JP6580849B2 - Terminal-modified soluble polyfunctional vinyl aromatic copolymer and process for producing the same - Google Patents

Description

  The present invention relates to a novel terminal-modified soluble polyfunctional vinyl aromatic copolymer having improved heat resistance, fluidity, compatibility and toughness, a method for producing the same, and electrical properties such as dielectric properties containing the copolymer. It is related with the curable composition which is excellent in this, and its hardened | cured material, and is used suitably for the electrical insulation material etc. of information communication equipment.

  With the increase in information traffic in recent years, information communication in the high frequency band has been actively performed, and in order to reduce the transmission loss in the higher frequency band, more excellent electrical characteristics, in particular, low dielectric constant and low There is a need for an electrical insulating material that has a dielectric loss tangent and in particular has a small change in dielectric properties after water absorption. In addition, as seen in recent mobile communication terminals, with the progress of advanced thinning, insulating materials having a lower dielectric constant are required. Furthermore, since printed circuit boards or electronic components using these electrical insulating materials are exposed to high-temperature solder reflow during mounting, a material having high heat resistance, that is, a high glass transition temperature is desired. In particular, recently, due to the use of lead-free solder having a high melting point due to environmental problems, there is an increasing demand for an electrically insulating material with higher heat resistance. In response to these requirements, curable resins using vinyl compounds having various chemical structures have been proposed.

  As such a cured resin, for example, in Patent Document 1, a divinyl aromatic compound and a monovinyl aromatic compound are polymerized in an organic solvent at a temperature of 20 to 100 ° C. in the presence of a Lewis acid catalyst and an initiator having a specific structure. The soluble polyfunctional vinyl aromatic copolymer obtained by making it to have been disclosed is disclosed. Patent Document 2 discloses a monomer component containing 20 to 100 mol% of a divinyl aromatic compound in the presence of a quaternary ammonium salt in the presence of a Lewis acid catalyst and a specific structure initiator at 20 to 120 ° C. A method for producing a soluble polyfunctional vinyl aromatic copolymer having a controlled molecular weight distribution by cationic polymerization at a temperature of 5 ° C is disclosed. The soluble polyfunctional vinyl aromatic copolymer obtained by the techniques disclosed in these two patent documents is excellent in solvent solubility and processability, and by using this, a cured product excellent in heat resistance having a high glass transition temperature. Can be obtained.

  Since the soluble polyfunctional vinyl aromatic copolymer obtained by these techniques has a polymerizable double bond in itself, it is cured to give a cured product having a high glass transition temperature. Therefore, it can be said that this hardened | cured material or soluble polyfunctional vinyl aromatic copolymer is a polymer excellent in heat resistance, or its precursor. And this soluble polyfunctional vinyl aromatic copolymer is copolymerized with other radical polymerizable monomers to give a cured product, and this cured product is also a polymer having excellent heat resistance.

  However, from the viewpoint of compatibility between the soluble polyfunctional vinyl aromatic copolymer disclosed in Patent Document 1 and Patent Document 2 and other curable resins, and heat-resistant discoloration after curing, the polarity is high. The compatibility or solubility between the epoxy compound and the phenol resin is not sufficient, and the thermal decomposition resistance to a high process temperature is not sufficient. Therefore, in many cases, an opaque composition is provided depending on the type of epoxy compound or phenol resin, and it becomes difficult to produce a uniform cured product of the epoxy compound or phenol resin and a soluble polyfunctional vinyl aromatic copolymer. In addition to the disadvantages of a low degree of freedom in compounding formulation design and low toughness of the cured product, there were cases where defects such as blistering and peeling occurred due to a high thermal history near 280 to 300 ° C. Furthermore, since the soluble polyfunctional vinyl aromatic copolymer disclosed in Patent Document 1 and Patent Document 2 is poor in fluidity, the filling property for a fine wiring pattern is insufficient. There was a disadvantage that the reliability after wet heat history was insufficient.

Patent Document 3 discloses (A) a Lewis acid catalyst, (B) a cocatalyst such as an ester compound, and (C) a divinyl aromatic compound (a) and a monovinyl aromatic in the presence of a polymerization additive such as an alcohol compound. Soluble polyfunctional copolymer obtained by copolymerizing the aromatic compound (b) having a chain hydrocarbon group or aromatic hydrocarbon group via an ether bond or thioether bond in a part of its end group Vinyl aromatic copolymers are disclosed.
However, when a polymerization additive such as an alcohol compound described in Patent Document 3 is used, the molecular weight of the soluble polyfunctional vinyl aromatic copolymer increases, so that the fluidity is insufficient, or the soluble polyfunctional vinyl aromatic There is a problem that the toughness is insufficient because the cross-linking density of the group copolymer is high. Therefore, sufficient mechanical properties cannot be obtained in the cured product of the curable composition, and the composite cured product has reliability due to insufficient adhesion at the interface and insufficient delamination strength. There was a problem of a decrease. Patent Document 3 describes that ether compounds such as diethyl ether and tetrahydrolane can be used as the promoter as the component (B). However, these ether compounds have a function as a co-catalyst, but have no reactivity with carbocations, and therefore cannot be used for terminal modification.

  Patent Document 4 discloses a copolymer obtained by copolymerizing divinyl aromatic compound (a) 20 to 99 mol% and monovinyl aromatic compound (b) 80 to 1 mol%, which has a terminal structure. The content of the structural unit having a phenolic hydroxyl group partially derived from the polymerization additive (c) and containing an unreacted vinyl group derived from the divinyl aromatic compound (a) is 10 to 90 mol%. A soluble polyfunctional vinyl aromatic copolymer having a phenolic hydroxyl group at the terminal is disclosed. Moreover, the resin composition for adhesives which uses the soluble polyfunctional vinyl aromatic copolymer which has a phenolic hydroxyl group at the terminal is disclosed by the Example of the said patent publication. However, since the soluble polyfunctional vinyl aromatic copolymer having a phenolic hydroxyl group at the terminal disclosed in the patent publication has low heat resistance, it has a large heat discoloration and does not have low dielectric properties. However, it has a drawback that it cannot be used as a substrate material in the field of advanced electronic equipment.

  On the other hand, Patent Document 5 discloses a polyfunctional vinyl aromatic copolymer having a terminal group derived from phenoxyethyl acrylate represented by Formula (1) of the document. However, although the soluble polyfunctional vinyl aromatic copolymer disclosed in this patent document has phenoxyethyl acrylate which is a poly (oxyalkylene) unit at the terminal, the toughness is improved, but in recent years, It does not have low dielectric properties in the high frequency band due to the increase in the amount of information communication, and requires high-performance, advanced electrical characteristics, thermal and mechanical characteristics as in advanced electrical and electronic fields. There is a problem that it cannot be applied to the advanced technology field. In addition, the soluble polyfunctional vinyl aromatic copolymer disclosed in these patent documents decreases the adhesiveness of the interface with the glass cloth after the history of wet heat, so that it can be used as a substrate material in a field where high reliability is required. Had the disadvantage that it could not be used.

  On the other hand, Patent Document 6 discloses a polyphenylene ether oligomer having vinyl groups at both ends, and a polyfunctional vinyl aromatic copolymer having a structural unit derived from a monomer composed of a divinyl aromatic compound and an ethyl vinyl aromatic compound; A curable resin composition is disclosed. However, the curable resin composition using the soluble polyfunctional vinyl aromatic copolymer disclosed in the patent publication lacks delamination strength, plating peel strength and dielectric properties after wet heat history. There was a drawback that it could not be used as a substrate material in the equipment field.

  Patent Document 7 discloses a polyfunctional vinyl aromatic copolymer having a structural unit derived from a monomer composed of a divinyl aromatic compound and an ethyl vinyl aromatic compound, an epoxy group, a cyanate group, a vinyl group, an ethynyl group, an isocyanate group, and A curable resin composition comprising a thermosetting resin containing one or more functional groups selected from the group consisting of hydroxyl groups is disclosed. However, since the curable resin composition using the soluble polyfunctional vinyl aromatic copolymer disclosed in the patent publication lacks plating properties, it is a high-performance advanced technology that requires a high degree of miniaturization. There was a problem that it could not be applied to the field.

JP 2004-123873 A Japanese Patent Laid-Open No. 2005-213443 JP 2007-332273 A JP 2008-189745 A JP 2010-229263 A WO2005 / 73264 JP 2006-274169 A

  The present invention relates to a novel terminal-modified soluble polyfunctional vinyl aromatic copolymer having a low dielectric constant and improved heat resistance, compatibility, adhesion and moldability, a method for producing the same, and the copolymer. The present invention relates to a curable composition having a low dielectric constant, which is excellent in filling property to fine patterns, adhesion, and dielectric loss tangent characteristics after wet heat history. In addition, the present invention relates to a film made of a curable composition containing the copolymer, and a cured product obtained by curing the film. Furthermore, this invention aims at providing the curable composite material which consists of this resin composition and a base material, the hardening body, the laminated body which consists of a hardening body and metal foil, and copper foil with resin.

（ここで、Ｙは炭素数１〜１２の炭化水素基を置換基として有してもよい未置換又は置換の炭素数６〜４０の芳香族炭化水素基を示し、Ｚは炭素数１〜３０の脂肪族炭化水素基、又は炭素数１〜１２の炭化水素基を置換基として有してもよい未置換若しくは置換の炭素数６〜４０の芳香族炭化水素基を示す。）
で表わされる芳香族系エーテル化合物（ｃ）であり、
その共重合体の末端の一部に下記式（１）

（ここで、Ｙ¹は式（５）のＹから1つのＨを取って生じる芳香族炭化水素基であり、Ｚは式（５）と同意である。）
で表される芳香族系エーテル化合物（ｃ）由来の末端基を有することを特徴とする末端変性可溶性多官能ビニル芳香族共重合体。 The present invention provides a divinyl aromatic compound (a), a monovinyl aromatic compound (b) and an ether compound in the presence of one or more catalysts (d) selected from the group consisting of Lewis acid catalysts, strong inorganic acids and organic sulfonic acids. A copolymer obtained by reacting with
The ether compound is represented by the following formula (5):

(Y represents an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms which may have a hydrocarbon group having 1 to 12 carbon atoms as a substituent, and Z represents 1 to 30 carbon atoms. Or an aliphatic hydrocarbon group having 1 to 12 carbon atoms or an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms which may have a hydrocarbon group having 1 to 12 carbon atoms as a substituent.)
An aromatic ether compound (c) represented by:
A part of the terminal of the copolymer has the following formula (1)

(Here, Y ¹ is an aromatic hydrocarbon group formed by taking one H from Y in formula (5), and Z is the same as in formula (5).)
A terminal-modified soluble polyfunctional vinyl aromatic copolymer having a terminal group derived from the aromatic ether compound (c) represented by the formula:

In the terminal-modified soluble polyfunctional vinyl aromatic copolymer, the number average molecular weight Mn is 300 to 100,000, and the introduction amount (c1) of the terminal group is represented by the following formula (2).
(C1) ≧ 1.0 (pieces / molecule) (2)
And the molar fraction (A) of the structural unit derived from the divinyl aromatic compound and the molar fraction (B) of the structural unit derived from the monovinyl aromatic compound in the copolymer are represented by the following formula (3):
0.05 ≦ (A) / {(A) + (B)} ≦ 0.95 (3)
And the molar fraction (C) of the terminal group is represented by the following formula (4):
0.005 ≦ (C) / {(A) + (B)} <5.0 (4)
And is soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform, and the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn is 100.0 or less. It is a preferred embodiment.

（ここで、Ｙは炭素数１〜１２の炭化水素基を置換基として有してもよい未置換又は置換の炭素数６〜４０の芳香族炭化水素基を示し、Ｚは炭素数１〜３０の脂肪族炭化水素基、又は炭素数１〜１２の炭化水素基を置換基として有してもよい未置換若しくは置換の炭素数６〜４０の芳香族炭化水素基を示す。）
で表わされる芳香族系エーテル化合物（ｃ）を０．００５≦（ｃ）／｛（ａ）＋（ｂ）｝＜５．０を満たすモル比の範囲で使用し、ルイス酸触媒、無機強酸及び有機スルホン酸からなる群から選ばれる一種以上の触媒（ｄ）を使用し、これらを含む重合原料類を誘電率２．０〜１５．０の溶媒に溶解させた均一溶液中、２０〜１２０℃の温度で重合させて、末端に下記式（１）

（ここで、Ｙ¹は式（５）のＹから1つのＨを取って生じる芳香族系炭化水素基であり、Ｚは式（５）と同意である。）
で表される芳香族系エーテル化合物（ｃ）由来の末端基を１．０（個／分子）以上有し、トルエン、キシレン、テトラヒドロフラン、ジクロロエタン又はクロロホルムに可溶である共重合体を得ることを特徴とする末端変性可溶性多官能ビニル芳香族共重合体の製造方法である。 The present invention also relates to a method for producing a copolymer by reacting a divinyl aromatic compound (a), a monovinyl aromatic compound (b) and an ether compound, the divinyl aromatic compound (a) and the monovinyl aromatic The divinyl aromatic compound (a) is used in an amount of 5 to 95 mol% and the monovinyl aromatic compound (b) is used in an amount of 95 to 5 mol% with respect to a total of 100 mol% of the compound (b). )

(Y represents an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms which may have a hydrocarbon group having 1 to 12 carbon atoms as a substituent, and Z represents 1 to 30 carbon atoms. Or an aliphatic hydrocarbon group having 1 to 12 carbon atoms or an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms which may have a hydrocarbon group having 1 to 12 carbon atoms as a substituent.)
The aromatic ether compound (c) represented by the formula is used in a molar ratio range satisfying 0.005 ≦ (c) / {(a) + (b)} <5.0, and a Lewis acid catalyst, an inorganic strong acid, and One or more catalysts (d) selected from the group consisting of organic sulfonic acids are used, and 20 to 120 ° C. in a homogeneous solution in which polymerization raw materials containing them are dissolved in a solvent having a dielectric constant of 2.0 to 15.0. Is polymerized at the temperature of the following formula (1)

(Here, Y ¹ is an aromatic hydrocarbon group formed by taking one H from Y in formula (5), and Z is the same as in formula (5).)
To obtain a copolymer having 1.0 (pieces / molecule) or more of terminal groups derived from the aromatic ether compound (c) represented by the formula, and being soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. This is a method for producing a terminal-modified soluble polyfunctional vinyl aromatic copolymer.

  In the method for producing a terminal-modified soluble polyfunctional vinyl aromatic copolymer, the catalyst (d) is a Lewis acid catalyst which is a metal fluoride or a complex thereof, or 1 mol of an aromatic ether compound (c). On the other hand, it is a preferable aspect to use the catalyst (d) in the range of 0.001 to 10 mol.

  Further, the present invention is a curable composition characterized by containing the above-mentioned terminal-modified soluble polyfunctional vinyl aromatic copolymer and a radical polymerization initiator, or in this curable composition, Furthermore, it is a preferred embodiment to contain a modified polyphenylene ether, particularly a modified polyphenylene ether having at least one phenolic hydroxyl group, aromatic vinyl group, methacryl group or acrylic group at the terminal. Alternatively, it is also a preferred embodiment of the present invention that this curable composition contains an epoxy resin having two or more epoxy groups in one molecule and a curing agent. Moreover, this invention is also a hardened | cured material formed by hardening | curing these curable compositions.

  Moreover, this invention is a film formed by shape | molding said curable composition in a film form. Furthermore, the present invention is a curable composite material comprising the above curable composition and a base material, wherein the base material is contained in a proportion of 5 to 90% by weight. A cured composite obtained by curing. The laminate further comprises a layer of the cured composite material and a metal foil layer. Moreover, this invention is a metal foil with resin characterized by having the film | membrane formed from said curable composition on the single side | surface of metal foil.

  In the cured product of the soluble polyfunctional vinyl aromatic copolymer modified at the terminal according to the present invention, heat resistance, compatibility, adhesiveness and moldability are improved. According to the production method of the present invention, the copolymer can be produced with high efficiency. Further, in the present invention, by using the terminal-modified soluble polyfunctional vinyl aromatic copolymer of the present invention as a curable compound, the molecule has a large free volume with a large molecular size and a good low dielectric constant. A cured product having characteristics can be obtained, and good adhesiveness, filling ability for a fine wiring pattern, plating property, and dielectric loss tangent property after wet heat history can be realized at the same time.

  The terminal-modified soluble polyfunctional vinyl aromatic copolymer of the present invention comprises a divinyl aromatic compound (a), a monovinyl aromatic compound (b) and an ether compound, which are selected from the group consisting of a Lewis acid catalyst, an inorganic strong acid and an organic sulfonic acid. A copolymer obtained by reaction in the presence of one or more selected catalysts (d), a structural unit derived from a divinyl aromatic compound (a) and a structural unit derived from a monovinyl aromatic compound (b) In addition, it has a terminal group derived from the aromatic ether compound (c) represented by the above formula (1) at the terminal of the copolymer.

（式中、Ｒ¹及びＲ²は独立して、炭素数６〜３０の芳香族炭化水素基を示す。）で表されるビニル基を含有する構造単位が挙げられる。ビニル芳香族化合物（ｂ）に由来する構造単位は、例えば、スチレンに由来する構造単位が挙げられる。なお、主鎖骨格に、他の構造単位、例えばインダン構造などを有してもよい。 Examples of the structural unit derived from the divinyl aromatic compound (a) include the formulas (a1) and (a2)

(Wherein, R ¹ and R ² independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms), and a structural unit containing a vinyl group. Examples of the structural unit derived from the vinyl aromatic compound (b) include a structural unit derived from styrene. Note that the main chain skeleton may have another structural unit such as an indane structure.

As an end group derived from the aromatic ether compound (c) represented by the formula (1), Y ¹ is an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms, but has a low dielectric constant. In view of solvent solubility, heat resistance, and availability of raw materials, preferred aromatic hydrocarbon groups (Y ¹ ) are phenyl group, toluyl group, xylenyl group, naphthyl group, biphenylyl group, and terphenylyl group. More preferred are a phenyl group and a naphthyl group, and particularly preferred is a phenyl group. These aromatic hydrocarbon groups (Y ¹ ) may have a substituent, and the substituent is a hydrocarbon group having 1 to 12 carbon atoms, particularly an alkyl group having 1 to 6 carbon atoms.

  On the other hand, as an end group derived from the aromatic ether compound (c) represented by the formula (1), Z is an aliphatic hydrocarbon group having 1 to 30 carbon atoms, or an unsubstituted or substituted carbon atom having 6 to 40 carbon atoms. A preferable aliphatic hydrocarbon group (Z) is a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group because of its solvent solubility, low dielectric properties, and easy availability of raw materials. Preferred aromatic hydrocarbon groups (Z) are toluyl group, xylenyl group, biphenyl group, and naphthyl group. More preferably, they are a methyl group, an ethyl group, a butyl group, and a phenyl group. When Z is an aromatic hydrocarbon group, it may have a substituent, and the substituent is a hydrocarbon group having 1 to 12 carbon atoms, particularly an alkyl group having 1 to 6 carbon atoms.

The terminal-modified soluble polyfunctional vinyl aromatic copolymer of the present invention is hereinafter abbreviated as “soluble polyfunctional vinyl aromatic copolymer” or simply “the present copolymer” unless misunderstanding occurs. There is also.

  In addition to the structural unit derived from the divinyl aromatic compound (a) and the structural unit derived from the monovinyl aromatic compound (b), the copolymer includes an aromatic ether compound (c) represented by the above formula (1). ) Derived end group as a structural unit. If the molar ratio of each structural unit is (A), (B), (C) and (A) + (B) = 1.0, it is preferable that the following is satisfied.

  The terminal group molar fraction (C) / {(A) + (B)} is preferably 0.005 or more and less than 5.0. More preferably, it is 0.01-1.5, More preferably, it is 0.05-1.0. By satisfy | filling said relationship, it can be set as this copolymer and resin composition which are excellent in fluidity | liquidity, adhesiveness, metal-plating property, and the dielectric loss tangent characteristic after a wet heat history. When the molar fraction of the end group is less than 0.005, the fluidity and adhesiveness are deteriorated, and when it is more than 2.0, the low dielectric loss tangent after being subjected to the wet heat history cannot be maintained. Heat resistance decreases.

The introduction amount (c1) of terminal groups per molecule of the copolymer is 1.0 (number / molecule) or more on average, and preferably 1.8 (number / molecule) or less. This is preferable because the adhesion of the polymer to different materials is improved. In the above formula (1), the end group derived from the aromatic ether compound (c) is preferably bonded to the main chain of the copolymer at the para position.

  Furthermore, the molar fraction (A) / {(A) + (B)} of the structural unit (A) is preferably 0.05 to 0.95, more preferably 0.15 to 0.95, More preferably, it is the range of 0.25-0.90 mol. The molar fraction (B) / {(A) + (B)} of the structural unit (B) is calculated from the molar fraction of the structural unit (A). From another viewpoint, it is preferable that the structural unit (A) is contained in an amount of 30 to 90 mol% with respect to 100 mol% in total of all the structural units {(A) + (B) + (C)}. The structural unit (A) derived from the divinyl aromatic compound contains a vinyl group as a crosslinking component for developing heat resistance, while the structural unit (B) derived from the monovinyl aromatic compound is involved in the curing reaction. Since it does not have a vinyl group, moldability and the like are imparted. Therefore, when the molar fraction of the structural unit (A) is less than 0.05, the heat resistance of the cured product is insufficient, and when it exceeds 0.95, the moldability is deteriorated.

  The Mn of the present copolymer (where Mn is the number average molecular weight in terms of standard polystyrene measured using gel permeation chromatography) is preferably 300 to 100,000, more preferably 400 to 50. , 000, more preferably 500 to 10,000. When the Mn is less than 300, the amount of the copolymer having no vinyl group contained in the copolymer is increased, so that the heat resistance of the cured product is lowered, and when the Mn exceeds 100,000, the gel Tends to be produced, and the viscosity becomes high, which tends to cause a decrease in molding processability. The value of the molecular weight distribution (Mw / Mn) obtained from Mn and the weight average molecular weight Mw is preferably 100.0 or less, more preferably 50.0 or less, still more preferably 1.5 to 10.0. Most preferably, it is 1.5-5.0. If Mw / Mn exceeds 100.0, problems such as deterioration of the processing characteristics of the copolymer and generation of gels tend to occur.

  The copolymer is soluble in a solvent selected from toluene, xylene, tetrahydrofuran, dichloroethane or chloroform, but is preferably soluble in any of the above solvents. In order to be a polyfunctional copolymer that is soluble in a solvent, it is necessary that some vinyl groups of divinylbenzene remain without being crosslinked and have an appropriate degree of crosslinking.

  Since the terminal of the copolymer is modified with the terminal group, the copolymer has high compatibility with an ether compound such as polyphenylene ether and an epoxy compound. Therefore, a curable composition containing a curable ether compound and an epoxy compound is excellent in uniform curability, and a cured product obtained by curing this is excellent in transparency.

  Next, the manufacturing method which can manufacture advantageously the soluble polyfunctional vinyl aromatic copolymer of this invention is demonstrated. The production method of the soluble polyfunctional vinyl aromatic copolymer of the present invention may be abbreviated as “the production method of the copolymer of the present invention” or “the present production method”.

  In this production method, a divinyl aromatic compound (a), a monovinyl aromatic compound (b), and an aromatic ether compound (c) are reacted to produce a copolymer.

  The amount of the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) used is 5 to 95 mol% of the divinyl aromatic compound (a) and 95 of the monovinyl aromatic compound (b) 95 with respect to a total of 100 mol% of both. ~ 5 mol%. Preferably, they are 15-70 mol% of divinyl aromatic compounds (a) and 85-30 mol% of monovinyl aromatic compounds (b). When the structural unit (a) is less than 5 mol%, the heat resistance of the cured product is insufficient, and when it exceeds 95 mol%, the moldability is deteriorated.

  The divinyl aromatic compound (a) plays an important role as a crosslinking component for branching the copolymer to make it polyfunctional and for developing heat resistance when the copolymer is thermoset. Examples of the divinyl aromatic compound (a) include divinylbenzene (m-isomer, p-isomer or a mixture thereof), divinylnaphthalene (including each isomer), and divinylbiphenyl (including each isomer). Although used preferably, it is not limited to these. Moreover, these can be used individually or in combination of 2 or more types. From the viewpoint of moldability, divinylbenzene (m-isomer, p-isomer or a mixture thereof) is more preferable.

  The monovinyl aromatic compound (b) improves the solvent solubility and processability of the copolymer. Examples of monovinyl aromatic compounds (b) include, but are not limited to, styrene, nuclear alkyl substituted monovinyl aromatic compounds, α-alkyl substituted monovinyl aromatic compounds, β-alkyl substituted styrenes, alkoxy substituted styrenes, and the like. It is not a thing. In order to prevent the gelation of the copolymer and to improve solubility in a solvent and processability, in particular, styrene, ethylvinylbenzene (m-isomer, p-isomer or a mixture thereof), ethylvinylbiphenyl (each Isomers are preferred) from the standpoint of cost and availability. From the viewpoint of dielectric properties and molding processability, ethyl vinylbenzene (m-isomer, p-isomer or a mixture thereof) is more preferable.

The aromatic ether compound (c) is represented by the above formula (5). Here, Y and Z in the formula (5) have the same meaning as Y ¹ and Z in the formula (1) except that Y ¹ is an aromatic hydrocarbon group formed by taking one H from Y. . The aromatic ether compound (c) undergoes a chain transfer reaction with a polymerization active species at the time of the polymerization reaction, and the above formula (1) enabling functionalization such as adhesiveness to the terminal of the copolymer of the present invention. The compound which plays the role which introduce | transduces the terminal group represented by this. Therefore, the aromatic ether compound (c) is also referred to as a polymerization additive, and this is also a monomer because it gives the above-mentioned end group (one of the structural units) to the copolymer. When the carbocation as an active species abstracts the hydrogen of the aromatic ether compound (c), the aromatic ether compound (c) is introduced as a terminating end into the growing polymer chain, and at the same time, the extracted hydrogen cation is The polymerization reaction proceeds as a polymerization active species.

As the aromatic ether compound (c), in the above formula (5), Y is an aromatic hydrocarbon group having 6 to 40 carbon atoms, and Z is an aliphatic hydrocarbon group having 1 to 30 carbon atoms, or carbon. Any aromatic hydrocarbon group of several 6 to 40 can be selected arbitrarily. Preferred Y is a phenyl group, a naphthyl group, a biphenyl group, and a terphenyl group because they have excellent dielectric properties and heat resistance. More preferable Y is a phenyl group or a naphthyl group. These aromatic hydrocarbon groups (Y) may have a substituent, and the substituent is a hydrocarbon group having 1 to 12 carbon atoms, particularly an alkyl group having 1 to 6 carbon atoms. On the other hand, preferable Z is a methyl group, an ethyl group, a propyl group, a butyl group as an aliphatic hydrocarbon group, or a phenyl group or biphenyl as an aromatic hydrocarbon group because the molecular weight during polymerization is easy to control. Group and naphthyl group. More preferable Z is a methyl group, an ethyl group, a butyl group, or a phenyl group. When Z is an aromatic hydrocarbon group, it may have a substituent, and the substituent is a hydrocarbon group having 1 to 12 carbon atoms, particularly an alkyl group having 1 to 6 carbon atoms.
Specifically, anisole, propoxybenzene, butoxybenzene, methoxynaphthalene, methoxybiphenyl, and biphenyl ether are preferably used from the viewpoints of reactivity, availability, and moldability. From the viewpoint of the reaction rate, anisole, butoxybenzene, and methoxynaphthalene are more preferably used.

  The aromatic ether compound (c) preferably satisfies a molar ratio of 0.005 ≦ (c) / {(a) + (b)} <5.0. More preferably, it is 0.01-1.5, More preferably, it is 0.05-1.0. If it is less than 0.005 mol, the molecular weight and molecular weight distribution increase, and the molding processability deteriorates. Moreover, when it exceeds 5.0, a superposition | polymerization speed | rate will fall remarkably, productivity will fall, and dielectric property will deteriorate. In the polymerization reaction, the aromatic ether compound (c) reacts with a carbocation which is a polymerization active species to form the end group and stop the growth. The amount used and the reaction conditions are selected so that the amount of terminal groups derived from the aromatic ether compound (c) is within the range described for the copolymer.

  Moreover, in the method for producing a copolymer of the present invention, in addition to the divinyl aromatic compound (a), the monovinyl aromatic compound (b), and the aromatic ether compound (c), as long as the effects of the present invention are not impaired. Other monomers (e) such as trivinyl aromatic compounds, trivinyl aliphatic compounds, divinyl aliphatic compounds and monovinyl aliphatic compounds can be used, and this unit can be introduced into the copolymer.

  Specific examples of the other monomer (e) include 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, 1,2,4-trivinylcyclohexane, ethylene glycol diacrylate. , Butadiene and the like, but are not limited thereto. These can be used alone or in combination of two or more. The other monomer (e) may be used within a range of less than 30 mol% of the total monomers. Thereby, the structural unit derived from the other monomer (e) is within a range of less than 30 mol% with respect to the total amount of the structural unit in the copolymer. The total monomer is the total of the divinyl aromatic compound (a), the monovinyl aromatic compound (b), the aromatic ether (c), and the other monomer (e). Moreover, when this copolymer does not contain another monomer (e), it is the sum total of a divinyl aromatic compound (a), a monovinyl aromatic compound (b), and an aromatic ether (c).

  In the polymerization reaction, a divinyl aromatic compound (a), a monovinyl aromatic compound (b) and an aromatic ether compound (c) are used using a catalyst (d) and, if necessary, other monomers (e). And a terminal-modified copolymer is obtained by cationic copolymerization at a temperature of 20 to 120 ° C. in a homogeneous solvent in which polymerization raw materials containing these are dissolved in a solvent having a dielectric constant of 2.0 to 15.0. Here, the obtained terminal-modified copolymer is a copolymer having 1.0 (number / molecule) or more of the above-mentioned terminal groups and soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform.

  As the catalyst (d), one or more selected from the group consisting of Lewis acid catalysts, strong inorganic acids and organic sulfonic acids are used.

  The Lewis acid catalyst can be used without particular limitation as long as it is a compound composed of a metal ion (acid) and a ligand (base) and can receive an electron pair. From the viewpoint of the thermal decomposition resistance of the copolymer obtained among the Lewis acid catalysts, in particular, B, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, Ti, W, Zn, Fe, V, etc. A bivalent to hexavalent metal fluoride or a complex thereof (such as an ether complex or a phenol complex) is preferable. Examples of strong inorganic acids include sulfuric acid, hydrochloric acid, and phosphoric acid. Specific examples of the organic sulfonic acid include benzenesulfonic acid and paratoluenesulfonic acid. These catalysts can be used alone or in combination of two or more. More preferably, from the viewpoint of control of the molecular weight and molecular weight distribution of the obtained copolymer and polymerization activity, the metal fluoride or a complex thereof, and an ether complex (diethyl ether, dimethyl ether, etc.) of boron trifluoride is most preferable. used.

  The catalyst (d) is preferably used in the range of 0.001 to 10 mol, more preferably 0.001 to 1 mol, per 1 mol of the aromatic ether compound (c). If it exceeds 10 moles, the polymerization rate becomes too high, which makes it difficult not only to control the molecular weight distribution but also to reduce the amount of end groups introduced in formula (1).

  In the method for producing a terminal-modified soluble polyfunctional vinyl aromatic copolymer of the present invention, one or more promoters (f) selected from ester compounds other than the aromatic ether compound (c) may be used as desired. it can. Examples of the promoter (f) include ethyl acetate, propyl acetate, and butyl acetate. In that case, the cocatalyst (f) can be used within a range of less than 300 wt%, more preferably less than 200 wt%, relative to the aromatic ether compound (c). Most preferably. It is less than 100 wt%. If the total amount of the cocatalyst (f) used exceeds 300 wt% with respect to the aromatic ether compound (c), the polymerization rate decreases and the yield of the copolymer decreases. The combined use of the aromatic ether compound (c) and the cocatalyst (f) makes it easy to control the polarity of the entire polymerization system, optimizes the dielectric constant of the solvent that affects the degree of polymerization, and The reactivity can be controlled. As a result, the molecular weight and molecular weight distribution of the copolymer can be controlled.

  The polymerization reaction is performed in one or more organic solvents having a dielectric constant of 2 to 15 as a solvent for dissolving the produced copolymer. Organic solvent is a compound that does not essentially inhibit cationic polymerization, and dissolves catalyst, polymerization additive, co-catalyst, monomer and polyfunctional vinyl aromatic copolymer to form a uniform solution. It is. The organic solvent is not particularly limited as long as the dielectric constant is in the range of 2 to 15, and can be used alone or in combination of two or more. When the dielectric constant of the solvent is less than 2, the molecular weight distribution becomes wide, which is not preferable. When it exceeds 15, the polymerization rate is remarkably reduced.

  As the organic solvent, toluene, xylene, n-hexane, cyclohexane, methylcyclohexane and ethylcyclohexane are particularly preferable from the viewpoint of a balance between polymerization activity and solubility. Further, the amount of the solvent used is such that the concentration of the copolymer in the polymerization solution at the end of the polymerization is 1 to 90 wt%, preferably 10 to 80 wt%, in consideration of the viscosity of the resulting polymerization solution and the ease of heat removal. Particularly preferably, it is determined to be 20 to 70 wt%. If this concentration is less than 1 wt%, the polymerization efficiency is low, resulting in an increase in cost. If it exceeds 90 wt%, the molecular weight and molecular weight distribution increase, resulting in a decrease in molding processability.

  When manufacturing this copolymer, it is preferable to superpose | polymerize at the temperature of 20-120 degreeC. More preferably, it is 40-100 degreeC. When the polymerization temperature exceeds 120 ° C., the selectivity of the reaction decreases, and thus problems such as an increase in molecular weight distribution and generation of gel occur. When polymerization is performed at a temperature lower than 20 ° C., the catalytic activity is remarkably reduced. There is a tendency that it is necessary to add the catalyst.

  The method for recovering the copolymer after the termination of the polymerization reaction is not particularly limited. For example, a commonly used method such as vacuum devolatilization under heating, a steam stripping method, or precipitation with a poor solvent may be used.

Next, the curable composition of this invention is demonstrated.
The curable composition of the present invention contains a terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) and a radical polymerization initiator (also referred to as a radical polymerization catalyst) (XB). As the radical polymerization initiator (XB), for example, the resin composition of the present invention is cured by causing a crosslinking reaction by means of heating or the like as described later. For the purpose of accelerating the crosslinking reaction, a radical polymerization initiator (XB) may be used. The amount of the radical polymerization initiator used for this purpose is 0.01 to 10% by weight, preferably 0.1 to 8% by weight, based on the sum of the components (XA) and (XB). Since the radical polymerization initiator is a radical polymerization catalyst, it is represented below by a radical polymerization initiator.

  A known substance is used as the radical polymerization initiator. Representative examples include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy ) Hexin-3, di-t-butyl peroxide, t-butylcumyl peroxide, α, α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (T-butylperoxy) hexane, dicumyl peroxide, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis (t-butylperoxy) butane, 2,2-bis (T-butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di (trimethylsilyl) par Although there are peroxides such as oxide and trimethylsilyltriphenylsilyl peroxide, they are not limited to these. Although not a peroxide, 2,3-dimethyl-2,3-diphenylbutane can also be used as a radical polymerization initiator (or polymerization catalyst). However, the catalyst and radical polymerization initiator used for curing the resin composition are not limited to these examples.

  If the blending amount of the radical polymerization initiator is in the range of 0.01 to 10 parts by weight with respect to the terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA), the reaction can be satisfactorily performed without inhibiting the curing reaction. proceed.

  Further, the terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) -containing curable composition can be copolymerized with the terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) of the present invention, if necessary. Other polymerizable monomers may be blended and cured.

  A known substance is used as the copolymerizable monomer. Typical examples are styrene, styrene dimer, alpha methyl styrene, alpha methyl styrene dimer, divinyl benzene, vinyl toluene, t-butyl styrene, chlorostyrene, dibromo styrene, vinyl naphthalene, vinyl biphenyl, acenaphthylene, divinyl benzyl ether. And allyl phenyl ether. By adding such a low molecular weight polymerizable monomer as a reactive diluent as long as the effect of the copolymer (XA) of the present invention is not impaired, for example, the viscosity of the curable resin composition is lowered and molding processability is reduced. Can be improved and the cost can be reduced. The monomer component of the divinyl aromatic compound (a) or the monovinyl aromatic compound (b) is left as a residual volatile component within a range of, for example, several percent to 20%, and such unreacted monomer is used as a reactive diluent. Also good.

  The curable composition containing the terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) of the present invention includes known thermosetting resins such as vinyl ester resins, polyvinyl benzyl resins, unsaturated polyester resins, Curable vinyl resin, modified polyphenylene ether resin, maleimide resin, epoxy resin, polycyanate resin, phenol resin, etc., and known thermoplastic resins such as polystyrene, polyphenylene ether, polyetherimide, polyethersulfone, PPS resin, poly Cyclopentadiene resin, polycycloolefin resin, etc. or known thermoplastic elastomers such as styrene-ethylene-propylene copolymer, styrene-ethylene-butylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer Polymer, water Styrene - butadiene copolymer, hydrogenated styrene - isoprene copolymer and or gums such as polybutadiene, it may be blended with polyisoprene.

  The curable composition of the present invention comprises a curable composition containing a terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) and a radical polymerization initiator (XB), a modified polyphenylene ether, particularly at least one terminal. You may contain the modified polyphenylene ether which has two phenolic hydroxyl groups, a vinyl group, a methacryl group, or an acryl group.

  The number average molecular weight of the modified polyphenylene ether is not particularly limited, but is preferably 800 to 7000, and more preferably 1000 to 5000. Most preferably, it is 1000-3000. Further, as described above, n is a positive integer of 50 or less, and is preferably a numerical value such that the number average molecular weight of the modified polyphenylene ether falls within such a range. Specifically, it is preferably 1 to 50. In addition, the number average molecular weight should just be what was measured by the general molecular weight measuring method here, and the value etc. which were specifically measured using gel permeation chromatography (GPC) are mentioned.

  When the number average molecular weight of the modified polyphenylene ether is within such a range, the toughness and moldability of the cured product of the obtained curable composition become higher. This is because when the number average molecular weight of the modified polyphenylene ether is within such a range, it has a relatively low molecular weight, so that the fluidity is improved while maintaining toughness. When a normal polyphenylene ether having such a low molecular weight is used, the heat resistance and toughness of the cured product tend to be lowered. However, since the modified polyphenylene ether used in the present embodiment has a polymerizable unsaturated double bond at the terminal, the modified polyphenylene ether and the thermally crosslinked curable resin are cured by curing together with a vinyl-based thermally crosslinked curable resin. Crosslinking with the resin proceeds suitably, and a cured product having sufficiently high heat resistance and toughness can be obtained. Therefore, the cured product of the obtained curable composition will be excellent in both heat resistance and toughness.

  The curable composition of the present invention comprises a terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) and a radical polymerization initiator (XB) for the purpose of improving the adhesion reliability between different materials. A curable composition characterized by containing an epoxy resin (XD) and a curing agent (XE) is also a preferred embodiment.

  The epoxy resin of component (XD) is not particularly limited, but the epoxy resin is an epoxy resin having two or more epoxy groups and an aromatic structure in one molecule, and two or more epoxy groups and a cyanurate structure in one molecule. It is preferable to use one or more epoxy resins selected from the group consisting of an epoxy resin having an epoxy resin and / or an epoxy resin having two or more epoxy groups and an alicyclic structure in one molecule. (XD) component includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alkylphenol novolac type epoxy resin, xylylene modified phenol novolac type epoxy resin, xylylene modified alkylphenol novolak type epoxy resin, biphenyl type epoxy It is more preferably one or more epoxy resins selected from the group consisting of resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resins, triglycidyl isocyanurate, cyclohexane type epoxy resins and adamantane type epoxy resins.

  Examples of the bisphenol F type epoxy resin used as the (XD) component include, for example, an epoxy resin mainly composed of 4,4′-methylenebis (2,6-dimethylphenol) diglycidyl ether, 4,4 ′ An epoxy resin mainly composed of diglycidyl ether of -methylenebis (2,3,6-trimethylphenol), and an epoxy resin mainly composed of diglycidyl ether of 4,4'-methylenebisphenol. Among them, an epoxy resin mainly composed of 4,4'-methylenebis (2,6-dimethylphenol) diglycidyl ether is preferable. The bisphenol F-type epoxy resin is commercially available as a trade name YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.

  Examples of the biphenyl type epoxy resin include epoxy resins such as 4,4'-diglycidylbiphenyl and 4,4'-diglycidyl-3,3 ', 5,5'-tetramethylbiphenyl. As said biphenyl type epoxy resin, it can obtain as Mitsubishi Chemical Corporation brand name YX-4000, YL-6121H as a commercial item.

  Examples of the dicyclopentadiene type epoxy resin include dicyclopentadiene dioxide and a phenol novolac epoxy monomer having a dicyclopentadiene skeleton.

  As naphthalene type epoxy resins, 1,2-diglycidylnaphthalene, 1,5-diglycidylnaphthalene, 1,6-diglycidylnaphthalene, 1,7-diglycidylnaphthalene, 2,7-diglycidylnaphthalene, triglycidylnaphthalene , And 1,2,5,6-tetraglycidylnaphthalene, naphthol / aralkyl epoxy resin, naphthalene skeleton modified cresol novolac epoxy resin, methoxynaphthalene modified cresol novolac epoxy resin, naphthylene ether epoxy resin, methoxynaphthalenedylene methylene Modified naphthalene type epoxy resins such as type epoxy resins.

  Examples of the adamantane type epoxy resin include 1- (2,4-diglycidyloxyphenyl) adamantane, 1- (2,3,4-triglycidyloxyphenyl) adamantane, and 1,3-bis (2,4-diphenyl). Glycidyloxyphenyl) adamantane, 1,3-bis (2,3,4-triglycidyloxyphenyl) adamantane, 2,2-bis (2,4-diglycidyloxyphenyl) adamantane, 1- (2,3,4) -Trihydroxyphenyl) adamantane, 1,3-bis (2,4-dihydroxyphenyl) adamantane, 1,3-bis (2,3,4-trihydroxyphenyl) adamantane, and 2,2-bis (2, 4-dihydroxyphenyl) adamantane and the like.

  Among the above epoxy resins, from the viewpoint of compatibility with the (XA) component, dielectric properties, and small warpage of the molded product, bisphenol F type epoxy resin, alkylphenol novolac type epoxy resin, xylylene modified phenol novolak type epoxy Resins, xylylene-modified alkylphenol novolac type epoxy resins, biphenyl type epoxy resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resins, triglycidyl isocyanurate, cyclohexane type epoxy resins and adamantene type epoxy resins are preferably used.

The weight average molecular weight (Mw) of the epoxy resin used as the (XD) component is preferably less than 10,000. More preferable Mw is 600 or less, and more preferably 200 or more and 550 or less. When Mw is less than 200, the volatility of the component (B) tends to be high, and the handleability of the cast film / sheet tends to deteriorate. On the other hand, if Mw exceeds 10,000, the cast film / sheet tends to be hard and brittle, and the adhesiveness of the cured product of the cast film / sheet tends to be lowered.
What is the B ingredient?

  The content of the component (XD) is preferably 5 parts by weight with respect to 100 parts by weight of the component (XA) and 100 parts by weight with the upper limit. More preferably, the lower limit of the content of the component (XD) is 10 parts by weight with respect to 100 parts by weight of the component (XA). On the other hand, a more preferred upper limit is 80 parts by weight, and a still more preferred upper limit is 60 parts by weight. When content of (XD) component satisfy | fills the said preferable minimum, the adhesiveness of the hardened | cured material of a cast film sheet can be improved further. When content of (XD) component satisfy | fills the said preferable upper limit, the handleability of the cast film sheet in an uncured state will become still higher, adhesiveness with a glass cloth will be improved, and reliability will become high.

  (XE) Component curing agent is a phenol resin, or an acid anhydride having an aromatic or alicyclic skeleton, a water additive of the acid anhydride, a modified product of the acid anhydride, a hydroxyl-terminated polyphenylene ether oligomer, And it is preferable that it is an active ester compound. By using these preferable curing agents, it is possible to obtain a curable composition that becomes a cured product having an excellent balance of heat resistance, moisture resistance and dielectric properties.

  The phenol resin used as the curing agent for the (XE) component is not particularly limited. Specific examples of the phenol resin include phenol novolak, o-cresol novolak, p-cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol, polyparavinylphenol, bisphenol A type novolak, phenol aralkyl resin, naphthol aralkyl resin, Biphenyl type phenol novolak resin, biphenyl type naphthol novolak resin, decalin modified novolak, poly (di-o-hydroxyphenyl) methane, poly (di-m-hydroxyphenyl) methane, poly (di-p-hydroxyphenyl) methane, etc. Is mentioned. Especially, since the softness | flexibility and flame retardance of an insulating sheet can be improved further, the phenol resin which has a melamine skeleton, the phenol resin which has a triazine skeleton, or the phenol resin which has an allyl group is preferable.

  Commercially available products of the phenol resin include MEH-8005, MEH-8010 and NEH-8015 (all of which are manufactured by Meiwa Kasei Co., Ltd.), YLH903 (manufactured by Japan Epoxy Resin Co., Ltd.), LA-7052, LA-7054, and LA-7751. LA-1356 and LA-3018-50P (all of which are manufactured by DIC), PS6313 and PS6492 (manufactured by Gunei Chemical Co., Ltd.), and the like.

  The structure of the acid anhydride having an aromatic skeleton used as a curing agent for the component (XE), a water additive of the acid anhydride, or a modified product of the acid anhydride is not particularly limited. Examples of the acid anhydride having an aromatic skeleton, a water addition of the acid anhydride, or a modified product of the acid anhydride include, for example, a styrene / maleic anhydride copolymer, benzophenone tetracarboxylic acid anhydride, pyromellitic acid anhydride, Trimellitic anhydride, 4,4'-oxydiphthalic anhydride, phenylethynylphthalic anhydride, glycerol bis (anhydrotrimellitate) monoacetate, ethylene glycol bis (anhydrotrimellitate), methyltetrahydrophthalic anhydride Acid, methylhexahydrophthalic anhydride, and trialkyltetrahydrophthalic anhydride, methylnadic acid anhydride, trialkyltetrahydrophthalic anhydride, acid anhydride having a dicyclopentadiene skeleton, or a modified product of the acid anhydride, etc. Is mentioned.

  Examples of commercially available acid anhydrides having an aromatic skeleton, water additives of the acid anhydrides, or modified products of the acid anhydrides include SMA Resin EF30, SMA Resin EF40, SMA Resin EF60, and SMA Resin EF80 (any of the above Is also manufactured by Sartomer Japan), ODPA-M and PEPA (all of which are manufactured by Manac), Rikagit MTA-10, Rikagit MTA-15, Rikagit TMTA, Rikagit TMEG-100, Rikagit TMEG-200, Rikagit TMEG-300, Rikagit TMEG-500, Rikagit TMEG-S, Rikagit TH, Rikagit HT-1A, Rikagit HH, Rikagit MH-700, Rikagit MT-500, Rikagit DSDA and Rikagit TDA-100 (all of which are manufactured by Shin Nippon Rika Co., Ltd.), and PICLON B4400, EPICLON B650, and EPICLON B570 (all manufactured by both DIC Corporation).

  The acid anhydride having an alicyclic skeleton, a water additive of the acid anhydride, or a modified product of the acid anhydride is an acid anhydride having a polyalicyclic skeleton, a water additive of the acid anhydride, or the A modified product of an acid anhydride, or an acid anhydride having an alicyclic skeleton obtained by addition reaction of a terpene compound and maleic anhydride, a water additive of the acid anhydride, or a modified product of the acid anhydride It is preferable. In this case, the flexibility, moisture resistance or adhesion of the insulating sheet can be further enhanced. Examples of the acid anhydride having the alicyclic skeleton, a water addition of the acid anhydride, or a modified product of the acid anhydride include methyl nadic acid anhydride, acid anhydride having a dicyclopentadiene skeleton, and the acid. Examples of the modified product include anhydrides.

  Examples of commercially available acid anhydrides having the alicyclic skeleton, water additions of the acid anhydrides, or modified products of the acid anhydrides include Rikagit HNA and Rikagit HNA-100 (all manufactured by Shin Nippon Rika Co., Ltd.) , And EpiCure YH306, EpiCure YH307, EpiCure YH308H, EpiCure YH309 (all of which are manufactured by Japan Epoxy Resin Co., Ltd.) and the like.

  As the (XE) component, a hydroxyl-terminated polyphenylene ether oligomer can also be used. The active ester compound used as the component (XE) may be any compound having an active ester group, but in the present invention, a compound having at least two active ester groups in the molecule is preferable. The active ester compound acts as a curing agent for the epoxy resin (XD).

  The active ester compound used as the component (XE) is an active ester obtained from a product obtained by reacting a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound from the viewpoint of heat resistance and the like. A compound is preferable, and an active ester compound obtained by reacting a carboxylic acid compound with one or more selected from the group consisting of a phenol compound, a naphthol compound, and a thiol compound is more preferable. An aromatic compound obtained from a reaction of a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group and having at least two active ester groups in the molecule is particularly preferred. The active ester compound used as the component (XE) may be linear or multi-branched, and the active ester compound is derived from a compound having at least two carboxylic acids in the molecule. When such a compound having at least two carboxylic acids in the molecule contains an aliphatic chain, the compatibility with the epoxy resin can be increased, and when it has an aromatic ring, Sexuality can be increased.

  Specific examples of the carboxylic acid compound for forming the active ester compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like. Among these, from the viewpoint of heat resistance, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid and terephthalic acid are preferred, phthalic acid, isophthalic acid and terephthalic acid are more preferred, and isophthalic acid and terephthalic acid are further preferred. preferable.

Specific examples of the thiocarboxylic acid compound for forming the active ester compound include thioacetic acid and thiobenzoic acid.
Specific examples of the phenol compound and naphthol compound for forming the active ester compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenol phthaline, methylated bisphenol A, methylated bisphenol F, and methylated bisphenol S. , Phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, tri Examples thereof include hydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, and phenol novolac. Among these, from the viewpoint of heat resistance and solubility, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl Diphenol and phenol novolak are preferable, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol and phenol novolak are more preferable, and dicyclopentadienyl diphenol and phenol novolak are more preferable.
Specific examples of the thiol compound for forming the active ester compound include benzenedithiol and triazinedithiol.

In the present invention, as the active ester compound, for example, active ester compounds disclosed in JP-A Nos. 2002-12650 and 2004-277460, or commercially available compounds can be used. Examples of commercially available active ester compounds include trade names “EXB9451, EXB9460, EXB9460S, HPC-8000-65T” (manufactured by DIC), trade names “DC808” (manufactured by Japan Epoxy Resins), trade names, and the like. “YLH1026” (manufactured by Japan Epoxy Resin Co., Ltd.) and the like can be mentioned.
The production method of the active ester compound is not particularly limited and can be produced by a known method. For example, it can be obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. it can.
The compounding amount of the active ester compound (XE) in the curable composition of the present invention is preferably 20 to 120 parts by weight, more preferably 40 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin (XD). More preferably, it is in the range of 50 to 90 parts by weight. By making the compounding quantity of active ester compound (XE) into the said range, the dielectric property as a hardened | cured material, heat resistance, and a linear expansion coefficient can be improved.

  The curing agent used as the (XE) component of the present invention includes o-cresol novolak, p-cresol novolak, and t-butylphenol from the viewpoints of compatibility with the (XA) component of the present invention, moisture resistance, and adhesiveness. Novolak, dicyclopentadiene cresol, polyparavinylphenol, xylylene-modified novolak, poly (di-o-hydroxyphenyl) methane, poly (di-m-hydroxyphenyl) methane, poly (di-p-hydroxyphenyl) methane, methyl Nadic acid anhydride, trialkyltetrahydrophthalic anhydride, or an acid anhydride having a dicyclopentadiene skeleton or a modified product of the acid anhydride, a hydroxyl-terminated polyphenylene ether oligomer, and an active ester compound are more preferable.

  The curable composition containing the terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) of the present invention includes an inorganic filler such as fused silica, crystalline silica, alumina, silicon nitride, aluminum nitride, decabromodiphenylethane, Use in combination with flame retardant imparting agents such as brominated polystyrene, especially useful as electrical or electronic component materials that require dielectric properties, flame retardancy, or heat resistance, especially semiconductor encapsulating materials and circuit board varnishes it can.

  The varnish for circuit board materials can be produced by dissolving the curable composition containing the divinylbenzyl ether compound of the present invention in an organic solvent such as toluene, xylene, tetrahydrofuran, dioxolane and the like. Specific examples of the circuit board material include a printed wiring board, a printed circuit board, a flexible printed wiring board, and a build-up wiring board.

  Cured products obtained by curing the curable composition containing the terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) of the present invention are molded products, laminates, cast products, adhesives, coating films, and films. Can be used. For example, the cured product of the semiconductor sealing material is a cast or molded product, and as a method of obtaining a cured product for such use, the compound is cast or molded using a transfer molding machine, an injection molding machine, or the like. Furthermore, a cured product can be obtained by heating at 80 to 230 ° C. for 0.5 to 10 hours. Moreover, the hardened | cured material of the varnish for circuit boards is a laminated body, and as a method of obtaining this hardened | cured material, the varnish for circuit boards is used for base materials, such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, and paper. It is impregnated and dried by heating to obtain a prepreg, which can be obtained alone or laminated with a metal foil such as a copper foil and subjected to hot press molding.

  Further, it is useful as a material for electronic parts, particularly as a high frequency electronic part material, by blending inorganic high dielectric powder such as barium titanate or inorganic magnetic substance such as ferrite.

  Moreover, the curable composition of this invention can be used together with metal foil (it is the meaning containing a metal plate. The following is the same) similarly to the hardening composite material mentioned later.

  Next, the curable composite material of the curable composition of the present invention and the cured product thereof will be described. A substrate is added to the curable composite material of the curable composition of the present invention in order to increase mechanical strength and increase dimensional stability.

  As such a substrate, known materials can be used. For example, various glass cloths such as roving cloth, cloth, chopped mat, and surfacing mat, asbestos cloth, metal fiber cloth, and other synthetic or natural inorganic fiber cloth. Woven fabrics or nonwoven fabrics obtained from liquid crystal fibers such as wholly aromatic polyamide fibers, wholly aromatic polyester fibers, polybenzozar fibers, woven fabrics or nonwoven fabrics obtained from synthetic fibers such as polyvinyl alcohol fibers, polyester fibers, acrylic fibers, Natural fiber cloth such as cotton cloth, linen cloth, felt, carbon fiber cloth, kraft paper, cotton paper, natural cellulosic cloth such as paper-glass mixed paper, paper, etc., each alone or in combination of two or more. Used.

The proportion of the substrate is 5 to 90 wt%, preferably 10 to 80 wt%, more preferably 20 to 70 wt% in the curable composite material. If the substrate is less than 5 wt%, the composite material is insufficient in dimensional stability and strength after curing, and if the substrate is more than 90 wt%, the dielectric properties of the composite material are inferior.
In the curable composite material of the present invention, a coupling agent can be used for the purpose of improving the adhesiveness at the interface between the resin and the substrate, if necessary. As the coupling agent, general ones such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zircoaluminate coupling agent can be used.

  As a method for producing the curable composite material of the present invention, for example, the curable composition of the present invention and other components as necessary are uniformly mixed in the above-mentioned aromatic or ketone-based solvents or mixed solvents thereof. And a method in which the substrate is impregnated and then dried. Impregnation is performed by dipping or coating. The impregnation can be repeated multiple times as necessary, and at this time, the impregnation can be repeated using a plurality of solutions having different compositions and concentrations, and finally adjusted to a desired resin composition and resin amount. Is possible.

  A cured composite material is obtained by curing the curable composite material of the present invention by a method such as heating. The manufacturing method is not particularly limited. For example, a plurality of curable composite materials are stacked, and each layer is bonded under heat and pressure, and at the same time, thermosetting is performed to obtain a cured composite material having a desired thickness. it can. It is also possible to obtain a cured composite material having a new layer structure by combining a cured composite material once cured with adhesive and a curable composite material. Lamination molding and curing are usually performed simultaneously using a hot press or the like, but both may be performed independently. That is, the uncured or semi-cured composite material obtained by lamination molding in advance can be cured by heat treatment or another method.

  Molding and curing are performed at a temperature of 80 to 300 ° C., a pressure of 0.1 to 1000 kg / cm 2, a time of 1 minute to 10 hours, and more preferably a temperature of 150 to 250 ° C. and a pressure of 1 to 500 kg / cm 2 Time: Can be performed in the range of 1 minute to 5 hours.

  The laminate of the present invention comprises a layer of the cured composite material of the present invention and a metal foil layer. Examples of the metal foil used here include a copper foil and an aluminum foil. The thickness is not particularly limited, but is in the range of 3 to 200 μm, more preferably 3 to 105 μm.

  As a method for producing the laminate of the present invention, for example, the above-described curable composition of the present invention and a curable composite material obtained from a substrate and a metal foil are laminated in a layer configuration according to the purpose, and heated. An example is a method in which the respective layers are bonded together under pressure and thermally cured. In the laminate of the curable composition of the present invention, the cured composite material and the metal foil are laminated in an arbitrary layer configuration. The metal foil can be used as a surface layer or an intermediate layer. In addition to the above, it is possible to make a multilayer by repeating lamination and curing a plurality of times.

  An adhesive can also be used for adhesion to the metal foil. Examples of the adhesive include, but are not limited to, epoxy, acrylic, phenol, and cyanoacrylate. The above lamination molding and curing can be performed under the same conditions as in the production of the cured composite material of the present invention.

The film of the present invention is obtained by forming the curable composition of the present invention into a film. The thickness is not particularly limited, but is in the range of 3 to 200 μm, more preferably 5 to 105 μm.
The method for producing the film of the present invention is not particularly limited. For example, the curable composition and other components as required are uniformly dissolved in an aromatic solvent, a ketone solvent, or a mixed solvent thereof. Alternatively, a method of dispersing, applying to a resin film such as a PET film, and drying may be used. The application can be repeated multiple times as necessary. In this case, the application can be repeated using a plurality of solutions having different compositions and concentrations, and finally the desired resin composition and resin amount can be adjusted. It is.

  The metal foil with resin of the present invention is composed of the curable composition of the present invention and the metal foil. Examples of the metal foil used here include a copper foil and an aluminum foil. Although the thickness is not specifically limited, The thickness of metal foil is 3-200 micrometers, More preferably, it is the range of 5-105 micrometers.

  The method for producing the resin-coated metal foil of the present invention is not particularly limited. For example, the curable composition and other components as necessary in an aromatic solvent, a ketone solvent or a mixed solvent thereof. A method of uniformly dissolving or dispersing, applying to a metal foil and then drying is exemplified. The application can be repeated a plurality of times as necessary. At this time, the application can be repeated using a plurality of solutions having different compositions and concentrations, and finally adjusted to a desired resin composition and resin amount. Is possible.

  The terminal-modified soluble polyfunctional vinyl aromatic copolymer of the present invention can be processed into a molding material, a sheet or a film, and has a low dielectric constant, a low water absorption rate and a high heat resistance in the fields of the electrical industry, the space / aircraft industry, etc. Can be used for a low dielectric material, an insulating material, a heat-resistant material, a structural material, and the like that can satisfy characteristics such as properties. In particular, it can be used as a single-sided, double-sided, multilayer printed board, flexible printed board, build-up board or the like. Furthermore, semiconductor-related materials or optical materials, paints, photosensitive materials, adhesives, sewage treatment agents, heavy metal scavengers, ion exchange resins, antistatic agents, antioxidants, antifogging agents, rustproofing agents It can be applied to anti-dyeing agents, bactericides, insect repellents, medical materials, flocculants, surfactants, lubricants, solid fuel binders, conductive treatment agents and the like. Further, examples of the optical component include a CD pickup lens, a DVD pickup lens, a Fax lens, an LBP lens, a Fresnel lens, a lenticular lens, a microlens array, an oligon mirror, and a prism. In addition, the curable composition of the present invention has high dielectric properties (low dielectric constant and low dielectric loss tangent) even after severe thermal history, and has high adhesion reliability even in severe environments. In addition, it has excellent resin fluidity, low linear expansion, and excellent wiring embedding flatness. Therefore, in the fields of electrical / electronics industry, space / aircraft industry, etc., molding defects such as warping etc. corresponding to the miniaturization and thinning that have been strongly demanded in recent years as dielectric materials, insulating materials, heat resistant materials, structural materials, etc. A cured molded product having no phenomenon can be provided. Furthermore, it is possible to realize a resin composition, a cured product, or a material including the same that is excellent in reliability due to excellent wiring embedding flatness and adhesion between different materials.

  EXAMPLES Next, the present invention will be described with reference to examples, but the present invention is not limited thereto. In addition, all the parts in each Example are a weight part. Moreover, the measurement of the softening temperature etc. in an Example performed sample preparation and a measurement with the method shown below.

1) Molecular weight and molecular weight distribution GPC (manufactured by Tosoh Corporation, HLC-8120GPC) is used for molecular weight and molecular weight distribution measurement, and tetrahydrofuran is used as a solvent, a flow rate is 1.0 ml / min, a column temperature is 38 ° C, and a calibration curve using monodisperse polystyrene is used. Used.

2) Structure of the copolymer The copolymer structure was determined by ¹³ C-NMR and ¹ H-NMR analysis using a JNM-LA600 nuclear magnetic resonance spectrometer manufactured by JEOL. Chloroform-d ₁ was used as a solvent, and the tetramethylsilane resonance line was used as an internal standard.

3) Calculation of terminal group introduction amount (c1) Derivative amount used to introduce terminal groups with respect to the total amount of monomers obtained from the results of the number average molecular weight, ¹ H-NMR measurement and elemental analysis obtained from the above GPC measurement From the above, the introduction amount (c1) of terminal groups contained in one molecule of the copolymer was calculated.

4) Sample preparation and measurement for measurement of glass transition temperature (Tg) and softening temperature of cured product The polymer solution was uniformly applied to a glass substrate so that the thickness after drying was 20 μm, and a hot plate was used. Heated at 90 minutes for 30 minutes and dried. The resin film obtained together with the glass substrate is set in TMA (thermomechanical analyzer), heated to 220 ° C. at a temperature rising rate of 10 ° C./min under a nitrogen stream, and further heat-treated at 220 ° C. for 20 minutes. The remaining solvent was removed and the polymer was cured. After allowing the glass substrate to cool to room temperature, an analytical probe is brought into contact with the sample in the TMA measuring apparatus, and scan measurement is performed from 30 ° C. to 360 ° C. at a temperature rising rate of 10 ° C./min under a nitrogen stream. The softening temperature was determined.

5) Evaluation of heat resistance and measurement of heat discoloration The heat resistance evaluation of this copolymer is carried out by setting a sample in a TGA (thermobalance) measuring device and from 30 ° C. to 400 ° C. at a heating rate of 10 ° C./min in a nitrogen stream. The measurement was performed by scanning up to 0 ° C., and the weight loss at 350 ° C. was determined as heat resistance. On the other hand, the measurement of heat discoloration was 6.0 g of this copolymer, 4.0 g of divinylbiphenyl, and 0.02 g of t-butylperoxy-2-ethylhexanoate (Nippon Yushi Co., Ltd., Perbutyl O). And heated at 200 ° C. for 1 hour under a nitrogen stream to obtain a cured product. And the amount of discoloration of the obtained hardened | cured material was confirmed visually, and heat-resistant discoloration property was evaluated by classifying into (circle): No thermal discoloration, (triangle | delta): Light yellow, and x: Yellow.

6) Measurement of compatibility The measurement of compatibility of the copolymer with an epoxy resin was carried out by using 5.0 g of a sample of 3.0 g of an epoxy resin (liquid bisphenol A type epoxy resin: manufactured by Japan Epoxy Resin, Epicoat 828), and , 2.0 g of phenol resin (melamine skeleton phenol resin: PS-6492, manufactured by Gunei Chemical Industry Co., Ltd.) was dissolved in 10 g of methyl ethyl ketone (MEK), and the transparency of the sample after dissolution was visually confirmed. The compatibility was evaluated by classifying into transparent, Δ: translucent, and X: opaque or insoluble.

Example 1
Divinylbenzene (mixture of 1,4-divinylbenzene and 1,3-divinylbenzene, the following examples are also the same) 4.37 mol (630.2 mL), ethylvinylbenzene (1-ethyl-4-vinylbenzene, and 1 -A mixture of ethyl-3-vinylbenzene, the following example is also the same) 3.34 mol (457.5 mL), 6.90 mol (749.9 mL) of anisole and 345 mL of toluene were charged into a 3.0 L reactor. At 50 ° C., 103.5 mmol (13.0 mL) of diethyl ether complex of boron trifluoride was added and allowed to react for 5 hours. After the polymerization solution was stopped with an aqueous sodium hydrogen carbonate solution, the oil layer was washed three times with pure water, and devolatilized at 60 ° C. to recover the polymer. The obtained polymer was weighed to confirm that 945.3 g of copolymer A was obtained.

元素分析結果と標準ポリスチレン換算の数平均分子量から算出される可溶性多官能ビニル芳香族重合体のアニソール由来の構造単位の導入量（ｃ１）は１．６（個／分子）であった。また、ジビニルベンゼン由来の構造単位を６１．３モル％及びエチルビニルベンゼン由来の構造単位を合計３８．７モル％含有していた（末端構造単位を除く）。共重合体Ａ中に含まれるビニル基含有量は、３４．８モル％であった（末端構造単位を除く）。
また、硬化物のＴＭＡ測定の結果、明確なＴｇは観察されなかった、軟化温度は３００℃以上であった。ＴＧＡ測定の結果、３５０℃における重量減少は３．７０ｗｔ％、耐熱変色性は○であった。一方、エポキシ樹脂との相溶性は○であった。
共重合体Ａはトルエン、キシレン、ＴＨＦ、ジクロロエタン、ジクロロメタン、クロロホルムに可溶であり、ゲルの生成は認められなかった。 Mn of the obtained copolymer A was 624, Mw was 2360, Mw / Mn was 3.79, and it was a random copolymer. By performing ¹³ C-NMR and ¹ H-NMR analysis, the chart of copolymer A shows the resonance line of the end group in which the benzene ring derived from anisole is bonded to the main chain end represented by the formula (11). Observed. In the formula (11), x and y each represent a mole fraction of the structural unit of the copolymer.

The introduction amount (c1) of structural units derived from anisole of the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis results and the number average molecular weight in terms of standard polystyrene was 1.6 (pieces / molecule). Moreover, 61.3 mol% of structural units derived from divinylbenzene and 38.7 mol% in total of structural units derived from ethylvinylbenzene were contained (excluding terminal structural units). The vinyl group content contained in the copolymer A was 34.8 mol% (excluding the terminal structural unit).
Moreover, clear Tg was not observed as a result of TMA measurement of hardened | cured material, and the softening temperature was 300 degreeC or more. As a result of TGA measurement, the weight loss at 350 ° C. was 3.70 wt%, and the heat discoloration resistance was ◯. On the other hand, the compatibility with the epoxy resin was ○.
Copolymer A was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was formed.

Example 2
Divinylbenzene 4.37 mol (630.2 mL), ethylvinylbenzene 3.34 mol (457.5 mL), 1-methoxynaphthalene 6.90 mol (994.8 g), toluene 345 mL were placed in a 3.0 L reactor. Then, 103.5 mmol (13.0 mL) of diethyl ether complex of boron trifluoride was added at 50 ° C. and reacted for 5 hours. After the polymerization solution was stopped with an aqueous sodium hydrogen carbonate solution, the oil layer was washed three times with pure water, and after separating the oil layer and the aqueous layer, unreacted substances were extracted from the oil layer using methanol to obtain a polymer. It was collected. The obtained polymer was weighed to confirm that 943.6 g of copolymer B was obtained.

元素分析結果と標準ポリスチレン換算の数平均分子量から算出される可溶性多官能ビニル芳香族重合体の１−メトキシナフタレン由来の構造単位の導入量（ｃ１）は１．８（個／分子）であった。また、ジビニルベンゼン由来の構造単位を６０．６モル％及びエチルビニルベンゼン由来の構造単位を合計３９．４モル％含有していた（末端構造単位を除く）。共重合体Ｂ中に含まれるビニル基含有量は、３５．３モル％であった（末端構造単位を除く）。
また、硬化物のＴＭＡ測定の結果、明確なＴｇは観察されなかった、軟化温度は３００℃以上であった。ＴＧＡ測定の結果、３５０℃における重量減少は３．６１ｗｔ％、耐熱変色性は○であった。一方、エポキシ樹脂との相溶性は○であった。
共重合体Ｂはトルエン、キシレン、ＴＨＦ、ジクロロエタン、ジクロロメタン、クロロホルムに可溶であり、ゲルの生成は認められなかった。 The obtained copolymer B had a Mn of 871, Mw of 3670, and Mw / Mn of 4.21, and was a random copolymer. By performing ¹³ C-NMR and ¹ H-NMR analysis, the chart of copolymer B shows the end group in which the naphthalene ring derived from 1-methoxynaphthalene is bonded to the end of the main chain represented by formula (12). Resonance lines were observed. In the formula (12), w and z each represent a mole fraction of the structural unit of the copolymer.

The amount (c1) of structural units derived from 1-methoxynaphthalene of the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis results and the number average molecular weight in terms of standard polystyrene was 1.8 (pieces / molecule). . Moreover, 60.6 mol% of structural units derived from divinylbenzene and 39.4 mol% of structural units derived from ethylvinylbenzene were contained in total (excluding terminal structural units). The vinyl group content contained in the copolymer B was 35.3 mol% (excluding the terminal structural unit).
Moreover, clear Tg was not observed as a result of TMA measurement of hardened | cured material, and the softening temperature was 300 degreeC or more. As a result of TGA measurement, the weight loss at 350 ° C. was 3.61 wt%, and the heat discoloration resistance was ◯. On the other hand, the compatibility with the epoxy resin was ○.
Copolymer B was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was formed.

Comparative Example 1
Divinylbenzene 2.03 mol (288.5 mL), ethylvinylbenzene 0.084 mol (12.0 mL), styrene 2.11 mol (241.7 mL), 2-phenoxyethyl methacrylate 2.25 mol (427.3 mL) Then, 100.0 mL of butyl acetate and 1150 mL of toluene were put into a 3.0 L reactor, 300 mmol of boron trifluoride diethyl ether complex was added at 50 ° C., and the mixture was reacted for 4 hours. After stopping the polymerization solution with an aqueous sodium hydrogen carbonate solution, the oil layer was washed three times with pure water, and the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a polymer. The obtained polymer was washed with methanol, filtered, dried and weighed to obtain 282.4 g of copolymer C.

共重合体Ｃの元素分析結果を行った結果、Ｃ：８７．３ｗｔ％、Ｈ：７．４ｗｔ％、Ｏ：５．２ｗｔ％であった。元素分析結果と標準ポリスチレン換算の数平均分子量から算出される可溶性多官能ビニル芳香族重合体の２−フェノキシエチルメタクリレート由来の構造単位の導入量（ｃ１）は２．３（個／分子）であった。また、ジビニルベンゼン由来の構造単位を５９．２モル％及びスチレンとエチルベンゼン由来の構造単位を合計４０．８モル％含有していた（末端構造単位を除く）。共重合体Ｃ中に含まれるビニル基含有量は、３５．３モル％であった（末端構造単位を除く）。
また、硬化物のＴＭＡ測定の結果、明確なＴｇは観察されなかった、軟化温度は３００℃以上であった。ＴＧＡ測定の結果、３５０℃における重量減少は４．８６ｗｔ％、耐熱変色性は○であった。一方、エポキシ樹脂との相溶性は△であった。
共重合体Ｃはトルエン、キシレン、ＴＨＦ、ジクロロエタン、ジクロロメタン、クロロホルムに可溶であり、ゲルの生成は認められなかった。 Mn of the obtained copolymer C was 2030, Mw was 5180, Mw / Mn was 2.55, and it was a random copolymer. By performing ¹³ C-NMR and ¹ H-NMR analysis, the resonance line of the terminal group derived from 2-phenoxyethyl methacrylate represented by the formula (13) was observed on the chart of the copolymer C. In the formula (13), a, b and c each represent a mole fraction of the structural unit of the copolymer.

As a result of conducting an elemental analysis result of the copolymer C, it was C: 87.3 wt%, H: 7.4 wt%, and O: 5.2 wt%. The introduction amount (c1) of the structural unit derived from 2-phenoxyethyl methacrylate of the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis result and the number average molecular weight in terms of standard polystyrene was 2.3 (pieces / molecule). It was. Further, it contained 59.2 mol% of structural units derived from divinylbenzene and 40.8 mol% in total of structural units derived from styrene and ethylbenzene (excluding terminal structural units). The vinyl group content contained in the copolymer C was 35.3 mol% (excluding the terminal structural unit).
Moreover, clear Tg was not observed as a result of TMA measurement of hardened | cured material, and the softening temperature was 300 degreeC or more. As a result of TGA measurement, the weight loss at 350 ° C. was 4.86 wt%, and the heat discoloration resistance was ◯. On the other hand, the compatibility with the epoxy resin was Δ.
Copolymer C was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was formed.

Comparative Example 2
Divinylbenzene 28.5 mol (4059 ml), ethyl vinylbenzene 1.5 mol (213.7 ml), styrene 10.0 mol (1145.8 ml), benzyl alcohol 16 mol (1655.7 ml), ethyl acetate 4.80 mol (468.9 ml), 7111 ml of toluene (dielectric constant: 2.3) and 6222 ml of cyclohexane (dielectric constant: 2.02) were put into a 30 L reactor, and 6.4 mol of boron trifluoride was added at 30 ° C. Diethyl ether complex was added and allowed to react for 5 hours. The polymerization reaction was stopped with 2845 g of calcium hydroxide, followed by filtration and washing with 5 L of distilled water three times. After 8.0 g of butylhydroxytoluene was dissolved in the polymerization solution, the solution was concentrated using an evaporator at 40 ° C. for 1 hour. The reaction mixture was poured into a large amount of methanol at room temperature to precipitate a polymer. The obtained polymer was washed with methanol, filtered, dried and weighed to obtain 3356 g of copolymer D (yield: 67.8 wt%).

共重合体Ａの元素分析を行った結果、Ｃ：９０．６ｗｔ％、Ｈ：７．５ｗｔ％、Ｏ：１．９ｗｔ％であった。元素分析結果と標準ポリスチレン換算の数平均分子量から算出される可溶性多官能ビニル芳香族重合体へのベンジルアルコール由来の構造単位の導入量（ｃ１）は２．７（個／分子）であった。また、ジビニルベンゼン由来の構造単位を合計４５．７モル％及びスチレン由来の構造単位とベンジルアルコール由来の構造単位とエチルビニルベンゼン由来の構造単位を合計５４．３モル％含有していた。また、ＴＭＡ測定の結果、明確なＴｇは観察されなかった。軟化温度は３００℃以上であった。ＴＧＡ測定の結果、３５０℃に於ける重量減少量は５．２０ｗｔ％、耐熱変色性は△であった。
共重合体Ｄはトルエン、キシレン、ＴＨＦ、ジクロロエタン、ジクロロメタン、クロロホルムに可溶であり、ゲルの生成は認められなかった。 Mw of the obtained copolymer D was 6710, Mn was 2250, Mw / Mn was 2.98, and it was a random copolymer. By performing ¹³ C-NMR and ¹ H-NMR analysis, the resonance line of the terminal group derived from benzyl alcohol represented by the formula (14) was observed on the chart of the copolymer D. In the formula (14), d, e, and f each represent a mole fraction of the structural unit of the copolymer.

As a result of conducting elemental analysis of the copolymer A, it was C: 90.6 wt%, H: 7.5 wt%, and O: 1.9 wt%. The amount (c1) of structural units derived from benzyl alcohol to the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis results and the number average molecular weight in terms of standard polystyrene was 2.7 (pieces / molecule). Further, the structural unit was derived from a total of 45.7 mol% of structural units derived from divinylbenzene, and a total of 54.3 mol% of structural units derived from styrene, structural units derived from benzyl alcohol, and structural units derived from ethylvinylbenzene. Moreover, clear Tg was not observed as a result of the TMA measurement. The softening temperature was 300 ° C. or higher. As a result of TGA measurement, the weight loss at 350 ° C. was 5.20 wt%, and the heat discoloration was Δ.
Copolymer D was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was observed.

Comparative Example 3
1.92 mol (273.5 mL) of divinylbenzene, 0.08 mol (11.4 mL) of ethylvinylbenzene, 2.0 mol (229.2 mL) of styrene, 2.00 mol (348.1 mL) of 2-phenoxyethyl acrylate Then, 250.0 mL of butyl acetate and 1000 mL of toluene were put into a 3.0 L reactor, and 80 mmol of boron trifluoride diethyl ether complex was added at 70 ° C. and reacted for 6 hours. After stopping the polymerization solution with an aqueous sodium hydrogen carbonate solution, the oil layer was washed three times with pure water, and the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a polymer. The obtained polymer was washed with methanol, filtered, dried, and weighed to obtain 164.2 g of copolymer E.

共重合体Ｅの元素分析結果を行った結果、Ｃ：８４．４ｗｔ％、Ｈ：７．３ｗｔ％、Ｏ：７．９ｗｔ％であった。元素分析結果と標準ポリスチレン換算の数平均分子量から算出される可溶性多官能ビニル芳香族重合体の２−フェノキシエチルアクリレート由来の構造単位の導入量（ｃ１）は３．５（個／分子）であった。また、ジビニルベンゼン由来の構造単位を５４．３モル％及びスチレンとエチルベンゼン由来の構造単位を合計４５．７モル％含有していた（末端構造単位を除く）。共重合体Ｅ中に含まれるビニル基含有量は、２１．８モル％であった（末端構造単位を除く）。
また、硬化物のＴＭＡ測定の結果、明確なＴｇは観察されなかった、軟化温度は３００℃以上であった。ＴＧＡ測定の結果、３５０℃における重量減少は５．５０ｗｔ％、耐熱変色性は○であった。一方、エポキシ樹脂との相溶性は△であった。
共重合体Ｅはトルエン、キシレン、ＴＨＦ、ジクロロエタン、ジクロロメタン、クロロホルムに可溶であり、ゲルの生成は認められなかった。 Mn of the obtained copolymer E was 2330, Mw was 4940, Mw / Mn was 2.12, and it was a random copolymer. By performing ¹³ C-NMR and ¹ H-NMR analysis, a resonance line of a terminal group derived from 2-phenoxyethyl acrylate represented by the formula (15) was observed on the chart of the copolymer E. In the formula (15), g, h, and i each represent a mole fraction of the structural unit of the copolymer.

As a result of conducting the elemental analysis result of the copolymer E, it was C: 84.4 wt%, H: 7.3 wt%, and O: 7.9 wt%. The introduction amount (c1) of the structural unit derived from 2-phenoxyethyl acrylate of the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis result and the number average molecular weight in terms of standard polystyrene was 3.5 (pieces / molecule). It was. Further, it contained 54.3 mol% of structural units derived from divinylbenzene and 45.7 mol% in total of structural units derived from styrene and ethylbenzene (excluding terminal structural units). The vinyl group content contained in the copolymer E was 21.8 mol% (excluding the terminal structural unit).
Moreover, clear Tg was not observed as a result of TMA measurement of hardened | cured material, and the softening temperature was 300 degreeC or more. As a result of the TGA measurement, the weight loss at 350 ° C. was 5.50 wt%, and the heat discoloration resistance was ◯. On the other hand, the compatibility with the epoxy resin was Δ.
Copolymer E was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was observed.

Example 3
4.37 mol (630.2 mL) of divinylbenzene, 3.34 mol (457.5 mL) of ethyl vinylbenzene, 6.90 mol (1174.4 g) of diphenyl ether and 345 mL of toluene were charged into a 3.0 L reactor. At 50 ° C., 103.5 mmol (13.0 mL) of diethyl ether complex of boron trifluoride was added and reacted for 5 hours. After the polymerization solution was stopped with an aqueous sodium hydrogen carbonate solution, the oil layer was washed three times with pure water, and after separating the oil layer and the aqueous layer, unreacted substances were extracted from the oil layer using methanol to obtain a polymer. It was collected. The obtained polymer was weighed to confirm that 1141.7 g of copolymer F was obtained.

元素分析結果と標準ポリスチレン換算の数平均分子量から算出される可溶性多官能ビニル芳香族重合体のジフェニルエーテル由来の構造単位の導入量（ｃ１）は１．７（個／分子）であった。また、ジビニルベンゼン由来の構造単位を５９．５モル％及びエチルビニルベンゼン由来の構造単位を合計４０．５モル％含有していた（末端構造単位を除く）。共重合体Ｆ中に含まれるビニル基含有量は、３３．７モル％であった（末端構造単位を除く）。
また、硬化物のＴＭＡ測定の結果、明確なＴｇは観察されなかった、軟化温度は３００℃以上であった。ＴＧＡ測定の結果、３５０℃における重量減少は２．９８ｗｔ％、耐熱変色性は○であった。一方、エポキシ樹脂との相溶性は○であった。
共重合体Ｆはトルエン、キシレン、ＴＨＦ、ジクロロエタン、ジクロロメタン、クロロホルムに可溶であり、ゲルの生成は認められなかった。 Mn of the obtained copolymer F was 1020, Mw was 5180, Mw / Mn was 5.08, and it was a random copolymer. By performing ¹³ C-NMR and ¹ H-NMR analysis, the chart of copolymer F shows the resonance line of the end group in which the benzene ring derived from diphenyl ether is bonded to the end of the main chain represented by formula (16). Observed. In the formula (16), j and k each represent a mole fraction of the structural unit of the copolymer.

The amount (c1) of structural units derived from diphenyl ether of the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis results and the number average molecular weight in terms of standard polystyrene was 1.7 (pieces / molecule). Further, it contained 59.5 mol% of structural units derived from divinylbenzene and 40.5 mol% in total of structural units derived from ethylvinylbenzene (excluding terminal structural units). The vinyl group content contained in the copolymer F was 33.7 mol% (excluding the terminal structural unit).
Moreover, clear Tg was not observed as a result of TMA measurement of hardened | cured material, and the softening temperature was 300 degreeC or more. As a result of TGA measurement, the weight loss at 350 ° C. was 2.98 wt%, and the heat discoloration resistance was ◯. On the other hand, the compatibility with the epoxy resin was ○.
Copolymer F was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was formed.

Example 4
Divinylbenzene 4.37 mol (630.2 mL), ethylvinylbenzene 3.34 mol (457.5 mL), divinylbiphenyl 1.16 mol (239.3 g), diphenyl ether 6.90 mol (1174.4 g), toluene 345 mL Was added to a 3.0 L reactor, and 103.5 mmol (13.0 mL) of diethyl ether complex of boron trifluoride was added at 50 ° C. and reacted for 5 hours. After the polymerization solution was stopped with an aqueous sodium hydrogen carbonate solution, the oil layer was washed three times with pure water, and after separating the oil layer and the aqueous layer, unreacted substances were extracted from the oil layer using methanol to obtain a polymer. It was collected. The obtained polymer was weighed, and it was confirmed that 1024.8 g of copolymer G was obtained.

元素分析結果と標準ポリスチレン換算の数平均分子量から算出される可溶性多官能ビニル芳香族重合体のジフェニルエーテル由来の構造単位の導入量（ｃ１）は１．６（個／分子）であった。また、ジビニルベンゼン由来の構造単位を５４．３モル％、エチルビニルベンゼン由来の構造単位を合計３６．４モル％、及び、ジビニルビフェニル由来の構造単位を９．３モル％含有していた（末端構造単位を除く）。共重合体Ｇ中に含まれるビニル基含有量は、４０．３モル％であった（末端構造単位を除く）。
また、硬化物のＴＭＡ測定の結果、明確なＴｇは観察されなかった、軟化温度は３００℃以上であった。ＴＧＡ測定の結果、３５０℃における重量減少は３．０５ｗｔ％、耐熱変色性は○であった。一方、エポキシ樹脂との相溶性は○であった。
共重合体Ｇはトルエン、キシレン、ＴＨＦ、ジクロロエタン、ジクロロメタン、クロロホルムに可溶であり、ゲルの生成は認められなかった。 Mn of the obtained copolymer G was 948, Mw was 4230, Mw / Mn was 4.46, and it was a random copolymer. By performing ¹³ C-NMR and ¹ H-NMR analysis, the chart of copolymer G shows the resonance line of the end group in which the benzene ring derived from diphenyl ether is bonded to the end of the main chain represented by formula (17). Observed. In the formula (17), l, m, and n each represent a mole fraction of the structural unit of the copolymer.

The introduction amount (c1) of structural units derived from diphenyl ether of the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis results and the number average molecular weight in terms of standard polystyrene was 1.6 (pieces / molecule). Further, it contained 54.3 mol% of structural units derived from divinylbenzene, 36.4 mol% in total of structural units derived from ethylvinylbenzene, and 9.3 mol% of structural units derived from divinylbiphenyl (terminal). Excluding structural units). The vinyl group content contained in the copolymer G was 40.3% by mole (excluding the terminal structural unit).
Moreover, clear Tg was not observed as a result of TMA measurement of hardened | cured material, and the softening temperature was 300 degreeC or more. As a result of TGA measurement, the weight loss at 350 ° C. was 3.05 wt%, and the heat discoloration resistance was ◯. On the other hand, the compatibility with the epoxy resin was ○.
Copolymer G was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was observed.

Example 5
Divinylbenzene 4.37 mol (630.2 mL), ethylvinylbenzene 3.34 mol (457.5 mL), divinylbiphenyl 1.16 mol (239.3 g), 3-phenoxytoluene 6.90 mol (1271.3 g) Then, 345 mL of toluene was put into a 3.0 L reactor, 103.5 mmol (13.0 mL) of diethyl ether complex of boron trifluoride was added at 50 ° C., and the reaction was performed for 5 hours. After the polymerization solution was stopped with an aqueous sodium hydrogen carbonate solution, the oil layer was washed three times with pure water, and after separating the oil layer and the aqueous layer, unreacted substances were extracted from the oil layer using methanol to obtain a polymer. It was collected. The obtained polymer was weighed to confirm that 1164.3 g of copolymer H was obtained.

元素分析結果と標準ポリスチレン換算の数平均分子量から算出される可溶性多官能ビニル芳香族重合体のジフェニルエーテル由来の構造単位の導入量（ｃ１）は１．３２（個／分子）であった。また、ジビニルベンゼン由来の構造単位を５３．７モル％、エチルビニルベンゼン由来の構造単位を合計３５．３モル％、及び、ジビニルビフェニル由来の構造単位を９．３モル％含有していた（末端構造単位を除く）。共重合体Ｈ中に含まれるビニル基含有量は、４１．１モル％であった（末端構造単位を除く）。
また、硬化物のＴＭＡ測定の結果、明確なＴｇは観察されなかった、軟化温度は３００℃以上であった。ＴＧＡ測定の結果、３５０℃における重量減少は３．１２ｗｔ％、耐熱変色性は○であった。一方、エポキシ樹脂との相溶性は○であった。
共重合体Ｈはトルエン、キシレン、ＴＨＦ、ジクロロエタン、ジクロロメタン、クロロホルムに可溶であり、ゲルの生成は認められなかった。 Mn of the obtained copolymer H was 1043, Mw was 5780, Mw / Mn was 5.54, and it was a random copolymer. By performing ¹³ C-NMR and ¹ H-NMR analysis, the chart of copolymer H shows the resonance line of the end group in which the benzene ring derived from phenoxytoluene is bonded to the end of the main chain represented by formula (18). Was observed. In the formula (18), l, m, and n each represent a mole fraction of the structural unit of the copolymer.

The introduction amount (c1) of structural units derived from diphenyl ether of the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis results and the number average molecular weight in terms of standard polystyrene was 1.32 (pieces / molecule). Further, it contained 53.7 mol% of structural units derived from divinylbenzene, 35.3 mol% in total of structural units derived from ethylvinylbenzene, and 9.3 mol% of structural units derived from divinylbiphenyl (terminal). Excluding structural units). The vinyl group content contained in the copolymer H was 41.1 mol% (excluding the terminal structural unit).
Moreover, clear Tg was not observed as a result of TMA measurement of hardened | cured material, and the softening temperature was 300 degreeC or more. As a result of TGA measurement, the weight loss at 350 ° C. was 3.12 wt%, and the heat discoloration resistance was ◯. On the other hand, the compatibility with the epoxy resin was ○.
Copolymer H was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was formed.

  Using the copolymers A to H obtained in Examples 1 to 5 and Comparative Examples 1 to 2, varnishes of curable resin compositions using these resins were prepared.

The components and abbreviations used in these examples and comparative examples are as follows.

<Modified polyphenylene ether>
Modified PPE-A: Polyphenylene oligomer having vinyl groups at both ends (Mn = 1160, manufactured by Mitsubishi Gas Chemical Co., Inc., 2,2 ′, 3,3 ′, 5,5′-hexamethylbiphenyl-4,4 ′ -Reaction product of diol, 2,6-dimethylphenol polycondensate and chloromethylstyrene)
Modified PPE-B: polyphenylene oligomer having vinyl groups at both ends (Mn = 2270, manufactured by Mitsubishi Gas Chemical Co., Inc., 2,2 ′, 3,3 ′, 5,5′-hexamethylbiphenyl-4,4 ′ -Reaction product of diol, 2,6-dimethylphenol polycondensate and chloromethylstyrene)
Modified PPE-C: polyphenylene oligomer having a vinyl group at one end (Mn = 2340, reaction product of polyphenylene ether (SA120 manufactured by SABIC Innovative Plastics) and chloromethylstyrene)
Modified PPE-D: Polyphenylene oligomer having an epoxy group at both ends (Mn = 1180, manufactured by Mitsubishi Gas Chemical Co., Inc., 2,2 ′, 3,3 ′, 5,5′-hexamethylbiphenyl-4,4 ′ -Reaction product of 2-diol, 2,6-dimethylphenol polycondensate and epichlorohydrin)
<Reactive diluent>
TAIC: triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.)
DCP: Tricyclodecane dimethanol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
A-DCP: Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
DVB630: Divinylbenzene DVB630 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)

<Epoxy resin>
o-Cresol novolac type epoxy resin: Epototo YDCN-700-3 (low viscosity type, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
Bisphenol F type liquid epoxy resin: Epicoat 806L, Mw = 370 (manufactured by Japan Epoxy Resin Co., Ltd.)
Naphthalene skeleton liquid epoxy resin: EPICLON HP-4032D, Mw = 304 (manufactured by DIC)
Naphthol type epoxy resin: ESN-475V, epoxy equivalent: 340 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)

<Curing agent>
Bisphenol A type liquid epoxy resin: Epicoat 828US, Mw = 370 (manufactured by Japan Epoxy Resin Co., Ltd.)
Biphenyl skeleton phenol resin: MEH-7851-S manufactured by Meiwa Kasei Co., Ltd.
Melamine skeleton phenol resin: PS-6492, manufactured by Gunei Chemical Industry Co., Ltd.
Allyl group-containing skeleton phenol resin: YLH-903, manufactured by Japan Epoxy Resin Co., Ltd.
Alicyclic skeleton acid anhydride: manufactured by Shin Nippon Rika Co., Ltd., MH-700
Aromatic skeleton acid anhydride: SMA Resin EF60, manufactured by Sartomer Japan

<High molecular weight resin>
Styrene copolymer: KRATON A1535 (manufactured by Kraton Polymers LLC)
Phenoxy resin: weight average molecular weight 37000, “YL7553BH30” manufactured by Mitsubishi Chemical Corporation (a 1: 1 solution of MEK and cyclohexanone having a nonvolatile content of 30% by mass)

<Radical polymerization initiator>
Park Mill D (Nippon Yushi Co., Ltd.)
Park Mill P (Nippon Yushi Co., Ltd.)
<Inorganic filler>
Amorphous spherical silica: manufactured by Admatechs, SE2050 SPE, average particle size 0.5 μm (treated with phenylsilane coupling agent)
<Curing accelerator>
Triphenylphosphine <stabilizer>
ADK STAB AO-60

  The properties of the obtained cured product were evaluated according to the following test methods.

7) Solution viscosity The solution viscosity of the curable resin composition was measured using an E-type viscometer at a measurement temperature of 25 ° C.

8) Bending strength and bending elongation at break The test piece used for the bending test was prepared by placing the curable resin composition on a mold under a vacuum press molding machine and placing the solvent under a heating vacuum. Volatilized. Thereafter, an upper mold was placed, heated and pressed under vacuum, and held at 200 ° C. for 1 hour to form a flat plate having a thickness of 1.0 mm. A test piece having a width of 5.0 mm, a thickness of 1.0 mm, a length of 120 mm was prepared from a flat plate obtained by molding, and a bending test was performed. The bending strength and bending elongation at break of the prepared bending test pieces were measured using a universal testing apparatus. The bending strength and the bending elongation at break are ◯ when the value is less than ± 10% with respect to the measurement value of the reference blend, ◎ when the value is 10% or more, and −10 to −20%. Evaluation was made with Δ for the range value and x for the value of −20% or less.

9) Linear expansion coefficient and glass transition temperature The test piece used for the test of the linear expansion coefficient and glass transition temperature of the curable resin composition was obtained by using the curable resin composition on a plate-shaped mold under a vacuum press molding machine. The varnish of the curable resin composition was placed on the substrate, and the solvent was devolatilized under heating vacuum. Thereafter, an upper mold was placed with a 0.2 mm spacer in between, a heat press was performed under vacuum, and the plate was held at 200 ° C. for 1 hour to form a flat plate having a thickness of 0.2 mm. A test piece having a width of 3.0 mm, a thickness of 0.2 mm, a length of 40 mm is prepared from the flat plate obtained by molding, and is set only on the chuck above the TMA (thermomechanical analyzer). Under an air stream, the temperature was raised to 220 ° C. at a heating rate of 10 ° C./min, and the remaining solvent was removed by heat treatment at 220 ° C. for 20 minutes, and the molding distortion in the test piece was removed. After allowing the TMA to cool to room temperature, the lower part of the test piece in the TMA measuring device is also set on the probe for analysis, and scan measurement is performed from 30 ° C. to 360 ° C. at a heating rate of 10 ° C./min in a nitrogen stream. The linear expansion coefficient was calculated from the dimensional change at 0 to 40 ° C. Moreover, the glass transition temperature was calculated | required by the tangent method.

10) Dielectric constant and dielectric loss tangent In accordance with JIS C2565 standard, cured after storing for 24 hours in a room at 23 ° C and 50% humidity after dry-drying using a cavity resonator method dielectric constant measuring device manufactured by AET Co., Ltd. Using a flat plate test piece, the dielectric constant and dielectric loss tangent at 18 GHz were measured.
Moreover, after leaving the hardened | cured material flat test piece to stand at 85 degreeC and 85% of relative humidity for 2 weeks, the dielectric constant and dielectric loss tangent were measured, and the dielectric constant and dielectric loss tangent after a heat-and-moisture resistance test were measured.

11) Copper foil peel strength A glass cloth (E glass, weight per unit area: 71 g / m ² ) was immersed in a varnish of a thermosetting resin composition, impregnated, and dried in an air oven at 80 ° C. for 10 minutes. At that time, the resin content (RC) of the obtained prepreg was adjusted to 50 wt%. Using this prepreg, a plurality of the above curable composite materials are laminated as necessary so that the thickness after molding becomes about 0.6 mm to 1.0 mm, and a copper foil having a thickness of 18 μm on both sides thereof (Product name: F2-WS copper foil, Rz: 2.0 μm, Ra: 0.3 μm) was placed and molded and cured by a vacuum press molding machine to obtain an evaluation laminate. Curing conditions were as follows: the temperature was increased at 3 ° C./min, the pressure was 3 MPa, and the temperature was maintained at 200 ° C. for 60 minutes to obtain a copper clad laminate for evaluation. A test piece having a width of 20 mm and a length of 100 mm was cut out from the cured laminate thus obtained, and a parallel cut having a width of 10 mm was made on the copper foil surface, and then 50 mm / 90 ° in the direction of 90 ° with respect to the surface. The copper foil was peeled off continuously at a speed of minutes, the stress at that time was measured with a tensile tester, and the minimum value of the stress was recorded as the copper foil peel strength (according to JIS C 6481). The copper foil peel strength test after the wet heat resistance test was measured in the same manner as described above after the test piece was left at 85 ° C. and a relative humidity of 85% for 2 weeks.

12) Copper plating peeling strength The copper-clad laminate prepared in the previous section was immersed in an aqueous solution of ammonium persulfate 150 g / L at 40 ° C. for 20 minutes to remove the copper foil by etching. Next, the laminate from which the sample was not removed was immersed in a circulated MLB conditioner 211 (trade name, manufactured by Rohm & Haas Japan Co., Ltd.) with a swelling aqueous solution at 80 ° C. for 5 minutes. Further, after 3 minutes of treatment at room temperature in running water, Circoposit MLB promoter 213 (trade name, manufactured by Rohm & Haas Japan Co., Ltd.) is used as a strongly alkaline aqueous solution of permanganate, and similarly at 80 ° C. for 10 minutes by the dip method. Immersion treatment. Next, immersion treatment was carried out at 40 ° C. for 5 minutes by the dipping method using MLB Neutralizer 216 (Rohm & Haas Japan Co., Ltd., trade name) as a neutralizing solution. After treatment with running water at room temperature for 3 minutes, conditioner solution CLC-501 (trade name, manufactured by Hitachi Chemical Co., Ltd.) was used for 5 minutes at 60 ° C., washed with running water, and pre-dip solution PD-201 (product). Name, manufactured by Hitachi Chemical Co., Ltd.) in an aqueous solution at room temperature for 3 minutes, treated in an aqueous solution containing a metal palladium solution HS-202B (trade name, manufactured by Hitachi Chemical Co., Ltd.) for 10 minutes at room temperature, and washed with water. Then, it was treated at room temperature for 5 minutes in an aqueous solution of activation treatment liquid ADP-501 (trade name, manufactured by Hitachi Chemical Co., Ltd.). Then, by using Cust-201 as an electroless copper plating solution, a base copper having a thickness of 0.5 μm is formed on both sides of the laminate by dipping at room temperature for 15 minutes, and further on the electrolytic copper. Then, the copper was plated up to a thickness of 20 μm. And it processes by etching into the copper width 10mm and 100mm length line from the above-mentioned test laminated plate cured product with plating, peels off one end thereof, and grips it with a gripper, in the vertical direction in accordance with JIS-C-6421. The minimum value of the load when peeled off at room temperature of about 50 mm was recorded as the copper plating peel strength.

13) Formability Using the copper clad laminate for evaluation formed in the previous section, the line width (L) is 0.5 mm and the line interval (S) is 1.0 mm (L / S = 0.5) in a lattice shape. /1.0 mm), a core material patterned was prepared. This core material was subjected to blackening treatment, and then a prepreg was further laminated thereon, followed by secondary molding, thereby producing an evaluation laminated substrate having an inner layer of a lattice pattern. About the created laminated substrate for evaluation, for example, it was confirmed whether defects such as voids due to insufficient fluidity of the resin varnish occurred. Thereafter, the laminated substrate for evaluation was immersed in boiling water for 4 hours and then immersed in a solder bath at 280 ° C. At that time, the presence of voids could not be confirmed, and even when immersed in a solder bath, it was swollen and no defects such as delamination or measling (white spots) were evaluated as “○”. In addition, the case where generation of any one of delamination and measling (white spots) was confirmed was evaluated as “x”.

Example 6
20 g of the copolymer-A obtained in Example 1, 0.2 g of Parkmill P as a polymerization initiator, 0.2 g of AO-60 as an antioxidant as a curing accelerator, and 8.6 g of toluene were dissolved in 8.6 g of curability. A resin composition (varnish A) was obtained.

  The prepared varnish A was dropped on the lower mold, the solvent was devolatilized at 130 ° C. under reduced pressure, the mold was assembled, and vacuum pressing was performed at 200 ° C. and 3 MPa for 1 hour to perform thermosetting. I let you. About the obtained thickness: 0.2 mm hardened | cured material flat plate test piece, various characteristics including the dielectric constant of 18 GHz and a dielectric loss tangent were measured. Moreover, after leaving the hardened | cured material flat test piece to stand at 85 degreeC and 85% of relative humidity for 2 weeks, the dielectric constant and dielectric loss tangent were measured, and the dielectric constant and dielectric loss tangent after a heat-and-moisture resistance test were measured. The results obtained from these measurements are shown in Table 1.

Examples 7-10, Comparative Examples 4-6
A curable resin composition (varnish) was obtained in the same manner as in Example 6 except that the formulation shown in Table 1 was used. And the hardened | cured material flat plate test piece was created like Example 6, and it tested and evaluated about the same item as Example 6. FIG. The results obtained by these tests are shown in Table 1.

Examples 11-21, Comparative Examples 7-11
A curable resin composition (varnish) was obtained in the same manner as in Example 6 except that the formulation shown in Tables 2 and 3 was used. And the hardened | cured material flat plate test piece was created like Example 6, and it tested and evaluated about the same item as Example 6. FIG. Furthermore, using the varnishes shown in these Examples and Comparative Examples, a prepreg, a test copper-clad laminate, and a test-coated laminate were prepared according to the methods described in 11) to 13) above. Then, copper foil peel strength, copper plating peel strength, and formability were evaluated. These test results are shown in Tables 2 and 3.

Claims (17)

A divinyl aromatic compound (a), a monovinyl aromatic compound (b) and an ether compound are reacted in the presence of one or more catalysts (d) selected from the group consisting of Lewis acid catalysts, strong inorganic acids and organic sulfonic acids. A copolymer obtained,
The ether compound is represented by the following formula (5):

(Y represents an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms which may have a hydrocarbon group having 1 to 12 carbon atoms as a substituent, and Z represents 1 to 30 carbon atoms. Or an aliphatic hydrocarbon group having 1 to 12 carbon atoms or an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms which may have a hydrocarbon group having 1 to 12 carbon atoms as a substituent.)
An aromatic ether compound (c) represented by:
A part of the terminal of the copolymer has the following formula (1)

(Here, Y ¹ is an aromatic hydrocarbon group formed by taking one H from Y in formula (5), and Z is the same as in formula (5).)
Having a terminal group derived from the aromatic ether compound (c) represented by formula (1) , and the terminal group introduction amount (c1) is 1.0 to 1.8 (pieces / molecule). Modified soluble polyfunctional vinyl aromatic copolymer.   2. The terminal-modified soluble polyfunctional vinyl aromatic copolymer according to claim 1, wherein the number average molecular weight Mn is 300 to 100,000. Mole fraction of the structural unit derived from the divinyl aromatic compound in the co-polymer (A) and the molar fraction of the structural unit derived from the monovinyl aromatic compound (B) is the following formula (3)
0.05 ≦ (A) / {(A) + (B)} ≦ 0.95 (3)
And the molar fraction (C) of the terminal group is represented by the following formula (4):
0.005 ≦ (C) / {(A) + (B)} < 2.0 (4)
And the terminal-modified soluble polyfunctional vinyl aromatic copolymer according to claim 1 or 2, which is soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform.   The terminal-modified soluble polyfunctional group according to any one of claims 1 to 3, wherein a molecular weight distribution (Mw / Mn) represented by a ratio of the weight average molecular weight Mw to the number average molecular weight Mn is 100.0 or less. Vinyl aromatic copolymer. A method for producing a copolymer by reacting a divinyl aromatic compound (a), a monovinyl aromatic compound (b), and an ether compound, the sum of the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) The divinyl aromatic compound (a) is used in an amount of 5 to 95 mol% and the monovinyl aromatic compound (b) is used in an amount of 95 to 5 mol%.

(Y represents an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms which may have a hydrocarbon group having 1 to 12 carbon atoms as a substituent, and Z represents 1 to 30 carbon atoms. Or an aliphatic hydrocarbon group having 1 to 12 carbon atoms or an unsubstituted or substituted aromatic hydrocarbon group having 6 to 40 carbon atoms which may have a hydrocarbon group having 1 to 12 carbon atoms as a substituent.)
The aromatic ether compound (c) represented by the formula is used in a molar ratio range satisfying 0.005 ≦ (c) / {(a) + (b)} < 2.0 , and a Lewis acid catalyst, an inorganic strong acid, and One or more catalysts (d) selected from the group consisting of organic sulfonic acids are used, and 20 to 120 ° C. in a homogeneous solution in which polymerization raw materials containing them are dissolved in a solvent having a dielectric constant of 2.0 to 15.0. Is polymerized at the temperature of the following formula (1)

(Here, Y ¹ is an aromatic hydrocarbon group formed by taking one H from Y in formula (5), and Z is the same as in formula (5).)
A copolymer having a terminal group derived from an aromatic ether compound (c) represented by the formula: 1.0 to 1.8 (pieces / molecule) and soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform A process for producing a terminal-modified soluble polyfunctional vinyl aromatic copolymer, characterized in that it is obtained.   The method for producing a terminal-modified soluble polyfunctional vinyl aromatic copolymer according to claim 5, wherein the catalyst (d) is a Lewis acid catalyst selected from metal fluorides or complexes thereof.   The terminal-modified soluble polyfunctional vinyl aroma according to claim 5 or 6, wherein the catalyst (d) is used within a range of 0.001 to 10 mol per 1 mol of the aromatic ether compound (c). A method for producing a group copolymer.   A curable composition comprising the terminal-modified soluble polyfunctional vinyl aromatic copolymer according to any one of claims 1 to 4 and a radical polymerization initiator.   9. The curable composition according to claim 8, comprising a modified polyphenylene ether having at least one phenolic hydroxyl group, aromatic vinyl group, methacryl group or acrylic group at the terminal.   Furthermore, an epoxy resin having two or more epoxy groups and an aromatic structure in one molecule, an epoxy resin having two or more epoxy groups and a cyanurate structure in one molecule, and two or more epoxy groups and an alicyclic structure in one molecule The curable composition according to claim 8 or 9, comprising one or more epoxy resins selected from the group consisting of epoxy resins having an epoxy resin, and an epoxy resin curing agent.   Hardened | cured material formed by hardening | curing the curable composition in any one of Claims 8-10.   The film formed by shape | molding the curable composition in any one of Claims 8-10 in a film form.   A curable composite material comprising the curable composition according to any one of claims 8 to 10 and a base material, the base material being contained at a ratio of 5 to 90% by weight.   A cured composite obtained by curing the curable composite material according to claim 13.   A laminate comprising the cured composite material layer according to claim 13 and a metal foil layer.   A metal foil with a resin, comprising a film formed from the curable composition according to claim 8 on one side of the metal foil. The varnish for circuit board materials formed by dissolving the curable composition in any one of Claims 8-10 in the organic solvent.