retardants of the same system may be used, and 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.

  Examples of the organic phosphorus compound 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- Examples thereof include cyclic organophosphorus 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.

  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 In 100 parts by weight of the epoxy resin composition containing all of the flame retardant and other fillers and additives, when using red phosphorus as a non-halogen flame retardant, in the range of 0.1 to 2.0 parts by weight It is preferable to mix, and when using an organophosphorus compound, it is also preferable to mix in the range of 0.1 to 10.0 parts by weight, particularly in the range of 0.5 to 6.0 parts by weight. Is preferred.

  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, (i) guanylmelamine sulfate, melem sulfate, sulfate (Iii) co-condensates of phenols such as phenol, cresol, xylenol, butylphenol and nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine and formguanamine and formaldehyde, (iii) (Ii) a mixture of a co-condensate of (ii) and a phenolic resin such as a phenol formaldehyde condensate, (iv) those obtained by further modifying (ii) and (iii) with paulownia oil, isomerized linseed oil, etc. It is.

  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. It is preferable to mix in the range of 0.05 to 10 parts by weight in 100 parts by weight of the epoxy resin composition containing all of the agent, non-halogen flame retardant and other fillers and additives. It is preferable to mix in the range of 5 parts by weight.

  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. It is preferable to mix in the range of 0.05 to 20 parts by weight in 100 parts by weight of the epoxy resin composition containing all of the agent, non-halogen flame retardant and other fillers and additives. 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 It is preferable to mix in an amount of 0.05 to 20 parts by weight in 100 parts by weight of the epoxy resin composition containing all of the agent, non-halogen flame retardant and other fillers and additives, and particularly 0.5 to 20 parts by weight. It is preferable to mix in the range of 15 parts by weight.

  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. It is preferable to mix in the range of 0.005 to 10 parts by weight in 100 parts by weight of the epoxy resin composition containing all of the epoxy resin, curing agent, non-halogen flame retardant and other fillers and additives.

  An inorganic filler can be blended in the epoxy resin composition of the present invention 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 weight or more with respect to the total amount of the epoxy 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.

  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 of the epoxy resin composition of the present invention include semiconductor sealing materials, resin compositions used for laminates and electronic circuit boards, resin casting materials, adhesives, interlayer insulation materials for build-up substrates, insulation Examples thereof include coating materials such as paints, and among these, they can be suitably used for semiconductor sealing materials.

  In order to produce an epoxy resin composition prepared for a semiconductor encapsulant, an epoxy resin, a curing agent, a compounding agent such as a filler, and the like, if necessary, an extruder, a kneader, a roll, etc. It is sufficient to obtain a melt-mixed type epoxy resin composition by mixing well until it is uniform. At that time, silica is usually used as the filler, and the filling rate is preferably in the range of 30 to 95% by weight per 100 parts by weight 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 weight or more, and in order to significantly increase these effects, 80 parts by weight 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 of the present invention into a printed circuit board composition, for example, a resin composition for a 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 weight 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 weight. 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 of the present invention is used as a resist ink, for example, a cationic polymerization catalyst is used as a curing agent for the epoxy resin composition (II), and a pigment, talc and filler are further added for resist ink. After making it into a composition, 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.

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

  Examples of a method for obtaining an interlayer insulating material for a build-up board from the epoxy resin composition of the present invention include, for example, a spray coating method, a curtain, and the like on a wiring board on which a circuit is formed by using the curable resin composition appropriately blended with rubber, filler and the like. After applying using a coating 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. 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.

  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 of about room temperature-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 phenol resin, it is possible to obtain an epoxy resin material that is safe for the environment and can exhibit high flame retardancy without using a halogen-based flame retardant. In addition, its excellent dielectric characteristics can realize high-speed operation speed of high-frequency devices. In addition, the phenol resin can be easily and efficiently produced by the production method of the present invention, and a molecular design corresponding to the target 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 weight unless otherwise specified. The melt viscosity at 150 ° C., GPC measurement, NMR, and MS spectrum were measured under the following conditions.
1) Melt viscosity at 150 ° C .: in accordance with ASTM D4287 2) Softening point measurement method: JIS K7234
3) GPC:
・ Device: HLC-8220 GPC manufactured by Tosoh Corporation, Column: TSK-GEL G2000HXL + G2000HXL + G3000HXL + G4000HXL manufactured by Tosoh Corporation
・ Solvent: Tetrahydrofuran ・ Flow rate: 1 ml / min
・ Detector: RI
4) NMR: NMR GSX270 manufactured by JEOL Ltd.
5) MS: Double Density Mass Spectrometer AX505H (FD505H) manufactured by JEOL Ltd.

Example 1 [Synthesis of phenol resin (A-1)]
A flask equipped with a thermometer, condenser, fractionator, nitrogen gas inlet, and stirrer was charged with 125.2 g (1.33 mol) of phenol, 72.5 g (0.67 mol) of anisole, and paraxylene dimethoxide. 166.2 g (1.00 mol) was charged, 3.6 g (0.038 mol) of methanesulfonic acid was added, the temperature was raised to 150 ° C., and methanol produced as a by-product was collected with a fractionating tube. Reacted for hours. After completion of the reaction, 1500 g of methyl isobutyl ketone was further added, transferred to a separatory funnel and washed with water. Next, after washing with water until the washing water shows neutrality, unreacted phenol and anisole and methyl isobutyl ketone are removed from the organic layer under heating and reduced pressure, and the following structural formula

で表される構造単位を有するフェノール樹脂（Ａ−１）２２６ｇを得た。回収した未反応のフェノール及びアニソールの重量測定の結果、及び得られたフェノール樹脂の水酸基の測定結果から、該フェノール樹脂中の水酸基含有芳香族炭化水素基の構造単位と、メトキシ基含有芳香族炭化水素基の構造単位とのモル比率は、前者／後者＝７６／２４であった。得られたフェノール樹脂の軟化点は７５℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は３．９ｄＰａ・ｓ、水酸基当量は２３３ｇ／ｅｑ．であった。得られたフェノール樹脂のＧＰＣチャートを図１に、Ｃ^１３ ＮＭＲチャートを図２に、ＭＳスペクトルを図３に示す。メトキシ基の残存は、ＮＭＲにおける５５ｐｐｍに観測されるメトキシ基のシグナル、及び水酸基当量から化合物中のメトキシ基は分解していないことを確認した。

226g of phenol resin (A-1) which has a structural unit represented by these was obtained. From the results of the weight measurement of the recovered unreacted phenol and anisole and the measurement result of the hydroxyl group of the obtained phenol resin, the structural unit of the hydroxyl group-containing aromatic hydrocarbon group in the phenol resin and the methoxy group-containing aromatic carbonization The molar ratio of the hydrogen group to the structural unit was the former / the latter = 76/24. The resulting phenol resin had a softening point of 75 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 3.9 dPa · s, and a hydroxyl group equivalent of 233 g / eq. Met. The GPC chart of the obtained phenol resin is shown in FIG. 1, the C ¹³ NMR chart is shown in FIG. 2, and the MS spectrum is shown in FIG. The residual methoxy group confirmed that the methoxy group in the compound was not decomposed from the methoxy group signal observed at 55 ppm in NMR and the hydroxyl group equivalent.

Example 2 [Synthesis of phenol resin (A-2)]
In Example 1, except that 133.5 g (1.42 mol) of phenol and 72.5 g (0.67 mol) of anisole were changed to 98.0 g (0.71 mol) of 1,2-dimethoxybenzene. In the same manner as in Example 1, the following structural formula

で表される構造単位を有するフェノール樹脂（Ａ−２）２５４ｇを得た。回収した未反応のフェノール及び１，２−ジメトキシベンゼンの重量測定の結果、及び得られたフェノール樹脂の水酸基の測定結果から、化合物中における水酸基含有芳香族炭化水素基の構造単位と、メトキシ基含有芳香族炭化水素基の構造単位とのモル比率は、前者／後者＝６７／３３であった。得られたフェノール樹脂の軟化点は７４℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は２．６ｄＰａ・ｓ、水酸基当量は２５４ｇ／ｅｑ．であった。得られたフェノール樹脂のＧＰＣチャートを図４にＣ^１３ ＮＭＲチャートを図５、ＭＳスペクトルを図６に示す。メトキシ基の残存は、ＮＭＲにおける５５ｐｐｍに観測されるメトキシ基のシグナル、及び水酸基当量から化合物中のメトキシ基は分解していないことを確認した。

254 g of a phenol resin (A-2) having a structural unit represented by From the results of the weight measurement of the recovered unreacted phenol and 1,2-dimethoxybenzene, and the measurement result of the hydroxyl group of the obtained phenol resin, the structural unit of the hydroxyl group-containing aromatic hydrocarbon group in the compound and the methoxy group content The molar ratio of the aromatic hydrocarbon group to the structural unit was the former / the latter = 67/33. The resulting phenol resin had a softening point of 74 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 2.6 dPa · s, and a hydroxyl group equivalent of 254 g / eq. Met. FIG. 4 shows a GPC chart of the obtained phenol resin, FIG. 5 shows a C ¹³ NMR chart, and FIG. 6 shows an MS spectrum. The residual methoxy group confirmed that the methoxy group in the compound was not decomposed from the methoxy group signal observed at 55 ppm in NMR and the hydroxyl group equivalent.

Example 3 [Synthesis of phenol resin (A-3)]
In Example 1, except that 125.2 g (1.33 mol) of phenol was changed to 143.8 g (1.33 mol) of o-cresol, the following structural formula was obtained.

で表される構造単位を有するフェノール樹脂（Ａ−３）２３９ｇを得た。回収した未反応のο−クレゾール及びアニソールの重量測定の結果、及び得られたフェノール樹脂の水酸基の測定結果から、該フェノール樹脂中の水酸基含有芳香族炭化水素基の構造単位と、メトキシ基含有芳香族炭化水素基の構造単位とのモル比率は、前者／後者＝８１／１９であった。得られたフェノール樹脂の軟化点は６４℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は１．２ｄＰａ・ｓ、水酸基当量は２３０ｇ／ｅｑ．であった。得られたフェノール樹脂のＧＰＣチャートを図７にＣ^１３ ＮＭＲチャートを図８、ＭＳスペクトルを図９に示す。メトキシ基の残存は、ＮＭＲにおける５５ｐｐｍに観測されるメトキシ基のシグナル、及び水酸基当量から化合物中のメトキシ基は分解していないことを確認した。

239g of phenol resin (A-3) which has a structural unit represented by these was obtained. From the results of the weight measurement of the recovered unreacted o-cresol and anisole and the measurement results of the hydroxyl group of the obtained phenol resin, the structural unit of the hydroxyl group-containing aromatic hydrocarbon group in the phenol resin and the methoxy group-containing aromatic The molar ratio of the group hydrocarbon group to the structural unit was the former / the latter = 81/19. The obtained phenol resin had a softening point of 64 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 1.2 dPa · s, and a hydroxyl group equivalent of 230 g / eq. Met. FIG. 7 shows a GPC chart of the obtained phenol resin, FIG. 8 shows a C ¹³ NMR chart, and FIG. 9 shows an MS spectrum. The residual methoxy group confirmed that the methoxy group in the compound was not decomposed from the methoxy group signal observed at 55 ppm in NMR and the hydroxyl group equivalent.

Example 4 [Synthesis of phenol resin (A-4)]
Except for changing 166.2 g (1.00 mol) of para-xylene dimethoxide in Example 1 to 242.3 g (1.00 mol) of 4,4′-bismethoxymethylbiphenyl, the same procedure as in Example 1 was performed. , The following structural formula

で表される構造単位を有するフェノール樹脂（Ａ−４）２８４ｇを得た。回収した未反応のフェノール及びアニソールの重量測定の結果、及び得られたフェノール樹脂の水酸基の測定結果から、該フェノール樹脂中の水酸基含有芳香族炭化水素基の構造単位と、メトキシ基含有芳香族炭化水素基の構造単位とのモル比率は、前者／後者＝７５／２５であった。得られたフェノール樹脂の軟化点は９７℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は２１ｄＰａ・ｓ、水酸基当量は２９６ｇ／ｅｑ．であった。得られたフェノール樹脂のＧＰＣチャートを図１０にＣ^１３ ＮＭＲチャートを図１１、ＭＳスペクトルを図１２に示す。メトキシ基の残存は、ＮＭＲにおける５５ｐｐｍに観測されるメトキシ基のシグナル、及び水酸基当量から化合物中のメトキシ基は分解していないことを確認した。

284 g of a phenol resin (A-4) having a structural unit represented by From the results of the weight measurement of the recovered unreacted phenol and anisole and the measurement result of the hydroxyl group of the obtained phenol resin, the structural unit of the hydroxyl group-containing aromatic hydrocarbon group in the phenol resin and the methoxy group-containing aromatic carbonization The molar ratio of the hydrogen group to the structural unit was the former / the latter = 75/25. The softening point of the obtained phenol resin was 97 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) was 21 dPa · s, and the hydroxyl group equivalent was 296 g / eq. Met. The GPC chart of the obtained phenol resin is shown in FIG. 10, the C ¹³ NMR chart is shown in FIG. 11, and the MS spectrum is shown in FIG. The residual methoxy group confirmed that the methoxy group in the compound was not decomposed from the methoxy group signal observed at 55 ppm in NMR and the hydroxyl group equivalent.

Example 5 [Synthesis of phenol resin (A-5)]
In the same manner as in Example 1 except that phenol was changed to 150.6 g (1.60 mol) and anisole was changed to 43.2 g (0.40 mol), the following structural formula was obtained.

で表される構造単位を有するフェノール樹脂（Ａ−５）１９０ｇを得た。回収した未反応のフェノール及びアニソールの重量測定の結果、及び得られたフェノール樹脂の水酸基の測定結果から、該フェノール樹脂中の水酸基含有芳香族炭化水素基の構造単位と、メトキシ基含有芳香族炭化水素基の構造単位とのモル比率は、前者／後者＝７９／２１であった。得られたフェノール樹脂の軟化点は７５℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は３．３ｄＰａ・ｓ、水酸基当量は２０２ｇ／ｅｑ．であった。得られたフェノール樹脂のＧＰＣチャートを図１３に示す。

The phenol resin (A-5) 190g which has a structural unit represented by these was obtained. From the results of the weight measurement of the recovered unreacted phenol and anisole and the measurement result of the hydroxyl group of the obtained phenol resin, the structural unit of the hydroxyl group-containing aromatic hydrocarbon group in the phenol resin and the methoxy group-containing aromatic carbonization The molar ratio of the hydrogen group to the structural unit was the former / the latter = 79/21. The obtained phenol resin had a softening point of 75 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 3.3 dPa · s, and a hydroxyl group equivalent of 202 g / eq. Met. A GPC chart of the obtained phenol resin is shown in FIG.

Example 6 [Synthesis of phenol resin (A-6)]
In Example 1, except that phenol was changed to 94.1 g (1.00 mol) and anisole was changed to 108.1 g (1.00 mol), the same structural formula as in Example 1 was obtained.

で表される構造単位を有するフェノール樹脂（Ａ−６）２１３ｇを得た。回収した未反応のフェノール及びアニソールの重量測定の結果、及び得られたフェノール樹脂の水酸基の測定結果から、該フェノール樹脂中の水酸基含有芳香族炭化水素基の構造単位と、メトキシ基含有芳香族炭化水素基の構造単位とのモル比率は、前者／後者＝５３／４７であった。得られたフェノール樹脂の軟化点は７６℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は４．５ｄＰａ・ｓ、水酸基当量は２７９ｇ／ｅｑ．であった。得られたフェノール樹脂のＧＰＣチャートを図１４に示す。

213 g of a phenol resin (A-6) having a structural unit represented by From the results of the weight measurement of the recovered unreacted phenol and anisole and the measurement result of the hydroxyl group of the obtained phenol resin, the structural unit of the hydroxyl group-containing aromatic hydrocarbon group in the phenol resin and the methoxy group-containing aromatic carbonization The molar ratio of the hydrogen group to the structural unit was the former / the latter = 53/47. The softening point of the obtained phenol resin was 76 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) was 4.5 dPa · s, and the hydroxyl group equivalent was 279 g / eq. Met. The GPC chart of the obtained phenol resin is shown in FIG.

Example 7 [Synthesis of phenol resin (A-7)]
In Example 1, 313.4 g (3.33 mol) of phenol, 180.5 (1.67 mol) of anisole, and 242.3 g (1 of paraxylene dimethoxide) of 4,4′-bis (methoxymethyl) biphenyl (1 0.0000 mol), except that the following structural formula

で表される構造単位を有するフェノール樹脂（Ａ−７）２７５ｇを得た。回収した未反応のフェノール及びアニソールの重量測定の結果、及び得られたフェノール樹脂の水酸基の測定結果から、該フェノール樹脂中の水酸基含有芳香族炭化水素基の構造単位と、メトキシ基含有芳香族炭化水素基の構造単位とのモル比率は、前者／後者＝８４／１６であった。得られたフェノール樹脂の軟化点は５８℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は０．７ｄＰａ・ｓ、水酸基当量は２５７ｇ／ｅｑ．であった。得られたフェノール樹脂のＧＰＣチャートを図１５に示す。

275 g of a phenol resin (A-7) having a structural unit represented by From the results of the weight measurement of the recovered unreacted phenol and anisole and the measurement result of the hydroxyl group of the obtained phenol resin, the structural unit of the hydroxyl group-containing aromatic hydrocarbon group in the phenol resin and the methoxy group-containing aromatic carbonization The molar ratio of the hydrogen group to the structural unit was the former / the latter = 84/16. The obtained phenol resin had a softening point of 58 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometry method, measurement temperature: 150 ° C.) of 0.7 dPa · s, and a hydroxyl group equivalent of 257 g / eq. Met. A GPC chart of the obtained phenol resin is shown in FIG.

Example 8 [Synthesis of phenol resin (A-8)]
In a flask equipped with a thermometer, cooling pipe, nitrogen gas introduction pipe, and stirrer, 125.2 g (1.33 mol) of phenol, 72.5 g (0.67 mol) of anisole, and 1,4-di (chloromethyl) Hydrogen chloride generated by charging 175.5 g (1.00 mol) of benzene and 23.7 g of 36% HCl aqueous solution while raising the temperature from 70 ° C. to 120 ° C. over 2 hours under a nitrogen gas stream with stirring The reaction was allowed to take place outside the system. The reaction was further carried out at 140 ° C. for 2 hours. After completion of the reaction, 1500 g of methyl isobutyl ketone was further added, transferred to a separatory funnel and washed with water. Next, after washing with water until the washing water shows neutrality, unreacted phenol and anisole and methyl isobutyl ketone are removed from the organic layer under heating and reduced pressure, and the following structural formula

で表される構造単位を有するフェノール樹脂（Ａ−８）２２６ｇを得た。回収した未反応のフェノール及びアニソールの重量測定の結果、及び得られたフェノール樹脂の水酸基の測定結果から、該フェノール樹脂中の水酸基含有芳香族炭化水素基の構造単位と、メトキシ基含有芳香族炭化水素基の構造単位とのモル比率は、前者／後者＝７６／２４であった。得られたフェノール樹脂の軟化点は７４℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は３．８ｄＰａ・ｓ、水酸基当量は２２９ｇ／ｅｑ．であった。得られたフェノール樹脂のＧＰＣチャートを図１６に示す。

226g of phenol resin (A-8) which has a structural unit represented by these was obtained. From the results of the weight measurement of the recovered unreacted phenol and anisole and the measurement result of the hydroxyl group of the obtained phenol resin, the structural unit of the hydroxyl group-containing aromatic hydrocarbon group in the phenol resin and the methoxy group-containing aromatic carbonization The molar ratio of the hydrogen group to the structural unit was the former / the latter = 76/24. The obtained phenol resin had a softening point of 74 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 3.8 dPa · s, and a hydroxyl group equivalent of 229 g / eq. Met. A GPC chart of the obtained phenol resin is shown in FIG.

Example 9 [Synthesis of phenol resin (A-9)]
In Example 1, 188.2 g (2.00 mol) of phenol, 72.5 g (0.67 mol) of anisole, 79.1 g (0.50 mol) of 2-methoxynaphthalene, and 3.6 g of methanesulfonic acid were added to para The following structural formula was obtained in the same manner as in Example 1 except that the amount was changed to 4.3 g of toluenesulfonic acid.

で表される構造単位を有するフェノール樹脂（Ａ−９）１８３ｇを得た。回収した未反応のフェノール及び２−メトキシナフタレンの重量測定の結果、及び得られたフェノール樹脂の水酸基の測定結果から、該フェノール樹脂中の水酸基含有芳香族炭化水素基の構造単位と、メトキシ基含有芳香族炭化水素基の構造単位とのモル比率は、前者／後者＝７２／２８であった。得られたフェノール樹脂の軟化点は６８℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は１．２ｄＰａ・ｓ、水酸基当量は２４０ｇ／ｅｑ．であった。得られたフェノール樹脂のＧＰＣチャートを図１７にＣ^１３ ＮＭＲチャートを図１８、ＭＳスペクトルを図１９に示す。メトキシ基の残存は、ＮＭＲにおける５５ｐｐｍに観測されるメトキシ基のシグナル、及び水酸基当量から化合物中のメトキシ基は分解していないことを確認した。

183 g of a phenol resin (A-9) having a structural unit represented by From the result of the weight measurement of the recovered unreacted phenol and 2-methoxynaphthalene, and the measurement result of the hydroxyl group of the obtained phenol resin, the structural unit of the hydroxyl group-containing aromatic hydrocarbon group in the phenol resin and the methoxy group content The molar ratio of the aromatic hydrocarbon group to the structural unit was the former / the latter = 72/28. The softening point of the obtained phenol resin was 68 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) was 1.2 dPa · s, and the hydroxyl equivalent was 240 g / eq. Met. FIG. 17 shows a GPC chart of the obtained phenol resin, FIG. 18 shows a C ¹³ NMR chart, and FIG. 19 shows an MS spectrum. The residual methoxy group confirmed that the methoxy group in the compound was not decomposed from the methoxy group signal observed at 55 ppm in NMR and the hydroxyl group equivalent.

Example 10 [Synthesis of phenol resin (A-10)]
In Example 9, except that phenol was changed to 157.2 g (1.67 mol) and 2-methoxynaphthalene was changed to 131.3 g (0.83 mol), the following structural formula was obtained.

で表される構造単位を有するフェノール樹脂（Ａ−１０）２３７ｇを得た。回収した未反応のフェノール及び２−メトキシナフタレンの重量測定の結果、及び得られたフェノール樹脂の水酸基の測定結果から、該フェノール樹脂中の水酸基含有芳香族炭化水素基の構造単位と、メトキシ基含有芳香族炭化水素基の構造単位とのモル比率は、前者／後者＝６３／３７であった。得られたフェノール樹脂の軟化点は７０℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は１．３ｄＰａ・ｓ、水酸基当量は３００ｇ／ｅｑ．であった。得られたフェノール樹脂のＧＰＣチャートを図２０にＣ^１３ ＮＭＲチャートを図２１、ＭＳスペクトルを図２２に示す。メトキシ基の残存は、ＮＭＲにおける５５ｐｐｍに観測されるメトキシ基のシグナル、及び水酸基当量から化合物中のメトキシ基は分解していないことを確認した。

237 g of a phenol resin (A-10) having a structural unit represented by From the result of the weight measurement of the recovered unreacted phenol and 2-methoxynaphthalene, and the measurement result of the hydroxyl group of the obtained phenol resin, the structural unit of the hydroxyl group-containing aromatic hydrocarbon group in the phenol resin and the methoxy group content The molar ratio of the aromatic hydrocarbon group to the structural unit was the former / the latter = 63/37. The resulting phenol resin had a softening point of 70 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 1.3 dPa · s, and a hydroxyl group equivalent of 300 g / eq. Met. A GPC chart of the obtained phenol resin is shown in FIG. 20, a C ¹³ NMR chart is shown in FIG. 21, and an MS spectrum is shown in FIG. The residual methoxy group confirmed that the methoxy group in the compound was not decomposed from the methoxy group signal observed at 55 ppm in NMR and the hydroxyl group equivalent.

Synthesis Example 1 (Synthesis of a compound described in JP-A-8-301980)
A 500 ml four-necked flask was charged with 166 g (1.0 mol) of p-xylylene glycol dimethyl ether, 44.5 g (0.25 mol) of anthracene, and 8.4 g of p-toluenesulfonic acid, and stirred under a nitrogen stream. The reaction was performed at 150 ° C. During this time, produced methanol was removed out of the system. After about 2 hours, when 16 g of methanol was produced, 216 g (2 mol) of o-cresol was added, and the mixture was further reacted at 150 ° C. for 2 hours. During this time, the methanol produced was removed out of the system. When the production of methanol is completed, it is neutralized with sodium carbonate, and excess o-cresol is distilled off under reduced pressure.

で表される構造単位を有するフェノール樹脂（Ａ’−１）２００ｇを得た。得られたフェノール樹脂の軟化点は８４℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法，測定温度：１５０℃）は４．４ｄＰａ・ｓ、水酸基当量は２５２ｇ／ｅｑ．であった。

200 g of a phenol resin (A′-1) having a structural unit represented by The resulting phenolic resin had a softening point of 84 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 4.4 dPa · s, and a hydroxyl group equivalent of 252 g / eq. Met.

Synthesis Example 2 (Synthesis of compound of JP-A-8-301980)
A 500 ml four-necked flask was charged with 166 g (1.0 mol) of p-xylylene glycol dimethyl ether, 42.5 g (0.25 mol) of diphenyl ether, and 12.5 g of p-toluenesulfonic acid while stirring under a nitrogen stream. The reaction was performed at 150 ° C. During this time, produced methanol was removed out of the system. After about 3 hours, when 16 g of methanol was produced, 202.5 g (1.88 mol) of o-cresol was added, and the mixture was further reacted at 150 ° C. for 2 hours. During this time, the methanol produced was removed out of the system. When the production of methanol is completed, it is neutralized with sodium carbonate, and excess o-cresol is distilled off under reduced pressure.

で表される構造単位を有するフェノール樹脂（Ａ’−２）２３７．５ｇを得た。を得た。得られたフェノール樹脂の軟化点は１００℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は１９ｄＰａ・ｓ、水酸基当量は２４９ｇ／ｅｑ．であった。

237.5 g of a phenol resin (A′-2) having a structural unit represented by Got. The resulting phenol resin had a softening point of 100 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 19 dPa · s, and a hydroxyl group equivalent of 249 g / eq. Met.

Synthesis Example 3 (Synthesis of compound disclosed in Japanese Patent Application Laid-Open No. 2004-010700)
Charge 108.0 g (1.0 mol) of ortho-cresol and 132.0 g (2.2 mol) of 50% formalin aqueous solution to the reaction vessel and add 133.3 g (1.0 mol) of 30% aqueous sodium hydroxide solution under cooling to 30 ° C. or less. The solution was dropped over 1 hour while maintaining the temperature. After completion of dropping, the temperature was raised to 40 ° C. and reacted for 2 hours. Subsequently, 126.0 g (1.0 mol) of dimethyl sulfate was added dropwise at 40 ° C. over 1 hour, and then the temperature was raised to 60 ° C. and reacted for 2 hours to synthesize a resole resin in which the phenolic hydroxyl group was methoxylated. After completion of the reaction, the aqueous layer was separated, and subsequently 282.0 g (3.0 mol) of phenol and 9.1 g of 35% hydrochloric acid were added and reacted at 90 ° C. for 4 hours. After completion of the reaction, the reaction solution was neutralized with 6.0 g of 25% aqueous ammonia solution, neutralized salts were removed by washing with water, heated to 200 ° C. at 60 mmHg to remove unreacted phenol, and the following structural formula

で表される構造単位を有するフェノール樹脂（Ａ’−３）を得た。得られたフェノール樹脂の軟化点は７７℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法，測定温度：１５０℃）は０．８ｄＰａ・ｓ、水酸基当量は１６０ｇ／ｅｑ．であった。

The phenol resin (A'-3) which has a structural unit represented by this was obtained. The resulting phenol resin had a softening point of 77 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 0.8 dPa · s, and a hydroxyl group equivalent of 160 g / eq. Met.

Synthesis example 4
While performing nitrogen gas purge to a flask equipped with a thermometer, dropping funnel, condenser, and stirrer, Mitsui Chemicals Co., Ltd. Millex XLC-4L168 parts, epichlorohydrin 463 g (5.0 mol), n-butanol 139 g, tetraethylbenzyl 2 g of ammonium 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. 590 g of methyl isobutyl ketone and 177 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 obtain the following structural formula.

で表される構造単位を有するエポキシ樹脂（Ｂ−１）を得た。該エポキシ樹脂のエポキシ当量は２４１ｇ／ｅｑであった。

The epoxy resin (B-1) which has a structural unit represented by this was obtained. The epoxy equivalent of the epoxy resin was 241 g / eq.

Synthesis Example 5 (Synthesis of epoxy resin described in JP-A-2003-201333)
In a 1-liter four-necked flask equipped with a stirrer and a heating device, 152 g (1.0 mol) of trimethylhydroquinone was dissolved in a mixed solvent of 500 g of toluene and 200 g of ethylene glycol monoethyl ether. To the solution, 4.6 g of paratoluenesulfonic acid was added, and 64 g (0.6 mol) of 41% benzaldehyde was added dropwise while paying attention to heat generation, and the mixture was stirred at 100 to 120 ° C. for 15 hours while distilling off water. Next, the mixture was cooled and the precipitated crystals were separated by filtration, washed repeatedly with water until neutral, and then dried to obtain 175 g of phenol resin (GPC purity: 99%).
While a nitrogen gas purge was applied to a flask equipped with a thermometer, dropping funnel, condenser, and stirrer, 175 g phenol resin, 463 g epichlorohydrin (53 mol), 53 g n-butanol, and 2.3 g tetraethylbenzylammonium chloride were dissolved. It was. After raising the temperature to 65 ° C., the pressure was reduced to an azeotropic pressure, and 82 g (1.0 mol) of 49% aqueous sodium hydroxide solution was added dropwise over 5 hours, and then the mixture was stirred for 0.5 hours under the same conditions. Continued.
During this time, the distillate distilled azeotropically was separated by a Dean-Stark trap, the aqueous 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. 550 g of methyl isobutyl ketone and 55 g of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 15 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours. Then, washing with 100 g of water was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after microfiltration, the solvent was distilled off under reduced pressure to obtain the following structural formula

で表されるエポキシ樹脂（Ｂ−２）を得た。このエポキシ樹脂のエポキシ当量は２６２ｇ／ｅｑであった。

The epoxy resin (B-2) represented by these was obtained. The epoxy equivalent of this epoxy resin was 262 g / eq.

Examples 11-25 and Comparative Examples 1-3
As the epoxy resin (B-1) to (B-2) and YX-4000H (tetramethylbiphenol type epoxy resin, epoxy equivalent: 188 g / eq) manufactured by Japan Epoxy Resin Co., Ltd., NC- manufactured by Nippon Kayaku Co., Ltd. 3000 (biphenyl aralkyl type epoxy resin, epoxy equivalent: 274 g / eq), EXA-4700 (naphthalene type epoxy resin, epoxy equivalent: 164 g / eq) manufactured by Dainippon Ink and Chemicals, (A-1) to (A-1) to (A-7), (A'-1) to (A'-3) were used as comparative curing agents, triphenylphosphine (TPP) as a curing accelerator, and condensed phosphate ester (Dahachi Chemical Industry as a flame retardant) PX-200), magnesium hydroxide (Echo Mug Z-10, manufactured by Air Water Co., Ltd.), inorganic filler Spherical silica (S-COL manufactured by Micron Co., Ltd.) as a material, γ-glycidoxytriethoxyxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.), carnauba wax (PEARL WAX manufactured by Serra Rica Noda Co., Ltd.) as a silane coupling agent No. 1-P), carbon black was used in the composition shown in Tables 1 to 3, and melted and kneaded for 5 minutes at a temperature of 85 ° C. using two rolls to obtain the desired composition. Was evaluated. Moreover, the physical property of hardened | cured material created the sample for evaluation by the following method using the said composition, measured heat resistance, a flame retardance, and a dielectric property with the following method, and shows a result in Tables 1-2. It was.

<Heat resistance>
Glass transition temperature: measured using a viscoelasticity measuring device (solid viscoelasticity measuring device RSAII manufactured by Rheometric Co., Ltd., double currant lever method; frequency 1 Hz, temperature rising rate 3 ° C./min).
<Curing property>
0.15 g of the epoxy resin composition is placed on a cure plate (made by THERMO ELECTRIC) heated to 175 ° C., and time measurement is started with a stopwatch. Stir the sample evenly with the tip of the rod and stop the stopwatch when the sample breaks into a string and remains on 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 Tables 1 and 2:
* 1: Maximum combustion time (seconds) in one flame contact
* 2: Total burning time of 5 test pieces (seconds)
* 3: Although the flame retardancy required for V-1 (ΣF ≦ 250 seconds and F _max ≦ 30 seconds) is not satisfied, it does not reach combustion (flame clamp arrival) and extinguishes.

Example 26 [Synthesis of Epoxy Resin (E-1)]
A flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer was purged with nitrogen gas while 233 g (1 equivalent of hydroxyl group) of the phenol resin (A-1) obtained in Example 1 and 463 g of epichlorohydrin (5. 0 mol), 139 g of n-butanol and 2 g of tetraethylbenzylammonium chloride were 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. 590 g of methyl isobutyl ketone and 177 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 obtain the following structural formula.

で表される構造単位を有するエポキシ樹脂（Ｅ−１）２６０ｇを得た。得られたエポキシ樹脂の軟化点は６５℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は４．０ｄＰａ・ｓ、エポキシ当量は３０３ｇ／ｅｑ．であった。

260 g of an epoxy resin (E-1) having a structural unit represented by The resulting epoxy resin had a softening point of 65 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometry method, measurement temperature: 150 ° C.) of 4.0 dPa · s, and an epoxy equivalent of 303 g / eq. Met.

FIG. 23 shows a GPC chart of the obtained epoxy resin, FIG. 24 shows a C ¹³ NMR chart, and FIG. 25 shows an MS spectrum. The residual methoxy group confirmed that the methoxy group in the compound was not decomposed from the signal of methoxy group observed at 55 ppm in NMR and the epoxy equivalent. The molar ratio between the structural unit of the glycidyloxy group-containing aromatic hydrocarbon group and the structural unit of the methoxy group-containing aromatic hydrocarbon group in the epoxy resin is the same as that when the phenol resin (A-1) was produced. It calculated | required from the measurement result of the collected unreacted phenol and anisole, and the measurement result of the hydroxyl group of the obtained phenol resin. As a result, the former / the latter was 76/24.

Example 27 [Synthesis of Epoxy Resin (E-2)]
The epoxidation reaction was performed in the same manner as in Example 26 except that the phenol resin (A-1) in Example 1 was changed to 254 g (1 equivalent of hydroxyl group) of the phenol resin (A-2) obtained in Example 2. The following structural formula

で表される構造単位を有するエポキシ樹脂（Ｅ−２）２７７ｇを得た。得られたエポキシ樹脂の軟化点は５６℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は１．２ｄＰａ・ｓ、エポキシ当量は３２８ｇ／ｅｑ．であった。

277 g of an epoxy resin (E-2) having a structural unit represented by The resulting epoxy resin had a softening point of 56 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometry method, measurement temperature: 150 ° C.) of 1.2 dPa · s, and an epoxy equivalent of 328 g / eq. Met.

FIG. 26 shows a GPC chart of the obtained epoxy resin, FIG. 27 shows a C ¹³ NMR chart, and FIG. 28 shows an MS spectrum. The residual methoxy group confirmed that the methoxy group in the compound was not decomposed from the signal of methoxy group observed at 55 ppm in NMR and the epoxy equivalent. The molar ratio between the structural unit of the glycidyloxy group-containing aromatic hydrocarbon group and the structural unit of the methoxy group-containing aromatic hydrocarbon group in the epoxy resin is the same as that when the phenol resin (A-2) was produced. It calculated | required from the measurement result of the hydroxyl group of the phenol resin obtained as a result of the weight measurement of the unreacted phenol and 1, 2- dimethoxybenzene which were collect | recovered. As a result, the former / the latter was 67/33.

Example 28 [Synthesis of Epoxy Resin (E-3)]
Except that the phenol resin (A-1) was changed to 230 g (hydroxyl group 1 equivalent) of the phenol resin (A-3) obtained in Example 3, the same structural formula as shown below was performed.

で表される構造単位を有するエポキシ樹脂（Ｅ−３）２５０ｇを得た。得られたエポキシ樹脂の軟化点は５７℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は２．４ｄＰａ・ｓ、エポキシ当量は２９７ｇ／ｅｑ．であった。

The epoxy resin (E-3) 250g which has a structural unit represented by this was obtained. The resulting epoxy resin had a softening point of 57 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometry method, measurement temperature: 150 ° C.) of 2.4 dPa · s, and an epoxy equivalent of 297 g / eq. Met.

The GPC chart of the obtained epoxy resin is shown in FIG. 29, the C ¹³ NMR chart is shown in FIG. 30, and the MS spectrum is shown in FIG. The residual methoxy group confirmed that the methoxy group in the compound was not decomposed from the signal of methoxy group observed at 55 ppm in NMR and the epoxy equivalent. In addition, the molar ratio of the structural unit of the glycidyloxy group-containing aromatic hydrocarbon group and the structural unit of the methoxy group-containing aromatic hydrocarbon group in the epoxy resin is the same as that when the phenol resin (A-3) was produced. It was determined from the results of the weight measurement of the recovered unreacted o-cresol and anisole and the measurement result of the hydroxyl group of the obtained phenol resin. As a result, the former / the latter was 81/19.

Example 29 [Synthesis of Epoxy Resin (E-4)]
Except that the phenol resin (A-1) was changed to 296 g (hydroxyl group 1 equivalent) of the phenol resin (A-4) obtained in Example 4, the following structural formula was obtained.

で表される構造単位を有するエポキシ樹脂（Ｅ−４）３２０ｇを得た。得られたエポキシ樹脂の軟化点は８５℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は１３．２ｄＰａ・ｓ、エポキシ当量は３７０ｇ／ｅｑ．であった。

320 g of an epoxy resin (E-4) having a structural unit represented by The resulting epoxy resin had a softening point of 85 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometry method, measurement temperature: 150 ° C.) of 13.2 dPa · s, and an epoxy equivalent of 370 g / eq. Met.

FIG. 32 shows a GPC chart of the resulting epoxy resin, FIG. 33 shows a C ¹³ NMR chart, and FIG. 34 shows an MS spectrum. The residual methoxy group confirmed that the methoxy group in the compound was not decomposed from the signal of methoxy group observed at 55 ppm in NMR and the epoxy equivalent. The molar ratio between the structural unit of the glycidyloxy group-containing aromatic hydrocarbon group and the structural unit of the methoxy group-containing aromatic hydrocarbon group in the epoxy resin is the same as that when the phenol resin (A-4) was produced. It calculated | required from the measurement result of the hydroxyl group of the phenol resin obtained as a result of the weight measurement of the unreacted phenol and anisole which collect | recovered. As a result, the former / the latter was 75/25.

Example 30 [Synthesis of Epoxy Resin (E-5)]
The phenol resin (A-1) was changed in the same manner as in Example 26 except that the phenol resin (A-6) obtained in Example 6 was changed to 279 g (1 equivalent of hydroxyl group).

で表される構造単位を有するエポキシ樹脂（Ｅ−５）３０１ｇを得た。得られたエポキシ樹脂の軟化点は６８℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は５．６ｄＰａ・ｓ、エポキシ当量は３５５ｇ／ｅｑ．であった。尚、化合物中の前記一般式（３）で表される構造単位と前記一般式（４）で表される構造単位のモル比率は、フェノール樹脂（Ａ−６）を製造した際の回収した未反応のフェノール及びアニソールの重量測定の結果、及び得られたフェノール樹脂の水酸基の測定結果から求めた。その結果、前者／後者＝５３／４７であった。得られたエポキシ樹脂のＧＰＣチャートを図３５に示す。

The epoxy resin (E-5) 301g which has a structural unit represented by this was obtained. The resulting epoxy resin had a softening point of 68 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 5.6 dPa · s, and an epoxy equivalent of 355 g / eq. Met. In addition, the molar ratio of the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) in the compound is the unrecovered amount when the phenol resin (A-6) was produced. It calculated | required from the measurement result of the hydroxyl group of the obtained phenol resin, and the result of the weight measurement of the phenol and anisole of reaction. As a result, the former / the latter was 53/47. A GPC chart of the obtained epoxy resin is shown in FIG.

Example 31 [Synthesis of Epoxy Resin (E-6)]
Except that the phenol resin (A-1) was changed to 240 g of the phenol resin (A-9) obtained in Example 9, an epoxidation reaction was performed in the same manner as in Example 1, and the following structural formula

で表される構造単位を有するエポキシ樹脂（Ｅ−６）２７０ｇを得た。得られたエポキシ樹脂の軟化点は６０℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は１．２ｄＰａ・ｓ、エポキシ当量は３１９ｇ／ｅｑ．であった。
得られたエポキシ樹脂のＧＰＣチャートを図３６に、Ｃ^１３ ＮＭＲチャートを図３７に、ＭＳスペクトルを図３８に示す。メトキシ基の残存は、ＮＭＲにおける５５ｐｐｍに観測されるメトキシ基のシグナル、及びエポキシ当量から化合物中のメトキシ基は分解していないことを確認した。尚、該エポキシ樹脂中のグリシジルオキシ基含有芳香族炭化水素基の構造単位と、メトキシ基含有芳香族炭化水素基の構造単位とのモル比率は、フェノール樹脂（Ａ−９）を製造した際の回収した未反応のフェノール及びアニソールの重量測定の結果と得られたフェノール樹脂の水酸基の測定結果から求めた。その結果、前者／後者＝７２／２８であった。

270 g of an epoxy resin (E-6) having a structural unit represented by The resulting epoxy resin had a softening point of 60 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometry method, measurement temperature: 150 ° C.) of 1.2 dPa · s, and an epoxy equivalent of 319 g / eq. Met.
The GPC chart of the obtained epoxy resin is shown in FIG. 36, the C ¹³ NMR chart is shown in FIG. 37, and the MS spectrum is shown in FIG. The residual methoxy group confirmed that the methoxy group in the compound was not decomposed from the signal of methoxy group observed at 55 ppm in NMR and the epoxy equivalent. The molar ratio of the structural unit of the glycidyloxy group-containing aromatic hydrocarbon group and the structural unit of the methoxy group-containing aromatic hydrocarbon group in the epoxy resin is the same as that when the phenol resin (A-9) was produced. It calculated | required from the measurement result of the collected unreacted phenol and anisole, and the measurement result of the hydroxyl group of the obtained phenol resin. As a result, the former / the latter was 72/28.

Synthesis Example 7 (Synthesis of epoxy resin described in JP-A-8-301980)
An epoxidation reaction was carried out in the same manner as in Example 26 except that the phenol resin (A′- 1 ) obtained in Synthesis Example 1 was used in place of the phenol resin (A-1).

で表される構造単位を有するエポキシ樹脂（Ｅ’−１）を得た。得られたエポキシ樹脂の軟化点は６１℃（Ｂ＆Ｒ法）、エポキシ当量は３２４ｇ／ｅｑ．であった。

The epoxy resin (E'-1) which has a structural unit represented by this was obtained. The resulting epoxy resin had a softening point of 61 ° C. (B & R method) and an epoxy equivalent of 324 g / eq. Met.

Synthesis Example 8 (Synthesis of epoxy resin described in JP-A-8-301980)
An epoxidation reaction was performed in the same manner as in Example 26 except that the phenol resin (A′- 2 ) obtained in Synthesis Example 2 was used instead of the phenol resin (A-1), and the following structural formula

で表される構造単位を有するエポキシ樹脂（Ｅ’−２）を得た。得られたエポキシ樹脂の軟化点は７９℃（Ｂ＆Ｒ法）、エポキシ当量は４２１ｇ／ｅｑ．であった。

The epoxy resin (E'-2) which has a structural unit represented by this was obtained. The resulting epoxy resin had a softening point of 79 ° C. (B & R method) and an epoxy equivalent of 421 g / eq. Met.

Examples 32-44 and Comparative Examples 4-5
(E-1) to (E-5) as epoxy resins, (B-2) obtained in Synthesis Example 5 as epoxy resins to be used in combination, (E′-1) and (E) as epoxy resins for comparison '-2), the phenol resin (A-1) obtained in Example 1 above, the phenol resin (A-2) obtained in Example 2 and the phenol obtained in Example 4 as curing agents. Resin (A-4) and Mitsui Chemicals XLC-LL (Zylock resin, hydroxyl group equivalent: 176 g / eq), triphenylphosphine (TPP) as a curing accelerator, and condensed phosphate ester (Dahachi Chemical Co., Ltd.) as a flame retardant Company PX-200), 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, and silane coupling agent Compositions shown in Tables 4 to 6 using γ-glycidoxytriethoxyxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.), carnauba wax (PEARL WAX No. 1-P manufactured by Celerica Noda Co., Ltd.), and carbon black. The mixture was melt kneaded for 5 minutes at a temperature of 85 ° C. using two rolls to obtain the epoxy resin composition of the present invention, and the curability was evaluated. Moreover, the physical property of hardened | cured material produced the sample for evaluation by the following method using the said composition, and measured heat resistance, a flame retardance, and a dielectric characteristic by the following method.

<Heat resistance>
Glass transition temperature: measured using a viscoelasticity measuring device (solid viscoelasticity measuring device RSAII manufactured by Rheometric Co., Ltd., double currant lever method; frequency 1 Hz, temperature rising rate 3 ° C./min).
<Curing property>
0.15 g of the epoxy resin composition is placed on a cure plate (made by THERMO ELECTRIC) heated to 175 ° C., and time measurement is started with a stopwatch. Stir the sample evenly with the tip of the rod and stop the stopwatch when the sample breaks into a string and remains on the plate. The time until this sample was cut and remained on the plate was defined as the gel time.
<Flame retardance evaluation>
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 Tables 1 and 2:
* 1: Maximum combustion time (seconds) in one flame contact
* 2: Total burning time of 5 test pieces (seconds)

FIG. 1 is a GPC chart of the phenol resin obtained in Example 1. FIG. 2 is a ¹³ C-NMR spectrum of the phenol resin obtained in Example 1. FIG. 3 is a mass spectrum of the phenol resin obtained in Example 1. FIG. 4 is a GPC chart of the phenol resin obtained in Example 2. FIG. 5 is a ¹³ C-NMR spectrum of the phenol resin obtained in Example 2. FIG. 6 is a mass spectrum of the phenol resin obtained in Example 2. FIG. 7 is a GPC chart of the phenol resin obtained in Example 3. FIG. 8 is a ¹³ C-NMR spectrum of the phenol resin obtained in Example 3. FIG. 9 is a mass spectrum of the phenol resin obtained in Example 3. FIG. 10 is a GPC chart of the phenol resin obtained in Example 4. FIG. 11 is a ¹³ C-NMR spectrum of the phenol resin obtained in Example 4. FIG. 12 is a mass spectrum of the phenol resin obtained in Example 4. FIG. 13 is a GPC chart of the phenol resin obtained in Example 5. FIG. 14 is a GPC chart of the phenol resin obtained in Example 6. FIG. 15 is a GPC chart of the phenol resin obtained in Example 7. FIG. 16 is a GPC chart of the phenol resin obtained in Example 8. FIG. 17 is a GPC chart of the phenol resin obtained in Example 9. 18 is a ¹³ C-NMR spectrum of the phenol resin obtained in Example 9. FIG. FIG. 19 is a mass spectrum of the phenol resin obtained in Example 9. FIG. 20 is a GPC chart of the phenol resin obtained in Example 10. FIG. 21 is a ¹³ C-NMR spectrum of the phenol resin obtained in Example 10. FIG. 22 is a mass spectrum of the phenol resin obtained in Example 10. FIG. 23 is a GPC chart of the epoxy resin obtained in Example 26. FIG. 24 is a ¹³ C-NMR spectrum of the epoxy resin obtained in Example 26. FIG. 25 is a mass spectrum of the epoxy resin obtained in Example 26. FIG. 26 is a GPC chart of the epoxy resin obtained in Example 27. FIG. 27 is the ¹³ C-NMR spectrum of the epoxy resin obtained in Example 27. FIG. 28 is a mass spectrum of the epoxy resin obtained in Example 27. FIG. 29 is a GPC chart of the epoxy resin obtained in Example 28. FIG. 30 is the ¹³ C-NMR spectrum of the epoxy resin obtained in Example 28. FIG. 31 is a mass spectrum of the epoxy resin obtained in Example 28. FIG. 32 is a GPC chart of the epoxy resin obtained in Example 29. FIG. 33 is the ¹³ C-NMR spectrum of the epoxy resin obtained in Example 29. FIG. 34 is a mass spectrum of the epoxy resin obtained in Example 29. FIG. 35 is a GPC chart of the epoxy resin obtained in Example 30. FIG. 36 is a GPC chart of the epoxy resin obtained in Example 31. FIG. 37 is the ¹³ C-NMR spectrum of the epoxy resin obtained in Example 31. FIG. 38 is a mass spectrum of the epoxy resin obtained in Example 31.

Claims (19)

An epoxy resin composition comprising an epoxy resin and a curing agent as essential components, wherein the curing agent comprises a hydroxy group-containing aromatic compound (a1), an alkoxy group-containing aromatic compound (a2), and the following structural formula (a3- a), (a3-b) or (a3-c)

(X in the formula (a3-a) represents a halogen atom, and in the formula (a3-b), R ₂ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms). Obtained by reacting with a compound, and
Phenolic hydroxyl group-containing aromatic hydrocarbon group (P),
Alkoxy group-containing aromatic hydrocarbon group (B), and a divalent aralkyl Len group (X)
Each structural part, and
The divalent aralkyl Len group (X) is represented by the following structural formula (1)

(R ₁ represents a hydrogen atom or a methyl group, and Ar represents a phenylene group, a biphenylene group, a diphenyl ether-4,4′-diyl group, or a naphthylene group.)
A divalent hydrocarbon group having a structure represented by:
The phenolic hydroxyl group-containing aromatic hydrocarbon group (P) and the alkoxy group-containing aromatic hydrocarbon group (B) and is attached through the divalent aralkyl Len group (X) structure,
Structure a phenolic hydroxyl group-containing aromatic hydrocarbon group (P) is bound to the other of the phenolic hydroxyl group-containing aromatic hydrocarbon group (P) via the divalent aralkyl Len group (X),
Or
Yes the alkoxy group-containing aromatic hydrocarbon group (B) is bonded to the other of the alkoxy group-containing aromatic hydrocarbon group (B) via the divalent aralkyl Len group (X) structure in the molecular structure An epoxy resin composition characterized by being a phenol resin. The alkoxy group-containing aromatic hydrocarbon group (B) is formed from a molecular structure selected from methoxybenzene, methoxynaphthalene, ethoxybenzene, ethoxynaphthalene, and compounds having a methyl group as a substituent on the aromatic nucleus. A monovalent or polyvalent aromatic hydrocarbon group,
The divalent aralkyl Len group (X) is represented by the following structural formula (1)

(R ₁ represents a hydrogen atom or a methyl group, and Ar represents a phenylene group, a biphenylene group, a diphenyl ether-4,4′-diyl group, or a naphthylene group.)
A divalent hydrocarbon group having a structure represented by:
The phenolic hydroxyl group-containing aromatic hydrocarbon group (P) is formed from a molecular structure selected from phenol, naphthol, and a compound having a methyl group as a substituent on these aromatic nuclei. The epoxy resin composition according to claim 1, which is an aromatic hydrocarbon group. 2. The abundance ratio of the phenolic hydroxyl group-containing aromatic hydrocarbon group (P) and the alkoxy group aromatic hydrocarbon group (B) is in the range of the former / the latter = 30/70 to 98/2. Or the epoxy resin composition of 2. The epoxy resin composition according to claim 1, 2 or 3, wherein the phenol resin has a hydroxyl equivalent of 150 to 500 g / eq. It is an epoxy resin composition as described in any one of Claims 1-4, Comprising: In addition to the said epoxy resin and the said hardening | curing agent, it further contains an inorganic filler in the ratio of 70-95 mass% in a composition. A semiconductor sealing material comprising an epoxy resin composition. A cured epoxy resin obtained by curing the epoxy resin composition according to any one of claims 1 to 4. Hydroxy group-containing aromatic compound (a1), alkoxy group-containing aromatic compound (a2), and the following structural formula (a3-a), (a3-b) or (a3-c)

(X in the formula (a3-a) represents a halogen atom, and in the formula (a3-b), R ₂ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms). Obtained by reacting with a compound, and
Phenolic hydroxyl group-containing aromatic hydrocarbon group (P),
Alkoxy group-containing aromatic hydrocarbon group (B), and a divalent aralkyl Len group (X)
Each structural part, and
The divalent aralkyl Len group (X) is represented by the following structural formula (1)

(R ₁ represents a hydrogen atom or a methyl group, and Ar represents a phenylene group, a biphenylene group, a diphenyl ether-4,4′-diyl group, or a naphthylene group.)
A divalent hydrocarbon group having a structure represented by:
The phenolic hydroxyl group-containing aromatic hydrocarbon group (P) and the alkoxy group-containing aromatic hydrocarbon group (B) and is attached through the divalent aralkyl Len group (X) structure,
Structure a phenolic hydroxyl group-containing aromatic hydrocarbon group (P) is bound to the other of the phenolic hydroxyl group-containing aromatic hydrocarbon group (P) via the divalent aralkyl Len group (X),
Or
Yes the alkoxy group-containing aromatic hydrocarbon group (B) is bonded to the other of the alkoxy group-containing aromatic hydrocarbon group (B) via the divalent aralkyl Len group (X) structure in the molecular structure A novel phenol resin having a melt viscosity of 0.3 to 5.0 dPa · s and a hydroxyl group equivalent of 150 to 500 g / eq measured at 150 ° C. measured with an ICI viscometer. The alkoxy group-containing aromatic hydrocarbon group (B) is formed from a molecular structure selected from methoxybenzene, methoxynaphthalene, ethoxybenzene, ethoxynaphthalene, and compounds having a methyl group as a substituent on the aromatic nucleus. A divalent or trivalent aromatic hydrocarbon group,
The divalent aralkyl Len group (X) is represented by the following structural formula (1)

(R ₁ represents a hydrogen atom or a methyl group, and Ar represents a phenylene group, a biphenylene group, or a diphenyl ether-4,4′-diyl group.)
A divalent hydrocarbon group having a structure represented by:
The phenolic hydroxyl group-containing aromatic hydrocarbon group (P) is formed from a molecular structure selected from phenol, naphthol, and a compound having a methyl group as a substituent on these aromatic nuclei. The novel phenol resin according to claim 7, which is an aromatic hydrocarbon group. An epoxy resin composition comprising an epoxy resin and a curing agent as essential components, wherein the epoxy resin is
Hydroxy group-containing aromatic compound (a1), alkoxy group-containing aromatic compound (a2), and the following structural formula (a3-a), (a3-b) or (a3-c)

(X in the formula (a3-a) represents a halogen atom, and in the formula (a3-b), R ₂ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms). It is obtained by reacting a compound with a phenol resin and then reacting it with an epihalohydrin, and
Glycidyloxy group-containing aromatic hydrocarbon group (E),
Alkoxy aromatic hydrocarbon group (B), and a divalent aralkyl Len group (X)
Each structure, and
The divalent aralkyl Len group (X) is represented by the following structural formula (1)

(R ₁ represents a hydrogen atom or a methyl group, and Ar represents a phenylene group, a biphenylene group, a diphenyl ether-4,4′-diyl group, or a naphthylene group.)
A divalent hydrocarbon group having a structure represented by:
The glycidyloxy group-containing aromatic hydrocarbon group (E) and the alkoxy group-containing aromatic hydrocarbon group (B) is attached through the divalent aralkyl Len group (X) structure,
Structure the glycidyloxy group-containing aromatic hydrocarbon group (E) is bonded to the other of the glycidyloxy group-containing aromatic hydrocarbon group (E) via the divalent aralkyl Len group (X),
Or
Having an alkoxy group-containing aromatic hydrocarbon group (B) is bonded to the other of the alkoxy group-containing aromatic hydrocarbon group (B) via the divalent aralkyl Len group (X) structure in the molecular structure An epoxy resin composition characterized by being a thing. The alkoxy group-containing aromatic hydrocarbon group (B) is formed from a molecular structure selected from methoxybenzene, methoxynaphthalene, ethoxybenzene, ethoxynaphthalene, and compounds having a methyl group as a substituent on the aromatic nucleus. A divalent or trivalent aromatic hydrocarbon group,
The divalent aralkyl Len group (X) is represented by the following structural formula (1)

(R ₁ represents a hydrogen atom or a methyl group, and Ar represents a phenylene group, a biphenylene group, or a diphenyl ether-4,4′-diyl group.)
A divalent hydrocarbon group having a structure represented by:
The glycidyloxy group-containing aromatic hydrocarbon group (E) is formed from a molecular structure selected from glycidyloxybenzene, glycidyloxynaphthalene, and compounds having a methyl group as a substituent on the aromatic nucleus 2 The epoxy resin composition according to claim 9, which is a valent or trivalent aromatic hydrocarbon group. The abundance ratio between the glycidyloxy group-containing aromatic hydrocarbon group (E) and the alkoxy group-containing aromatic hydrocarbon group (B) is in the range of the former / the latter = 30/70 to 98/2. The epoxy resin composition according to 9 or 10. The epoxy resin composition according to claim 9, 10 or 11, wherein the epoxy resin has an epoxy equivalent of 200 to 700 g / eq. The curing agent is
Phenolic hydroxyl group-containing aromatic hydrocarbon group (P),
Alkoxy group-containing aromatic hydrocarbon group (B), and a divalent aralkyl Len group (X)
Each structural part, and
The divalent aralkyl Len group (X) is represented by the following structural formula (1)

(R ₁ represents a hydrogen atom or a methyl group, and Ar represents a phenylene group, a biphenylene group, a diphenyl ether-4,4′-diyl group, or a naphthylene group.)
A divalent hydrocarbon group having a structure represented by:
The phenolic hydroxyl group-containing aromatic hydrocarbon group (P) and the alkoxy group-containing aromatic hydrocarbon group (B) and is attached through the divalent aralkyl Len group (X) structure,
Structure a phenolic hydroxyl group-containing aromatic hydrocarbon group (P) is bound to the other of the phenolic hydroxyl group-containing aromatic hydrocarbon group (P) via the divalent aralkyl Len group (X),
Or
Having an alkoxy group-containing aromatic hydrocarbon group (B) is bonded to the other of the alkoxy group-containing aromatic hydrocarbon group (B) via the divalent aralkyl Len group (X) structure in the molecular structure The epoxy resin composition according to any one of claims 9 to 12, which is a phenol resin. It is an epoxy resin composition as described in any one of Claims 9-13, Comprising: In addition to the said epoxy resin and the said hardening | curing agent, it further contains an inorganic filler in the ratio of 70-95 mass% in a composition. A semiconductor sealing material comprising an epoxy resin composition. A cured epoxy resin obtained by curing the epoxy resin composition according to any one of claims 9 to 13. Hydroxy group-containing aromatic compound (a1), alkoxy group-containing aromatic compound (a2), and the following structural formula (a3-a), (a3-b) or (a3-c)

(X in the formula (a3-a) represents a halogen atom, and in the formula (a3-b), R ₂ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms). It is obtained by reacting a compound with a phenol resin and then reacting it with an epihalohydrin, and
Glycidyloxy group-containing aromatic hydrocarbon group (E),
Alkoxy group-containing aromatic hydrocarbon group (B), and a divalent aralkyl alkylene group (X)
Each structure, and
The divalent aralkyl Len group (X) is represented by the following structural formula (1)

(R ₁ represents a hydrogen atom or a methyl group, and Ar represents a phenylene group, a biphenylene group, a diphenyl ether-4,4′-diyl group, or a naphthylene group.)
A divalent hydrocarbon group having a structure represented by:
The glycidyloxy group-containing aromatic hydrocarbon group (E) and the alkoxy group-containing aromatic hydrocarbon group (B) is attached through the divalent aralkyl Len group (X) structure,
Structure the glycidyloxy group-containing aromatic hydrocarbon group (E) is bonded to the other of the glycidyloxy group-containing aromatic hydrocarbon group (E) via the divalent aralkyl Len group (X),
Or
Yes the alkoxy group-containing aromatic hydrocarbon group (B) is bonded to the other of the alkoxy group-containing aromatic hydrocarbon group (B) via the divalent aralkyl Len group (X) structure in the molecular structure A novel epoxy resin having a melt viscosity at 150 ° C. of 0.3 to 5.0 dPa · s and an epoxy equivalent of 200 to 700 g / eq measured with an ICI viscometer. The alkoxy group-containing aromatic hydrocarbon group (B) is formed from a molecular structure selected from methoxybenzene, methoxynaphthalene, ethoxybenzene, ethoxynaphthalene, and compounds having a methyl group as a substituent on the aromatic nucleus. A divalent or trivalent aromatic hydrocarbon group,
The divalent aralkyl Len group (X) is represented by the following structural formula (1)

(R ₁ represents a hydrogen atom or a methyl group, and Ar represents a phenylene group, a biphenylene group, or a diphenyl ether-4,4′-diyl group.)
A divalent hydrocarbon group having a structure represented by:
The glycidyloxy group-containing aromatic hydrocarbon group (E) is formed from a molecular structure selected from glycidyloxybenzene, glycidyloxynaphthalene, and compounds having a methyl group as a substituent on the aromatic nucleus 2 The novel epoxy resin according to claim 16, which is a valent or trivalent aromatic hydrocarbon group. Hydroxy group-containing aromatic compound (a1), alkoxy group-containing aromatic compound (a2), and the following structural formula (a3-a), (a3-b) or (a3-c)

(X in the formula (a3-a) represents a halogen atom, and in the formula (a3-b), R ₂ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms). A method for producing a novel phenol resin, comprising reacting a compound. A method for producing a novel epoxy resin, comprising reacting epichlorohydrin with the novel phenol resin obtained according to claim 18.

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