WO2017115813A1

WO2017115813A1 - Soluble polyfunctional vinyl aromatic copolymer, method for producing same and curable composition

Info

Publication number: WO2017115813A1
Application number: PCT/JP2016/088966
Authority: WO
Inventors: 川辺　正直; 道貴太田
Original assignee: 新日鉄住金化学株式会社
Priority date: 2015-12-28
Filing date: 2016-12-27
Publication date: 2017-07-06
Also published as: TWI706963B; TW201736413A; JP6833723B2; JPWO2017115813A1

Abstract

Provided are: a soluble polyfunctional vinyl aromatic copolymer which has improved heat resistance, thermal decomposition resistance, solubility in solvents, processability and compatibility with specific resins; and a curable composition of this soluble polyfunctional vinyl aromatic copolymer . A soluble polyfunctional vinyl aromatic copolymer which contains a repeating structural unit derived from a divinyl aromatic compound (a) and a repeating unit derived from a monovinyl aromatic compound (b), and which is characterized in that, the repeating structural unit derived from a divinyl aromatic compound (a) is a unit having an unsaturated hydrocarbon group, which is a vinyl group-containing unit and/or a vinylene group-containing unit; and the copolymer has, as a terminal group, a vinylene group-containing terminal group that is derived from the divinyl aromatic compound (a) and/or the monovinyl aromatic compound (b). This soluble polyfunctional vinyl aromatic copolymer is also characterized by being polymerizable and by being soluble in a solvent.

Description

Soluble polyfunctional vinyl aromatic copolymer, process for producing the same and curable composition

The present invention relates to a novel soluble polyfunctional vinyl aromatic copolymer having improved heat resistance, compatibility, transparency and toughness, a method for producing the same, and a curable composition containing the copolymer. Furthermore, it is related with the film which consists of the curable composition, the hardened | cured material obtained by hardening | curing, the curable composite material which consists of a curable composition and a base material, the laminated body which consists of hardened | cured material and metal foil, and copper foil with resin.

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. Furthermore, since printed circuit boards or electronic components using these electrically 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, since lead-free solder having a high melting point is used from the viewpoint of environmental problems, there is an increasing demand for an electrically insulating material with higher heat resistance. In response to these requirements, conventionally, curable resins using vinyl compounds having various chemical structures have been proposed.

As such a cured resin, for example, Patent Document 1 includes a phenyl group and a double bond in the main chain by polymerizing a divinyl aromatic compound in the presence of a sulfonate anion or a perchlorate anion. It is disclosed that a solvent-soluble polydivinylbenzene having a structure represented by the formula (a2) of the present application (hereinafter simply referred to as “formula (a2)”) is obtained. And in patent document 1, what is illustrated as a solvent which can be used at the time of superposition | polymerization in order to synthesize | combine the polydivinylbenzene which has a structure represented only by a formula (a2) is an aromatic compound like benzene etc., A saturated aliphatic hydrocarbon such as n-hexane, a saturated alicyclic hydrocarbon such as cyclohexane or methylcyclohexane, or a halide such as chloroform or trichloroethane. It is disclosed that the polarity of the solvent is preferably nonpolar or low in polarity, and that the monomer concentration is preferably 20 vol% or less. Furthermore, it is described that when a highly polar solvent is used, a crosslinking reaction is likely to occur, which is not preferable.
Therefore, in Patent Document 1, a divinyl aromatic compound can be copolymerized with a monovinyl aromatic compound, and the copolymer obtained by copolymerizing the monovinyl aromatic compound has some useful properties. Is not disclosed at all. In addition, there is a description about the possibility of forming a polymer having a vinyl group in the side chain by using a polar compound in combination with the polymerization, but it is disclosed that a bridging reaction easily occurs and is not preferable. .
Therefore, when a solvent-soluble copolymer obtained by copolymerizing a divinyl aromatic compound with a monovinyl aromatic compound is used as a cured resin for an insulating material that requires a high degree of heat resistance, based on the disclosed technology of Patent Document 1, This results in deterioration of molding processability due to a decrease in curing reactivity and a decrease in curing reactivity, and is not suitable for industrial implementation.

In Patent Document 2, a divinyl aromatic compound is copolymerized with a styrene having a lower alkyl group, a halogenated alkyl group, an acyl group, an acyloxyl group, a hydroxyl group, or a halogen atom as a monovinyl aromatic compound. It is disclosed. However, in the copolymer synthesized according to the technique disclosed in Patent Document 2, the main chain is composed of polydivinylbenzene having a structure represented by the formula (a2) containing a phenyl group and a double bond in the main chain. The styrenes are introduced as end groups added to the ends. Therefore, in Patent Document 2, it is preferable that the molar ratio of styrenes to divinylbenzene is in the range of 5 to 0.01 in order to increase the yield of the copolymer while maintaining solvent solubility. Is disclosed. Actually, in the example of Patent Document 2, acetyl perchlorate or trifluoromethanesulfonic acid is used as a catalyst as a catalyst, benzene is used as a solvent, and the molar ratio of styrenes and divinylbenzene is It is disclosed that by carrying out in the range of divinylbenzene / styrenes = 0.33-3, an oligomer having a vinyl group disappeared and terminal-terminated with styrenes is recovered.
However, when a solvent-soluble copolymer obtained by copolymerizing styrenes and divinylbenzene is used as a cured resin for an insulating material that requires high heat resistance and electrical characteristics, based on the disclosed technology of Patent Document 2, Decrease in molding processability due to lowering and curing reactivity, which is not suitable for industrial implementation.

Patent Document 3 discloses divinyl aromatic compounds and monovinyl aromatic compounds in an organic solvent, such as a Lewis acid catalyst, 1-chloroethylbenzene, 1-bromoethylbenzene, bis (1-chloro-1-methylethyl) benzene, and the like. A soluble polyfunctional vinyl aromatic copolymer obtained by polymerizing at a temperature of 20 to 100 ° C. in the presence of an initiator having a specific structure is disclosed. Patent Document 4 discloses a monomer component containing 20 to 100 mol% of a divinyl aromatic compound in the presence of a quaternary ammonium salt, using a Lewis acid catalyst and an initiator having a specific structure. A method for producing a soluble polyfunctional vinyl aromatic copolymer having a controlled molecular weight distribution by cationic polymerization at a temperature of 0 ° 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 itself has a polymerizable double bond, 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 the compatibility between the soluble polyfunctional vinyl aromatic copolymer and other curable resins disclosed in Patent Document 3 and Patent Document 4 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, there are many cases in which a heterogeneous composition is given 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. . Therefore, there are cases in which the degree of freedom of the compounding formulation design is small and the toughness of the cured product is low, and in addition, there are cases where defects such as blistering and peeling occur due to a high thermal history near 280 to 300 ° C.

On the other hand, the soluble polyfunctional vinyl aromatic copolymer disclosed in Patent Document 3 and Patent Document 4 includes a phenyl group and a double bond in the main chain, that is, a structure represented by the formula (a2). Although it is disclosed that it can be introduced, the formula (a1) with respect to the sum of formula (a1) and formula (a2) is actually included in the copolymers disclosed in Examples of Patent Document 3 and Patent Document 4. The molar fraction of the structural unit represented by () was 0.98 to 0.99, and the structure represented by the formula (a2) was present only in a very limited amount.

Patent Document 5 discloses a copolymer obtained by copolymerizing a divinyl aromatic compound (a) and a monovinyl aromatic compound (b), and an ether bond or a thioether bond is interposed in part of the end group. A soluble polyfunctional vinyl aromatic copolymer having a chain hydrocarbon group or an aromatic hydrocarbon group is disclosed.
However, since this soluble polyfunctional vinyl aromatic copolymer has insufficient toughness, sufficient mechanical properties cannot be obtained in the cured product of the curable composition. There were problems such as insufficient delamination strength and reduced reliability. Moreover, although it is described that an ester compound can be used as a cocatalyst, examples of specifically usable ester compounds include soluble polyfunctional vinyl aromatic copolymers such as ethyl acetate and methyl propionate. It was an ester compound that does not have a function of introducing a functional group at the end of the. Therefore, the terminal group of the soluble polyfunctional vinyl aromatic copolymer disclosed in Patent Document 5 is a chain hydrocarbon compound having an alcoholic hydroxyl group, an aromatic hydrocarbon compound and a chain having a thioalcohol mercapto group. It contained a chain hydrocarbon group or an aromatic hydrocarbon group via either an ether bond or a thioether bond derived from a chain hydrocarbon compound and an aromatic hydrocarbon compound.

In addition, the soluble polyfunctional vinyl aromatic copolymer disclosed in Patent Document 5 can be introduced with a structure represented by the formula (a2) containing a phenyl group and a double bond in the main chain. Although disclosed, the moles of the structural unit represented by the formula (a1) with respect to the sum of the formula (a1) and the formula (a2) in the copolymer actually disclosed in the examples of Patent Document 5 The fraction was 0.98 to 0.99, and the structure represented by the formula (a2) was present only in a very limited amount.

Patent Document 6 and Patent Document 7 include a polyfunctional vinyl aromatic copolymer having an end group derived from an aromatic ether compound, and a soluble polyfunctional vinyl aroma having an end group derived from a thio (meth) acrylate compound. Group copolymers are disclosed. However, although the soluble polyfunctional vinyl aromatic copolymer disclosed in these Patent Documents 6 and 7 has improved toughness, it has low dielectric properties in a high frequency band accompanying an increase in information communication volume in recent years. There is a problem that it cannot be applied to a field that requires high-performance, high-level electrical characteristics, thermal and mechanical characteristics, such as the advanced electrical and electronic fields. In addition, these soluble polyfunctional vinyl aromatic copolymers have a drawback in that they cannot be used as substrate materials in fields requiring high reliability because adhesion at the interface with the glass cloth decreases after wet heat history. It was.
The soluble polyfunctional vinyl aromatic copolymer disclosed in Patent Documents 6 and 7 can be introduced with a structure represented by the formula (a2) containing a phenyl group and a double bond in the main chain. Was not disclosed.

Patent Document 8 discloses curing comprising a polyphenylene ether oligomer having vinyl groups at both ends, and a polyfunctional vinyl aromatic copolymer having a structural unit derived from a monomer comprising a divinyl aromatic compound and an ethyl vinyl aromatic compound. A functional resin composition is disclosed. However, since the curable resin composition using this soluble polyfunctional vinyl aromatic copolymer has insufficient delamination strength, plating peel strength and dielectric properties after wet heat history, as a substrate material in the field of advanced electronics Had the disadvantage that it could not be used.

Patent Document 9 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, and 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. However, the curable resin composition using the soluble polyfunctional vinyl aromatic copolymer has a problem that it cannot be applied to a high-functional advanced technology field that requires a high degree of miniaturization because the plating property is insufficient. was there.

JP-A-56-62808 JP 58-76411 A JP 2004-123873 A Japanese Patent Laying-Open No. 2005-213443 JP 2007-332273 A JP 2010-229263 A JP 2010-209279 A WO2005 / 73264 JP 2006-274169 A

In consideration of such background art, the present invention has a low dielectric property in a high frequency band accompanying an increase in the amount of information communication in recent years, and has advanced electrical / thermal / mechanical characteristics required for high-performance electrical / mechanical characteristics. It is an object of the present invention to provide a material that can be applied to the field of electronics, particularly a material useful for use as a laminate as an electrical insulating material.
From this viewpoint, the present invention provides a novel soluble polyfunctional vinyl aromatic copolymer having improved heat resistance, compatibility, transparency and toughness, a method for producing the same, and a curable composition containing the copolymer. A film comprising the curable composition, a cured product obtained by curing, a curable composite material comprising the curable composition and a substrate, a laminate comprising the cured product and a metal foil, and copper with resin The purpose is to provide a foil.

As a result of intensive studies, the inventors of the present invention polymerized a divinyl aromatic compound (a) and a monovinyl aromatic compound (b) together with a Lewis base compound in an oxo acid catalyst that selectively generates a vinylene group. As a result, 1,2-addition polymerization, which generates a vinyl group (vinylene group) in the course of the reaction, proceeds while a vinylene group-containing unit or vinylene group-containing end group is generated by a β-hydrogen elimination reaction. The present inventors have found that a molecular weight can be controlled without using a transfer agent, and that a copolymer obtained by such polymerization solves the above-mentioned problems, thereby completing the present invention.

The present invention is a polyfunctional vinyl aromatic copolymer containing a structural unit derived from a divinyl aromatic compound (a) and a structural unit derived from a monovinyl aromatic compound (b), the divinyl aromatic compound (a ) Derived from a vinyl group-containing unit represented by the following formula (a1), a vinylene group-containing unit represented by the following formula (a2), and a crosslinked structural unit represented by the following formula (a3): The structural unit having a vinylene group-containing terminal unit represented by the following formula (ta1) and derived from the monovinyl aromatic compound (b) is a structural unit represented by the following formula (b1) and the following formula (tb1 It is a soluble polyfunctional vinyl aromatic copolymer characterized by having a vinylene group-containing terminal unit represented by formula (II) and being soluble in a solvent and polymerizable.

(In the formula, R ¹ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms.)

(In the formula, R ¹ is the same as in formula (a1).)

(In the formula, R ¹ is the same as in formula (a1).)

(In the formula, R ¹ is the same as in formula (a1).)

(Wherein R ² represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, and R ³ represents hydrogen or a hydrocarbon group having 1 to 12 carbon atoms.)

(In the formula, R ² and R ³ are the same as those in the formula (b1).)

The present invention preferably contains 20 mol% to 95 mol% of a structural unit derived from the divinyl aromatic compound (a), and has the formula (a1), formula (a2), formula (a3), and formula (ta1). The molar fraction of the structural units represented by formula (b1) and formula (tb1) satisfies the following formula (1) and the following formula (2):
0.2 ≦ [(a1) + (a3) + (ta1)] / [(a1) + (a2) + (a3) + (b1) + (ta1) + (tb1)] ≦ 0.9 (1)
(ta1) / [(ta1) + (tb1)]> 0.2 (2)
The soluble polyfunctional group according to claim 1, having a number average molecular weight Mn of 300 to 100,000, a molecular weight distribution (Mw / Mn) of 100.0 or less, and being soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. Vinyl aromatic copolymer.

In the present invention, a divinyl aromatic compound (a) and a monovinyl aromatic compound (b) are converted from an inorganic acid, an organic sulfonic acid and a perchloric acid compound in the presence of a Lewis base compound (c) as a promoter component. A method for producing a polyfunctional vinyl aromatic copolymer by polymerizing using one or more catalysts (d) selected from the group consisting of a divinyl aromatic compound (a) and a monovinyl aromatic compound (b ) Is used in an amount of 5 to 95 mol% of the divinyl aromatic compound (a) and 95 to 5 mol% of the monovinyl aromatic compound (b), and the total amount of all monomers is 100 mol. On the other hand, the Lewis base compound (c) is used in an amount of 0.005 to 500 mol, and a polymerization raw material containing them is dissolved in a solvent having a dielectric constant of 2.0 to 15.0 to form a uniform solution at a temperature of 20 to 120 ° C. Obtained by polymerization A soluble polyfunctional vinyl aromatic copolymer characterized and.

Further, the present invention provides a divinyl aromatic compound (a) and a monovinyl aromatic compound (b) in the presence of a Lewis base compound (c) as a promoter component, an inorganic acid, an organic sulfonic acid and a perchloric acid type. A method for producing a soluble polyfunctional vinyl aromatic copolymer by polymerization using at least one catalyst (d) selected from the group consisting of compounds, comprising divinyl aromatic compound (a) and 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). The Lewis base compound (c) is used in an amount of 0.005 to 500 moles per 100 moles, and a polymerization raw material containing them is dissolved in a solvent having a dielectric constant of 2.0 to 15.0 to form a uniform solution at 20 to 120 ° C. Polymerized at a temperature of Is a manufacturing method of the soluble polyfunctional vinyl aromatic copolymer according to claim Rukoto.

In the above-mentioned method for producing a soluble polyfunctional vinyl aromatic copolymer, it is desirable to use the catalyst (d) in a range of 0.001 to 10 mol per 1 mol of the Lewis base compound (c).

The present invention also provides a curable composition comprising the above-mentioned soluble polyfunctional vinyl aromatic copolymer and a radical polymerization initiator.

The curable composition can further contain a thermosetting resin or a thermoplastic resin.

In this case, the thermosetting resin is preferably a modified polyphenylene ether (XC). Further, the thermosetting resin is 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 / or 2 in one molecule. One or more epoxy resins (XD) selected from the group consisting of the above epoxy groups and epoxy resins having an alicyclic structure may be used. Moreover, 1 or more types of vinyl compounds (XF) which have 1 or more unsaturated hydrocarbon groups in a molecule | numerator may be sufficient.

Furthermore, the present invention is a cured product obtained by curing the above curable composition, or a film obtained by molding the above curable composition into a film.

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, and A cured composite material obtained by curing the curable composite material, and a laminate comprising the cured composite material layer and a metal foil layer.

Further, the present invention provides a resin-coated metal foil having a film formed from the above curable composition on one side of the metal foil, or a circuit board obtained by dissolving the above curable composition in an organic solvent It is a varnish for materials.

The cured product obtained from the soluble polyfunctional vinyl aromatic copolymer of the present invention or a material containing the same has improved heat resistance, compatibility, transparency, and toughness. Moreover, according to the production method of the present invention, the copolymer can be produced with high efficiency. Further, by using the soluble polyfunctional vinyl aromatic copolymer of the present invention as a curable compound, the molecule has a free volume with a large molecular size and a small number of polar groups. A cured product having characteristics can be obtained, and good adhesion, plating properties and dielectric loss tangent characteristics after wet heat history can be realized simultaneously.

The soluble polyfunctional vinyl aromatic copolymer of the present invention comprises a monomer comprising a divinyl aromatic compound (a) and an ethyl vinyl aromatic compound (b) in the presence of a Lewis base compound (c) as a promoter component. A polyfunctional vinyl aromatic copolymer obtained by polymerization using one or more catalysts (d) selected from the group consisting of inorganic acids, organic sulfonic acids and perchloric acid compounds, In the copolymer, the structural unit derived from the divinyl aromatic compound (a) represented by the above formulas (a1) to (a3), and the ethyl vinyl aromatic compound (b) represented by the above formula (b1) Having a structural unit of Further, a vinylene group-containing terminal group derived from the divinyl aromatic compound (a) represented by the above formula (ta1) or a monovinyl aromatic compound represented by the above formula (tb1) (b ) -Derived vinylene group-containing end groups. It is soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. The soluble polyfunctional vinyl aromatic copolymer of the present invention is abbreviated as a soluble polyfunctional vinyl aromatic copolymer or simply a copolymer when no misunderstanding occurs.

The soluble polyfunctional vinyl aromatic copolymer of the present invention has a structural unit derived from the divinyl aromatic compound (a) and a structural unit derived from the ethyl vinyl aromatic compound (b) in the copolymer or at the terminal. The molar fraction of the structural unit represented by formula (a1), formula (a2), formula (a3), formula (ta1), formula (b1), and formula (tb1) satisfies the following formula (1). Is preferred.
0.2 ≦ [(a1) + (a3) + (ta1)] / [(a1) + (a2) + (a3) + (b1) + (ta1) + (tb1)] ≦ 0.9 (1)
The significance of the above formula (1) is as follows. When the reactivity is compared, the vinyl group is higher than the vinylene group. The structural units (a1) and (ta1) contain a pendant vinyl group. The structural unit (a3) can be regarded as after the reaction of the pendant vinyl group. For this reason, the total molar fraction of (a1) + (a3) + (ta1) is prescribed | regulated. Note that (ta1) includes a vinylene group, but a vinyl group is dominant.
In other words, vinyl groups (including pendant vinyl groups that have undergone reaction) are susceptible to a curing reaction when used as a curable resin composition. These structural units are (a1), (a3) and (ta1). On the other hand, vinylene groups are less susceptible to curing reaction when used as a curable resin composition. The structural units are (a2), (ta1) and (tb21). Further, substituents other than the vinyl group of the monomer of the mono (ethyl) vinyl aromatic compound do not undergo any further reaction after undergoing one reaction in the polymerization reaction. The structural units are (b1) and (tb1).
When the total molar fraction represented by the above formula (1) exceeds 0.9, the molecular weight increases and the moldability decreases. On the other hand, if it is less than 0.2, the ratio of the pendant vinyl represented by (a1) decreases, and the internal olefin structure is the main component, so that the heat resistance and curability are lowered. More preferably, it is in the range of 0.5 to 0.7.

Moreover, it is preferable that the molar fraction of a terminal group satisfies the following.
(ta1) / [(ta1) + (tb1)]> 0.2 (2)
When the molar fraction of the terminal group represented by the above formula (2) is larger than 0.2, the copolymer of the present invention has good curability. On the other hand, when the molar fraction of the terminal group represented by the above formula (2) is 0.2 or less, the curability tends to be lowered. A more preferred lower limit is 0.25, a further preferred lower limit is 0.40, and a further preferred lower limit is 0.50. On the other hand, a preferable upper limit is 0.95, a more preferable upper limit is 0.90, and a more preferable upper limit is 0.85. When the total molar fraction represented by the above formula (1) exceeds 0.95, the molding processability of the cured product tends to decrease.

The molar fraction (a1) / [(a1) + (a2) + (a3)] of the vinyl group-containing unit is preferably 0.2 or more and less than 0.9. More preferably, it is 0.25 to 0.85, and more preferably 0.3 to 0.8. By introducing the structural unit of the copolymer of the present invention so as to satisfy the above relationship, it has a low dielectric loss tangent, high toughness, excellent heat resistance, and compatibility with other resins. In addition, the resin composition can be made excellent in transparency and molding processability. When the molar fraction of the above formula (a1) is smaller than 0.2, heat resistance and molding processability are deteriorated. When it is larger than 0.9, compatibility with other resins cannot be maintained, and a fine wiring pattern is obtained. There is also a tendency for the resin filling property to decrease.
On the other hand, the total molar fraction [(a2) + (a3)] / [(a1) + (a2) + (a3)] of the vinylene group-containing unit (a2) and the crosslinked structural unit (a3) is 0.1 or more , Less than 0.8. Preferably, it is 0.15 to 0.75, more preferably 0.2 to 0.8. By introducing the structural unit of the copolymer of the present invention so as to satisfy the above relationship, it has a low dielectric loss tangent, high toughness, excellent heat resistance, and compatibility with other resins. In addition, the resin composition can be made excellent in transparency and molding processability. When the molar fraction of the formula (a2) and the formula (a3) is smaller than 0.1, the moldability tends to be lowered, and the resin filling property to a fine wiring pattern tends to be lowered. Moreover, when larger than 0.8, there exists a tendency for hardening reactivity to fall and for heat resistance to fall.

Further, the soluble polyfunctional vinyl aromatic copolymer of the present invention comprises a structural unit (A) derived from the divinyl aromatic compound (a) and a structural unit (B) derived from the monovinyl aromatic compound (b). The molar fraction (A) / {(A) + (B)} of the structural unit (A) is preferably 0.2 to 0.95, more preferably 0.4 to 0.90, still more preferably Is in the range of 0.50 to 0.85 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 20 to 950 mol% with respect to a total of 100 mol% of all the structural units. The structural unit (A) derived from the divinyl aromatic compound (a) contains a vinyl group as a crosslinking component for developing heat resistance, while the structural unit (B) derived from the monovinyl aromatic compound (b). Since it does not have a vinyl group involved in the curing reaction, it imparts moldability and the like. Accordingly, when the molar fraction of the structural unit (A) is less than 0.2, the heat resistance of the cured product is insufficient, and when it exceeds 0.95, the moldability is deteriorated. That is, when the content of the structural unit (A) is small, the heat resistance is lowered with a decrease in the crosslink density, so that a good shape can be maintained when subjected to a thermal history in an optical waveguide formation process or the like. If the amount is too large, the etching characteristics deteriorate and it becomes difficult to form an optical waveguide having a fine microstructure.

A structural unit having one vinyl group or one vinylene group, for example, the units (a1) and (a2) gives the copolymer polymerizability, and the copolymer is polyfunctional to make a curable resin. The unit (a3), which is a structural unit having no vinyl group or vinylene group, gives a crosslinked structure and increases the degree of branching. However, if the crosslinking proceeds too much, the unit cures and becomes insoluble in the solvent. It is necessary that (a1) and unit (a2) exist. In this invention, the vinylene group containing unit (a2) produced | generated in the reaction process, the vinylene group containing terminal group (ta1), and (tb1) are contained as an essential component.

Structural units having a vinyl group or vinylene unsaturated hydrocarbon group derived from the vinyl aromatic compound (a) and the monovinyl aromatic compound (b), that is, the unsaturated group represented by the formulas (a1) and (a2) The total mol% of the group-containing structural unit and the unsaturated group-containing end group represented by the formulas (ta1) and (tb1) is preferably 40 mol with respect to the total 100 mol% of all the structural units in the copolymer. 0.0 to 80.0 mol%, more preferably 50.0 to 70.0 mol%.

In each of the above formulas (a1), (a2), formula (a3) and formula (ta1), R ¹ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, which is a divinyl aromatic compound (a) It is understood from the explanation. Specifically, R ¹ is preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a phenylene group, a biphenylene group, or a naphthylene group. In the formulas (b1) and (tb1), R ² represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, and R ³ represents hydrogen or a hydrocarbon group having 1 to 12 carbon atoms. Since it is derived from the monovinyl aromatic compound (b), it can be understood from the description. Specifically, R ² is preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a phenylene group, a biphenylene group, or a naphthylene group. R ³ is preferably hydrogen or a saturated hydrocarbon group having 1 to 12 carbon atoms, more preferably hydrogen or a saturated hydrocarbon group having 1 to 6 carbon atoms, and still more preferably hydrogen or a carbon number having 1 to 12 carbon atoms. 3 saturated hydrocarbon groups.

The soluble polyfunctional vinyl aromatic copolymer of the present invention has an Mn (where Mn is a number average molecular weight in terms of standard polystyrene measured using gel permeation chromatography) of 300 to 100,000, preferably Is 400 to 50,000, more preferably 500 to 10,000. When Mn is less than 300, the amount of the monofunctional copolymer contained in the copolymer increases, so the heat resistance of the cured product decreases. On the other hand, when Mn exceeds 100,000, a gel is formed. Since it becomes easy and the viscosity becomes high, the molding processability is lowered, which is not preferable. The molecular weight distribution (Mw / Mn) is 100.0 or less, preferably 50.0 or less, more preferably 1.5 to 30.0. Most preferably, it is 2.0 to 20.0. When Mw / Mn exceeds 100.0, problems such as deterioration of the processing characteristics of the copolymer and generation of a gel occur.

The soluble polyfunctional vinyl aromatic copolymer of the present invention is soluble in a solvent selected from toluene, xylene, tetrahydrofuran, dichloroethane or chloroform, but is preferably soluble in any of the above solvents. Here, “soluble in a solvent” means that 5 g or more, preferably 10 g or more is dissolved in 100 g of a solvent at 25 ° C. 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. The polymerization method will be described later.

The soluble polyfunctional vinyl aromatic copolymer of the present invention includes structural units represented by the above formula (a1), formula (a2), formula (a3) and formula (b1), and formula (ta1) and formula (tb1). Therefore, the compatibility with the ether compound and the epoxy compound having the rigidity of the main chain is high. Accordingly, when the curable resin composition with a curable ether compound and an epoxy compound having a rigid structure is cured, it is excellent in uniform curability and transparency.

Next, a production method capable of advantageously producing a soluble polyfunctional vinyl aromatic copolymer will be described.

Preferably, the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) are converted from an inorganic acid, an organic sulfonic acid, and a perchloric acid compound in the presence of a Lewis base compound (c) as a promoter component. One or more catalysts (d) selected from the group can be used for reaction to produce a copolymer.

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 thermally cured. As examples of the divinyl aromatic compound (a), divinylbenzene (including each isomer), divinylnaphthalene (including each isomer), and divinylbiphenyl (including each isomer) are preferably used. Is not to be done. 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 of isomers thereof) is more preferable.

Monovinyl aromatic compound (b) improves the solvent solubility and processability of the copolymer. Examples of the monovinyl aromatic compound (b) include a nuclear alkyl-substituted ethyl vinyl aromatic compound, an α-alkyl substituted ethyl vinyl aromatic compound, a β-alkyl substituted ethyl vinyl aromatic compound, and an alkoxy substituted ethyl vinyl aromatic compound. It is not limited to. In order to prevent the gelation of the copolymer and to improve solubility in solvents and processability, in particular ethylvinylbenzene (including each isomer), ethylvinylbiphenyl (including each isomer), and ethylvinylnaphthalene (Including each isomer) is preferred and used from the viewpoint of cost and availability. From the viewpoint of dielectric properties and cost, ethyl vinylbenzene (m-isomer, p-isomer or a mixture of isomers thereof) is more preferable.

In addition, in the copolymer production method, in addition to the divinyl aromatic compound (a) and the monovinyl aromatic compound (b), a trivinyl aromatic compound, a trivinyl aliphatic compound, and divinyl are used as long as the effects of the present invention are not impaired. These monomers can be introduced into the copolymer using other monomers (e) such as aliphatic compounds and monovinyl aliphatic compounds.

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 component (e) is within a range of less than 30 mol% with respect to the total amount of the structural unit in the copolymer.

Specific examples of the Lewis base compound (c) as a promoter component include 1) ester compounds such as ethyl acetoacetate, butyl acetate, phenyl acetate and methyl propionate, and 2) methyl mercaptopropionic acid, ethyl mercaptopropionic acid and the like. Thioester compounds, 3) ketone compounds such as methyl ethyl ketone, methyl isobutyl ketone, benzophenone, 4) methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, etc. Amine compounds, 5) ether compounds such as diethyl ether and tetrahydrolane, 6) thioether compounds such as diethyl sulfide and diphenyl sulfide, 7) tripropylphosphine, tributy One or more Lewis base compounds selected from the group consisting of phosphine compounds such as phosphine, trihexylphosphine, tricyclohexylphosphine, trioctylphosphine, vinylphosphine, propenylphosphine, cyclohexenylphosphine, dialkenylphosphine, and trialkenylphosphine (c ). Among these, ester compounds and ketone compounds are preferably used from the viewpoint that they can act synergistically with the component (d) catalyst to easily control the polymerization rate and the molecular weight distribution of the polymer.

The Lewis base compound (c) as a co-catalyst component is electron-donating, and coordinates with the hydrogen at the β-position of the carbocation species that are polymerization-active species during the polymerization reaction, whereby the catalyst (d) and β- It controls the interaction between hydrogen and regulates the relative reaction frequency between β-hydrogen elimination reaction and vinyl group 1,2-addition reaction. Therefore, by adding the Lewis base compound (c), the soluble polyfunctional vinyl aromatic copolymer of the present invention has the formulas (a1), (a2), (a) derived from the divinyl aromatic compound and the ethylvinyl aromatic compound. The abundance ratios of the structural units represented by the formula (a3) and the formula (b1) and the terminal groups represented by the formula (ta1) and the formula (tb1) can be widely controlled. That is, the Lewis base compound (c) is a structural unit represented by formula (a1), formula (a2), formula (a3) and formula (b1), and terminal represented by formula (ta1) and formula (tb1). It is a compound that makes it possible to control the abundance ratio of groups and to impart functions such as heat resistance, toughness, and low dielectric properties of the copolymer.

An example of such a reaction is shown below.

As the Lewis base compound (c), ethyl acetate, propyl acetate, butyl acetate, phenyl acetate, and methyl ethyl ketone, and methyl isobutyl ketone are preferably used from the viewpoint of reactivity, availability, and heat resistance of the cured product. . From the viewpoint of reaction rate, propyl acetate, butyl acetate, methyl ethyl ketone, and methyl isobutyl ketone are more preferably used.

The Lewis base compound (c) is used in an amount of 0.005 to 500 mol, preferably 0.01 to 100 mol, more preferably 0.1 to 50 mol, per 100 mol of all monomers. When the amount is less than 0.005 mol, the introduction amount of the repeating structural unit represented by the above formula (a1) with respect to the formula (a2) and the formula (a3) is reduced, and not only functions such as toughness are lowered, but also heat resistance The moldability is deteriorated and the curability is also deteriorated. On the other hand, if it is used in excess of 500 mol, the polymerization rate is remarkably lowered, the productivity is lowered, and the dielectric properties are deteriorated.

The polymerization reaction uses a divinyl aromatic compound (a), an ethyl vinyl aromatic compound (b), a Lewis base compound (c), and a catalyst (d). A copolymer can be obtained by cationic copolymerization at a temperature of 20 to 120 ° C. in a homogeneous solvent dissolved in 15.0 solvent.

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

The catalyst (d) can be used without particular limitation as long as it is a compound that generates a sulfonate anion or a perchlorate anion and can accept an electron pair. Examples of inorganic acids that generate sulfonate anions include sulfuric acid, fluorosulfuric acid, chlorosulfuric acid, and bischlorosulfuric acid. Specific examples of the organic sulfonic acid include methyl sulfuric acid, trifluoromethane sulfonic acid, perfluoroethane sulfonic acid, benzene sulfonic acid, paratoluene sulfonic acid, methane sulfonic acid anhydride, and benzene sulfonic acid anhydride. Perchlorate compounds that generate perchlorate anions include perchloric acid, acetyl perchlorate, butyryl perchlorate, benzoyl perchlorate, dioxonium perchlorate, triphenylmethyl perchlorate, tropylium. Park Lorate etc. can be mentioned. These catalysts can be used alone or in combination of two or more.
Methyl sulfuric acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, or methanesulfonic anhydride is most preferably used from the viewpoint of controlling the molecular weight and molecular weight distribution of the obtained copolymer and polymerization activity.

The catalyst (d) is used in an amount of 0.001 to 10 mol, more preferably 0.005 to 5 mol, per 1 mol of the Lewis base compound (c) as a co-catalyst. . If it exceeds 10 moles, the polymerization rate becomes too high, making it difficult to control the molecular weight distribution.

The polymerization reaction is preferably carried out in one or more organic solvents having a dielectric constant of 2.0 to 15.0 as a solvent for dissolving the produced soluble polyfunctional vinyl aromatic 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. The dielectric constant is not particularly limited as long as it 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 or ethylcyclohexane is particularly preferable from the viewpoint of a balance between polymerization activity and solubility. The amount of the solvent used is such that the concentration of the copolymer in the polymerization solution is 1 to 90 wt%, preferably 10 to 80 wt%, particularly at the end of the polymerization, in consideration of the viscosity of the polymerization solution obtained and ease of heat removal. 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.

The polymerization reaction temperature is preferably 20 to 120 ° C, more preferably 40 to 100 ° C. If the polymerization temperature is too high, the selectivity of the reaction will be reduced, causing problems such as an increase in molecular weight distribution and gel generation. If the polymerization temperature is too low, the catalytic activity will be significantly reduced, so a large amount of catalyst must be added. Arise.

The method for recovering the copolymer after the polymerization reaction is stopped is not particularly limited. For example, a commonly used method such as 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 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). The radical polymerization initiator is also a radical polymerization catalyst, but is represented by a radical polymerization initiator below.

A known substance is used for 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. However, the radical polymerization initiator used for hardening of this resin composition is not limited to these examples.

When the amount of the radical polymerization initiator is in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the soluble polyfunctional vinyl aromatic copolymer (XA), the reaction can be satisfactorily performed without inhibiting the curing reaction. Progresses.

If necessary, the polymerizable polyfunctional vinyl aromatic copolymer (XA) -containing curable composition may be mixed with another polymerizable monomer copolymerizable with the copolymer (XA) and cured.

A known substance is used as such a copolymerizable polymerizable monomer. Typical examples are styrene, styrene dimer, alphamethylstyrene, alphamethylstyrene dimer, divinylbenzene, vinyltoluene, t-butylstyrene, chlorostyrene, dibromostyrene, vinylnaphthalene, vinylbiphenyl, acenaphthylene, divinylbenzyl ether. And allyl phenyl ether.

The curable composition containing the soluble polyfunctional vinyl aromatic copolymer (XA) includes known thermosetting resins such as vinyl ester resins, polyvinyl benzyl resins, unsaturated polyester resins, curable vinyl resins, and modified polyphenylenes. Ether resins, maleimide resins, epoxy resins, polycyanate resins, phenol resins, and other known thermoplastic resins such as polystyrene, polyphenylene ether, polyether imide, polyether sulfone, PPS resins, polycyclopentadiene resins, polycycloolefins Resins, etc. or known thermoplastic elastomers such as styrene-ethylene-propylene copolymer, styrene-ethylene-butylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene Butazier Copolymers, hydrogenated styrene - isoprene copolymer and or gums such as polybutadiene, may be blended with polyisoprene.

The curable composition comprises a modified polyphenylene ether (XC) represented by the following formula (7) together with a soluble polyfunctional vinyl aromatic copolymer (XA) and a radical polymerization initiator (XB), particularly at least one terminal. A group having a polymerizable unsaturated double bond, for example, a modified polyphenylene ether (XC) having a phenolic hydroxyl group, a vinyl group, or a (meth) acryl group may be contained. The terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) and the modified polyphenylene ether (XC) have good compatibility, overcoming the problem of reduced reliability due to a decrease in compatibility, It exhibits improved properties such as high low dielectric properties and toughness, as well as properties such as formability and delamination strength in any formulation.

In formula (7), m represents 1 or 2, and L represents a polyphenylene ether chain represented by the following formula (8). M represents a hydrogen atom, a group represented by the following formula (9). When m is 1, M is not a hydrogen atom, and when m is 2, at least one of the two M is hydrogen. It is not an atom. T represents a hydrogen atom when m is 1, and represents a group represented by an alkylene group, the following formula (10), or the following formula (11) when m is 2.

In the formula (8), n represents a positive integer of 50 or less, and R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, formyl A group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group;

In formula (9), X is an organic group having 1 or more carbon atoms and may contain an oxygen atom. Y is a vinyl group. j represents an integer of 0 or 1.

In formula (10), R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, formyl group, alkylcarbonyl group, alkenylcarbonyl group, or alkynyl. A carbonyl group is shown.

In formula (11), R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, formyl A group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group; F is a linear, branched or cyclic hydrocarbon group having 20 or less carbon atoms, including the case of 0 carbon atoms. )

The modified polyphenylene ether (XC) used in the present embodiment is not particularly limited as long as it is a modified polyphenylene ether represented by the above formula (7).

The modified polyphenylene ether represented by the formula (7) is one in which m in the formula (7) is 1 or 2. In other words, the modified polyphenylene ether represented by the formula (7) is specifically a modified polyphenylene ether represented by TLMM or MLTLM.

L represents a polyphenylene ether chain represented by the formula (8). In the formula (8), n represents a positive integer of 50 or less. R ⁵ , R ⁶ , R ⁷ , and R ⁸ are independent of each other. That is, R ⁵ , R ⁶ , R ⁷ , and R ⁸ may be the same group or different groups. R ⁵ , R ⁶ , R ⁷ , and R ⁸ represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. Among these, a hydrogen atom and an alkyl group are preferable.

M represents a hydrogen atom or a group represented by the formula (9). M represents a group represented by the formula (9) instead of a hydrogen atom when m is 1, that is, when the modified polyphenylene ether is TLM. In addition, when M is 2, that is, when the modified polyphenylene ether is MLTLM, at least one of the two Ms is not a hydrogen atom, and the heat resistance of the cured product It is preferable that the two Ms are groups represented by the formula (9) for the reasons of property and toughness.

T represents a hydrogen atom when m is 1, that is, when the modified polyphenylene ether is TLM. The modified polyphenylene ether represented by TLM is a modified polyphenylene ether represented by HLM. In the case where T is m, that is, when the modified polyphenylene ether is MLTLM, an alkylene group, a group represented by the formula (10), or a formula (11) The group represented by these is shown. Among these, m is preferably 2, T is an alkylene group, m is 2, and T is a 2,2-propylene group because of the toughness of the cured product and the solubility of the modified polyphenylene ether. Is preferred.

In the formula (10), R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, Or an alkynylcarbonyl group is shown. R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ may be the same group or different groups.

Specific examples of the functional groups listed in R ⁵ to R ²¹ include the following.

The alkyl group is not particularly limited. For example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specific examples include a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group.

The alkenyl group is not particularly limited, but for example, an alkenyl group having 2 to 18 carbon atoms is preferable, and an alkenyl group having 2 to 10 carbon atoms is more preferable. Specific examples include a vinyl group, an allyl group, and a 3-butenyl group.

Further, the alkynyl group is not particularly limited, but for example, an alkynyl group having 2 to 18 carbon atoms is preferable, and an alkynyl group having 2 to 10 carbon atoms is more preferable. Specific examples include an ethynyl group and a prop-2-yn-1-yl group (propargyl group).

The alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group. For example, an alkylcarbonyl group having 2 to 18 carbon atoms is preferable, and an alkylcarbonyl group having 2 to 10 carbon atoms is more preferable. . Specific examples include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a hexanoyl group, an octanoyl group, and a cyclohexylcarbonyl group.

The alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group. For example, an alkenylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkenylcarbonyl group having 3 to 10 carbon atoms is more preferable. . Specifically, an acryloyl group, a methacryloyl group, a crotonoyl group, etc. are mentioned, for example.

The alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group. For example, an alkynylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkynylcarbonyl group having 3 to 10 carbon atoms is more preferable. . Specifically, a propioyl group etc. are mentioned, for example.

The number average molecular weight of the modified polyphenylene ether (XC) is not particularly limited, but is preferably 800 to 7000, more preferably 1000 to 5000. Most preferably, it is 1000 to 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 (XC) 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 (XC) used in this embodiment has a polymerizable unsaturated double bond at the terminal, the modified polyphenylene ether and the thermally crosslinked resin are cured by curing together with a vinyl-based thermally crosslinked curable resin. Crosslinking with the mold curable resin suitably proceeds, 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 an epoxy resin (XD) and a cured resin together with a soluble polyfunctional vinyl aromatic copolymer (XA) and a radical polymerization initiator (XB) for the purpose of improving the adhesion reliability between different materials. It is also a preferred embodiment to contain an agent (XE).

The epoxy resin of component (XD) is not particularly limited, but is an epoxy resin having two or more epoxy groups and an aromatic structure in one molecule, and an epoxy resin having 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 epoxy resins 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 component (XD) include epoxy resins mainly composed of 4,4′-methylenebis (2,6-dimethylphenol) diglycidyl ether, 4,4′-methylenebis. Examples thereof include an epoxy resin mainly composed of (2,3,6-trimethylphenol) diglycidyl ether and an epoxy resin mainly composed of 4,4′-methylenebisphenol diglycidyl ether. Among them, an epoxy resin mainly composed of 4,4'-methylenebis (2,6-dimethylphenol) diglycidyl ether is preferable. For example, it can be obtained as a commercial product under the 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'-diglycidyl biphenyl and 4,4'-diglycidyl-3,3 ', 5,5'-tetramethylbiphenyl. For example, they are commercially available as trade names YX-4000 and YL-6121H manufactured by Mitsubishi Chemical Corporation.

Examples of the dicyclopentadiene type epoxy resin include dicyclopentadiene dioxide and phenol novolac epoxy monomers 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 type epoxy resin, naphthalene skeleton modified cresol novolak type epoxy resin, methoxynaphthalene modified cresol novolak type epoxy resin, naphthylene ether type epoxy resin, methoxynaphthalene dimethylene Modified naphthalene type epoxy resins such as type epoxy resins.

Examples of adamantane type epoxy resins include 1- (2,4-diglycidyloxyphenyl) adamantane, 1- (2,3,4-triglycidyloxyphenyl) adamantane, and 1,3-bis (2,4-diglycidyloxy). Phenyl) adamantane, 1,3-bis (2,3,4-triglycidyloxyphenyl) adamantane, 2,2-bis (2,4-diglycidyloxyphenyl) adamantane, 1- (2,3,4-tri Hydroxyphenyl) adamantane, 1,3-bis (2,4-dihydroxyphenyl) adamantane, 1,3-bis (2,3,4-trihydroxyphenyl) adamantane, and 2,2-bis (2,4- And dihydroxyphenyl) adamantane.

Among the epoxy resins, from the viewpoint of compatibility with the component (XA), dielectric properties, and small warpage of the molded product, bisphenol F type epoxy resin, alkylphenol novolak type epoxy resin, xylylene modified phenol novolak type epoxy resin, 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 this component increases, and the handleability of the cast film / sheet tends to deteriorate. On the other hand, when 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.

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. A more preferred lower limit is 10 parts by weight. 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.

The curing agent of the component (XE) is a phenol resin, an acid anhydride having an aromatic skeleton or an alicyclic skeleton, an acid anhydride water additive, a modified acid anhydride, a hydroxyl-terminated polyphenylene ether oligomer, and an activity. It is preferable to select appropriately from ester compounds. 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.

(XE) The phenol resin used as a curing agent for the 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. Can be mentioned. Among these, in order to further increase the flexibility and flame retardancy of the insulating sheet, a phenol resin having a melamine skeleton, a phenol resin having a triazine skeleton, or a phenol resin having an allyl group is preferable.

Examples of commercially available phenol resins 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. , LA1356 and LA3018-50P (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 (XE) component, its water additive or a modified product is not particularly limited. Examples of the acid anhydride having an aromatic skeleton, a water additive or a modified product thereof include, for example, styrene / maleic anhydride copolymer, benzophenonetetracarboxylic acid anhydride, pyromellitic acid anhydride, trimellitic acid anhydride, 4,4 '-Oxydiphthalic anhydride, phenylethynylphthalic anhydride, glycerol bis (anhydrotrimellitate) monoacetate, ethylene glycol bis (anhydrotrimellitate), methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, And trialkyltetrahydrophthalic anhydride, methylnadic acid anhydride, trialkyltetrahydrophthalic anhydride, acid anhydride having a dicyclopentadiene skeleton, or a modified product of the acid anhydride, and the like.

Examples of commercially available acid anhydrides having an aromatic skeleton, water additives or modified products thereof include SMA Resin EF30, SMA Resin EF40, SMA Resin EF60, and SMA Resin EF80 (all of which are manufactured by Sartomer Japan), ODPA- M and PEPA (both of which are manufactured by Manac), Rikagit MTA10, Rikagit MTA15, 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 TDA100 (all of which are manufactured by Shin Nippon Rika), and EPICLON B4400, PICLON B650, and EPICLON B570 (all manufactured by both DIC Corporation).

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

Examples of commercially available acid anhydrides having an alicyclic skeleton, water additives or modified products thereof include Rikajit HNA and Rikajito HNA100 (both are manufactured by Shin Nippon Rika Co., Ltd.), and EpiCure YH306, EpiCure YH307, EpiCure YH308H and EpiCure YH309 (all are made by Japan Epoxy Resin Co., Ltd.) and the like.

As the (XE) component, a hydroxyl-terminated polyphenylene ether oligomer can also be used. A hydroxyl group-terminated polyphenylene ether oligomer represented by the following formula (12) can be exemplified.

In formula (12), p represents 1 or 2, E represents a polyphenylene ether chain represented by the following formula (13), G represents a hydrogen atom, and p represents an integer of 1 or 2. . V represents a hydrogen atom when p is 1, and when p is 2, it represents an alkylene group or a group represented by the following formula (14) or formula (15).

In the formula (13), q represents a positive integer of 50 or less, and R ²² , R ²³ , R ²⁴ , and R ²⁵ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, formyl A group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group;

In formula (14), R ²⁶ , R ²⁷ , R ²⁸ , and R ²⁹ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynyl group. A carbonyl group is shown.

In formula (15), R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , and R ³⁷ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, formyl A group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group; W is a linear, branched or cyclic hydrocarbon group having 20 or less carbon atoms, including the case of 0 carbon atoms.

(XE) An active ester compound can also be used as a component. Any compound having an active ester group may be used, but in the present invention, a compound having at least two active ester groups in the molecule is preferable.

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 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 may be linear or multi-branched, and when the active ester compound is derived from a compound having at least two carboxylic acids in the molecule, such at least two carboxylic acids When the compound having an in-molecule contains an aliphatic chain, the compatibility with the epoxy resin can be increased, and when the compound has an aromatic ring, the heat resistance 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 preferable, phthalic acid, isophthalic acid and terephthalic acid are more preferable, and isophthalic acid and terephthalic acid are more preferable. .
Specific examples of the thiocarboxylic acid compound for forming the active ester compound include thioacetic acid and thiobenzoic acid.

Specific examples of hydroxy compounds for forming active ester compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenol phthaline, methylated bisphenol A, methylated bisphenol F, 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, trihydroxybenzophenone, Examples thereof include tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, phenol novolac and the like. 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.

As the active ester compound, for example, active ester compounds disclosed in JP-A Nos. 2002-12650 and 2004-277460, or commercially available ones 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 amount of the active ester compound (XE) is preferably in the range of 20 to 120 parts by weight, more preferably 40 to 100 parts by weight, and still more preferably 50 to 90 parts by weight with respect to 100 parts by weight of the epoxy resin (XD). It is. By making the compounding quantity of an 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.

Curing agents used as the (XE) component include o-cresol novolak, p-cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol from the viewpoint of compatibility with the (XA) component, moisture resistance, and adhesion. , Polyparavinylphenol, xylylene-modified novolak, poly (di-o-hydroxyphenyl) methane, poly (di-m-hydroxyphenyl) methane, poly (di-p-hydroxyphenyl) methane, methyl nadic anhydride, tri Alkyltetrahydrophthalic anhydride, an acid anhydride having a dicyclopentadiene skeleton or a modified product thereof, a hydroxyl group-terminated polyphenylene ether oligomer, or an active ester compound is more preferable.

The curable composition containing the 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, brominated Use in combination with a flame retardant imparting agent such as polystyrene is particularly useful as an electrical or electronic component material that requires dielectric properties, flame retardancy, or heat resistance, particularly as a semiconductor sealing material or a circuit board varnish.

When used as a varnish for circuit board materials, it can be produced by dissolving the curable composition 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.

A cured product obtained by curing a curable composition containing the soluble polyfunctional vinyl aromatic copolymer (XA) of the present invention is used as a molded product, a laminate, a cast product, an adhesive, a coating film, or a film. it can. For example, a cured product of a semiconductor sealing material is a cast or molded product. As a method for obtaining a cured product for such use, a curable composition is cast, or a transfer molding machine, an injection molding machine, or the like is used. The 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, varnish for circuit boards is used for base materials, such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper It is impregnated and heat-dried 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.

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

The curable composition of the present invention can be used by laminating with a metal foil (meaning including a metal plate; the same shall apply hereinafter) as in the case of the cured composite material described 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, polybenzozal fibers, woven fabrics or nonwoven fabrics obtained from synthetic fibers such as polyvinyl alcohol fibers, polyester fibers, acrylic fibers, Examples include natural fiber cloth such as cotton cloth, linen cloth, felt, carbon fiber cloth, craft paper, cotton paper, natural cellulosic cloth such as paper-glass mixed paper, paper, etc., each alone or 2 Used in combination with more than seeds.

The amount of the base material used is 5 to 90 wt% in the curable composite material, preferably 10 to 80 wt%, more preferably 20 to 70 wt%. 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, 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 materials such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zircoaluminate coupling agent, and the like can be used.

As a method for producing a curable composite material, for example, the curable composition and other components as necessary are uniformly dissolved or dispersed in the above-mentioned aromatic or ketone-based solvent or a mixed solvent thereof, The method of drying after impregnating a base material is mentioned. Impregnation is performed by dipping or coating. Impregnation can be repeated multiple times as necessary. At this time, it is possible to repeat the impregnation using a plurality of solutions having different compositions and concentrations, and finally adjust the resin composition and the amount of resin as desired. It is.

A cured composite material is obtained by curing the curable composite material 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, an 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: 1 minute to 5 hours.

In the present invention, the laminate is composed of the cured composite material layer and the 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 a laminate, for example, a curable composite material obtained from a curable composition and a substrate, and a metal foil are laminated in a layer structure according to the purpose, and at the same time, the layers are bonded together under heat and pressure. Examples of the method include thermosetting. In the laminated body of a curable composition, a hardening composite material and metal foil are laminated | stacked by arbitrary layer structures. The metal foil can be used as a surface layer or an intermediate layer. In addition, it is possible to make a multilayer by repeating lamination and curing a plurality of times.

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

In the present invention, the film is obtained by forming the curable composition 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 is not particularly limited. For example, the curable composition and other components as required are uniformly dissolved or dispersed in an aromatic solvent, a ketone solvent, or a mixed solvent thereof. And a method of drying after applying to a resin film such as a PET film. 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 the resin composition and resin amount desired can be adjusted. is there.

In the present invention, the metal foil with resin is composed of the curable composition and the metal foil. 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 5 to 105 μm.

The method for producing the resin-coated metal foil is not particularly limited. For example, the curable composition and other components as required may be uniformly mixed in an aromatic or ketone solvent or a mixed solvent thereof. Examples include a method of dissolving or dispersing, applying to a metal foil, and drying. 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 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, a high heat resistance, etc. in fields such as the electrical industry, the space / aircraft industry, etc. It can be used for a low dielectric material, an insulating material, a heat resistant material, a structural material, etc. that can satisfy the above characteristics. 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.

The curable composition of the present invention has a high dielectric property (low dielectric constant and low dielectric loss tangent) even after severe thermal history, and gives a cured product having high adhesion reliability even under severe conditions, Moreover, 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.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples. In addition, all the parts in each example are parts by weight, and the physical properties were measured by the following methods.

1) Molecular weight and molecular weight distribution of copolymer (soluble polyfunctional aromatic copolymer) For measurement of molecular weight and molecular weight distribution, GPC (manufactured by Tosoh Corporation, HLC-8120GPC) was used, tetrahydrofuran as a solvent, flow rate of 1.0 ml / min. The column temperature was 38 ° C., and a calibration curve using monodisperse polystyrene was used.

2) Copolymer structure: 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) Analysis of end groups For the end groups of the copolymer, the consumption of each monomer during polymerization was measured using a GC-2010 gas chromatograph measuring device manufactured by Shimadzu Corporation, with 4-acetylbiphenyl as an internal standard substance. It was measured. Furthermore, the number average molecular weight was measured using GPC (manufactured by Tosoh Corporation, HLC-8120GPC) using tetrahydrofuran as a solvent, a flow rate of 1.0 ml / min, a column temperature of 38 ° C., and a calibration curve using monodisperse polystyrene. Then, the content of the structural unit of the copolymer such as vinyl group and vinylene group was determined by ¹³ C-NMR and ¹ H-NMR analysis using a JNM-LA600 type nuclear magnetic resonance spectrometer manufactured by JEOL. Chloroform-d1 was used as a solvent, and the tetramethylsilane resonance line was used as an internal standard. And content of ta1 and tb1 was computed from these measurement results.

4) Measurement of glass transition temperature (Tg) and softening temperature of cured product Copolymer solution was uniformly applied to a glass substrate so that the thickness after drying was 20 μm, and 30 minutes in 90 minutes using a hot plate. Heated 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 copolymer 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.
The glass transition temperature is measured by setting the above test piece in a DMA (dynamic viscoelasticity device) measuring device and scanning from 30 ° C. to 320 ° C. at a temperature rising rate of 3 ° C./min under a nitrogen stream. The Tg was determined from the peak top of the tan δ curve.

5) Evaluation of heat resistance and measurement of heat discoloration The heat resistance of the copolymer is evaluated by setting the sample in a TGA (thermobalance) measuring device, and at a temperature increase rate of 10 ° C./min under a nitrogen stream at 30 ° C. to 400 ° C. The measurement was performed by scanning until the weight loss at 350 ° C. was determined as heat resistance. On the other hand, the measurement of heat discoloration was carried out using 6.0 g of copolymer, 4.0 g of benzyl methacrylate, and 0.02 g of t-butyl peroxy-2-ethylhexanoate (manufactured by NOF Corporation, Perbutyl O). The mixture was mixed 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 the compatibility of the copolymer with the epoxy resin was carried out by using 5.0 g of a sample of 3.0 g of epoxy resin (liquid bisphenol A type epoxy resin: manufactured by Japan Epoxy Resin, Epicoat 828), and phenol. 2.0 g of resin (melamine skeleton phenolic resin: manufactured by Gunei Chemical Industry Co., Ltd., PS-6492) is dissolved in 10 g of methyl ethyl ketone (MEK), and the transparency of the sample after dissolution is visually confirmed. , Δ: translucent, x: opaque or not dissolved, and the compatibility was evaluated.

Example 1
Divinylbenzene (a mixture of 1,4-divinylbenzene and 1,3-divinylbenzene, the following examples are also the same) 1.82 mol (259.6 mL), ethylvinylbenzene (1-ethyl-4-vinylbenzene and 1-ethylbenzene) A mixture of ethyl-3-vinylbenzene, also in the following example) 0.43 mol (60.9 mL), 0.28 mol (36.9 mL) n-butyl acetate, and 140 mL toluene were added to a 1.0 L reactor. The solution in which 40 mmol of methanesulfonic acid was dissolved in 0.12 mol (15.7 mL) of n-butyl acetate was added at 70 ° C., and reacted for 6 hours. After the polymerization solution was stopped with calcium hydroxide, filtration was performed using activated alumina as a filter aid. Then, it was devolatilized at 60 ° C. under reduced pressure to recover the polymer. The obtained polymer was weighed to confirm that 222.6 g of copolymer A was obtained.

Mn of the obtained copolymer A was 1085, Mw was 12400, and Mw / Mn was 11.4. By performing GC analysis, GPC measurement, FT-IR, ¹³ C-NMR and ¹ H-NMR analysis, the copolymer A is obtained by the above formulas (a1), (a2), (a3), (ta1), (b1 ) And structural units derived from the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by (tb1) were quantified. From the result, the divinyl aroma calculated by the formula [(a1) + (a3) + (ta1)] / [(a1) + (a2) + (a3) + (b1) + (ta1) + (tb1)] The molar fraction of the structural unit containing the specific unsaturated hydrocarbon group derived from the group compound (a) was 0.51. Moreover, from content of the terminal structural unit of the copolymer A derived from the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by the formula (ta1) and the formula (tb1), the formula (ta1) / The molar fraction of the terminal structural unit containing a vinyl group calculated by [(ta1) + (tb1)] was 0.67. The copolymer A contained 84.0 mol% of the structural units derived from the divinyl aromatic compound (a) and 16.0 mol% in total of the structural units derived from the monovinyl aromatic compound (b). Unsaturated hydrocarbon derived from divinyl aromatic compound (a) and monovinyl aromatic compound (b) represented by the above formulas (a1), (a2), (ta1) and (tb1) contained in copolymer A The group content was 64.2 mol%.
Moreover, Tg was 256 degreeC as a result of DMA measurement of hardened | cured material. On the other hand, as a result of TMA measurement of the cured product, the softening temperature was 300 ° C. or higher. As a result of TGA measurement, the weight loss at 350 ° C. was 1.21 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
In a 1.0 L reactor, 1.82 mol (259.6 mL) of divinylbenzene, 0.43 mol (60.9 mL) of ethyl vinylbenzene, 0.28 mol (36.9 mL) of n-butyl acetate, and 140 mL of toluene were added. Then, a solution prepared by dissolving 40 mmol of p-toluenesulfonic acid monohydrate in 0.12 mol (15.7 mL) of n-butyl acetate at 70 ° C. was added and reacted for 6 hours. After the polymerization solution was stopped with calcium hydroxide, filtration was performed using activated alumina as a filter aid. Then, it was devolatilized at 60 ° C. under reduced pressure to recover the polymer. The obtained polymer was weighed to confirm that 124.3 g of copolymer B was obtained.

Mn of the obtained copolymer B was 748, Mw was 3420, and Mw / Mn was 4.57. By performing GC analysis, GPC measurement, FT-IR, ¹³ C-NMR, and ¹ H-NMR analysis, the copolymer B has the formulas (a1), (a2), (a3), (ta1), (b1 ) And structural units derived from the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by (tb1) were quantified. From the result, the divinyl aroma calculated by the formula [(a1) + (a3) + (ta1)] / [(a1) + (a2) + (a3) + (b1) + (ta1) + (tb1)] The molar fraction of the structural unit containing the specific unsaturated hydrocarbon group derived from the group compound (a) was 0.60. Moreover, from content of the terminal structural unit of the copolymer B derived from the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by the formula (ta1) and the formula (tb1), the formula (ta1) / The molar fraction of the terminal structural unit containing a vinyl group calculated by [(ta1) + (tb1)] was 0.71. The copolymer B contained 82.3 mol% of the structural units derived from the divinyl aromatic compound (a) and 17.7 mol% in total of the structural units derived from the monovinyl aromatic compound (b). Unsaturated hydrocarbon derived from divinyl aromatic compound (a) and monovinyl aromatic compound (b) represented by the above formulas (a1), (a2), (ta1) and (tb1) contained in copolymer B The group content was 67.8 mol%.
Moreover, Tg was 247 degreeC as a result of DMA measurement of hardened | cured material. On the other hand, as a result of TMA measurement of the cured product, the softening temperature was 300 ° C. or higher. As a result of TGA measurement, the weight loss at 350 ° C. was 1.41 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), ethyl vinylbenzene 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.

Mn of the obtained copolymer C was 2030, Mw was 5180, and Mw / Mn was 2.55. By performing ¹³ C-NMR and ¹ H-NMR analysis, a resonance line derived from the end of 2-phenoxyethyl methacrylate was observed in copolymer C. 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 amount (c1) of structural units derived from 2-phenoxyethyl methacrylate in the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis results and the number average molecular weight in terms of standard polystyrene was 2.3 (pieces / molecule). It was. By performing GC analysis, GPC measurement, FT-IR, ¹³ C-NMR and ¹ H-NMR analysis, the copolymer C is obtained by the above formulas (a1), (a2), (a3), (ta1), (ta The structural units derived from the divinyl aromatic compound (a) and the ethyl vinyl aromatic compound (b) represented by b1) and (tb1) were quantified. From the results, the structural units represented by the formulas (a2), (ta1) and (tb1) among the above structural units were not observed. Therefore, the divinyl aromatic compound calculated by the formula [(a1) + (a3) + (ta1)] / [(a1) + (a2) + (a3) + (b1) + (ta1) + (tb1)] The molar fraction of the structural unit containing the specific unsaturated hydrocarbon group derived from (a) and the monovinyl aromatic compound (b) was 0.59.
On the other hand, the content of the terminal structural unit of the copolymer C derived from the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by the formula (ta1) and the formula (tb1) is represented by the formula (ta1) and Since none of the structural units represented by the formula (tb1) was detected in the analysis, the terminal structure containing a vinyl group calculated by the formula (ta1) / [(ta1) + (tb1)] The mole fraction of units can be considered as zero. 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, Tg was 197 degreeC as a result of DMA measurement of hardened | cured material. As a result of TMA measurement of the cured product, the softening temperature was 300 ° C. or higher. 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
1.82 mol (259.6 mL) of divinylbenzene, 0.43 mol (60.9 mL) of ethylvinylbenzene, and 140 mL of toluene were charged into a 1.0 L reactor, and 40 mmol of p-toluenesulfone was added at 70 ° C. Acid monohydrate was added and allowed to react for 6 hours. After the polymerization solution was stopped with calcium hydroxide, filtration was performed using activated alumina as a filter aid. Then, it was devolatilized at 60 ° C. under reduced pressure to recover the polymer. The obtained polymer was weighed to confirm that 187.3 g of copolymer D was obtained.

Mn of the obtained copolymer D was 1024, Mw was 7820, and Mw / Mn was 7.64. When GC analysis, GPC measurement, FT-IR, ¹³ C-NMR and ¹ H-NMR analysis were performed, the above formulas (a1), (a2), (a3), (ta1), (b1) and (tb1) The structural unit derived from the divinyl aromatic compound (a) and the ethyl vinyl aromatic compound (b) represented by From the results, the copolymer D has the formula [(a1) + (a3) + (ta1)] / [(a1) + (a2) + (a3) + (b1) + (ta1) + (tb1)] The molar fraction of the structural unit containing the specific unsaturated hydrocarbon group derived from the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) calculated by the formula (1) was 0.04. Moreover, from content of the terminal structural unit of the copolymer B derived from the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by the formula (ta1) and the formula (tb1), the formula (ta1) / The molar fraction of the terminal structural unit containing a vinyl group calculated by [(ta1) + (tb1)] was 0.05. The copolymer D contained 83.1 mol% of structural units derived from divinylbenzene and 16.9 mol% in total of structural units derived from monovinylbenzene. The unsaturated hydrocarbon group content derived from the divinyl aromatic compounds (a) and monovinyl aromatic compounds (b) represented by the above formulas (a1) to (a3) contained in the copolymer D is 81.3. Mol%.
Moreover, Tg was 136 degreeC as a result of DMA measurement of hardened | cured material. On the other hand, as a result of TMA measurement of the cured product, the softening temperature was 125 ° C. As a result of TGA measurement, the weight loss at 350 ° C. was 7.31 wt%, and the heat discoloration property was Δ. On the other hand, the compatibility with the epoxy resin was ○.
Copolymer D was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was observed.

Example 3
Divinyl biphenyl 1.80 mol (324.4 g), ethyl vinyl biphenyl 0.45 mol (81.1 g), n-butyl acetate 0.28 mol (36.9 mL), and 140 mL of toluene in a 1.0 L reactor Then, a solution of 40 mmol of methanesulfonic acid dissolved in 0.12 mol (15.7 mL) of n-butyl acetate at 70 ° C. was added and reacted for 6 hours. After the polymerization solution was stopped with calcium hydroxide, filtration was performed using activated alumina as a filter aid. Then, it was devolatilized at 60 ° C. under reduced pressure to recover the polymer. The obtained polymer was weighed to confirm that 259.5 g of copolymer E was obtained.

Mn of the obtained copolymer E was 1342, Mw was 13960, and Mw / Mn was 10.4. By performing GC analysis, GPC measurement, FT-IR, ¹³ C-NMR and ¹ H-NMR analysis, the copolymer E is converted into the above formulas (a1), (a2), (a3), (ta1), (b1 ) And structural units derived from the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by (tb1) were quantified. From the result, the divinyl aroma calculated by the formula [(a1) + (a3) + (ta1)] / [(a1) + (a2) + (a3) + (b1) + (ta1) + (tb1)] The molar fraction of the structural unit containing the specific unsaturated hydrocarbon group derived from the group compound (a) was 0.60. Moreover, from content of the terminal structural unit of the copolymer E derived from the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by the formula (ta1) and the formula (tb1), the formula (ta1) / The molar fraction of the terminal structural unit containing a vinyl group calculated by [(ta1) + (tb1)] was 0.57. The copolymer E contained 82.6 mol% of the structural units derived from the divinyl aromatic compound (a) and 17.4 mol% in total of the structural units derived from the monovinyl aromatic compound (b). Unsaturated hydrocarbon derived from divinyl aromatic compound (a) and monovinyl aromatic compound (b) represented by the above formulas (a1), (a2), (ta1) and (tb1) contained in copolymer E The group content was 68.2 mol%.
Moreover, Tg was 271 degreeC as a result of DMA measurement of hardened | cured material. On the other hand, as a result of TMA measurement of the cured product, the softening temperature was 300 ° C. or higher. As a result of TGA measurement, the weight loss at 350 ° C. was 1.36 wt%, and the heat discoloration resistance was ◯. On the other hand, the compatibility with the epoxy resin was ○.
Copolymer E was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was observed.

Example 4
In a 1.0 L reactor, 1.82 mol (259.6 mL) of divinylbenzene, 0.43 mol (60.9 mL) of ethyl vinylbenzene, 0.28 mol (36.9 mL) of n-butyl acetate, and 140 mL of toluene were added. Then, a solution prepared by dissolving 60 mmol of methanesulfonic acid in 0.12 mol (15.7 mL) of n-butyl acetate at 60 ° C. was added and reacted for 12 hours. After the polymerization solution was stopped with calcium hydroxide, filtration was performed using activated alumina as a filter aid. Then, it was devolatilized at 60 ° C. under reduced pressure to recover the polymer. The obtained polymer was weighed to confirm that 167.8 g of copolymer F was obtained.

Mn of the obtained copolymer F was 1450, Mw was 19700, and Mw / Mn was 13.6. By performing GC analysis, GPC measurement, FT-IR, ¹³ C-NMR and ¹ H-NMR analysis, the copolymer A is obtained by the above formulas (a1), (a2), (a3), (ta1), (b1 ) And (tb1) and the structural units derived from the divinyl aromatic compound (a) and the ethyl vinyl aromatic compound (b) were quantified. From the result, the divinyl aroma calculated by the formula [(a1) + (a3) + (ta1)] / [(a1) + (a2) + (a3) + (b1) + (ta1) + (tb1)] The mole fraction of the structural unit containing the specific unsaturated hydrocarbon group derived from the aromatic compound (a) and the ethyl vinyl aromatic compound (b) was 0.74. Moreover, from content of the terminal structural unit of the copolymer F derived from the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by the formula (ta1) and the formula (tb1), the formula (ta1) / The molar fraction of the terminal structural unit containing a vinyl group calculated by [(ta1) + (tb1)] was 0.61. The copolymer F contained 83.6 mol% of structural units derived from the divinyl aromatic compound (a) and 16.4 mol% in total of structural units derived from the monovinyl aromatic compound (a). Unsaturated hydrocarbon derived from divinyl aromatic compound (a) and ethylvinyl aromatic compound (b) represented by the above formulas (a1), (a2), (ta1) and (tb1) contained in copolymer F The group content was 58.6 mol%.
Moreover, Tg was 271 degreeC as a result of DMA measurement of hardened | cured material. On the other hand, as a result of TMA measurement of the cured product, the softening temperature was 300 ° C. or higher. As a result of TGA measurement, the weight loss at 350 ° C. was 1.12 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.

Using the copolymers A to F obtained in Examples 1 to 4 and Comparative Examples 1 to 2, evaluation of the properties of varnishes and cured products of the curable resin compositions using these resins was performed by the following method. went.

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 produced 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%. The 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.
Regarding the glass transition temperature, the above test piece is set in a DMA (dynamic viscoelasticity device) measuring device and scanned from 30 ° C. to 320 ° C. at a temperature rising rate of 3 ° C./min under a nitrogen stream. Measurement was performed and Tg was obtained from the peak top of the tan δ curve.

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 stacked 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 a laminate for evaluation. 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 continuously peeled off 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. (Conforms 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 Production of laminated plate with plated copper The copper-clad laminate produced in the previous section was immersed in an aqueous solution of 150 g / L ammonium persulfate 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 swelling aqueous Circposite MLB conditioner 211 (trade name, manufactured by Rohm & Haas Japan Co., Ltd.) at 80 ° C. for 5 minutes by the dipping method. 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 performed at 40 ° C. for 5 minutes by a dip method using MLB Neutralizer 216 (Rohm & Haas Japan Co., Ltd., trade name) as a neutralizing solution. After washing with running water at room temperature for 3 minutes, using conditioner solution CLC-501 (trade name, manufactured by Hitachi Chemical Co., Ltd.) for 5 minutes at 60 ° C., washing with running water, pre-dip solution PD-201 (product) Name, manufactured by Hitachi Chemical Co., Ltd.) in aqueous solution at room temperature for 3 minutes, treated in aqueous solution containing metallic 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.

Then, the above cured test laminate with plating is etched into a line having a copper width of 10 mm and a length of 100 mm, and one end thereof is peeled off and is gripped with a gripper, and is vertically aligned 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) core material patterned. This core material was subjected to blackening treatment, and then a prepreg was further laminated thereon, followed by secondary molding to produce a laminated substrate for evaluation having an inner layer of a lattice pattern. About the produced 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 there was no occurrence of defective phenomena such as delamination and measling (white spots). Although not seen, the case where warpage or bleedout (separation of the compound) occurred was evaluated as “Δ”, and the case where the defect phenomenon occurred was evaluated as “x”.

Example 5
A curable resin obtained by dissolving 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, and 8.6 g of toluene as a curing accelerator. A 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 6-8, Comparative Examples 3-4
A curable resin composition (varnish) was obtained in the same manner as in Example 5 except that the formulation shown in Table 1 was used. And the hardened | cured material flat plate test piece was produced like Example 5, and it tested and evaluated about the same item as Example 5. FIG. The results obtained by these tests are shown in Table 1.

Examples 9 to 23, Comparative Examples 5 to 7
A curable resin composition (varnish) was obtained in the same manner as in Example 5 except that the formulation shown in Tables 2 and 3 was used. And the hardened | cured material flat plate test piece was produced like Example 5, and it tested and evaluated about the same item as Example 5. FIG. The results obtained by these tests are shown in Table 1. Furthermore, using the varnishes shown in these Examples and Comparative Examples, a prepreg, a test copper clad laminate, and a test plated laminate were produced according to the methods described in 11) to 13) above. Then, copper foil peel strength, copper plating peel strength, and formability were evaluated. The test results are shown in Tables 2 and 3.

Example 24
Divinylbenzene 8.91 mol (1269.1 mL), ethyl vinylbenzene 2.09 mol (297.7 mL), methyl ethyl ketone 0.40 mol (36.3 mL), toluene 1100 mL were charged into a 3.0 L reactor, A solution prepared by dissolving 0.50 mmol of trifluoromethanesulfonic acid in 0.10 mol (9.0 mL) of methyl ethyl ketone at 70 ° C. was added and reacted for 6 hours. The polymerization solution was stopped with an aqueous sodium hydrogen carbonate solution, washed with water, and filtered using activated alumina as a filter aid. Then, it was devolatilized at 60 ° C. under reduced pressure to recover the polymer. The obtained polymer was weighed to confirm that 1698.7 g of copolymer G was obtained.

Mn of the obtained copolymer G was 884, Mw was 11800, and Mw / Mn was 13.4. By performing GC analysis, GPC measurement, FT-IR, 13C-NMR and 1H-NMR analysis, the copolymer G is converted into the above formulas (a1), (a2), (a3), (ta1), (b1) and The repeating structural unit derived from the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by (tb1) was quantified. From the result, the divinyl aroma calculated by the formula [(a1) + (a3) + (ta1)] / [(a1) + (a2) + (a3) + (b1) + (ta1) + (tb1)] The molar fraction of the structural unit containing the specific unsaturated hydrocarbon group derived from the group compound (a) was 0.54. Moreover, from content of the terminal structural unit of the copolymer A derived from the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by the formula (ta1) and the formula (tb1), the formula (ta1) / The molar fraction of the terminal structural unit containing a vinyl group calculated by [(ta1) + (tb1)] was 0.71. Copolymer G contained 82.4 mol% of structural units derived from divinyl aromatic compound (a) and 17.6 mol% in total of structural units derived from monovinyl aromatic compound (b). Unsaturated hydrocarbon derived from divinyl aromatic compound (a) and monovinyl aromatic compound (b) represented by the above formulas (a1), (a2), (ta1) and (tb1) contained in copolymer G The group content was 64.7 mol%.
Moreover, Tg was 264 degreeC as a result of DMA measurement of hardened | cured material. On the other hand, as a result of TMA measurement of the cured product, the softening temperature was 300 ° C. or higher. As a result of TGA measurement, the weight loss at 350 ° C. was 1.35 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 25
Divinylbenzene 8.91 mol (1269.1 mL), Ethylvinylbenzene 2.09 mol (297.7 mL), Styrene 1.00 mol (115.0 mL), Propyl acetate 0.40 mol (46.0 mL), Toluene 1000 mL Was added to a 3.0 L reactor, and a solution prepared by dissolving 0.70 mmol of trifluoromethanesulfonic acid in 0.10 mol (11.5 mL) of propyl acetate at 50 ° C. was added and reacted for 7 hours. . The polymerization solution was stopped with an aqueous sodium hydrogen carbonate solution, and then washed with water. Then, it was devolatilized at 60 ° C. under reduced pressure to recover the polymer. The obtained polymer was weighed to confirm that 1643.5 g of copolymer H was obtained.

Mn of the obtained copolymer H was 947, Mw was 13800, and Mw / Mn was 14.6. By performing GC analysis, GPC measurement, FT-IR, 13C-NMR and 1H-NMR analysis, the copolymer H is converted into the above formulas (a1), (a2), (a3), (ta1), (b1) and The repeating structural unit derived from the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by (tb1) was quantified. From the result, the divinyl aroma calculated by the formula [(a1) + (a3) + (ta1)] / [(a1) + (a2) + (a3) + (b1) + (ta1) + (tb1)] The molar fraction of the structural unit containing the specific unsaturated hydrocarbon group derived from the group compound (a) was 0.51. Moreover, from content of the terminal structural unit of the copolymer H derived from the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) represented by the formula (ta1) and the formula (tb1), the formula (ta1) / The molar fraction of the terminal structural unit containing a vinyl group calculated by [(ta1) + (tb1)] was 0.65. The copolymer H contained 83.1 mol% of structural units derived from the divinyl aromatic compound (a) and 16.9 mol% in total of structural units derived from the monovinyl aromatic compound (b). Unsaturated hydrocarbon derived from divinyl aromatic compound (a) and monovinyl aromatic compound (b) represented by the above formulas (a1), (a2), (ta1) and (tb1) contained in copolymer H The group content was 61.3 mol%.
Moreover, Tg was 217 degreeC as a result of DMA measurement of hardened | cured material. On the other hand, as a result of TMA measurement of the cured product, the softening temperature was 300 ° C. or higher. As a result of TGA measurement, the weight loss at 350 ° C. was 1.42 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.

Examples 26 and 27
A curable resin composition (varnish) was obtained in the same manner as in Example 5 except that the copolymers G and H obtained in Examples 24 and 25 were used to obtain the compounding formulations shown in Table 4. It was. And the hardened | cured material flat plate test piece was produced like Example 5, and it tested and evaluated about the same item as Example 5. FIG. The results obtained by these tests are shown in Table 4.

In Tables 1 to 4, the components used are as follows.
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 vinyl group at one end (Mn = 2340, reaction product of polyphenylene ether (SA120 manufactured by SABIC Innovative Plastics) and chloromethylstyrene)
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.)
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.)
Bisphenol A type liquid epoxy resin: Epicoat 828US, Mw = 370 (manufactured by Japan Epoxy Resin Co., Ltd.)
Fluorene skeleton epoxy resin: manufactured by Osaka Gas Chemical Co., Ltd., trade name: Oncoat EX1011, Mw = 486
Modified PPE-D: Polyphenylene oligomer having epoxy groups 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)
Biphenyl skeleton phenol resin: MEH-7851-S manufactured by Meiwa Kasei Co., Ltd.
Melamine skeleton phenolic resin: manufactured by Gunei Chemical Industry Co., Ltd., PS-6492
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
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)
Amorphous spherical silica: manufactured by Admatechs, SE2050 SPE, average particle size 0.5 μm (treated with phenylsilane coupling agent)
Radical polymerization initiator: Park Mill D, Park Mill P, manufactured by NOF Corporation, NOFMER BC-90 (2,3-dimethyl-2,3-diphenylbutane)
Curing accelerator: Triphenylphosphine Stabilizer: ADK STAB AO-60

The soluble polyfunctional vinyl aromatic copolymer of the present invention can be processed into a molding material, a sheet or a film. In the fields of electrical and electronic industry, space / aircraft industry, etc., low dielectric materials, insulating materials, heat resistant materials, structures It can be used for materials. In addition, semiconductor-related materials, optical materials, paints, photosensitive materials, adhesives, sewage treatment agents, heavy metal scavengers, ion exchange resins, antistatic agents, antioxidants, antifogging agents, rustproofing agents, and antifouling It can be applied to agents, fungicides, insect repellents, medical materials, flocculants, surfactants, lubricants, binders for solid fuels, conductive treatment agents, and the like.

Claims

A polyfunctional vinyl aromatic copolymer containing a structural unit derived from a divinyl aromatic compound (a) and a structural unit derived from a monovinyl aromatic compound (b), which is derived from a divinyl aromatic compound (a) The structural unit is a vinyl group-containing unit represented by the following formula (a1), a vinylene group-containing unit represented by the following formula (a2), a crosslinked structural unit represented by the following formula (a3), and the following formula (ta1 And the structural unit derived from the monovinyl aromatic compound (b) is represented by the structural unit represented by the following formula (b1) and the following formula (tb1). A soluble polyfunctional vinyl aromatic copolymer having a vinylene group-containing terminal unit, solvent-soluble and polymerizable.

(In the formula, R 1 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms.)

(In the formula, R 1 is the same as in formula (a1).)

(In the formula, R 1 is the same as in formula (a1).)

(In the formula, R 1 is the same as in formula (a1).)

(In the formula, R 2 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, and R 3 represents hydrogen or a hydrocarbon group having 6 to 30 carbon atoms.)

(In the formula, R 2 and R 3 are the same as those in the formula (b1).)
Containing 20 mol% to 95 mol% of the structural unit derived from the divinyl aromatic compound (a), the formula (a1), the formula (a2), the formula (a3), the formula (ta1), the formula (b1) and the formula The molar fraction of the structural unit represented by (tb1) satisfies the following formula (1) and the following formula (2),
0.2 ≦ [(a1) + (a3) + (ta1)] / [(a1) + (a2) + (a3) + (b1) + (ta1) + (tb1)] ≦ 0.9 (1)
(ta1) / [(ta1) + (tb1)]> 0.2 (2)
The soluble polyfunctional group according to claim 1, having a number average molecular weight Mn of 300 to 100,000, a molecular weight distribution (Mw / Mn) of 100.0 or less, and being soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. Vinyl aromatic copolymer.
The divinyl aromatic compound (a) and the monovinyl aromatic compound (b) are selected from the group consisting of inorganic acids, organic sulfonic acids and perchloric acid compounds in the presence of the Lewis base compound (c) as the promoter component. In which a polyfunctional vinyl aromatic copolymer is produced by polymerization using at least one catalyst (d), which is a total of 100 of divinyl aromatic compound (a) and 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% with respect to mol%. The compound (c) is used in an amount of 0.005 to 500 mol, and a polymerization raw material containing them is dissolved in a solvent having a dielectric constant of 2.0 to 15.0 to obtain a uniform solution, and polymerized at a temperature of 20 to 120 ° C. Characterized by Soluble polyfunctional vinyl aromatic copolymer.
The divinyl aromatic compound (a) and the monovinyl aromatic compound (b) are selected from the group consisting of inorganic acids, organic sulfonic acids and perchloric acid compounds in the presence of the Lewis base compound (c) as the promoter component. In which a polyfunctional vinyl aromatic copolymer is produced by polymerization using at least one catalyst (d), which is a total of 100 of divinyl aromatic compound (a) and 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% with respect to mol%. The compound (c) is used in an amount of 0.005 to 500 mol, and a polymerization raw material containing them is dissolved in a solvent having a dielectric constant of 2.0 to 15.0 to form a uniform solution, and polymerization is performed at a temperature of 20 to 120 ° C. Special features Method for producing a polyfunctional vinyl aromatic copolymer according to claim 1.
The production of the soluble polyfunctional vinyl aromatic copolymer according to claim 4, wherein the catalyst (d) is used in an amount of 0.001 to 10 mol per 1 mol of the Lewis base compound (c). Method.
A curable composition comprising the soluble polyfunctional vinyl aromatic copolymer according to claim 1 and a radical polymerization initiator.
The curable composition according to claim 6, further comprising a thermosetting resin or a thermoplastic resin.
The curable composition according to claim 7, wherein the thermosetting resin is a modified polyphenylene ether (XC).
The thermosetting resin is 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 / or two or more in one molecule. The curable composition according to claim 7, wherein the curable composition is one or more epoxy resins (XD) selected from the group consisting of an epoxy resin having an epoxy group and an alicyclic structure.
The curable composition according to claim 7, wherein the thermosetting resin is one or more vinyl compounds (XF) having one or more unsaturated hydrocarbon groups in a molecule.
A cured product obtained by curing the curable composition according to any one of claims 6 to 10.
A film obtained by forming the curable composition according to any one of claims 6 to 10 into a film shape.
A curable composite material comprising the curable composition according to any one of claims 6 to 10 and a base material, wherein the base material is contained in a proportion of 5 to 90% by weight. .
A cured composite material obtained by curing the curable composite material according to claim 13.
A laminate comprising the cured composite material layer according to claim 14 and a metal foil layer.
A resin-coated metal foil comprising a film formed from the curable composition according to any one of claims 6 to 10 on one side of the metal foil.
A circuit board material varnish obtained by dissolving the curable composition according to any one of claims 6 to 10 in an organic solvent.