Composition and cured product thereof

Abstract

The present disclosure provides a method for obtaining a cured body of a resin containing an epoxy compound and an aromatic vinyl group as a functional group, an epoxy resin-based composition having improved low dielectric properties, a cured body thereof, an electrical insulating material, and the like. The present disclosure provides a composition comprising an epoxy compound, a resin having an aromatic vinyl group as a functional group, and an active vinyl compound, a cured body thereof, and an electrical insulating material. The resin having an aromatic vinyl group as a functional group is preferably an olefin-aromatic vinyl compound-aromatic polyene copolymer. The active vinyl compound is preferably one or more compounds selected from the group consisting of maleimide compounds and cyanate ester compounds.

Description

Technical Field

[0001] This invention relates to compositions comprising epoxy compounds, resins having aromatic vinyl groups as functional groups, active vinyl compounds and their cured forms, as well as electrically insulating materials. Background Technology

[0002] With the development of communication frequencies towards the gigahertz band and especially the millimeter-wave band above 30 gigahertz, more stringent requirements have been placed on the low dielectric properties of insulating materials used in multilayer substrates, transmission lines, and antennas formed by CCL and FCCL. Fluoropolymer resins such as perfluoroethylene possess excellent low dielectric constant, low dielectric loss, and excellent heat resistance, but they face challenges in molding and film forming. Furthermore, adhesion to copper foil in wiring remains an issue, making their application in multilayer substrates difficult. On the other hand, substrates and insulating materials using post-cured resins such as epoxy resins, unsaturated polyester resins, polyimide resins, and phenolic resins are widely used due to their heat resistance and ease of handling, but they have relatively high dielectric constants and dielectric losses, which need to be improved for high-frequency insulating materials.

[0003] Therefore, hydrocarbon resins, which inherently possess low dielectric properties, have attracted considerable attention. Previously, to convert hydrocarbon resins, which are thermoplastic resins, into curable resins, it was necessary to introduce functional groups. However, generally speaking, free radicals or functional groups that undergo thermal crosslinking reactions are polar, and therefore, introducing these functional groups into hydrocarbon resins would deteriorate the dielectric properties. When attempting to introduce functional groups composed solely of hydrocarbons, such as aromatic vinyl groups, the use of expensive intermolecular reactions between hydrocarbon monomers is common (Patent Document 1), which is often uneconomical. A cured body has been proposed, obtained using a specific coordination polymerization catalyst, and formed from an ethylene-olefin (aromatic vinyl compound)-aromatic polyene copolymer and a nonpolar vinyl compound copolymer with a specific composition and coordination. In this copolymer, only one of the two aromatic vinyl groups of the aromatic polyene (divinylbenzene) unit is selectively copolymerized while the remaining aromatic vinyl group is retained, thus easily obtaining a crosslinkable hydrocarbon copolymer macromonomer with aromatic vinyl functional groups. The cured body obtained from the composition of this olefin-aromatic vinyl compound-aromatic polyene copolymer and by-products has characteristics such as low dielectric constant and low dielectric loss tangent (Patent Documents 2, 3, 4). Furthermore, a dendritic copolymer with aromatic vinyl groups, obtained by copolymerizing styrene monomers and aromatic polyenes (divinylbenzene) via cationic polymerization, has been proposed (Patent Document 5). However, although these copolymers exhibit excellent low dielectric properties, they do not react with epoxy resins widely used in this insulating material, and therefore have long been considered unsuitable for use as additives in epoxy resins.

[0004] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2004-087639 Patent Document 2: International Publication No. 2021 / 112087 Patent Document 3: International Publication No. 2021 / 112088 Patent Document 4: International Publication No. 2022 / 014599 Patent Document 5: International Publication No. 2018 / 181842 Summary of the Invention

[0005] The problem that the invention aims to solve Methods for obtaining cured articles of resins containing epoxy compounds and aromatic vinyl groups are provided, as well as epoxy resin compositions with improved low dielectric properties and their cured articles, and electrically insulating materials, etc.

[0006] Methods for solving problems In order to solve the above-mentioned problems, the inventors conducted in-depth research and conceived of means to solve these problems, thus completing the present invention. Specifically, it includes a resin composition comprising an epoxy compound, a resin having aromatic vinyl groups as functional groups, and an active vinyl compound; a cured body formed from this resin composition; and an electrically insulating material, etc. The present invention provides various specific embodiments as shown below.

[0007] Method 1. A composition comprising: an epoxy compound; a resin having aromatic vinyl groups as functional groups; and an active vinyl compound.

[0008] Method 2. The composition of Method 1, wherein the aforementioned resin having aromatic vinyl groups as functional groups is an olefin-aromatic vinyl compound-aromatic polyene copolymer.

[0009] Method 3. The composition of method 1 or 2, wherein the aforementioned active vinyl compound is one or more compounds selected from the group consisting of maleimide compounds and cyanate ester compounds.

[0010] Method 4. The composition of any one of methods 1 to 3 further comprises a compound having one or more functional groups selected from the group consisting of amino, phenolic hydroxyl, carboxyl and carboxylic anhydride groups.

[0011] Method 5. The composition of any one of methods 2 to 4, wherein the aforementioned olefin-aromatic vinyl compound-aromatic polyene copolymer satisfies all of the following conditions (1) to (4): (1) The number average molecular weight of the aforementioned copolymer is 500 or more and less than 30,000; (2) The aforementioned aromatic vinyl compound monomers are aromatic vinyl compounds with 8 to 20 carbon atoms, and the content of the aforementioned aromatic vinyl compound monomer units is 0 to 98% by mass. (3) The aforementioned aromatic polyene monomer is selected from one or more polyenes having a number of carbon atoms of 5 to 20 having a plurality of vinyl and / or vinylidene monomers in the molecule, and the content of vinyl and / or vinylidene monomers from the aforementioned aromatic polyene monomer unit is 2 to 30 in terms of number average molecular weight. (4) May contain one or more olefin monomer units selected from those with 2 to 20 carbon atoms. In the presence of the aforementioned aromatic vinyl compound monomer units and the aforementioned aromatic polyene monomer units, the total of the olefin monomer units is converted to 100 by mass in solid form.

[0012] Method 6. A cured body obtained from a composition of any one of methods 1 to 5.

[0013] Method 7. The cured body of method 6 is an electrically insulating material.

[0014] Method 8. CCL substrate, FCCL substrate, interlayer insulating material or cover layer, wherein the cured body comprises a method 6 or 7.

[0015] Invention Effects According to the present invention, epoxy resin compositions and epoxy cured products with excellent low dielectric properties, as well as electrically insulating materials, can be provided. These compositions and cured products are useful as insulating materials for high-frequency applications, particularly for multilayer printed circuit boards. Detailed Implementation

[0016] The embodiments of the present invention will now be described in detail. However, these embodiments are merely examples to illustrate the present invention, and the present invention is not limited thereto. That is, the present invention can be optionally modified and implemented without departing from its spirit.

[0017] The compositions involved in this embodiment are described in further detail below. In this specification, the term "sheet" also encompasses the concept of a film. Furthermore, in this specification, when referred to as a film, the concept of a sheet is also included. In this specification, "composition" refers to the concept of a varnish. That is, the liquid component in the composition is described as a varnish. In this specification, the term "interlayer insulating material" includes the concept of an adhesive sheet or an interlayer adhesive. Epoxy compounds refer to compounds having one or more epoxy groups within their molecules, sometimes also called epoxy prepolymers or simply epoxy resins; their molecular weight is not limited, and they also include polymeric compounds. Additionally, reactive vinyl compounds refer to compounds having one or more reactive vinyl groups within their molecules; their molecular weight is not limited, and they also include polymeric compounds.

[0018] In this specification, unless otherwise specified, the numerical range includes both its lower and upper limits. For example, the expression of a numerical range such as "1 to 100" includes both its lower limit "1" and its upper limit "100". The same applies to the expression of other numerical ranges.

[0019] The resin composition (composition) provided by one embodiment of the present invention is a resin composition comprising an epoxy compound, a resin having aromatic vinyl groups as functional groups, and an active vinyl compound.

[0020] Here, as the epoxy compound, known compounds or polymers having multiple epoxy groups within the molecule that have been conventionally used as insulating materials for substrates can be used. Any epoxy compound (resin) conventionally known can be used as such an epoxy compound. Examples of epoxy compounds include bisphenol A type, bisphenol F type, phenol novolac type, cresol novolac type, biphenyl novolac type, phenol aralkyl type, biphenyl aralkyl type, aliphatic type, various amine types, etc., but are not particularly limited to these. Preferably, a biphenyl aralkyl type epoxy compound having a biphenyl aralkyl skeleton is preferred. For example, the biphenyl aralkyl type epoxy resin described in paragraphs 0007 to 0098 of International Publication No. 2010-061980 is a particularly preferred example, the entire contents of which are incorporated herein by reference.

[0021] Examples of resins having aromatic vinyl (styrene) functional groups include olefin-aromatic vinyl compound-aromatic polyene copolymers and polyether resins with styrene groups (including polyphenylene ether and polyether ketone), but are not particularly limited to these. Such polymers are available from Mitsubishi Gas Chemical Co., Ltd. under the trade name "OPE-2St," and aromatic polyethers (ELPAC HC-F series) from JSR Corporation are also preferred. Furthermore, dendritic copolymers with aromatic vinyl functional groups obtained by cationic polymerization of aromatic vinyl compounds (styrene, ethyl vinylbenzene, etc.) and aromatic polyene compounds (divinylbenzene), as described in International Publication No. 2018 / 181842 (ODV or PDV of NIPPON STEEL Chemical & Material Co. Ltd.), are also preferred. The number average molecular weight of the resin having aromatic vinyl (styrene) functional groups is preferably 500 or more and less than 30,000.

[0022] An active vinyl compound is a compound having one or more active vinyl groups within its molecule. Here, an active vinyl group refers to a vinyl group capable of reacting with aromatic vinyl groups and epoxy groups; specific examples include maleimide groups or cyanate ester groups. Other specific examples of active vinyl compounds include maleimide compounds and cyanate ester compounds. Preferably, the active vinyl compound is not a resin having aromatic vinyl groups as functional groups. As a maleimide compound that can be used in this embodiment, known compounds having one or more maleimide groups within their molecules, or polymeric materials (maleimide resins), which have been conventionally used as insulating materials for substrates, can be used. Such maleimides are described, for example, in International Publication No. 2016 / 114287, Japanese Patent Application Publication No. 2008-291227, and International Publication No. 2020 / 054601. In particular, the maleimide resin described in paragraphs 0009 to 0097 of International Publication No. 2020 / 054601 is preferred, the entire contents of which are incorporated herein by reference. Maleimide compounds and resins can be purchased from, for example, Daiwa Chemical Industries, Nippon Kayaku Co., Ltd., and Designer Molecules Inc. Alternatively, the bismaleimide resin "SLK" manufactured by Shin-Etsu Chemical Co., Ltd. These maleimides are preferably bismaleimides, considering their solubility in organic solvents, high-frequency characteristics, high adhesion to conductors, and moldability of prepreg blanks. These maleimides can also be used as polyamino bismaleimide compounds, considering their solubility in organic solvents, high-frequency characteristics, high adhesion to conductors, and moldability of prepreg blanks. Polyamino bismaleimide compounds can be obtained, for example, by a Michael addition reaction of a compound having two maleimide groups at the ends with an aromatic diamine compound having two primary amino groups in the molecule. Cyanate ester compounds are also described as cyanate ester compounds, as described in, for example, Japanese Patent Application Publication No. 2006-124494, International Publication No. 2011 / 083818, and International Publication No. 2013 / 021869, and are supplied by Mitsubishi Gas Chemical Corporation as BT resins containing cyanate ester compounds.

[0023] <Olefin-Aromatic Vinyl Compound-Aromatic Polyene Copolymer> An olefin-aromatic vinyl compound-aromatic polyene copolymer, which is most preferably used as a resin having aromatic vinyl (styrene) functional groups, is a copolymer obtained by copolymerizing olefins (olefin monomers), aromatic vinyl compounds (aromatic vinyl compound monomers), and aromatic polyenes (aromatic polyene monomers). It should be noted that olefin-aromatic vinyl compound-aromatic polyene copolymers are sometimes simply referred to as "copolymers". In addition, each monomer in the copolymer is sometimes referred to as an olefin monomer unit, an aromatic vinyl compound monomer unit, and an aromatic polyene monomer unit, respectively. The copolymer can be a copolymer that satisfies all of the following conditions (1) to (3), and preferably a copolymer that satisfies all of the following conditions (1) to (4).

[0024] (1) The number average molecular weight of the copolymer is 500 or more and 30,000 or less, preferably 500 or more and less than 30,000. It should be noted that the number average molecular weight (Mn) in this specification is calculated by converting the molecular weight to standard polystyrene by GPC (gel permeation chromatography). More specifically, follow the methods and conditions described in the examples.

[0025] (2) The aromatic vinyl compound monomer is an aromatic vinyl compound with 8 to 20 carbon atoms, and the content of the aromatic vinyl compound monomer unit is 0 to 70 by mass.

[0026] (3) The aromatic polyene monomer is selected from one or more polyenes having a number of carbon atoms of 5 to 20 with multiple vinyl and / or vinylidene monomers in the molecule, and the content of vinyl and / or vinylidene monomers from the aromatic polyene monomer unit is 2 or more and less than 30 in terms of number average molecular weight.

[0027] (4) May contain one or more olefin monomer units selected from those having 2 to 20 carbon atoms, and in the presence of aromatic vinyl compound monomer units and aromatic polyene monomer units, the total of the aforementioned olefin monomer units is 100 by mass.

[0028] In this copolymer, the olefin monomer is selected from one or more α-olefins having 2 to 20 carbon atoms and cyclic olefins having 5 to 20 carbon atoms. The olefin monomer is preferably a compound consisting of carbon and hydrogen that is substantially free of oxygen, nitrogen, and halogens (i.e., formed from carbon and hydrogen by 99% by mass or more, preferably a compound formed solely of carbon and hydrogen). Examples of α-olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, and 3,5,5-trimethyl-1-hexene, but these are not particularly limited. Examples of cyclic olefins having 5 to 20 carbon atoms include norbornene and cyclopentene, but these are not particularly limited. Preferably, a combination of ethylene and α-olefins or cyclic olefins other than ethylene, or ethylene alone, can be used as the olefin monomer.

[0029] Aromatic polyene monomers refer to polyenes having 5 to 20 carbon atoms in their molecules, comprising multiple vinyl groups and / or vinylides. Preferred aromatic polyene monomers include various divinylbenzenes or mixtures thereof in the ortho, meta, and para positions; divinylnaphthalene; divinylanthracene; p-2-propenylstyrene; p-3-butenylstyrene; and other aromatic polyene monomers with aromatic vinyl structures. Aromatic polyene monomers are preferably compounds substantially free of oxygen, nitrogen, and halogens and composed of carbon and hydrogen (i.e., formed from carbon and hydrogen by 99% or more by mass, preferably compounds formed solely of carbon and hydrogen). Additionally, difunctional aromatic vinyl compounds as described in Japanese Patent Application Publication No. 2004-087639, such as 1,2-bis(vinylphenyl)ethane (abbreviated as BVPE), may also be used as aromatic polyene monomers. Among these, various divinylbenzenes or mixtures thereof in the ortho, meta, and para positions are preferred, and mixtures of meta-divinylbenzene and p-divinylbenzene are most preferred. In this specification, these divinylbenzenes are referred to as divinylbenzene-type monomers. When using divinylbenzene as an aromatic polyene, the curing efficiency is high and it is easy to cure.

[0030] The content of aromatic vinyl compound monomer units in this copolymer can be 0% by mass or more and 70% by mass or less, preferably 1% by mass or more and 70% by mass or less, and more preferably 10% by mass or more and 70% by mass or less. When the content of aromatic vinyl compound monomer units is 70% by mass or less, at least one of the glass transition temperatures of the cured composition will be lower than near room temperature, which can improve toughness and elongation under low temperature conditions, and is therefore preferred. When the content of aromatic vinyl compound monomer units is 1% by mass or more, more preferably 10% by mass or more, the following effects are easily obtained: the aromaticity of this copolymer is improved, the compatibility with flame retardants and fillers is improved, the leaching of flame retardants can be avoided, and the filling capacity of fillers can be improved. In addition, when the content of aromatic vinyl compound monomer units is 1% by mass or more, more preferably 10% by mass or more, it is easy to obtain a cured composition with high adhesion strength to copper foil and copper wiring.

[0031] In this copolymer, the content of vinyl and / or vinylidene units from aromatic polyene monomers, preferably the vinyl content, can be 2 to 30 units, more preferably 2 to less than 30 units, and even more preferably 20 units or less than 20 units, based on the number average molecular weight. When the content of vinyl and / or vinylidene units is 2 or more, the crosslinking efficiency is high, and there is a tendency to easily obtain a cured body with sufficient crosslinking density. Regarding the vinyl content from aromatic polyene units (divinylbenzene units) in the copolymer, based on the number average molecular weight, it can be determined, for example, by converting the number average molecular weight (Mn) of standard polystyrene obtained using GPC (gel permeation chromatography) known to those skilled in the art, and using… 1 H-NMR measurements and / or quantitative measurements 13 The composition is obtained by comparing the C-NMR determination with the vinyl content from the aromatic polyene units. Such a method is obvious and known to those skilled in the art. Alternatively, methods described in patent documents in the prior art literature of this specification can also be used.

[0032] In this copolymer, the content of olefin monomer units is preferably 10% by mass or more, more preferably 20% by mass or more. It should be noted that the total of the aforementioned olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units is 100% by mass. When the olefin monomer unit is ethylene and α-olefins other than ethylene, or is ethylene alone, the content of the olefin monomer unit is preferably 10% by mass or more, more preferably 30% by mass or more, and most preferably 50% by mass or more. In this case, the following tendencies are observed: the toughness (elongation) and impact resistance of the final cured body are improved, and cracking during curing and cracking of the cured body during thermal cycling tests are less likely to occur. Furthermore, when the olefin monomer unit is ethylene and cyclic olefins, or is cyclic olefins alone, the content of the cyclic olefin monomer unit is preferably 30% by mass or more, more preferably 50% by mass or more, and most preferably 70% by mass or more. Under such circumstances, the glass transition temperature of the final cured body can be set to 100°C or higher, preferably 150°C or higher, and most preferably 180°C or higher, which tends to easily obtain cured products with excellent heat resistance.

[0033] Examples of olefin-aromatic vinyl compound-aromatic polyene copolymers include ethylene-styrene-divinylbenzene copolymers, ethylene-1-octene-divinylbenzene copolymers, ethylene-norbornene-divinylbenzene copolymers, ethylene-propylene-styrene-divinylbenzene copolymers, ethylene-1-hexene-styrene-divinylbenzene copolymers, ethylene-1-octene-styrene-divinylbenzene copolymers, ethylene-divinylbenzene copolymers, ethylene-norbornene-divinylbenzene copolymers, norbornene-styrene-divinylbenzene copolymers, etc., but are not particularly limited to these.

[0034] In this resin composition, the proportions of the epoxy compound, the active vinyl compound, and the resin having aromatic vinyl groups as functional groups (e.g., olefin-aromatic vinyl compound-aromatic polyene copolymer) are selected according to their composition and structure. Preferably, when the total of these three is 100% by mass, the content of the epoxy compound is 5% to 50% by mass, the active vinyl compound is 30% to 80% by mass, and the content of the resin having aromatic vinyl groups as functional groups (e.g., olefin-aromatic vinyl compound-aromatic polyene copolymer) is 5% to 50% by mass.

[0035] This resin composition preferably includes a curing agent in addition to the components described above. The inclusion of a curing agent enables effective curing. As such a curing agent, known curing agents used in the curing of epoxy compounds are preferred. Specifically, compounds having multiple functional groups such as amino, phenolic hydroxyl, carboxyl, and carboxylic anhydride groups can be exemplified, namely amine-based curing agents, phenolic curing agents, carboxylic acid-based curing agents, and carboxylic anhydride-based curing agents, but are not particularly limited to these. Furthermore, reactive ester-based curing agents and imidazole-based curing agents, which are particularly effective for epoxy compounds, can also be used as curing agents. The amount of such known curing agents used in the curing of epoxy compounds and maleimide compounds is not particularly limited, but is preferably in the range of 5 to 50 parts by weight relative to 100 parts by weight of this resin composition, calculated as an added amount.

[0036] In addition to the curing agents described above, free radical polymerization initiators (free radical generators), cationic polymerization initiators, and anionic polymerization initiators that are useful for curing aromatic vinyl groups can also be used as curing agents for this resin composition. Free radical polymerization initiators are preferred, but their type is not particularly limited. Organic peroxide-based (peroxide) and azo-based polymerization initiators are further preferred, and can be freely selected depending on the application and conditions. A list of organic peroxides can be downloaded from the Nippon Oil Company website, for example, https: / / www.nof.co.jp / product-search / family / 1020001. Furthermore, direct curing using radiation or electron beams is also possible. Additionally, aromatic vinyl groups can be crosslinked and cured by thermal polymerization of the contained raw materials even without the specific use of a curing agent. The amount of curing agent used in the curing of aromatic vinyl groups is not particularly limited; generally, it is preferably 0.01 to 10 parts by weight, relative to 100 parts by weight of the varnish of this embodiment, added as an additive. When using curing agents such as peroxide-based or azo-based polymerization initiators, their half-life should be considered, and curing should be carried out at an appropriate temperature and time. The conditions can be chosen according to the curing agent, but a temperature range of approximately 50°C to 200°C is generally suitable.

[0037] Solvent For the composition of this embodiment, an appropriate solvent may be added as needed. Furthermore, the amount used is not particularly limited. The solvent is used to adjust the viscosity and flowability of the composition. Especially when the resin composition of this embodiment is in the form of a varnish, a solvent is preferred. As a solvent, a high boiling point at atmospheric pressure, i.e., low volatility, results in a more uniform thickness of the coated film; therefore, a solvent with a certain or higher boiling point is preferred. At atmospheric pressure, the boiling point is preferably approximately 75°C or higher, more preferably 100°C or higher and 300°C or lower, and even more preferably 130°C or higher and 300°C or lower. As a solvent, solvents known in the art can be used without particular limitation, such as cyclohexane, cyclohexanone, methyl ethyl ketone (MEK), toluene, ethylbenzene, xylene, mesitylene, tetrahydronaphthalene, acetone, limonene, mixed alkanes, mixed aromatic solvents, etc. The amount of solvent used in the composition of this embodiment can be set appropriately according to the desired performance and is optional. It is preferably 5 to 500 parts by mass relative to 100 parts by mass of the copolymer, more preferably 10 to 300 parts by mass, and most preferably 50 to 150 parts by mass.

[0038] It should be noted that the composition of this embodiment may contain additives commonly used in resins in the art, such as antioxidants, weathering agents, light stabilizers, lubricants, compatibilizers, and antistatic materials, to the extent that the desired effect or purpose is not impaired. The composition and varnish of this embodiment are obtained by mixing and dissolving the aforementioned raw materials and additives, but these mixing and dissolving methods can be any known methods.

[0039] <Molded Body> The shape of the molded article obtained from the composition of this embodiment is optional. These compositions can exhibit the properties of thermoplastic resins. Therefore, without crosslinking, known molding and processing methods for thermoplastic resins, such as extrusion molding, injection molding, compression molding, transfer molding, blow molding, etc., can be used to mold the article into shapes such as chips, sheets, tubes, strips, granules, etc., in a substantially uncured state, and then crosslinking (curing) can be performed.

[0040] In the composition of this embodiment, the shape of the molded body and cured body obtained from the varnish is optional. For example, by coating it onto a substrate, or by laminating it with a copper foil or substrate after impregnating it with a cloth, non-woven fabric, or porous substrate such as glass fiber, and then heating and curing it under pressure, single-layer or multi-layer substrates can be produced. The varnish of this embodiment and the molded body obtained from it can be cured using known methods with reference to the curing conditions (temperature, time, pressure) of the contained raw materials and curing agent. When the curing agent used is a peroxide, the curing conditions can be determined with reference to the half-life temperature, etc., disclosed for each peroxide. Curing can be a single stage or multiple stages. In particular, by setting the curing to multiple stages, it is also possible to have a molded body (prepreg blank) in a semi-cured state in between. In particular, the sheet can be in a semi-cured state to the extent that it can maintain the sheet shape, or it can be fully cured after being laminated with other substrates or copper foils. To achieve a semi-cured state, the following methods can be exemplified: using a combination of various curing agents with different half-life temperatures, adjusting their amounts; appropriately adjusting the curing time and / or curing temperature; or changing the curing mode (e.g., using light curing for semi-curing, or using peroxide for primary curing). Conventional solvent drying processes can also be effectively utilized in such semi-curing processes. Alternatively, when using a press or similar device for heating and pressurizing, multi-stage heating conditions can introduce a semi-cured state midway through the process, suppressing varnish exudation and uneven thickness. The degree of curing of the molded body, especially sheets, can be quantitatively determined using known dynamic viscoelasticity (DMA) measurements and gel fraction.

[0041] <Substrate for impregnation> Examples of substrates used for impregnating the varnish in this embodiment include known fiber substrates such as glass fiber, polyamide fiber, and alumina fiber. The use of various coupling agents to improve affinity with these fibers is also known. Additionally, porous fluoropolymers such as PTFE can also be used.

[0042] <Curved body and molded body obtained from the composition of this embodiment> The cured body obtained from the composition of this embodiment is sufficiently cured, and the gel fraction determined according to ASTM is preferably 90% by mass or more. Furthermore, the dielectric constant of the cured body at 10 GHz is preferably 5.0 or less and 2.0 or more, more preferably 4 or less and 2.0 or more, and most preferably 3.5 or less and 2.0 or more. The dielectric loss tangent is preferably 0.03 or less and 0.001 or more, more preferably 0.01 or less and 0.001 or more. Compared to compositions containing epoxy compounds and reactive vinyl compounds but without resins having aromatic vinyl functional groups, compositions containing epoxy compounds and reactive vinyl compounds with resins having aromatic vinyl functional groups exhibit sufficient crosslinking and lower dielectric constant and lower dielectric loss tangent. Thus, the cured body obtained from the composition of this embodiment is particularly preferred as a high-frequency electrical insulating material, for example, at 3 GHz and above, especially due to its low dielectric loss tangent.

[0043] The cured bodies obtained from the compositions of this embodiment are particularly suitable as electrical insulating materials for high-frequency signals, and these cured bodies can be suitably used in CCL substrates, FCCL substrates, interlayer insulating materials, or capping layers. Furthermore, this embodiment can also provide CCL substrates, FCCL substrates, interlayer insulating materials, or capping layers formed from this copolymer or compositions comprising it. The cured bodies obtained from the compositions of this embodiment are considered particularly useful as insulating materials for encapsulation substrates due to their high crosslinking density.

[0044] Example The present invention will be described below by way of examples, but the present invention is not to be construed as being limited to the following examples.

[0045] The analysis of the olefin-aromatic vinyl compound-aromatic polyene copolymers obtained in the synthetic examples and comparative synthetic examples was carried out by the following methods. The content of vinyl units from ethylene, styrene, and divinylbenzene in the copolymer was determined using... 1 H-NMR and quantitative modes used as needed 13 C-NMR measurements were performed using known methods, based on the peak area intensities attributed to each structure. Samples were dissolved in deuterated-1,1,2,2-tetrachloroethane, and measurements were conducted at 80–130 °C.

[0046] Regarding the molecular weight of the copolymer, the number-average molecular weight (Mn) converted to standard polystyrene was determined using GPC (gel permeation chromatography). The determination was performed under the following conditions.

[0047] Column: 4 TSK-GEL MultiporeHXL-M 7.8×300mm (manufactured by Tosoh) are used in series for connection.

[0048] Column temperature: 40℃ Solvent: THF Liquid delivery flow: 1.0ml / min. Detector: RI detector <Gel fraction> According to ASTM D2765-84, determine the gel fraction as the insoluble component of boiling toluene.

[0049] <Dielectric constant and dielectric loss (dielectric loss tangent)> The dielectric constant and dielectric loss tangent of the cured composition were measured using the cavity resonator perturbation method (Agilent Technologies 8722ES network analyzer, Kanto Electron Application Development cavity resonator) using a 1mm × 1.5mm × 80mm sample cut from the composition sheet at 23°C and 10GHz.

[0050] <Synthesis Example; Copolymer Manufacturing P-1> Referring to the manufacturing methods described in Japanese Patent Application Publication No. 2009-161743, Japanese Patent Application Publication No. 2010-280771, and International Publication No. 2022 / 014599, rac diphenylmethylene (1-indenyl) (cyclopentadienyl) zirconium dichloride (structure shown in formula (1) below) and MMAO (modified methylaluminoxane, manufactured by Tosoh Finechem) were used as catalysts, toluene was used as solvent, and styrene, divinylbenzene, and ethylene were used as raw materials. Polymerization was carried out in a 10L polymerization reactor equipped with a stirrer and a heating and cooling jacket to obtain a polymerization liquid. The obtained polymerization liquid was added to a sufficiently large amount of methanol in small portions, stirred, and decanted to obtain a copolymer. The obtained copolymer was spread thinly in a tray and thoroughly vacuum dried at room temperature to obtain a semi-solid ethylene-styrene-divinylbenzene copolymer, namely P-1. The composition and molecular weight of the obtained P-1 are shown in Table 1.

[0051] [Chemical Formula 1] The divinylbenzene (DVB) used in the polymerization was produced under the trade name “Divinylbenzene (96%)” manufactured by NIPPON STEEL Chemical & Material Co. Ltd. (liquid at room temperature, a mixture of meta and para forms, containing 96% by mass of divinylbenzene, with the balance being ethylvinylbenzene).

[0052] [Table 1] As other raw materials used in the composition, NC-3000-L (Nippon Kayaku Corporation) is used as an epoxy compound, MIR-3000-70MT (Nippon Kayaku Corporation) is used as a maleimide compound, phenyl aralkyl phenolic resin and KAYAHARD GPH-65 (Nippon Kayaku Corporation) are used as curing agent 1, and PERBUTYL P (Nippon Yu Corporation) is used as curing agent 2.

[0053] <Examples 1 and 2> Using a container equipped with a heating and cooling jacket and stirring blades, a mixture of toluene and MEK (methyl ethyl ketone) (50% by mass / 50% by mass) was added as a solvent. P-1 (ethylene-styrene-divinylbenzene copolymer) obtained in the synthesis example, epoxy compound NC-3000-L, maleimide compound MIR-3000-70MT, phenyl aralkyl phenolic resin KAYAHARD GPH-65, and PERBUTYL P were stirred and mixed according to the proportions in Table 2 until dissolved. The resulting composition was poured into a Teflon (registered trademark) molding frame (7cm long, 7cm wide, 0.2mm, 0.5mm, or 3.0mm thick) placed on a PET sheet on a glass plate. After thorough air drying at 25°C, it was further dried in a vacuum dryer at 60°C for at least 3 hours to obtain an uncured sheet. Then, for the uncured sheet, a Teflon sheet and a Teflon mold of optional thickness were placed in a press, pressurized at 5 MPa, heated at 150°C for 30 minutes, and then heated at 200°C for 120 minutes. The Teflon sheet and Teflon mold were then removed to obtain the cured sheet. Test samples were cut from the cured sheets of various thicknesses to determine the gel fraction, dielectric constant, and dielectric loss tangent.

[0054] <Comparative Example 1> The procedure was the same as in Example 1, but P-1 (ethylene-styrene-divinylbenzene copolymer) was not used to prepare the cured sheet, and the measurements were performed in the same manner.

[0055] [Table 2] Table 2 shows the gel fraction, dielectric constant, and dielectric loss tangent of the cured products (cured sheets, cured bodies) obtained in each embodiment and comparative example. The cured sheets obtained in the embodiments show a high gel fraction, indicating thorough curing. Furthermore, they exhibit the low dielectric constant and low dielectric loss tangent values ​​necessary for high-frequency insulation. Additionally, compared to the comparative example that did not use ethylene-styrene-divinylbenzene copolymer, its dielectric constant and dielectric loss tangent values ​​are even lower.

Claims

1. A composition comprising: an epoxy compound; a resin having aromatic vinyl groups as functional groups; and an active vinyl compound.

2. The composition of claim 1, wherein, The resin having aromatic vinyl groups as functional groups is an olefin-aromatic vinyl compound-aromatic polyene copolymer.

3. The composition of claim 1, wherein, The active vinyl compound is a compound selected from one or more of the group consisting of maleimide compounds and cyanate ester compounds.

4. The composition of claim 1, further comprising a compound having one or more functional groups selected from the group consisting of amino, phenolic hydroxyl, carboxyl, and carboxylic anhydride groups.

5. The composition of claim 2, wherein, The olefin-aromatic vinyl compound-aromatic polyene copolymer satisfies all of the following conditions (1) to (4): (1) The number average molecular weight of the copolymer is greater than 500 and less than 30,000; (2) The aromatic vinyl compound monomer is an aromatic vinyl compound with 8 to 20 carbon atoms, and the content of the aromatic vinyl compound monomer unit is 0 to 98% by mass. (3) The aromatic polyene monomer is selected from one or more polyenes having a plurality of vinyl and / or vinylidenes in the molecule with a carbon number of 5 to 20, and the content of vinyl and / or vinylidenes from the aromatic polyene monomer unit is 2 to 30 in terms of number average molecular weight. (4) May contain one or more olefin monomer units selected from those having 2 to 20 carbon atoms, and in the presence of the aromatic vinyl compound monomer unit and the aromatic polyene monomer unit, the total of the olefin monomer units is 100 by mass.

6. A cured body obtained from the composition of claim 1.

7. The cured body as described in claim 6 is an electrically insulating material.

8. A CCL substrate, an FCCL substrate, an interlayer insulating material or a cover layer, comprising the cured body as described in claim 6.

9. A CCL substrate, an FCCL substrate, an interlayer insulating material or a cover layer, comprising the cured body as described in claim 7.

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