Copolymer and laminate containing same

Abstract

To provide: a composition which affords a cured material having an excellent low dielectric property and high adhesion to metal foil; and a laminate comprising the same.SOLUTION: A laminate comprises: a resin layer comprising an olefin-aromatic vinyl compound-aromatic polyene copolymer, which satisfies the following conditions (1) to (4); and metal foil. (1) The number average molecular weight of the copolymer is 5000 to 100000; (2) the aromatic vinyl compound monomer is a C8-20 aromatic vinyl compound, a content of which being 10 mass% or more and less than 60 mass%; (3) the aromatic polyene is a C5-20 polyene having a plurality of viny groups and / or vinylene groups in a molecule, a content of which being 1.5 or more and less than 20 groups per the number average molecular weight; and (4) the olefin is a C2-20 olefin, where the olefin is ethylene only or contains an α-olefin other than ethylene accounts in a mass ratio of 1 / 7 or less and the total monomer units of the olefin, the aromatic vinyl compound, and the aromatic polyene amounts to 100 mass%.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a copolymer and to a laminate comprising a resin layer containing the copolymer and a metal foil. [Background technology]

[0002] As communication frequencies move into the gigahertz range and higher, there is an increasing need for insulating materials with low dielectric properties. Polyolefins such as polyethylene and aromatic vinyl compound polymers such as polystyrene have no polar groups in their molecular structures and are therefore known to be materials that exhibit excellent low dielectric constants and low dielectric loss tangents. However, because their heat resistance depends on the crystalline melting point or glass transition temperature, there are issues with their heat resistance as electrical insulators, and furthermore, because they are thermoplastic resins, there are issues with the film-forming process (Patent Document 1).

[0003] Fluorine-based resins such as perfluoroethylene have the characteristics of low dielectric constant, low dielectric loss, and excellent heat resistance, but are difficult to process and form into films, making them poorly suited for devices. There are also issues with the adhesive strength to the copper foil of wiring. On the other hand, substrates and insulating materials using post-curing resins such as epoxy resins, unsaturated polyester resins, polyimide resins, and phenolic resins have been widely used due to their heat resistance and ease of handling, but their dielectric constant and dielectric loss are relatively high, and improvements are needed as insulating materials for high frequencies (Patent Document 2).

[0004] An electrical insulating material made of a graft or block copolymer made of olefin-based and styrene-based polymer segments has been proposed (Patent Document 3). This material focuses on the inherent low dielectric constant and low dielectric loss of olefin-based and styrene-based hydrocarbon polymers. The manufacturing method involves general graft polymerization of commercially available polyethylene and polypropylene in the presence of styrene monomer, divinylbenzene monomer, and a radical polymerization initiator, but this method has the problem that the graft efficiency does not increase and the polymer uniformity is insufficient. Furthermore, the obtained polymer contains gel, and there are problems with poor processability and filling properties. This material is a thermoplastic resin and does not have sufficient heat resistance, so it is necessary to add a heat-resistant resin such as 4-methyl-1-pentene. It is difficult to apply this material to a molding method in which it is applied or filled in a specified location and then cured.

[0005] Patent Document 4 describes an insulating layer made of a crosslinked structure containing a hydrocarbon compound having multiple aromatic vinyl groups as a crosslinking component. The cured product of this crosslinking component specifically described in the examples is rigid, and it is considered difficult to fill a large amount of filler.

[0006] Patent Document 5 shows a cured product obtained from a specific polymerization catalyst and made of an ethylene-olefin (aromatic vinyl compound)-polyene copolymer and a non-polar vinyl compound copolymer with a specific composition and blending. The cured product specifically described in the examples of Patent Document 5 has the characteristics of a low dielectric constant and a low dielectric loss tangent, but is very soft, and therefore it is necessary to improve the mechanical strength such as the elastic modulus at room temperature and high temperature. In thin-film insulating materials, such as interlayer insulating materials for FPC and FCCL, and coverlay applications, it is preferable to improve dimensional stability such as the thickness during the mounting process or during use after mounting. In addition, the cured product of the composition specifically described in the examples has room for improvement in adhesion to metal foil, especially copper foil. Patent Document 6 shows a cured product obtained from a similar specific polymerization catalyst and made of an ethylene-olefin (aromatic vinyl compound)-polyene copolymer and a non-polar vinyl compound copolymer with a specific composition and blending, but the cured product of the composition specifically described in the examples has room for improvement in adhesion to metal foil, especially copper foil, and low-temperature properties. Patent Document 7 also describes a cured product of a composition containing a similar copolymer, but the cured product of the composition specifically described in the Examples has room for improvement in adhesion to metal foil, particularly copper foil.

[0007] In addition, the curable compositions disclosed in Patent Documents 5, 6, and 7 contain a relatively large amount of monomer components (aromatic vinyl compounds and aromatic polyenes) and are in the form of a varnish. This not only results in an odor, but also makes it difficult to produce B-stage sheets (semi-cured sheets). These curable compositions have the problem that the production equipment is complicated. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Special Publication No. 52-31272 [Patent Document 2] Japanese Patent Application Publication No. 6-192392 [Patent Document 3] Japanese Patent Application Publication No. 11-60645 [Patent Document 4] JP 2004-087639 A [Patent Document 5] JP 2010-280771 A [Patent Document 6] JP 2009-161743 A [Patent Document 7] JP 2010-280860 A Summary of the Invention [Problem to be solved by the invention]

[0009] The above-mentioned prior art techniques have not provided any substance that gives a cured product having excellent low dielectric properties and mechanical properties as well as high adhesion to metal foil, and there is a demand for such a substance. [Means for solving the problem]

[0010] That is, the present invention can provide the following aspects.

[0011] A laminate comprising a resin layer containing an olefin-aromatic vinyl compound-aromatic polyene copolymer, which satisfies the following conditions (1) to (4), and a metal foil. (1) The number average molecular weight of the copolymer is 5,000 or more, and preferably 20,000 or more and 100,000 or less. (2) The aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of aromatic vinyl compound monomer units is 10% by mass or more and less than 60% by mass. (3) The aromatic polyene is one or more selected from polyenes having 5 to 20 carbon atoms and having a plurality of vinyl groups and / or vinylene groups in the molecule, and the content of vinyl groups and / or vinylene groups derived from aromatic polyene units is 1.5 or more and less than 20 per number average molecular weight. (4) The olefin is one or more olefins selected from olefins having 2 to 20 carbon atoms, the olefin is ethylene alone, or the mass ratio of an α-olefin monomer component other than ethylene to the ethylene monomer component contained in the olefin is 1 / 7 or less, and the total of the olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units is 100 mass%.

[0012] An olefin-aromatic vinyl compound-aromatic polyene copolymer satisfying the following conditions (1) to (4): (1) The number average molecular weight of the copolymer is 5,000 or more, and preferably 20,000 or more and 100,000 or less. (2) The aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of aromatic vinyl compound monomer units is 10% by mass or more and less than 60% by mass. (3) The aromatic polyene is one or more selected from polyenes having 5 to 20 carbon atoms and having a plurality of vinyl groups and / or vinylene groups in the molecule, and the content of vinyl groups and / or vinylene groups derived from aromatic polyene units is 1.5 or more and less than 20 per number average molecular weight. (4) The olefin is one or more olefins selected from olefins having 2 to 20 carbon atoms, the olefin is ethylene alone, or the mass ratio of an α-olefin monomer component other than ethylene to the ethylene monomer component contained in the olefin is 1 / 7 or less, and the total of the olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units is 100 mass%. Effect of the Invention

[0013] A cured product (cured body) of the copolymer of the present invention or a laminate containing the copolymer and a metal foil has high adhesion to the metal foil, excellent low dielectric properties, and can exhibit high mechanical properties at room temperature and high temperatures. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The following will be described in more detail. In this specification, the term "sheet" includes the concept of a film. In addition, even if the term "film" is used in this specification, it has the same meaning as the term "sheet". In this specification, the term "resin layer" refers to a layer containing the composition of the present invention, and the shape of the layer is arbitrary. In general, the layer is in the form of a sheet, and the size in the lateral direction and the thickness in the longitudinal direction of the layer relative to the metal foil are arbitrary. The resin layer may also contain other materials contained in known insulating layers, such as fillers and flame retardants, and may be fibers or nonwoven fabrics such as glass or ceramics impregnated with the composition. Furthermore, the layer is not limited to a sheet shape, and may be a hemispherical shape like a potting material, or a stripe shape, and the shape of the layer is arbitrary. In this specification, the metal foil is a concept including the wiring of the metal, and the shape of the layer may be arbitrary, and may be foil-like, linear, or dot-like. The metal foil may be a commercially available metal foil, or may be formed through any process such as deposition or plating. The numerical range in this specification includes the upper and lower limits of the range, unless otherwise specified. In this specification, the content may also be referred to as the content.

[0015] In this specification, the laminate refers to a structure including at least the resin layer and the metal foil in contact with each other and bonded to each other, and the laminate may have any lamination form. In general, the laminate may have at least the resin layer and the metal foil in a layered form, and the number of layers may be any. The resin layer and the metal foil may be adjacent to each other, or may include another layer interposed therebetween. Examples of the laminate include CCL, FCCL, PC, FPC, etc.

[0016] <Composition> In this specification, the composition may be referred to as a resin composition or a curable composition. The composition of the present invention includes the olefin-aromatic vinyl compound-aromatic polyene copolymer having a certain range of composition and molecular weight, and may also include one or more selected from "curing agent", "monomer", "additive resin", "solvent", "filler", "flame retardant", and "surface modifier".

[0017] <Olefin-aromatic vinyl compound-aromatic polyene copolymer> General methods for producing an olefin-aromatic vinyl compound-aromatic polyene copolymer that can be used in the present invention are described in, for example, JP 2009-161743 A, JP 2010-280771 A, and International Publication WO 00 / 37517. The olefin-aromatic vinyl compound-aromatic polyene copolymer (hereinafter sometimes simply referred to as the "copolymer") satisfies all of the following conditions (1) to (4). (1) The number average molecular weight of the copolymer is 5,000 or more, and preferably 20,000 or more and 100,000 or less. (2) The aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of aromatic vinyl compound monomer units is 10% by mass or more and less than 60% by mass. (3) The aromatic polyene is one or more selected from polyenes having 5 to 20 carbon atoms and having a plurality of vinyl groups and / or vinylene groups in the molecule, and the content of vinyl groups and / or vinylene groups derived from aromatic polyene units is 1.5 or more and less than 20 per number average molecular weight. (4) The olefin is one or more olefins selected from olefins having 2 to 20 carbon atoms, the olefin is ethylene alone, or the mass ratio of α-olefin monomer units other than ethylene to the ethylene monomer units contained in the olefin is 1 / 7 or less, and the total of the olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units is 100 mass%.

[0018] Furthermore, the number average molecular weight of the present copolymer is 5,000 or more, preferably from 20,000 to 100,000, and more preferably from 30,000 to 100,000.

[0019] The present olefin-aromatic vinyl compound-aromatic polyene copolymer can be obtained by copolymerizing each of the monomers of an olefin, an aromatic vinyl compound, and an aromatic polyene.

[0020] In the present copolymer, the preferred olefin monomer unit content is 35% by mass or more, and particularly preferably 45% by mass or more. Here, the total of the olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units is 100% by mass. When the olefin monomer unit content is 35% by mass or more, the toughness (elongation) of the finally obtained cured product is improved, and cracks during curing, a decrease in the impact resistance of the cured product, and cracks during a heat cycle test of the cured product do not occur. In the present copolymer, the preferred olefin monomer unit content is 90% by mass or less.

[0021] The olefin monomer is at least one selected from α-olefins having 2 to 20 carbon atoms and cyclic olefins having 5 to 20 carbon atoms, and is a compound consisting of carbon and hydrogen without substantially containing oxygen, nitrogen, or halogen. Examples of α-olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decane, 1-dodecane, 4-methyl-1-pentene, and 3,5,5-trimethyl-1-hexene. Examples of cyclic olefins having 5 to 20 carbon atoms include norbornene and cyclopentene. The olefin is preferably a combination of ethylene and an α-olefin other than ethylene or a cyclic olefin, or ethylene alone. When the olefin is ethylene alone, or the mass ratio of the α-olefin monomer component to the ethylene monomer component contained in the olefin is 1 / 7 or less, more preferably 1 / 10 or less, the breaking strength (breaking strength) and breaking elongation (breaking elongation) of the obtained cured product can be increased, and the peel strength with copper foil or copper wiring can be increased, which is preferable. More preferably, the content of α-olefin monomer units other than ethylene contained in the copolymer is 6 mass% or less, most preferably 4 mass% or less, or the olefin is ethylene alone. In this case, the peel strength with copper foil or copper wiring can be further increased, which is more preferable. In the combination of ethylene and an α-olefin other than ethylene, the glass transition temperature of the ethylene-α-olefin-aromatic vinyl compound-aromatic polyene sequence of the finally obtained cured product can be freely adjusted within the range of about -60°C to -5°C depending on the type and content of the α-olefin.

[0022] The aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and examples thereof include styrene, paramethylstyrene, paraisobutylstyrene, various vinylnaphthalenes, and various vinylanthracenes.

[0023] The aromatic polyene monomer is a polyene having 5 to 20 carbon atoms and having multiple vinyl groups and / or vinylene groups in its molecule, preferably a polyene having 8 to 20 carbon atoms. The aromatic polyene monomer is preferably a polyene having 8 to 20 carbon atoms and having multiple vinyl groups in its molecule, more preferably a compound having an aromatic vinyl structure such as ortho-, meta-, or para-various divinylbenzenes or mixtures thereof, divinylnaphthalene, divinylanthracene, p-2-propenylstyrene, or p-3-butenylstyrene, which is substantially free of oxygen, nitrogen, or halogen and is composed of carbon and hydrogen. In addition, a bifunctional aromatic vinyl compound described in JP-A-2004-087639, for example, 1,2-bis(vinylphenyl)ethane (abbreviation: BVPE), can also be used. Among these, preferably, ortho-, meta-, or para-various divinylbenzenes or mixtures thereof are used, and most preferably, a mixture of meta- and para-divinylbenzene is used. In this specification, these divinylbenzenes are referred to as "divinylbenzenes." When divinylbenzenes are used as the aromatic polyene, they are preferred because they have high curing efficiency and are easy to cure when a curing treatment is carried out.

[0024] The above-mentioned olefin, aromatic vinyl compound, and aromatic polyene monomers may contain other polar groups, such as olefins containing oxygen atoms, nitrogen atoms, etc., aromatic vinyl compounds containing oxygen atoms or nitrogen atoms, or aromatic polyenes containing oxygen atoms or nitrogen atoms, etc., but the total mass of these monomers containing polar groups is preferably 10 mass% or less of the total mass of the composition, more preferably 3 mass% or less, and most preferably does not contain any monomers containing polar groups. By making it 10 mass% or less, the low dielectric properties (low dielectric constant / low dielectric loss) of the cured product obtained by curing the composition can be improved.

[0025] The number average molecular weight of the copolymer is 5000 or more, preferably 20,000 to 100,000, and particularly preferably 30,000 to 100,000. When the number average molecular weight is 5000 or more, preferably 20,000 or more, it is possible to easily impart good physical properties such as high strength at break and high elongation at break to the finally obtained cured product, and it is preferable because it is easy to impart toughness. Specifically, it is preferable that the tensile elongation at break (tensile elongation at break) is 30% or more. By making the number average molecular weight 20,000 or more, the composition becomes less sticky in the uncured state, and the effect of improving thermoplasticity is obtained. If the number average molecular weight exceeds 100,000, it may be difficult to mold the composition before curing. The content of aromatic vinyl compound monomer units contained in the copolymer is 10% by mass or more and less than 60% by mass. If the content of aromatic vinyl compound monomer units is 60% by mass or more, the glass transition temperature of the finally obtained cured product of the composition may be near room temperature, and the toughness at low temperatures may decrease. Or, elongation may decrease, which is not preferable. In addition, when the content of aromatic vinyl compound monomer units is 60% by mass or more, the peel strength with copper foil may be lower than that when it is less than 60% by mass. The content of aromatic vinyl compound monomer units contained in the copolymer is particularly preferably 10% by mass or more and 55% by mass or less. When the content of aromatic vinyl compound monomer units is less than 10% by mass, the aromaticity of the copolymer decreases, and compatibility with flame retardants and fillers becomes poor, and the flame retardant may bleed out or the filler may not be filled. In addition, when the content of aromatic vinyl compound monomer units is 10% by mass or more, a cured product of the composition having high peel strength with metal foils (particularly copper foils) and copper wiring can be obtained.

[0026] In the present copolymer, the content of vinyl groups and / or vinylene groups derived from aromatic polyene units (hereinafter, the content may be referred to as the content) is 1.5 or more and less than 20, preferably 3 or more and less than 20, per number average molecular weight of the copolymer. If it is less than 1.5, the crosslinking efficiency is low, and it may be difficult to increase the storage modulus at high temperatures. The content of vinyl groups and / or vinylene groups may be collectively referred to as the "vinyl group content" below. By setting the vinyl group content within the above range, it is preferable to increase the crosslinking efficiency and crosslinking density while maintaining or improving mechanical properties such as breaking strength and breaking elongation at room temperature, and to easily increase the storage modulus at high temperatures. This effect is particularly remarkable when the amount of monomer used is relatively low. The vinyl group content derived from aromatic polyene units (divinylbenzene units) per number average molecular weight in the present copolymer is calculated by the number average molecular weight (Mn) calculated in terms of standard polystyrene obtained by GPC (gel permeation chromatography) method known to those skilled in the art, and 1 It can be obtained by comparing the vinyl group content and vinylene group content derived from aromatic polyene units obtained by H-NMR measurement. For example, 1 By comparing the intensities of the peak areas obtained by H-NMR measurement, if the content of vinyl groups derived from aromatic polyene units in the copolymer is 0.095% by mass, and the number average molecular weight calculated as standard polystyrene by GPC measurement is 68,000, the molecular weight of the vinyl groups derived from aromatic polyene units in the number average molecular weight is the product of these, 64.8, which is divided by the formula weight of the vinyl groups, 27, to obtain 2.4. In other words, the content of vinyl groups derived from aromatic polyene units per number average molecular weight in this copolymer is 2.4. 1 The assignment of peaks obtained by H-NMR measurement is known from the literature. 1 A method for determining the composition of a copolymer from a comparison of peak areas obtained by H-NMR measurement is also known. In this specification, the content of divinylbenzene units in a copolymer is determined based on the peak intensity ( 1The content of divinylbenzene units is calculated from the vinyl group content derived from the divinylbenzene unit, assuming that one vinyl group is derived from one divinylbenzene unit in the copolymer.

[0027] In the present copolymer, examples of the olefin-aromatic vinyl compound-aromatic polyene copolymer include an ethylene-styrene-divinylbenzene copolymer, an ethylene-propylene-styrene-divinylbenzene copolymer, an ethylene-1-hexene-styrene-divinylbenzene copolymer, and an ethylene-1-octene-styrene-divinylbenzene copolymer.

[0028] <Hardening agent> As a curing agent that can be used in the composition of the present invention, for example, in the curable resin, it is possible to use a known curing agent that can be used in the polymerization or curing of conventional aromatic polyenes and aromatic vinyl compounds. Examples of such curing agents include radical polymerization initiators, cationic polymerization initiators, and anionic polymerization initiators, and preferably radical polymerization initiators can be used. Preferred are organic peroxides and azo polymerization initiators, and can be freely selected depending on the application and conditions. A catalog listing examples of organic peroxides can be found on the NOF Corporation website, for example. https: / / www.nof.co.jp / business / chemical / product01a.html https: / / www.nof.co.jp / business / chemical / product01b.html https: / / www.nof.co.jp / business / chemical / product01c.html It can be downloaded from. Examples of organic peroxides are also described in the catalogs of Wako Pure Chemical Industries, Ltd. and Tokyo Chemical Industry Co., Ltd. The curing agent used in the present invention can be obtained from these companies. Also, a known photopolymerization initiator using light, ultraviolet light, or radiation can be used as the curing agent. Examples of curing agents using a photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanionic polymerization initiator. Such photopolymerization initiators can be obtained, for example, from Tokyo Chemical Industry Co., Ltd. Furthermore, curing by radiation or electron beam itself is also possible. It is also possible to perform crosslinking and curing by thermal polymerization of the raw materials contained without containing a curing agent.

[0029] There is no particular limit to the amount of the curing agent used, but generally, 0.01 to 10 parts by mass is preferred per 100 parts by mass of the composition. When using a curing agent such as an organic peroxide or an azo polymerization initiator, the curing process is carried out at an appropriate temperature and time, taking into consideration its half-life. In this case, the conditions are arbitrary according to the curing agent, but generally, a temperature range of about 50°C to 180°C is appropriate.

[0030] <Monomer> The monomer that can be used in the composition of the present invention is 1 to 500 parts by mass, preferably 1 to 200 parts by mass, per 100 parts by mass of the copolymer. When the monomer is 200 parts by mass or less, it is preferable because it is easy to impart toughness to the finally obtained cured product. Specifically, it is preferable because it is possible to make the tensile elongation at break of the cured product 30% or more. In order to make a thermoplastic composition, the less the monomer, the easier it is to handle, and it is preferably 30 parts by mass or less, particularly preferably 10 parts by mass or less, per 100 parts by mass of the copolymer. In addition, it is not necessary to substantially contain a monomer. The monomer that can be suitably used in the composition of the present invention is an aromatic vinyl compound monomer, an aromatic polyene monomer, and / or a polar monomer, and its molecular weight is preferably less than 1000, more preferably less than 500. The monomer that can be suitably used in the composition of the present invention may be any monomer that can be cured by various curing agents, and is preferably a monomer that can be polymerized by a radical polymerization initiator, and the aromatic vinyl compound and aromatic polyene are more preferable. Also, BVPE (1,2-bis(vinylphenyl)ethane) described in JP-A-2003-212941 can be suitably used. From the viewpoint of increasing the mechanical strength (elastic modulus) of the cured product at high temperatures, the aromatic polyene monomer is preferably 1 part by mass or more and 30 parts by mass or less per 100 parts by mass of the copolymer. Also, a relatively small amount of polar monomer can be used for the purpose of imparting adhesion to other materials required as an insulating material or improving crosslink density. Examples of the polar monomer include various maleimides, bismaleimides, maleic anhydride, glycidyl (meth)acrylate, triallyl isocyanurate (TAIC), tri(meth)acryl isocyanurate, trimethylolpropane tri(meth)acrylate, etc. Maleimides and bismaleimides that can be used in the present invention are described in, for example, International Publication WO2016 / 114287 and JP2008-291227A, and can be purchased from, for example, Daiwa Kasei Kogyo Co., Ltd. or Designer Molecules Inc. Of these maleimide group-containing compounds, bismaleimides are preferred from the viewpoints of solubility in organic solvents, high frequency characteristics, high adhesion to conductors, moldability of prepregs, and the like.

[0031] As the bismaleimide, for example, a compound represented by the following formula (d1) can be used.

[0032] Formula (d1) [ka] In the formula, R2 represents a divalent organic group having an aromatic ring.

[0033] Examples of the compound represented by formula (d1) include the compound represented by the following formula (d2).

[0034] Formula (d2) [ka] (In the formula, R3 represents a single bond or methylene, R4 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 0 to 4.)

[0035] An example of the compound represented by formula (d2) is bismaleimide BMI-3000H (m-phenylene bismaleimide) manufactured by Daiwa Chemical Industry Co., Ltd.

[0036] The bismaleimides may be used as polyamino bismaleimide compounds. The polyamino bismaleimide compounds are obtained, for example, by a Michael addition reaction between a compound having two maleimide groups at the terminal and an aromatic diamine compound having two primary amino groups in the molecule. When a small amount of addition is to be used to obtain high crosslinking efficiency, it is preferable to use a polar monomer having a multifunctional group of two or more functional groups, and examples of such a monomer include bismaleimides, triallyl isocyanurate (TAIC), and trimethylolpropane tri(meth)acrylate. The amount of the polar monomer that may be contained in the composition of the present invention is in the range of 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the copolymer. By using 10 parts by mass or less, the dielectric constant and dielectric loss tangent of the obtained cured product are lowered. For example, the dielectric constant is lower than 3.0, and the dielectric loss tangent is lower than 0.005.

[0037] <Additive resin> The composition of the present invention may contain, relative to 100 parts by mass of the copolymer contained therein, one or more resins selected from a hydrocarbon-based elastomer, a polyphenylene ether, and an aromatic polyene-based resin (hereinafter simply referred to as "additive resin"), preferably in a total amount of 1 to 500 parts by mass.

[0038] <Hydrocarbon elastomer> The amount of the hydrocarbon-based elastomer used in the composition of the present invention is preferably 1 to 500 parts by mass, more preferably 1 to 200 parts by mass, based on 100 parts by mass of the copolymer. The hydrocarbon-based elastomer that can be suitably used in the composition of the present invention has a number average molecular weight of 20,000 or more, preferably 30,000 or more, and is a single or multiple elastomers selected from ethylene-based or propylene-based elastomers, conjugated diene-based polymers, aromatic vinyl compound-conjugated diene-based block copolymers or random copolymers, and hydrogenated products thereof. The number average molecular weight of the hydrocarbon-based elastomer is 1,000 or more, more preferably 2,000 or more, even more preferably 20,000 or more, and most preferably 30,000 or more. The number average molecular weight of the hydrocarbon-based elastomer is preferably 80,000 or less, more preferably 60,000 or less. Examples of ethylene-based elastomers include ethylene-α-olefin copolymers such as ethylene-octene copolymer and ethylene-1-hexene copolymer, EPR, and EPDM, and examples of propylene-based elastomers include atactic polypropylene, low stereoregular polypropylene, and propylene-α-olefin copolymers such as propylene-1-butene copolymer.

[0039] Examples of the conjugated diene polymer include polybutadiene and 1,2-polybutadiene. Examples of the aromatic vinyl compound-conjugated diene block or random copolymer and their hydrogenated products (hydrogenated products) include SBS, SIS, SEBS, SEPS, SEEPS, SEEBS, etc. Suitable 1,2-polybutadiene is available, for example, as a product of JSR Corporation, and also available from Nippon Soda Co., Ltd. under the product names of liquid polybutadiene: B-1000, 2000, and 3000. Examples of the copolymer containing a 1,2-polybutadiene structure that can be used suitably include "Ricon 100" from TOTAL CRAY VALLEY. When the resin or resins selected from these hydrocarbon elastomers are liquid (having a viscosity of approximately 300,000 mPa s or less) particularly at room temperature (25°C), from the viewpoints of the handleability and moldability (handleability as a thermoplastic resin) of the composition of the present invention in an uncured state, the amount used is preferably in the range of 1 to 100 parts by mass, more preferably 1 to 30 parts by mass, and particularly preferably 1 to 20 parts by mass per 100 parts by mass of the copolymer.

[0040] <Polyphenylene ether> As the polyphenylene ether, a commercially available known polyphenylene ether can be used. The number average molecular weight of the polyphenylene ether is arbitrary, and considering the moldability of the composition, the number average molecular weight is preferably 10,000 or less, and most preferably 5,000 or less. The number average molecular weight is preferably 500 or more, and most preferably 1,000 or more. In addition, when the composition of the present invention is added for the purpose of curing the composition, it is preferable that the molecular end is modified and / or that one molecule has multiple functional groups. Examples of the functional group include functional groups such as allyl groups, vinyl groups, and epoxy groups, and most preferably, radically polymerizable functional groups, such as vinyl groups, particularly (meth)acrylic groups and aromatic vinyl groups. In other words, in the composition of the present invention, bifunctional polyphenylene ethers in which both ends of the molecular chain are modified with radically polymerizable functional groups are particularly preferred. Examples of such polyphenylene ethers include Noryl (registered trademark) SA9000 manufactured by SABIC, and particularly preferably, bifunctional polyphenylene ether oligomer (OPE-2St) manufactured by Mitsubishi Gas Chemical Company, Inc. can be used. The amount of polyphenylene ether used in the composition of the present invention is preferably 1 to 200 parts by mass, and more preferably 30 to 100 parts by mass, based on 100 parts by mass of the copolymer.

[0041] <Aromatic polyene resin> Aromatic polyene resins include divinylbenzene reactive hyperbranched copolymers (PDV) manufactured by Nippon Steel Chemical & Material Co., Ltd. Such PDVs are described, for example, in the literature "Synthesis of polyfunctional aromatic vinyl copolymers and development of new IPN-type low dielectric loss materials using them" (Kawabe Masanao et al., Journal of the Japan Institute of Electronics Packaging, p. 125, Vol. 12 No. 2 (2009)). Other examples of aromatic polyene resins include aromatic polyene polymer resins having the above-mentioned aromatic polyene monomer as the main constituent unit.

[0042] <Solvent> If necessary, an appropriate solvent may be added to the composition of the present invention. The amount of the solvent used is not particularly limited. The solvent is used to adjust the viscosity and fluidity of the composition. In particular, when the composition of the present invention is in the form of a varnish, the solvent is preferably used. The amount of the varnish used is generally in the range of 50 to 1000 parts by mass per 100 parts by mass of the copolymer. As the solvent, cyclohexane, toluene, ethylbenzene, xylene, tetralin, acetone, limonene, mixed alkanes, mixed aromatic solvents, etc. are preferably used.

[0043] In the case of a thermoplastic composition, the amount of solvent is preferably small, preferably less than 1 part by mass per 100 parts by mass of the copolymer of the present invention, and from the viewpoint of moldability and handling of the composition as a thermoplastic resin before curing, and from the viewpoint of removal during and after curing, it is more preferable that substantially no solvent is used. By substantially no solvent, it is preferable that the amount is 5 parts by mass or less, more preferably 1 part by mass or less, and most preferably 0 part by mass.

[0044] The composition of the present invention may further contain one or more selected from a filler, a flame retardant, and a surface modifier. The composition of the present invention can become a matrix of a cured product, and when cured, contains one or more selected from these fillers, flame retardants, and surface modifiers, so that the cured product easily exhibits impact resistance and toughness even after curing because the composition of the present invention can become a matrix of a cured product and has excellent filling properties for other materials when cured.

[0045] <Filling agent> Also, if necessary, known inorganic or organic fillers can be added. These fillers are added for the purpose of controlling the thermal expansion coefficient, controlling the thermal conductivity, and reducing the cost, and the amount used is arbitrary depending on the purpose. In particular, when adding an inorganic filler, it is preferable to use a known surface modifier, such as a silane coupling agent. In particular, when the objective of the present invention is to obtain a composition excellent in low dielectric constant and low dielectric loss, boron nitride (BN) or silica, especially fused silica, is preferable as the inorganic filler. From the viewpoint of low dielectric properties, since the dielectric constant becomes particularly high when a large amount is added, it is preferable to use less than 500 parts by mass, more preferably less than 400 parts by mass of the filler per 100 parts by mass of the copolymer. Furthermore, in order to improve and enhance the low dielectric properties (low dielectric constant, low dielectric loss tangent), a hollow filler or a filler with a shape with many voids may be added.

[0046] Also, instead of inorganic fillers, organic fillers such as high molecular weight or ultra-high molecular weight polyethylene can be used. From the viewpoint of heat resistance, it is preferable that the organic fillers themselves are crosslinked, and they are preferably used in the form of fine particles or powder. These organic fillers can suppress increases in dielectric constant and dielectric loss tangent. The amount of organic filler used is preferably 10 to 70 volume % and more preferably 30 to 50 volume % in 100 parts by mass of the composition. The amount of filler used is most preferably 1 part by mass or more and less than 400 parts by mass relative to 100 parts by mass of the copolymer.

[0047] On the other hand, by mixing and dispersing a high dielectric constant insulating filler having a dielectric constant of preferably 3 to 10,000, more preferably 5 to 10,000 at 1 GHz in the composition of the present invention, it is possible to produce an insulating cured product having a high dielectric constant insulating layer having a dielectric constant of preferably 3.1 to 20 while suppressing an increase in dielectric loss tangent (dielectric loss). By increasing the dielectric constant of a film made of an insulating cured product, it is possible to miniaturize circuits and increase the capacity of capacitors, which can contribute to miniaturization of high frequency electrical components. A high dielectric constant, low dielectric loss tangent insulating layer is suitable for applications such as capacitors, inductors for resonant circuits, filters, and antennas. Examples of the high dielectric constant insulating filler used in the present invention include inorganic fillers or metal particles that have been subjected to insulation treatment. Specific examples are known high dielectric constant inorganic fillers such as barium titanate and strontium titanate, and other examples are specifically described in, for example, JP-A-2004-087639.

[0048] <Flame retardants> The composition of the present invention may contain a known flame retardant. From the viewpoint of maintaining a low dielectric constant and a low dielectric loss tangent, preferred flame retardants are known organic phosphorus-based flame retardants such as phosphoric acid esters or condensates thereof, known bromine-based flame retardants, and red phosphorus. Among phosphoric acid esters, compounds having multiple xylenyl groups in the molecule are particularly preferred from the viewpoint of flame retardancy and low dielectric loss tangent. In addition to the flame retardant, antimony compounds such as antimony trioxide, antimony tetraoxide, antimony pentoxide, and sodium antimonate, or nitrogen-containing compounds such as melamine, triallyl-1,3,5-triazine-2,3,4-(1H,3H,5H)-trione, and 2,4,6-triaryloxy-1,3,5-triazine may be used as a flame retardant assistant. The total amount of these flame retardants and flame retardant assistants is usually preferably 1 to 100 parts by mass per 100 parts by mass of the composition. In addition, 30 to 200 parts by mass of the polyphenylene ether (PPE) resin having a low dielectric constant and excellent flame retardancy may be used per 100 parts by mass of the flame retardant.

[0049] <Surface modifier> The composition of the present invention may contain various surface modifiers for the purpose of improving adhesion to fillers, copper plates, and wiring. The amount of the surface modifier used is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the composition of the present invention other than the surface modifier. Examples of the surface modifier include various silane coupling agents and titanate coupling agents. The various silane coupling agents and titanate coupling agents may be used singly or in combination.

[0050] In the present invention, the flow temperature of the curable resin or composition can be adjusted according to the purpose and molding method by changing the blending ratio of the copolymer, monomer, additive resin, and if necessary, solvent of the composition within the above range, and further by changing the blending ratio of the flame retardant, filler, and surface modifier. Specifically, the composition of the present invention can be in the form of a product called a "thermoplastic composition" or "varnish." Here, in this specification, thermoplastic preferably means uncured, but also includes the concept of a semi-cured state (such as a B-stage sheet) or a partially cured state.

[0051] The composition of the present invention can be obtained by mixing, dissolving or melting the copolymer and the curing agent as described above, and, if necessary, one or more selected from the group consisting of monomers, solvents, additive resins, fillers, flame retardants and surface modifiers. Any known method can be used for mixing, dissolving or melting.

[0052] <Thermoplastic composition and molded article> The composition of the present invention uses a copolymer having a molecular weight in a certain range or more. When a relatively small amount of monomer is contained, below a certain amount, it mainly contains the copolymer, and therefore it can exhibit the properties of a thermoplastic resin. Therefore, under conditions that do not cause crosslinking, the thermoplastic composition of the present invention can be molded into shapes such as sheets, tubes, strips, pellets, etc. in a substantially uncured state by a known molding method for thermoplastic resins, and then crosslinked (cured). Specifically, the number average molecular weight of the copolymer used in the thermoplastic composition is preferably 20,000 to 100,000, more preferably 30,000 to 100,000. Furthermore, the amount of the monomer that can be used in the thermoplastic composition of the present invention is 10 parts by mass or less per 100 parts by mass of the copolymer. More preferably, 0.3 parts by mass or more per 100 parts by mass of the copolymer is an aromatic polyene monomer such as divinylbenzene or BVPE. Most preferably, an aromatic polyene monomer such as divinylbenzene or BVPE is substantially used as the monomer. Furthermore, it is preferable that the thermoplastic composition or the composition does not substantially contain a solvent. By satisfying all of these conditions, the thermoplastic composition of the present invention can be easily molded as a thermoplastic resin in an uncured state.

[0053] The thermoplastic composition of the present invention is as follows. When the additive resin contains a certain proportion or more of the hydrocarbon-based elastomer (excluding liquid resin) or polyphenylene ether, it is easy to mold the composition as a thermoplastic resin in an uncured state. Specifically, the amount of the hydrocarbon-based elastomer (excluding liquid resin) and / or polyphenylene ether used is preferably in the range of 30 to 200 parts by mass per 100 parts by mass of the copolymer. In this case, the number average molecular weight of the copolymer used is preferably 5,000 or more and 100,000 or less. The above thermoplastic composition can be molded into various shapes such as a sheet in advance by utilizing its thermoplasticity at or below the action temperature of the curing agent, and can be heated and cured to bond after combining a semiconductor element, wiring, or a substrate with a laminate as necessary.

[0054] That is, the thermoplastic composition according to a preferred embodiment of the present invention is as follows. The molded or cured product is made of a thermoplastic composition that contains 10 parts by mass or less of a monomer per 100 parts by mass of an olefin-aromatic vinyl compound-aromatic polyene copolymer that satisfies the following conditions (1) to (4) and is substantially free of a solvent. Hereinafter, the cured product refers to, for example, a cured product of a molded product. (1) The number average molecular weight of the copolymer is 20,000 or more and 100,000 or less. (2) The aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of aromatic vinyl compound monomer units is 10% by mass or more and less than 60% by mass. (3) The aromatic polyene is one or more selected from polyenes having 5 to 20 carbon atoms and having a plurality of vinyl groups and / or vinylene groups in the molecule, and the content of vinyl groups derived from aromatic polyene units is 1.5 or more and less than 20 per number average molecular weight. (4) The olefin is a single or multiple olefins selected from olefins having 2 to 20 carbon atoms, the olefin is ethylene alone, or the mass ratio of α-olefin monomer components other than ethylene to the ethylene monomer component contained in the olefin is 1 / 10 or less, more preferably the content of α-olefin monomer components other than ethylene in the copolymer is 4 mass% or less, and the total of the olefin monomer units, the aromatic vinyl compound monomer units, and the aromatic polyene monomer units is 100 mass%.

[0055] Furthermore, the number average molecular weight of the present copolymer may be preferably 30,000 or more and 100,000 or less. In addition, the composition may contain one or more selected from "curing agent", "additive resin", "filler", "flame retardant", and "surface modifier". Furthermore, the present invention can provide a cured product of the above molded article and the present molded article, in which the molded article is a sheet. The sheet may be uncured (semi-cured) to the extent that it can maintain the sheet shape, or may be completely cured. The degree of curing of the composition can be quantitatively measured by a known dynamic viscoelasticity measurement method (DMA, Dynamic Mechanical Analysis).

[0056] Alternatively, the thermoplastic composition according to another preferred embodiment of the present invention is as follows: The molded article or cured product is made of a thermoplastic composition containing 100 parts by mass of an olefin-aromatic vinyl compound-aromatic polyene copolymer satisfying the following conditions (1) to (4), and further containing 1 to 200 parts by mass in total of one or more resins selected from a hydrocarbon-based elastomer, a polyphenylene ether-based resin, and an aromatic polyene-based resin. (1) The number average molecular weight of the copolymer is 20,000 or more and 100,000 or less. (2) The aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of aromatic vinyl compound monomer units is 10% by mass or more and less than 60% by mass. (3) The aromatic polyene is one or more selected from polyenes having 5 to 20 carbon atoms and having a plurality of vinyl groups and / or vinylene groups in the molecule, and the content of vinyl groups derived from aromatic polyene units is 3 or more and less than 20 per number average molecular weight. (4) The olefin is a single or multiple olefins selected from olefins having 2 to 20 carbon atoms, the olefin is ethylene alone, or the mass ratio of α-olefin monomer components other than ethylene to the ethylene monomer component contained in the olefin is 1 / 10 or less, more preferably the content of α-olefin monomer components other than ethylene in the copolymer is 4 mass% or less, and the total of the olefin monomer units, the aromatic vinyl compound monomer units, and the aromatic polyene monomer units is 100 mass%. Furthermore, the number average molecular weight of the copolymer is preferably 30,000 to 100,000. In addition, the copolymer may contain a single or multiple selected from "curing agent", "monomer", "solvent", "filler", "flame retardant", and "surface modifier". Furthermore, the molded article and the cured product of this molded article are in the form of a sheet.

[0057] The composition of the present invention may be provided as a sheet obtained by molding the composition, which is heated and melted at a temperature below the action temperature or decomposition temperature of the curing agent, by a known method. Molding into a sheet may be performed by extrusion molding using a T-die, a two-roll machine, or extrusion lamination onto a substrate film. In this case, the composition, the mass ratio of copolymer / monomer, or the solvent, additive resin, and flame retardant are selected and adjusted so that the composition melts at the action temperature or decomposition temperature of the curing agent or below and becomes solid at around room temperature. In this case, the sheet is substantially in an uncured state. After that, the sheet is processed through various processing and assembly steps, and finally treated at a temperature and time above the action temperature or decomposition temperature of the curing agent to completely cure. Such a method is a general technique used for ethylene-vinyl acetate resin-based crosslinking sealant sheets for solar cells (photovoltaic power generation devices).

[0058] <Compositions in semi-cured state (B-stage sheets, etc.) and molded products> The composition of the present invention can also be made into a molded product, such as a sheet or tube, in a partially crosslinked state, for example, a state in which a part of the curing agent contained therein is reacted and semi-cured (so-called B-stage state). For example, by adopting a plurality of curing agents and / or curing conditions with different curing temperatures, it is possible to semi-cur it and control the melt viscosity and fluidity to make it into a B-stage state. That is, it is also possible to mold the present curable resin or composition into an easy-to-handle B-stage sheet by the first-stage curing (partial curing), laminate it on an electronic device or substrate, and then perform the second-stage curing (complete curing) to make it into a final shape. In this case, the composition of the composition, i.e., the mass ratio of copolymer / monomer, is selected, and a solvent, an additive resin, and a flame retardant are added if necessary, and the composition containing a curing agent such as peroxide is adjusted to a partially cured sheet shape (B-stage state), and after molding and assembling the device, it can be heated under pressure to completely cure. As a method for partially curing the composition, any known method can be used. For example, peroxides having different decomposition temperatures are used in combination, and one method is to obtain a semi-cured sheet by treating for a predetermined period of time at a temperature at which only one of the peroxides is substantially active, and finally, to completely cure the sheet by treating for a sufficient period of time at a temperature at which all of the curing agents are active.

[0059] <Varnish-like composition and molded body thereof> The composition of the present invention can be made into a viscous liquid varnish depending on its composition and blending ratio. For example, a sufficient amount of solvent can be used to make the composition into a varnish. In particular, when the composition is used as a varnish, it is preferable to add an appropriate solvent to the composition of the present invention. The solvent is used to adjust the viscosity and fluidity of the composition as a varnish. As a solvent, a solvent with a boiling point of a certain level or higher is preferable because a high boiling point under atmospheric pressure, that is, a low volatility, makes the thickness of the applied film uniform. A preferred boiling point is about 130°C or higher and 300°C or lower under atmospheric pressure. Examples of solvents suitable for such varnish include xylene, mesitylene, ethylbenzene, limonene, ethylene glycol methyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol monobutyl ether. The amount of the solvent used is preferably in the range of 10 to 2000 parts by mass per 100 parts by mass of the composition of the present invention.

[0060] The varnish-like composition of the present invention and a molded article thereof contain an olefin-aromatic vinyl compound-aromatic polyene copolymer that satisfies the following conditions (1) to (4). (1) The number average molecular weight of the copolymer is 5,000 or more and 100,000 or less. (2) The aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of aromatic vinyl compound monomer units is 10% by mass or more and less than 60% by mass. (3) The aromatic polyene is one or more selected from polyenes having 5 to 20 carbon atoms and having a plurality of vinyl groups and / or vinylene groups in the molecule, and the content of vinyl groups derived from aromatic polyene units is 1.5 or more, preferably 3 or more and less than 20, per number average molecular weight. (4) The olefin is a single or multiple olefins selected from olefins having 2 to 20 carbon atoms, the olefin is ethylene alone, or the mass ratio of α-olefin monomer components other than ethylene to the ethylene monomer component contained in the olefin is 1 / 10 or less, more preferably the content of α-olefin monomer components other than ethylene in the copolymer is 4 mass% or less, and the total of the olefin monomer units, the aromatic vinyl compound monomer units, and the aromatic polyene monomer units is 100 mass%. The varnish preferably has a low viscosity to facilitate application and impregnation, and therefore the number average molecular weight of the copolymer is more preferably 5,000 or more and 70,000 or less. In addition, one or more selected from the above-mentioned "additive resin", "hardening agent", "monomer", "solvent", "filler", "flame retardant", and "surface modifier" may be included.

[0061] In particular, when used as a varnish using a solvent, the "monomer" used is preferably non-volatile. By being non-volatile compared to the solvent used, for example, it is possible to prevent the monomer from volatilizing together with the solvent in the solvent removal step after application of the varnish. As a monomer suitable for use as a varnish using a solvent, the above-mentioned polar monomers, which are generally non-volatile, are preferred. Particularly preferred examples of the polar monomer include various maleimides and bismaleimides.

[0062] The varnish-like composition of the present invention can also be produced by using a polymerization liquid containing the copolymer of the present invention obtained by polymerization. For example, the polymerization liquid may be concentrated or treated to remove residual monomers, and if necessary, a solvent, other resin components, various additives, etc. may be added to adjust the component concentration or solution viscosity, etc., to produce the composition.

[0063] The varnish can be applied to or impregnated onto a substrate, and the solvent or the like can be removed by drying or the like to produce an uncured or semi-cured molded article. Generally, this molded article has the form of a sheet, film, or tape.

[0064] <Curing> The thermoplastic composition, molded body, semi-cured (B-stage sheet, etc.) composition, molded body, and varnish-like composition and molded body can be cured by a known method with reference to the curing conditions (temperature, time, pressure) of the curing agent contained. When the curing agent used is a peroxide, the curing conditions can be determined with reference to the half-life temperature and the like disclosed for each peroxide.

[0065] <Cured product obtained from the composition> The dielectric constant of the cured product obtained from the copolymer of the present invention is 3.0 or less and 2.0 or more, preferably 2.8 or less and 2.0 or more, particularly preferably 2.5 or less and 2.0 or more, at 10 GHz. The dielectric loss tangent is 0.005 or less and 0.0003 or more, preferably 0.003 or less and 0.0005 or more. These dielectric constants and dielectric loss tangents can be determined by any method known to those skilled in the art, for example, by the resonator method (cavity resonator perturbation method or balanced disk resonator method). The volume resistivity of the resulting cured product is preferably 1×10 15 Ω·cm or more. These values ​​are preferable values ​​for a high-frequency electrical insulating material of, for example, 3 GHz or more. The copolymer used in the composition of the present invention is relatively soft and rich in tensile elongation, so that the cured product obtained from the composition using the copolymer has the characteristics of being relatively soft, having high impact resistance, and being able to follow the thermal expansion of the substrate while exhibiting sufficient mechanical properties. That is, the cured product of the present invention has a tensile modulus measured at room temperature (23°C) of less than 3 GPa, 5 MPa or more, preferably 10 MPa or more, and more preferably 20 MPa or more. In particular, when a relatively large amount of filler is blended, the tensile modulus may be 3 GPa or more and 20 GPa or less. In addition, the tensile strength at break is preferably less than 50 MPa, 10 MPa or more, preferably 15 MPa or more, and the tensile elongation at break (tensile elongation at break) is preferably 30% or more, more preferably 50% or more. In particular, when a relatively large amount of filler is blended, the tensile elongation at break may be less than 30%. The cured product of the composition of the present invention can have sufficient heat resistance for practical use. Specifically, from a practical standpoint, the cured product of the composition of the present invention has a storage modulus at 300°C of 5 × 10 5Pa or more, preferably 1×10 6 Pa or more, most preferably 1.2×10 6 Pa or more. Those skilled in the art can easily prepare a cured product by determining the composition formulation having the above physical property parameters with reference to the information described in this specification and the publicly known documents. The cured product obtained from the composition of the present invention can exhibit practically sufficient heat resistance and mechanical properties at high temperatures even under conditions in which the aromatic polyene as a monomer or monomer component in the composition is suppressed to a certain ratio or less. As described above, suppressing the aromatic polyene as a monomer or monomer component to a certain ratio or less is also important in order to maintain the moldability as a thermoplastic resin even in an uncured state.

[0066] The uncured or semi-cured thermoplastic composition of the present invention can be bonded to a metal foil for wiring (usually copper foil, but also foil of any metal or its alloy that can be used for wiring, such as nickel, aluminum, iron, etc.) by curing with a heat and pressure treatment, without applying an adhesive or performing an adhesive treatment. Specifically, in the olefin-aromatic vinyl compound-aromatic polyene copolymer, a copolymer having an aromatic vinyl compound monomer unit content of 10% by mass or more is used, and the olefin is ethylene alone, or the mass ratio of the α-olefin monomer component other than ethylene to the ethylene monomer component contained in the olefin is 1 / 7 or less, so that a peel strength of 1.0 N / mm or more can be obtained as measured according to Japanese Industrial Standards (JIS) C6481:1996. More preferably, in the copolymer, the olefin is ethylene alone, or the mass ratio of the α-olefin monomer component other than ethylene to the ethylene monomer component contained in the olefin is 1 / 10 or less, more preferably the content of the α-olefin monomer component other than ethylene in the copolymer is 4 mass% or less, the peel strength can be further improved, for example, a peel strength of 1.3 N / mm or more can be provided, which is more preferable. It is generally known that the dielectric properties of laminates such as copper-clad laminate sheets are deteriorated by applying adhesives or adhesive treatments, and it is preferable that the peel strength of 1.0 N / mm or more can be provided without such treatments, as measured according to Japanese Industrial Standards (JIS) C6481:1996. Thus, the uncured or semi-cured thermoplastic composition of the present invention can be bonded to metal foil for wiring by a curing treatment such as a heat and pressure treatment, without applying an adhesive or performing an adhesive treatment. However, in the present invention, with regard to the adhesion to metal foil or other members, other measures for providing adhesion (adhesive application, adhesive treatment, etc.), including the addition of the above-mentioned "surface modifier", are not precluded in any way.

[0067] <Metal foil> The metal foil of the present invention may be any metal foil that can be used for wiring or substrates, and examples thereof include copper foil, aluminum foil, and nickel foil. The thickness is not particularly limited, but is generally in the range of 1 to 500 μm, and preferably 5 to 100 μm. Preferably, a copper foil that is compatible with high frequencies can be used as the metal foil, and may be a rolled copper foil or an electrolytic copper foil. For example, the copper foil may be a copper foil having a surface roughness (maximum height) Rz as defined in JIS B0601:2001 of preferably 5 μm or less, and particularly preferably 3 μm or less. Such copper foils can be obtained from Furukawa Electric Co., Ltd., JX Metals Corporation, Mitsui Mining & Smelting Co., Ltd., and the like.

[0068] <General usage> The composition of the present invention can be used as various insulating materials for wiring, preferably for high-frequency signal wiring, such as coverlays, solder resists, build-up materials, interlayer insulating agents, bonding sheets, interlayer adhesives, and bump sheets for flip-chip bonders.Furthermore, it can be used as an adhesive layer for substrates such as single-layer or multi-layer printed circuit boards, flexible printed circuit boards, CCL (copper clad laminate), and FCCL (flexible copper clad laminate) substrates.

[0069] <Method for producing a laminate containing a copolymer or composition and a metal foil, and a cured product thereof> The method for producing the laminate containing the metal foil and the cured product thereof is not particularly limited, and a known method is used. For example, a thermoplastic composition in an uncured or B-stage state and a metal foil are laminated by a known method, and the laminate is heated and pressed under appropriate conditions to obtain a cured product of the laminate. Alternatively, a varnish-like composition can be applied or coated onto the metal foil, and these can be further laminated as necessary and cured by heating. The laminate may be a laminate containing a resin layer containing an olefin-aromatic vinyl compound-aromatic polyene copolymer and a metal foil adjacent to the resin layer. When a solvent is used in the varnish, the solvent may be removed under appropriate conditions before curing and then cured, or the solvent may be removed by heating after curing, or curing and removal of the solvent may be performed simultaneously. These can be appropriately adjusted by selecting a solvent or monomer with an appropriate vapor pressure and a curing agent with appropriate curing conditions.

[0070] <Applications of the laminate containing the copolymer or composition and the metal foil, and the cured product thereof> The laminate containing the metal foil of the present invention and its cured product are used, for example, in the manufacture of electronic components such as a printed circuit board, a flexible copper-clad laminate obtained by laminating a copper foil to a resin sheet (film), a flexible printed wiring board obtained by forming an electronic circuit on a flexible copper-clad laminate, a flexible printed wiring board with a reinforcement plate obtained by laminating a flexible printed wiring board and a reinforcement plate, a multilayer board obtained by overlapping and bonding a flexible copper-clad laminate and a flexible printed wiring board, and a flexible flat cable (also called FFC) obtained by laminating a copper wiring to a base film. In this specification, the metal foil or copper foil is a concept that includes metal wiring or copper wiring.

[0071] <Uses of uncured or partially cured sheets of the composition> The composition of the present invention has a high adhesive strength with metal foil, and can be used as a coverlay, solder resist, build-up material, interlayer insulating agent, interlayer adhesive, build-up film, bonding sheet, coverlay sheet, bump sheet for flip chip bonder, and potting material. An uncured sheet or a partially cured sheet of the composition of the present invention can be suitably used as a high frequency electrical insulating material. For example, it can be suitably used as a build-up film, bonding sheet, coverlay sheet, bump sheet for flip chip bonder, or an insulating layer or adhesive layer for a substrate. By using the composition as a substitute for epoxy resins or silicone resins that have been used conventionally, a cured insulating layer or a cured matrix phase with a low dielectric constant and low dielectric loss can be formed by performing a curing process. The thickness of the sheet is generally 1 to 300 microns. The sheet may contain or be impregnated with woven or nonwoven fabrics such as glass cloth or ceramic fibers, or may be multilayered with these. In addition, as an antenna cable for a mobile phone or the like, a flexible and bendable wiring that is partially or completely insulated with the sheet can be used instead of a conventional coaxial cable. For example, by using LCP (liquid crystal polymer), PPE sheet, fluorine-based resin, polyimide resin, etc. as a base material and covering wiring with the sheet of the present invention or the B-stage sheet (coverlay sheet) and curing it, it can be insulated or adhered to the base material and used as an insulating material.

[0072] A laminate containing a metal foil in which the cured product obtained by using the composition of the present invention is an insulating layer can be a wiring board with excellent high frequency characteristics with low dielectric loss. In this case, in addition to low dielectric loss, the advantages are heat resistance that can withstand soldering, and a certain degree of softness, elongation, and impact resistance that can withstand stress due to heat cycles or thermal expansion differences. For example, it can be produced by laminating and pressing a core material such as a cloth made of glass or quartz, a nonwoven fabric, a film material, a ceramic substrate, a glass substrate, a general-purpose resin plate such as epoxy, a general-purpose laminate, etc., and a conductor foil with an insulating layer made of this cured product. Also, a slurry or solution containing a curable composition may be applied to the core material, dried, and cured to form an insulating layer. The thickness of the insulating layer is generally 1 to 300 microns. Such a multilayer wiring board can also be used by multilayering and integrating.

[0073] The composition or copolymer of the present invention can also be cured together with an LCP (Liquid Crystal Polymer) layer under relatively mild curing conditions to provide high adhesive strength. The LCP layer may specifically be an LCP sheet or film. Therefore, for example, it can be a laminate containing an LCP sheet, a metal foil, preferably a copper foil, and the composition of the present invention. The number of layers of the laminate and the order of lamination are optional. As an example of the present invention, the composition of the present invention is useful as an adhesive layer between a metal foil (copper foil) and an LCP sheet. The composition of the present invention can exhibit high adhesiveness to both the metal foil and the LCP sheet. Conventionally, the adhesion between an LCP sheet and a copper foil required heating to the melting point of the LCP (approximately 280°C to 330°C or a temperature close thereto) and pressing. However, by using the composition of the present invention as an adhesive layer, it is possible to bond the LCP and the metal foil at a lower temperature, substantially by pressing at a temperature close to the curing temperature of the composition of the present invention. In this case, the low dielectric constant and low dielectric loss tangent value of the cured product of the composition of the present invention impart usefulness to the laminate, particularly as wiring for high-frequency signal transmission. Another example of the laminate of the present invention is a structure in which a metal wiring, preferably a copper wiring, arranged on an LCP layer is covered with a cured layer of the composition of the present invention from the side opposite the LCP layer, for use as a so-called coverlay on an LCP substrate wiring.

[0074] Here, LCP (liquid crystal polymer) refers to a thermoplastic polymer that has a liquid crystal state or optically birefringent properties when melted. Examples of LCP include lyotropic liquid crystal polymers that exhibit liquid crystallinity in a solution state and thermotropic liquid crystal polymers that exhibit liquid crystallinity when melted. Liquid crystal polymers are classified into I type, II type, and III type depending on the heat deformation temperature, and any type may be used. Examples of liquid crystal polymers include thermoplastic aromatic liquid crystal polyesters, and thermoplastic aromatic liquid crystal polyester amides in which amide bonds are introduced therein. The LCP may be a polymer in which an isocyanate-derived bond such as an imide bond, a carbonate bond, a carbodiimide bond, or an isocyanurate bond is further introduced into an aromatic polyester or an aromatic polyester amide. As the LCP, a molten liquid crystal forming polyester consisting of 2-hydroxy-6-naphthoic acid and parahydroxybenzoic acid, for example, LCP resin (product number A-5000, melting point 280°C) manufactured by Ueno Pharmaceutical Co., Ltd. may be used. The melting point of the LCP is preferably 220 to 400°C, more preferably 260 to 380°C, as determined by the DSC method. When the melting point is within the above range, a film or sheet having excellent extrusion moldability and excellent heat resistance can be obtained. Such an LCP can be obtained, for example, from Ueno Pharmaceutical Co., Ltd., Sumitomo Chemical Co., Ltd., and Polyplastics Co., Ltd. Here, the LCP sheet refers to a known LCP sheet, and the thickness thereof is optional. The LCP sheet can be obtained by a known method such as a T-die extrusion method, an inflation method, or an endless belt (double belt press) method. EXAMPLES

[0075] The present invention will be described below with reference to examples, but the present invention should not be construed as being limited to the following examples.

[0076] The copolymers obtained in the Synthesis Examples and Comparative Synthesis Examples were analyzed by the following methods.

[0077] The contents of vinyl group units derived from ethylene, hexene, styrene, and divinylbenzene in the copolymer were 1 determined from the peak area intensities attributed to each by 1H-NMR measurement. The sample was dissolved in 1,1,2,2-tetrachloroethane, and the measurement was carried out at 80 to 130 °C.

[0078] The molecular weight was determined as the number average molecular weight (Mn) in terms of standard polystyrene using GPC (gel permeation chromatography). The measurement was carried out under the following conditions.

[0079] (When the number average molecular weight is 1000 or more) Column: Two TSK-GEL MultiporeHXL-M φ7.8×300 mm (manufactured by Tosoh Corporation) were connected in series and used. Column temperature: 40 °C Solvent: THF Liquid feed flow rate: 1.0 ml / min. Detector: RI detector (differential refractive index detector)

[0080] When the copolymer is difficult to dissolve in the THF solvent, for example, in the case of an ethylene-styrene-divinylbenzene copolymer with a styrene content of less than 40% by mass, the molecular weight in terms of standard polystyrene was determined by the following high-temperature GPC method. The measurement was carried out under the following conditions. Apparatus: HLC-8121GPC / HT manufactured by Tosoh Corporation Column: Three TSKgelGMHHR-H(20)HT, φ7.8×300 mm Column temperature: 140 °C, Detector: RI, Solvent: ortho-dichlorobenzene, Liquid feed flow rate: 1.0 ml / min, Sample concentration: 0.1 wt / vol%, sample injection volume: 100 μL

[0081] <DSC measurement> DSC measurements were performed under a nitrogen stream using a Seiko Electronics DSC6200. That is, 10 mg of resin was used, 10 mg of α-alumina was used as a reference, and an aluminum pan was used, and the temperature was raised from room temperature to 240°C at a heating rate of 10°C / min under a nitrogen atmosphere, and then cooled to -120°C at 20°C / min. DSC measurements were then performed while heating to 240°C at a heating rate of 10°C / min to determine the glass transition temperature. The glass transition temperature here is the extrapolated glass transition onset temperature of JIS K7121:2012, and is the temperature at the intersection of a straight line extending the low-temperature side baseline to the high-temperature side and a tangent drawn at the point where the gradient of the curve of the stepwise change part of the glass transition is maximum.

[0082] <Tensile test> In accordance with JIS K-6251:2017, a film sheet with a thickness of approximately 1 mm was cut into a No. 2 dumbbell 1 / 2 test piece shape and measured using an Orientec Co., Ltd. Tensilon UCT-1T model at 23°C and a tensile speed of 500 mm / min to determine the tensile modulus, tensile strength at break (breaking strength), and tensile elongation at break (breaking elongation).

[0083] <Measurement of storage modulus> A dynamic viscoelasticity measuring device (RSA-III, Rheometrics) was used to measure at a frequency of 1 Hz and at a temperature range of -60°C to +300°C. Measurement samples (3 mm x 40 mm) were cut out from films with thicknesses of approximately 0.1 mm to 0.3 mm and measured to determine the storage modulus. The main measurement parameters involved in the measurement are as follows: Measurement frequency 1Hz Heating rate: 3℃ / min Sample measurement length: 13 mm Test Type = Dynamic Temperature Ramp (DTempRamp) Initial Static Force 5.0g Auto Tension Sensitivity 1.0g Max Auto Tension Rate 0.033mm / s Max Applied Strain 1.5% Min Allowed Force 1.0g Distortion 0.1%

[0084] <Water absorption rate> Measurements were performed in accordance with ASTM D570-98.

[0085] <Dielectric constant and dielectric loss (dielectric tangent)> The dielectric constant and dielectric tangent of the cured composition were measured using a cavity resonator perturbation method (Agilent Technologies 8722ES network analyzer, Kanto Electronics Application Development cavity resonator) at 23°C and 10 GHz using a 1 mm × 1.5 mm × 80 mm sample cut out from a composition sheet.

[0086] <Olefin-aromatic vinyl compound-aromatic polyene copolymer> Copolymers P-1 to P-7 were obtained by appropriately changing the monomer type, monomer amount, ratio, polymerization pressure, and polymerization temperature with reference to the manufacturing methods described in JP 2009-161743 A, JP 2010-280771 A, and International Publication WO00 / 37517. The total of olefin monomer units (ethylene, 1-hexene), aromatic vinyl compound monomer units (styrene), and aromatic polyene monomer units (divinylbenzene) was 100% by mass. Table 1 shows the composition, number average molecular weight, and glass transition temperature of the copolymers.

[0087] The raw materials are as follows: The divinylbenzene used was divinylbenzene (meta-para mixture, divinylbenzene purity 81%) manufactured by Nippon Steel Chemical & Material Co., Ltd. The bifunctional polyphenylene ether oligomer (OPE-2St, number average molecular weight 1200, toluene solution) manufactured by Mitsubishi Gas Chemical Co., Ltd. was further diluted with toluene, a large amount of methanol was added to perform methanol precipitation, and the powdered polyphenylene ether oligomer was obtained by drying in air and drying under reduced pressure. This powder was used when kneading with a Brabender and when preparing a varnish. The SEBS used was H-1041 (number average molecular weight 58000) manufactured by Asahi Kasei Chemicals Co., Ltd. The curing agent used was Percumyl D (dicumyl peroxide), Perbutyl O (t-butylperoxy-2-ethylhexanoate), or Perhexyne 25B (2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3) manufactured by NOF Corporation. As the 1,2-polybutadiene, liquid polybutadiene manufactured by Nippon Soda Co., Ltd., product name B-3000 (number average molecular weight 3200) was used.

[0088] [Table 1]

[0089] [Table 2]

[0090] Example 1 Using a Brabender Plasticorder (PL2000 model manufactured by Brabender), resin P-1 (ethylene-styrene-divinylbenzene copolymer) and monomers that had been kneaded in advance were added and kneaded for 5 minutes at 100°C and a rotation speed of 50 rpm, and then 1 part by mass of a curing agent (dicumyl peroxide, Percumyl D, manufactured by NOF Corp.) was added per 100 parts by mass of the total of resin and monomer (total of raw materials other than the curing agent), and kneaded under conditions of 100°C, a rotation speed of 50 rpm, and 5 minutes to prepare a composition. The obtained curable composition was sandwiched between a mold and two Teflon (registered trademark) sheets, closely adhered and sealed, and pressed by a hot press method (120°C, time 5 minutes, pressure 1.5 MPa) to obtain sheets (uncured sheets) of various thicknesses (thickness 1.0 mm, 0.5 mm, etc.). The obtained sheet together with the Teflon (registered trademark) sheet was sandwiched between glass plates, a load was applied to make them adhere tightly, and the sheet was cured by heat treatment at 120° C. for 30 minutes, 150° C. for 30 minutes, and then 180° C. for 120 minutes. After curing, the glass plates, Teflon (registered trademark) sheet, and mold were removed to obtain a cured sheet of the composition of the present invention.

[0091] Examples 2 to 5 The composition was prepared according to the same procedure as in Example 1, with the composition shown in Table 2 (the composition in the table indicates parts by mass). However, in Examples 3 and 4, the raw materials other than the curing agent were kneaded at 120°C and a rotation speed of 30 rpm for 10 minutes, and then the curing agent was added and kneaded for another 5 minutes under these conditions. In Example 3, Perhexine 25B was used as the curing agent. Uncured sheets were obtained by press molding in the same manner as in Example 1. The properties (room temperature) of the uncured sheets in Examples 1 to 5 were all soft resin-like sheets, which were easy to handle as sheets, and even after peeling them off from the Teflon (registered trademark) sheet after pressing, the self-adhesiveness of the sheet itself was low, and it could be handled as a single sheet. In other words, it was easy to mold and process as a thermoplastic resin in an uncured state. In addition, Examples 3 and 4 were cured by heating at 120°C for 30 minutes, 150°C for 30 minutes, and then 200°C for 120 minutes. In Example 5, 1,2-polybutadiene was added before adding the curing agent.

[0092] Examples 6 to 7, Comparative Examples 1 to 3 In a container equipped with a heating / cooling jacket and stirring blade, the raw materials other than the curing agent were charged in the composition shown in Table 2, heated to 60°C, and stirred to obtain a varnish-like (viscous liquid) composition. The curing agent was then added and stirred to dissolve. Perbutyl O was used as the curing agent. The obtained varnish-like composition was sandwiched between a mold and two Teflon (registered trademark) sheets, tightly adhered and sealed, sandwiched between glass plates, weighted to adhere, and heated in a dryer at 80°C for 12 hours to harden. After hardening, the glass plates, Teflon (registered trademark) sheets, and mold were removed to obtain a hardened sheet of the composition.

[0093] In Comparative Examples 1 and 2, the mass ratio of the α-olefin monomer component other than ethylene to the ethylene monomer component contained in the olefin exceeds 1 / 7. In Comparative Example 3, the content of aromatic vinyl compound monomer units is 60 mass % or more.

[0094] Examples 8 to 10, Comparative Example 4 In a container equipped with a heating / cooling jacket and stirring blade, the raw materials other than the curing agent were charged according to the composition in Table 2, heated to 60°C, and stirred to obtain a varnish-like (viscous liquid) composition. The curing agent was then added and stirred to dissolve. Dicumyl peroxide was used as the curing agent in Examples 8 and 10, and Perhexine 25B was used in Example 9. In Examples 8 and 9, 1,2-polybutadiene was added before the curing agent was added. The obtained varnish-like composition was poured into a Teflon (registered trademark) mold on a Teflon (registered trademark) sheet, and the solvent was removed in a blower dryer at about 100°C for 6 hours. The Teflon (registered trademark) mold was then carefully removed to obtain a soft resin-like sheet. The obtained sheet was further sandwiched between a mold and two Teflon (registered trademark) sheets, tightly adhered, and sealed, and pressed by a hot press method (120°C, time 5 minutes, pressure 1.5MPa) to obtain sheets (uncured sheets) of various thicknesses (thickness 1.0 mm, 0.5 mm, etc.). This sheet was easy to handle, and even when peeled off from the Teflon (registered trademark) sheet, the sheet itself had low self-adhesiveness and could be handled as a single sheet. In other words, it was easy to mold and process as a thermoplastic resin in an uncured state. The obtained sheet was sandwiched between glass plates together with the Teflon (registered trademark) sheet, and a load was applied to make it adhere, and in Examples 8 and 9, it was heated at 120°C for 30 minutes, 150°C for 30 minutes, and then 180°C for 120 minutes to be cured. In Example 10 and Comparative Example 4, it was heated at 120°C for 30 minutes, 150°C for 30 minutes, and then 200°C for 120 minutes to be cured. After curing, the glass plates, Teflon (registered trademark) sheets, and molds were removed to obtain a cured sheet of the composition of the present invention.

[0095] The cured compositions obtained in Examples 1 to 10 were capable of measuring the elastic modulus even at 300°C in a viscoelastic spectrum measurement without melting or breaking, and the storage elastic modulus at 300°C (573K) was 5×10, which satisfies the conditions of the present application. 5 Pa or more, practically 1×10 6Pa or more. All of the films exhibited a tensile modulus of elasticity of less than 3 GPa and 3 MPa or more. Furthermore, all of the films had a tensile strength at break of 5 MPa or more, and all of the films had a tensile elongation at break of 50% or more. The dielectric constant and dielectric tangent also satisfied the range of the present invention. The water absorption of the cured films obtained in Examples 1 to 10 was less than 0.1 mass%. On the other hand, the cured product of the sheet obtained in Comparative Example 1 had an excessively low tensile modulus at room temperature and a low tensile strength at break. The sheet obtained in Comparative Example 2 had a low tensile strength at break.

[0096] <Peel strength from copper foil> The copper foil used was (VSP series, TQ-M7-VSP, thickness 12 μm) manufactured by Mitsui Mining & Smelting Co., Ltd. The peel strength with the copper foil was measured in accordance with Japanese Industrial Standards (JIS) C6481:1996 and evaluated by 90° peeling.

[0097] <Peel strength from roughened surface of copper foil> The copper foil used was manufactured by Mitsui Mining & Smelting Co., Ltd. (VSP series, TQ-M7-VSP, thickness 12 μm, surface roughness 1.1 μm). The uncured sheets (thickness 0.3 to 0.5 mm) obtained in each of the Examples and Comparative Examples (excluding Examples 6 and 7, and Comparative Examples 1 to 3) were placed on the roughened surface of the copper foil, and heated and pressurized using a frame heating press at a pressure of 5 MPa and 120°C for 30 minutes, then 150°C for 30 minutes, and then 180°C for 120 minutes, to obtain laminates in which the sheet and copper foil were bonded and cured.

[0098] The copper foil was placed on the Teflon sheet on the glass plate with the roughened surface facing up, and a Teflon (registered trademark) formwork (thickness 0.3 mm) was placed on top of the copper foil, into which the compositions obtained in Examples 6 and 7 and Comparative Examples 1 to 3 were poured, and the Teflon sheet and glass plate were then placed on top of each other, and the two were pressed together under pressure, and then heated at 120°C for 30 minutes, 150°C for 30 minutes, and then 180°C for 120 minutes to harden the sheets. After hardening, the glass plate, Teflon (registered trademark) sheet, and formwork were removed, and a laminate was obtained in which the sheet and the copper foil were bonded and hardened.

[0099] <Embrittlement temperature (low temperature embrittlement)> The measurements were made according to JIS K 7216:1980. The compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 4 were molded into test pieces B-shaped for embrittlement testing, and cured under the same conditions as the sheets to obtain samples, all of which had embrittlement temperatures of -10°C or lower. The low-temperature brittleness in Table 2 is indicated by ○ (Good). On the other hand, the embrittlement temperatures of the samples obtained in Comparative Examples 3 and 4 were higher than -5°C. The low-temperature brittleness in Table 2 is indicated by × (NG).

[0100] <Olefin-aromatic vinyl compound-aromatic polyene copolymer> Copolymer P-8 was obtained by appropriately changing the monomer amounts, ratios, polymerization pressure, and polymerization temperature with reference to the production methods described in JP-A-2009-161743 and JP-A-2010-280771. The total of the olefin monomer unit (ethylene), the aromatic vinyl compound monomer unit (styrene), and the aromatic polyene monomer unit (divinylbenzene) was 100% by mass. Table 3 shows the composition, number average molecular weight, and glass transition temperature of the copolymer.

[0101] [Table 3]

[0102] Example 11 Using P-8, a varnish was prepared using toluene as the solvent in the composition (parts by mass) shown in Table 4, and a soft resin-like uncured sheet and a cured sheet thereof were prepared in the same manner as in Examples 8 to 10. However, bismaleimide BMI-3000H (m-phenylene bismaleimide) manufactured by Daiwa Kasei Kogyo Co., Ltd. was used as the polar monomer. The measured values ​​evaluated in the same manner as above are shown in Table 4.

[0103] Example 12 Using P-8, a varnish was prepared using toluene as the solvent in the proportions (parts by mass) shown in Table 4, and a soft resin-like uncured sheet and its cured sheet were prepared in the same manner as in Examples 8 to 10. However, fused silica filler SFP-130MC manufactured by Denka Co., Ltd. was used as the raw material. 40% by volume of silica filler was used for 60% by volume of the resin component. The measured values ​​evaluated in the same manner as above are shown in Table 4.

[0104] [Table 4]

[0105] Examples 13 and 14 <Evaluation as an adhesive between copper foil and LCP (liquid crystal polymer) sheet> The varnish obtained in Example 11 and the varnish obtained in Example 12 (however, the varnish before the silica filler was added) were used to evaluate the adhesion between the copper foil and the LCP sheet as follows. The above-mentioned copper foil was used as the copper foil, and the LCP sheet was used as the LCP sheet, which was obtained by the method described in International Publication WO2020 / 153391 using LCP resin (product number A-5000, melting point 280 ° C.) manufactured by Ueno Pharmaceutical Co., Ltd., and a sheet having a thickness of 100 μm was used. The varnish was applied onto the LCP sheet, and the solvent was first removed by air drying at 60 ° C., and then the solvent was carefully and thoroughly removed so as not to cause foaming under normal pressure to vacuum at 60 ° C. The thickness of the varnish layer after removing the solvent was about 50 μm. The roughened surface of the copper foil was adhered to the varnish side of the sheet from which the solvent had been removed, and the sheet was heat-treated at 120 ° C. for 30 minutes, 150 ° C. for 30 minutes, and then 180 ° C. for 120 minutes while applying a pressure of 5 MPa with a vacuum press machine to harden it. The sheet was cut to a width of 10 mm and a length of 100 mm, and the peel strength between the LCP sheet and the copper foil was evaluated by 90° peeling in accordance with Japanese Industrial Standards (JIS) C6481:1996. When the varnish obtained in Example 11 was used, the peel strength was 1.7 N / mm. When the varnish obtained in Example 12 (not including silica filler) was used, the peel strength was 1.3 N / mm. When the peeled surface was observed, peeling occurred at the interface between the varnish-derived cured product and the LCP sheet, and it was concluded that the peel strength between the LCP sheet and the varnish-derived cured product was 1.7 N / mm and 1.3 N / mm, respectively. It was also concluded that the peel strength between the copper foil and the varnish-derived cured product in the same test piece was higher than the above values.

[0106] Comparative Example 5 Using only the copper foil and the LCP sheet, heat and pressure bonding was carried out in a press under the same conditions as in Examples 11 and 12, but the two did not substantially adhere to each other.

[0107] From the above results, the cured product obtained by curing the composition of the present invention has a high elastic modulus under excellent high temperature conditions, exhibits an elastic modulus in a specific range, good breaking strength, and breaking elongation, and exhibits low water absorption and low dielectric properties (low dielectric constant and dielectric dissipation factor). The peel strength with copper foil was also sufficient for practical use. Furthermore, it exhibits a low brittle temperature and high cold resistance. Furthermore, it can exhibit high peel strength with LCP (liquid crystal polymer) sheets under relatively mild conditions. Therefore, it can be suitably used as an electrical insulating material for high frequencies. In particular, the composition of the present invention can be used in an uncured state as a coverlay film, a solder resist film, a build-up film, a bonding sheet, a coverlay sheet, a bump sheet for flip chip bonders, an interlayer insulating agent, and an interlayer adhesive. These can be used by laminating, applying coating, impregnating, etc. with other members and curing them. The composition of the present invention can be cured and used as a printed circuit board, a flexible printed circuit board, and an FCCL (flexible copper clad laminate) substrate. Furthermore, it can be used as an insulating layer for a CCL substrate and a PCB substrate.

Claims

1. A varnish comprising a composition containing an olefin-aromatic vinyl compound-aromatic polyene copolymer and a solvent, which satisfies the following conditions (1) to (4), wherein the composition does not contain a monomer or contains 30 parts by mass or less of a monomer per 100 parts by mass of the olefin-aromatic vinyl compound-aromatic polyene copolymer. (1) The number average molecular weight of the copolymer is 5,000 or more and 100,000 or less. (2) The aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of the aromatic vinyl compound monomer unit is 10% by mass or more and less than 60% by mass. (3) The aromatic polyene is one or more selected from polyenes having 5 to 20 carbon atoms and having a plurality of vinyl groups and / or vinylene groups in the molecule, and the content of the vinyl groups and / or vinylene groups derived from the aromatic polyene units is 3 or more and less than 20 per number average molecular weight. (4) The olefin is a single or multiple olefins selected from olefins having 2 to 20 carbon atoms, the olefin is ethylene alone, or the mass ratio of an α-olefin monomer component other than ethylene to the ethylene monomer component contained in the olefin is 1 / 7 or less, and the total of the olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units is 100 mass%.

2. An uncured molded body comprising the varnish of claim 1.

3. The molded article according to claim 2, which is in the form of a sheet, film or tape.

4. A build-up film, a bonding sheet, a coverlay sheet, a bump sheet for a flip chip bonder, or an insulating layer or adhesive layer for a substrate, comprising the molded article according to claim 3.

5. preparing a polymerization liquid containing a copolymer obtained by polymerization; concentrating or removing residual monomers, and adding solvent to adjust component concentrations and / or solution viscosity; A method for producing the varnish according to claim 1, comprising:

6. An interlayer insulating material, an interlayer adhesive, a build-up film, or a bonding sheet comprising an olefin-aromatic vinyl compound-aromatic polyene copolymer that satisfies the following conditions (1) to (4), and which does not contain a monomer or contains 30 parts by mass or less of a monomer per 100 parts by mass of the olefin-aromatic vinyl compound-aromatic polyene copolymer: (1) The number average molecular weight of the copolymer is 5,000 or more and 100,000 or less. (2) The aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of the aromatic vinyl compound monomer unit is 10% by mass or more and less than 60% by mass. (3) The aromatic polyene is one or more selected from polyenes having 5 to 20 carbon atoms and having a plurality of vinyl groups and / or vinylene groups in the molecule, and the content of the vinyl groups and / or vinylene groups derived from the aromatic polyene units is 3 or more and less than 20 per number average molecular weight. (4) The olefin is a single or multiple olefins selected from olefins having 2 to 20 carbon atoms, the olefin is ethylene alone, or the mass ratio of an α-olefin monomer component other than ethylene to the ethylene monomer component contained in the olefin is 1 / 7 or less, and the total of the olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units is 100 mass%.

7. A coverlay or solder resist comprising an olefin-aromatic vinyl compound-aromatic polyene copolymer satisfying the following conditions (1) to (4), and containing no monomer or containing 30 parts by mass or less of a monomer per 100 parts by mass of the olefin-aromatic vinyl compound-aromatic polyene copolymer: (1) The number average molecular weight of the copolymer is 5,000 or more and 100,000 or less. (2) The aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of the aromatic vinyl compound monomer unit is 10% by mass or more and less than 60% by mass. (3) The aromatic polyene is one or more selected from polyenes having 5 to 20 carbon atoms and having a plurality of vinyl groups and / or vinylene groups in the molecule, and the content of the vinyl groups and / or vinylene groups derived from the aromatic polyene units is 3 or more and less than 20 per number average molecular weight. (4) The olefin is a single or multiple olefins selected from olefins having 2 to 20 carbon atoms, the olefin is ethylene alone, or the mass ratio of an α-olefin monomer component other than ethylene to the ethylene monomer component contained in the olefin is 1 / 7 or less, and the total of the olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units is 100 mass%.

8. A bump sheet for a flip chip bonder, comprising an olefin-aromatic vinyl compound-aromatic polyene copolymer that satisfies the following conditions (1) to (4), and containing no monomer or 30 parts by mass or less of a monomer per 100 parts by mass of the olefin-aromatic vinyl compound-aromatic polyene copolymer: (1) The number average molecular weight of the copolymer is 5,000 or more and 100,000 or less. (2) The aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of the aromatic vinyl compound monomer unit is 10% by mass or more and less than 60% by mass. (3) The aromatic polyene is one or more selected from polyenes having 5 to 20 carbon atoms and having a plurality of vinyl groups and / or vinylene groups in the molecule, and the content of the vinyl groups and / or vinylene groups derived from the aromatic polyene units is 3 or more and less than 20 per number average molecular weight. (4) The olefin is a single or multiple olefins selected from olefins having 2 to 20 carbon atoms, the olefin is ethylene alone, or the mass ratio of an α-olefin monomer component other than ethylene to the ethylene monomer component contained in the olefin is 1 / 7 or less, and the total of the olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units is 100 mass%.

9. A build-up film, a bonding sheet, a coverlay sheet, or an insulating layer or an adhesive layer for a substrate, comprising an uncured sheet or a partially cured sheet containing an olefin-aromatic vinyl compound-aromatic polyene copolymer satisfying the following conditions (1) to (4), and containing no monomer or containing 30 parts by mass or less of a monomer per 100 parts by mass of the olefin-aromatic vinyl compound-aromatic polyene copolymer: (1) The number average molecular weight of the copolymer is 5,000 or more and 100,000 or less. (2) The aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of the aromatic vinyl compound monomer unit is 10% by mass or more and less than 60% by mass. (3) The aromatic polyene is one or more selected from polyenes having 5 to 20 carbon atoms and having a plurality of vinyl groups and / or vinylene groups in the molecule, and the content of the vinyl groups and / or vinylene groups derived from the aromatic polyene units is 3 or more and less than 20 per number average molecular weight. (4) The olefin is a single or multiple olefins selected from olefins having 2 to 20 carbon atoms, the olefin is ethylene alone, or the mass ratio of an α-olefin monomer component other than ethylene to the ethylene monomer component contained in the olefin is 1 / 7 or less, and the total of the olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units is 100 mass%.

10. A bump sheet for a flip chip bonder, comprising an uncured sheet or a partially cured sheet containing an olefin-aromatic vinyl compound-aromatic polyene copolymer that satisfies the following conditions (1) to (4), and containing no monomer or containing 30 parts by mass or less of a monomer per 100 parts by mass of the olefin-aromatic vinyl compound-aromatic polyene copolymer: (1) The number average molecular weight of the copolymer is 5,000 or more and 100,000 or less. (2) The aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of the aromatic vinyl compound monomer unit is 10% by mass or more and less than 60% by mass. (3) The aromatic polyene is one or more selected from polyenes having 5 to 20 carbon atoms and having a plurality of vinyl groups and / or vinylene groups in the molecule, and the content of the vinyl groups and / or vinylene groups derived from the aromatic polyene units is 3 or more and less than 20 per number average molecular weight. (4) The olefin is a single or multiple olefins selected from olefins having 2 to 20 carbon atoms, the olefin is ethylene alone, or the mass ratio of an α-olefin monomer component other than ethylene to the ethylene monomer component contained in the olefin is 1 / 7 or less, and the total of the olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units is 100 mass%.

11. A printed circuit board, a flexible copper-clad laminate, a flexible printed wiring board, a flexible printed wiring board with a reinforcing plate, or a multilayer board obtained by overlapping and bonding a flexible copper-clad laminate and a flexible printed wiring board, the laminate comprising an olefin-aromatic vinyl compound-aromatic polyene copolymer and a metal foil, which satisfies the following conditions (1) to (4), and which does not contain a monomer or contains 30 parts by mass or less of a monomer per 100 parts by mass of the olefin-aromatic vinyl compound-aromatic polyene copolymer, or a cured product thereof. (1) The number average molecular weight of the copolymer is 5,000 or more and 100,000 or less. (2) The aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of the aromatic vinyl compound monomer unit is 10% by mass or more and less than 60% by mass. (3) The aromatic polyene is one or more selected from polyenes having 5 to 20 carbon atoms and having a plurality of vinyl groups and / or vinylene groups in the molecule, and the content of the vinyl groups and / or vinylene groups derived from the aromatic polyene units is 3 or more and less than 20 per number average molecular weight. (4) The olefin is a single or multiple olefins selected from olefins having 2 to 20 carbon atoms, the olefin is ethylene alone, or the mass ratio of an α-olefin monomer component other than ethylene to the ethylene monomer component contained in the olefin is 1 / 7 or less, and the total of the olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units is 100 mass%.

12. A flexible flat cable (FFC) having copper wiring bonded to a base film, the FFC comprising an olefin-aromatic vinyl compound-aromatic polyene copolymer and a metal foil, which satisfy the following conditions (1) to (4), and which contains no monomer or a laminate containing 30 parts by mass or less of a monomer per 100 parts by mass of the olefin-aromatic vinyl compound-aromatic polyene copolymer, or a cured product thereof: (1) The number average molecular weight of the copolymer is 5,000 or more and 100,000 or less. (2) The aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of the aromatic vinyl compound monomer unit is 10% by mass or more and less than 60% by mass. (3) The aromatic polyene is one or more selected from polyenes having 5 to 20 carbon atoms and having a plurality of vinyl groups and / or vinylene groups in the molecule, and the content of the vinyl groups and / or vinylene groups derived from the aromatic polyene units is 3 or more and less than 20 per number average molecular weight. (4) The olefin is a single or multiple olefins selected from olefins having 2 to 20 carbon atoms, the olefin is ethylene alone, or the mass ratio of an α-olefin monomer component other than ethylene to the ethylene monomer component contained in the olefin is 1 / 7 or less, and the total of the olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units is 100 mass%.

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