Resin composition, resin sheet, layered product, cured product and circuit board material

Abstract

The present invention provides: a cured sheet product and a circuit board material which exhibit low dielectric properties and excellent adhesion to conductors, and which exhibit heat resistance; and a resin composition, a resin sheet, and a layered product which exhibit low dielectric properties, exhibit heat resistance, and can produce the cured sheet product and the circuit board material.　A resin composition according to the present invention contains: at least one type of thermoplastic resin (A) selected from the group consisting of a styrene-based thermoplastic elastomer, an olefin-based thermoplastic elastomer and an ethylene-based polymer; and an aromatic heterocyclic compound (B) having two or more ethylenically unsaturated bonds in the molecule. The content of the thermoplastic resin(s) (A) is more than 50 mass% and less than 99 mass% based on the total mass of solids in the resin composition.

Description

Resin composition, resin sheet, laminate, cured product, and circuit board material

[0001] The present invention relates to a resin composition, a resin sheet, a laminate, a cured product, and a circuit board material. This application claims priority based on Japanese Patent Application No. 2024-49294 filed with the Japan Patent Office on March 26, 2024, and Japanese Patent Application No. 2024-84017 filed with the Japan Patent Office on May 23, 2024, the contents of which are incorporated herein by reference.

[0002] In recent years, as the performance and functionality of electrical and electronic devices have become more sophisticated, communication frequencies have become increasingly higher in order to improve communication speeds and the amount of information transmitted. When digital signals are transmitted through a circuit board, a portion of the transmitted digital signal is converted into heat within the circuit board, resulting in transmission loss. Since the amount of transmission loss is expressed as the product of the dielectric constant and the dielectric loss tangent, achieving low loss during communication requires materials with low dielectric constants and dielectric loss tangents, i.e., components with low dielectric properties. Transmission signals, particularly in the high-frequency range, are more likely to be converted into heat, so materials with even lower dielectric properties are in demand. In addition, as the circuits in electrical and electronic devices become more highly integrated, the amount of heat generated inside them increases, so circuit board materials also need to be heat-resistant.

[0003] As materials having low dielectric properties, for example, thermosetting resins such as polyphenylene ether resin compositions containing an epoxy compound and a cyanate compound (e.g., Patent Document 1), maleimide resins (e.g., Patent Document 2), and thermoplastic resins such as cyclic olefin resin compositions (e.g., Patent Document 3) have been proposed.

[0004] JP 2010-059363 A JP 2012-255059 A International Publication No. 2006 / 095511

[0005] Thermosetting resins generally have higher dielectric constants and dielectric loss tangents than thermoplastic resins. To impart low dielectric properties to thermosetting resins, it is necessary to add large amounts of inorganic particles, etc. However, using large amounts of inorganic particles, etc., not only complicates the manufacturing process, but also makes the sheet brittle and impairs adhesion to conductors such as copper foil. On the other hand, thermoplastic resins exhibit low dielectric properties but lack good heat resistance.

[0006] An object of the present invention is to provide a cured sheet and a circuit board material that have low dielectric properties, excellent conductor adhesion, and heat resistance, as well as a resin composition, a resin sheet, and a laminate that can be used to produce the cured sheet and the circuit board material that have low dielectric properties and heat resistance.

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by using a resin composition containing a thermoplastic resin and a specific compound in a specific ratio.

[0008] Preferred embodiments of the present invention include, but are not limited to, the following. [1] A resin composition comprising: at least one thermoplastic resin (A) selected from the group consisting of a styrene-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, and an ethylene-based polymer; and an aromatic heterocyclic compound (B) having two or more ethylenically unsaturated bonds in the molecule, wherein the content of the thermoplastic resin (A) is more than 50% by mass and less than 99% by mass, based on the total mass of the solid content of the resin composition. [2] The resin composition according to [1], wherein the thermoplastic resin (A) contains a styrene-based thermoplastic elastomer. [3] The resin composition according to [2], wherein the styrene content of the styrene-based thermoplastic elastomer (A) is 10% by mass or more and 70% by mass or less. [4] The resin composition according to any one of [1] to [3], wherein the mass-average molecular weight of the aromatic heterocyclic compound (B) is 1,000 or more and 50,000 or less. [5] The aromatic heterocyclic compound (B) is a compound having a unit represented by the following formula (1) and a terminal group Z represented by the following formula (2): [1] The resin composition according to any one of [1] to [4].

[0009]

[0010] In formula (1), L １ and L ２ are each independently —O— or —S—, and X １ is a divalent organic group, and Y １ is a divalent substituted or unsubstituted nitrogen-containing aromatic heterocycle.

[0011]

[0012] In formula (2), Z represents an alkyl group having 3 to 30 carbon atoms and having an ethylenically unsaturated bond, an aryl group having 6 to 20 carbon atoms and having an ethylenically unsaturated bond, or an aralkyl group having 3 to 30 carbon atoms and having an ethylenically unsaturated bond, and the alkyl group having 3 to 30 carbon atoms, the aryl group having 6 to 20 carbon atoms and having an ethylenically unsaturated bond, and the aralkyl group having 3 to 30 carbon atoms and having an ethylenically unsaturated bond may have a substituent, and when the alkyl group having 3 to 30 carbon atoms, the aryl group having 6 to 20 carbon atoms and having an ethylenically unsaturated bond, or the aralkyl group having 3 to 30 carbon atoms and having an ethylenically unsaturated bond has a substituent, the substituent is a group other than a hydroxy group.

[0013] [6] The X １ [7] The resin composition according to [5], wherein X is a divalent organic group having a substituted or unsubstituted aromatic hydrocarbon ring. １ is a divalent organic group represented by the following formula (3):

[0014]

[0015] In formula (3), R ３ is a single bond, -O-, -S-, -SO ２ represents -, -C(=O)O- or a divalent organic group. ４ and R ５ each independently represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. The linear or branched alkyl group having 1 to 20 carbon atoms, the cycloalkyl group having 5 to 20 carbon atoms, the linear or branched alkenyl group having 1 to 20 carbon atoms, and the aryl group having 6 to 20 carbon atoms may be substituted with a halogen atom or a substituent having an ethylenically unsaturated double bond. m and n each independently represent an integer of 0 to 4. When m and n each are 2 or more, multiple R ４ and R ５may be the same or different from one another and may be bonded in any combination to form part of a ring structure.

[0016] [8] The X １ is a divalent organic group represented by the following formula (4):

[0017]

[0018] In formula (4), R ３ , R ４ and R ５ are R in the formula (3), respectively. ３ , R ４ and R ５ is synonymous with.

[0019] [9] R ３ is a divalent organic group represented by the following formula (5):

[0020]

[0021] In formula (5), R ６ and R ７ R each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen atom, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group. ６ and R ７ may be bonded to each other to form a ring.

[0022]

[10] The X １ The resin composition according to any one of [5] to [9], wherein the divalent organic group represented by the following formula (6) is contained:

[0023]

[0024] In formula (6), R ４represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. The linear or branched alkyl group having 1 to 20 carbon atoms, the cycloalkyl group having 5 to 20 carbon atoms, and the aryl group having 6 to 20 carbon atoms may be substituted with a halogen atom or a substituent having an ethylenically unsaturated double bond. m is an integer of 0 to 4. When m is 2 or more, multiple R ４ may be the same or different and may be bonded in any combination to form part of a ring structure.

[0025]

[11] The divalent organic group represented by the formula (4) is the following formula (7a), the following formula (7b), the following formula (7c), the following formula (7d), the following formula (7e), the following formula (7f), the following formula (7g), the following formula (7h), the following formula (7i), the following formula (7j), the following formula (7k), the following formula (7l), the following formula (7m), the following formula (7n), the following formula (7o), the following formula (7p), the following formula (7q), the following formula (7r), the following formula (7s), the following formula (7t), the following formula (7u), the following formula (7v), the following formula (7w), the following formula (7x), the following formula (7y) the following formula (7z), the following formula (7aa) and the following formula (7ab) A resin composition according to any one of [8] to

[10] , comprising one or more divalent organic groups represented by any one selected from the group consisting of:

[0026]

[0027]

[12] The Y １ is one or more divalent unsubstituted or substituted nitrogen-containing aromatic heterocycles selected from the group consisting of the following formulas (2-1), (2-2), (2-3), and (2-4):

[0028]

[0029] In formula (2-1), R １is a group selected from the group consisting of a hydrogen atom, a fluorine atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a group in which the substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, the substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, or the halogenated alkyl group having 1 to 20 carbon atoms is partially substituted with at least one atom selected from oxygen atoms and sulfur atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms. ２ are each independently a group selected from the group consisting of a hydrogen atom, a fluorine atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms. In formulas (2-2), (2-3), and (2-4), 1 is each independently an integer of 0 to 2. When 1 is 2, multiple R ２ may be the same or different and may be bonded in any combination to form part of a ring structure.

[0030]

[13] The resin composition according to any one of [1] to

[12] , wherein the mass ratio (B / A) of the content of the aromatic heterocyclic compound (B) to the content of the thermoplastic resin (A) is less than 0.8.

[14] The resin composition according to any one of [1] to

[13] , further comprising a cyclic polyolefin resin copolymer (C).

[15] The resin composition according to

[14] , wherein the cyclic polyolefin resin copolymer (C) is a copolymer having an alicyclic structure in a polyolefin side chain.

[16] The resin composition according to

[14] or

[15] , wherein the mass ratio (C / A) of the content of the cyclic polyolefin resin copolymer (C) to the content of the thermoplastic resin (A) is less than 0.8.

[17] A resin sheet comprising the resin composition according to any one of [1] to

[16] .

[18] The resin sheet according to

[17] , wherein the weight loss rate when heated from 35°C to 300°C at a rate of 10°C / min under atmospheric conditions is 12% or less, as measured using a thermogravimetric analyzer.

[19] A laminate comprising the resin sheet according to

[17] or

[18] , and a release film provided on one or both surfaces of the resin sheet.

[20] A cured product of the resin composition according to any one of [1] to

[16] .

[21] The cured product according to

[20] , having a thermal expansion coefficient of 200 ppm / °C or less.

[22] The cured product according to

[20] or

[21] , having a dielectric constant at a frequency of 10 GHz of less than 0.002.

[23] A circuit board material, in which an insulating layer which is a cured product of the resin composition according to any one of [1] to

[16] , and a conductor are laminated together.

[24] A resin sheet comprising: at least one thermoplastic resin (A) selected from the group consisting of a styrene-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, and an ethylene-based polymer; and an aromatic heterocyclic compound (B) having two or more ethylenically unsaturated bonds in the molecule; wherein the resin sheet is heat-pressed at 200°C and 0.2 MPa for 30 minutes to produce a cured product having a dielectric loss tangent of 0.002 or less and a storage modulus (200°C) of 0.01 MPa or more.

[25] A resin sheet comprising: at least one thermoplastic resin (A) selected from the group consisting of a styrene-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, and an ethylene-based polymer; and a resin having a unit represented by the following formula (1): wherein the resin sheet is heat-pressed at 200°C and 0.2 MPa for 30 minutes to obtain a cured product having a dielectric loss tangent of 0.002 or less and a storage modulus (200°C) of 0.01 MPa or more.

[0031]

[0032] In formula (1), L １ and L ２ are each independently —O— or —S—, and X １ is a divalent organic group, and Y １ is a divalent substituted or unsubstituted nitrogen-containing aromatic heterocycle.

[0033]

[26] The Y １ is one or more divalent unsubstituted or substituted nitrogen-containing aromatic heterocycles selected from the group consisting of the following formulas (2-1), (2-2), (2-3), and (2-4): The resin sheet according to

[25] .

[0034]

[0035] In formula (2-1), R １is a group selected from the group consisting of a hydrogen atom, a fluorine atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a group in which the substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, the substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, or the halogenated alkyl group having 1 to 20 carbon atoms is partially substituted with at least one atom selected from oxygen atoms and sulfur atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms. ２ are each independently a group selected from the group consisting of a hydrogen atom, a fluorine atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms. In formulas (2-2), (2-3), and (2-4), 1 is each independently an integer of 0 to 2. When 1 is 2, multiple R ２ may be the same or different and may be bonded in any combination to form part of a ring structure.

[0036] According to the present invention, it is possible to obtain a cured product and a circuit board material that have low dielectric properties, excellent conductor adhesion, and heat resistance, as well as a resin composition, a resin sheet, and a laminate that can be used to produce the cured product and the circuit board material that have low dielectric properties and heat resistance.

[0037] In this specification, the term "film" conceptually encompasses sheets, films, and tapes.

[0038] When the term "substrate" is used, such as a circuit board or a resin board, it encompasses plates, sheets, and films.

[0039] In this specification, when it is stated that "x to y" (x and y are any numbers), it means "x or more and y or less" unless otherwise specified, and also includes the meaning of "preferably greater than x" or "preferably smaller than y." In this specification, when it is stated that "x or more" (x is any number), it means "preferably greater than x" unless otherwise specified, and when it is stated that "y or less" (y is any number), it also means "preferably smaller than y" unless otherwise specified. In this specification, "x and / or y (x and y are any configurations)" means at least one of x and y, and can mean three possibilities: x only, y only, or x and y. For numerical ranges described in stages in this specification, the upper or lower limit of a numerical range in one stage can be arbitrarily combined with the upper or lower limit of a numerical range in another stage. Furthermore, in the numerical ranges described in this specification, the upper or lower limit of the numerical range can also be replaced with the values ​​shown in the examples.

[0040] The following describes in detail an embodiment of the present invention. However, the following description is an example of an embodiment of the present invention, and the present invention is not limited to the following description as long as it does not go beyond the gist of the present invention.

[0041] [Resin Composition] A resin composition according to one embodiment of the present invention (hereinafter also referred to as "the composition") contains at least one thermoplastic resin (A) selected from the group consisting of a styrene-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, and an ethylene-based polymer, and an aromatic heterocyclic compound (B) having two or more ethylenically unsaturated bonds in the molecule. Based on the total mass of the solid content of the resin composition, the content of the thermoplastic resin (A) is more than 50 mass% and less than 99 mass%. Each component will be described below.

[0042] 1. Thermoplastic Resin (A) The thermoplastic resin (A) of the present composition is at least one selected from the group consisting of a styrene-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, and an ethylene-based polymer. The thermoplastic resin (A) may be used alone or in combination of two or more.

[0043] Examples of styrene-based thermoplastic elastomers include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), and hydrogenated versions thereof, such as styrene-ethylene-butadiene-styrene block copolymers (SEBS), styrene-ethylene-propylene-styrene block copolymers (SEPS), and styrene-isobutylene-styrene block copolymers (SIBS).

[0044] The olefin-based thermoplastic elastomer has a polyolefin (excluding cyclic polyolefins, which will be described later) as a hard segment and a rubber component as a soft segment. The olefin-based thermoplastic elastomer may be a mixture (polymer blend) of a polyolefin and a rubber component, a crosslinked product obtained by crosslinking a polyolefin and a rubber component, or a polymer obtained by polymerizing a polyolefin and a rubber component.

[0045] Examples of polyolefins include polypropylene, polyethylene, etc. Examples of rubber components include diene rubbers such as isoprene rubber, butadiene rubber, butyl rubber, propylene-butadiene rubber, acrylonitrile-butadiene rubber, and acrylonitrile-isoprene rubber, ethylene-propylene non-conjugated diene rubber, and ethylene-butadiene copolymer rubber.

[0046] Examples of ethylene-based polymers include homopolymers of ethylene and copolymers of ethylene and other monomers. The copolymer of ethylene and other monomers preferably contains ethylene as the main component. Here, "containing ethylene as the main component" means that the copolymer contains 50 mol % or more, preferably 60 mol % or more, of ethylene structural units. The other monomer copolymerized with ethylene is not particularly limited as long as it is a monomer copolymerizable with ethylene.

[0047] Suitable examples of ethylene polymers include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), polyethylene obtained by polymerization using a metallocene catalyst, etc. Among these, it is particularly preferable to use linear low-density polyethylene (LLDPE) because of its high flexibility.

[0048] Styrene-based thermoplastic elastomers and olefin-based thermoplastic elastomers are preferred because they have excellent flexibility and toughness.

[0049] Among the thermoplastic resins (A) exemplified above, when a combination is selected in which the thermoplastic resin (A) itself is particularly unlikely to react with the aromatic heterocyclic compound (B), the molecular chains of the thermoplastic resin (A) and the aromatic heterocyclic compound (B) form a structure in which they are partially and physically entangled with each other. In this case, the low dielectric properties of the thermoplastic resin (A) are maintained while the crosslink density is increased in a pseudo manner compared to the thermoplastic resin (A) alone. This is thought to result in an improved modulus of elasticity and improved heat resistance.

[0050] From this viewpoint, among the thermoplastic resins (A), styrene-based thermoplastic elastomers are preferred, styrene-isobutylene-styrene-block copolymers (SIBS) and styrene-ethylene-butadiene-styrene block copolymers (SEBS) are more preferred, and styrene-ethylene-butadiene-styrene block copolymers (SEBS) are even more preferred.

[0051] From the above viewpoint, the thermoplastic resin (A) and the aromatic heterocyclic compound (B) are preferably in a combination that does not react with each other. From the viewpoint of preventing the thermoplastic resin (A) from reacting with the aromatic heterocyclic compound (B), it is preferable that the thermoplastic resin (A) does not have a reactive unsaturated bond.

[0052] When a styrene-based thermoplastic elastomer is used as the thermoplastic resin (A), the styrene content is preferably 10% by mass or more, more preferably 15% by mass or more. The styrene content is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and even more preferably 40% by mass or less. When the styrene content is within the above range, the thermoplastic resin (A) has a low dielectric tangent and an appropriate modulus of elasticity, thereby achieving both low dielectric properties and heat resistance, and also exhibiting good handleability.

[0053] The thermoplastic resin (A) may be modified by a known method. Examples of the modified product include a reaction product of the thermoplastic resin (A) with at least one of the above-mentioned unsaturated carboxylic acid and its anhydride. By modifying the thermoplastic resin (A), the polarity of the polymer increases, which is expected to improve adhesion to a metal layer such as a copper foil.

[0054] Examples of unsaturated carboxylic acids and anhydrides thereof include acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acids, and other unsaturated carboxylic acids and their anhydrides. Specific examples of acid anhydrides include maleic anhydride, citraconic anhydride, and nadic anhydrides.

[0055] Examples of nadic acids or anhydrides thereof include endo-cis-bicyclo[2.2.1]hept-2,3-dicarboxylic acid (nadic acid), methyl-endo-cis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (methylnadic acid), and the like, and anhydrides thereof.

[0056] Among these unsaturated carboxylic acids and / or their anhydrides, acrylic acid, maleic acid, nadic acid, maleic anhydride, and nadic acid anhydride are preferred. One type of unsaturated carboxylic acid and / or its anhydride may be used alone, or two or more types may be used in combination.

[0057] The content of the thermoplastic resin (A) in this composition is more than 50% by mass and less than 99% by mass, based on the total mass of the solid content of the resin composition. By having the thermoplastic resin (A) within this range, the effects of low dielectric properties and copper foil adhesion can be achieved. When the content of the thermoplastic resin (A) is more than 50% by mass, based on the total mass of the solid content of the resin composition, a resin composition can be obtained in which the thermoplastic resin (A) and the aromatic heterocyclic ring (B) have good compatibility. The reason for this good compatibility is unclear, but it is thought that the entanglement of the polymers inhibits the free diffusion of the aromatic heterocyclic ring compound (B), suppressing layer separation when they are mixed, making it easier to form a uniform film. From the viewpoints of low dielectric properties, copper foil adhesion, and compatibility, the content of the thermoplastic resin (A) is more preferably more than 50% by mass, even more preferably 55% by mass or more, and particularly preferably 60% by mass or more, based on the total mass of the solid content of the resin composition. On the other hand, the upper limit is more preferably less than 99% by mass, and even more preferably 90% by mass or less. The content of the thermoplastic resin (A) referred to here is the content in the solid content excluding the solvent from the resin composition.

[0058] The storage modulus of the thermoplastic resin (A) at 24°C is preferably 0.1 MPa or more, more preferably 1 MPa or more. The storage modulus is preferably less than 2000 MPa, more preferably less than 1500 MPa, even more preferably less than 1000 MPa, even more preferably less than 500 MPa, even more preferably less than 300 MPa, even more preferably less than 100 MPa, and even more preferably less than 50 MPa. By setting the storage modulus below the upper limit, the flexibility of the resulting cured sheet is improved. By setting the storage modulus to equal to or greater than the lower limit, the heat resistance and handleability of the resulting cured sheet are improved.

[0059] The storage modulus is a value obtained by molding the thermoplastic resin (A) into a sheet having a thickness of about 300 μm to prepare a test piece, and measuring the dynamic viscoelasticity using a viscoelasticity spectrometer. The measurement conditions may be the same as those described in the examples.

[0060] The density of the thermoplastic resin (A) is 0.98 g / cm ３ Preferably, 0.95 g / cm or less ３ More preferably, 0.91 g / cm or less ３ On the other hand, the lower limit of the density is not particularly limited, but is preferably 0.80 g / cm ３ When the density is equal to or less than the above value, the flexibility of the obtained cured sheet is good.

[0061] The density can be measured in accordance with ASTM D792 using a test piece obtained by molding the thermoplastic resin (A) into a sheet having a thickness of about 300 μm.

[0062] The dielectric loss tangent of the thermoplastic resin (A) at 10 GHz is preferably 0.002 or less, more preferably 0.0015 or less, even more preferably 0.0011 or less, and particularly preferably 0.001 or less. On the other hand, there is no particular lower limit, and it is sufficient if it is 0 or more. The smaller the dielectric loss tangent, the smaller the dielectric loss, and therefore, when the composition is used as a circuit board material, the more efficient and faster the transmission of electrical signals can be achieved.

[0063] The dielectric loss tangent is a value obtained by forming the thermoplastic resin (A) into a sheet having a thickness of about 300 μm to prepare a test piece, and measuring the dielectric loss tangent at a temperature of 23° C. and a frequency of 10 GHz in accordance with JIS C2565:1992.

[0064] 2. Aromatic heterocyclic compound (B) The aromatic heterocyclic compound (B) is a compound having an aromatic heterocycle and two or more ethylenically unsaturated bonds in the molecule. The aromatic heterocyclic compound (B) may be used alone or in combination of two or more. The number of ethylenically unsaturated bonds in the aromatic heterocyclic compound (B), i.e., the number of functional groups, may be bifunctional or trifunctional or higher. The aromatic heterocyclic compound (B) having an ethylenically unsaturated double bond improves the crosslinking density, thereby improving heat resistance and curability.

[0065] Specific examples of the aromatic heterocyclic group in the aromatic heterocyclic compound (B) include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. Examples of the aromatic heterocyclic group include a divalent group of a 5- to 6-membered monocyclic ring or a 2- to 4-condensed ring, and a group in which a plurality of these are linked. Among these, structures containing nitrogen are preferred, pyridazine ring, pyrazine ring, pyrimidine ring and triazine ring are more preferred, and pyrimidine ring and triazine ring are even more preferred.

[0066] When a plurality of aromatic heterocycles are linked, they may have the same structure or different structures. When a plurality of aromatic heterocycles are linked, typically, a structure in which 2 to 10 rings are linked is mentioned, and a structure in which 2 to 5 rings are linked is preferred.

[0067] In the aromatic heterocyclic structure, the number of carbon atoms is usually not limited, but is preferably 3 to 60, and the upper limit of the number of carbon atoms is more preferably 48 or less, and even more preferably 30 or less.

[0068] The aromatic heterocyclic group may have a substituent.

[0069] The aromatic heterocyclic compound (B) is preferably a compound having a unit represented by the following formula (1) and a terminal group Z represented by the following formula (2).

[0070]

[0071] In formula (1), L １ and L ２ are each independently —O— or —S—, and X１ is a divalent organic group, and Y １ is a divalent substituted or unsubstituted nitrogen-containing aromatic heterocycle.

[0072]

[0073] In formula (2), Z represents an alkyl group having 3 to 30 carbon atoms and having an ethylenically unsaturated bond, an aryl group having 6 to 20 carbon atoms and having an ethylenically unsaturated bond, or an aralkyl group having 3 to 30 carbon atoms and having an ethylenically unsaturated bond, and the alkyl group having 3 to 30 carbon atoms, the aryl group having 6 to 20 carbon atoms and having an ethylenically unsaturated bond, and the aralkyl group having 3 to 30 carbon atoms and having an ethylenically unsaturated bond may have a substituent. When the alkyl group having 3 to 30 carbon atoms, the aryl group having 6 to 20 carbon atoms and having an ethylenically unsaturated bond, or the aralkyl group having 3 to 30 carbon atoms and having an ethylenically unsaturated bond has a substituent, the substituent is a group other than a hydroxy group.

[0074] In formula (1), L １ and L ２ are divalent linking groups, each independently representing -O- or -S-. Among these, an ether group is preferred in terms of easy availability of raw materials, wide structural expandability of the raw materials, ease of adjusting the heat resistance and solvent solubility of the aromatic heterocyclic compound (B), and a wide variety of resin synthesis methods.

[0075] (X １ In formula (1), X １ is a divalent organic group, and the structure is not particularly limited. １ is preferably a divalent organic group having an aromatic ring or an aliphatic ring.

[0076] Examples of organic groups having a divalent aromatic ring include the following organic group example (X-1), organic group example (X-2), organic group example (X-3), organic group example (X-4), organic group example (X-5), organic group example (X-6), organic group example (X-7), organic group example (X-8), organic group example (X-9), organic group example (X-10), organic group example (X-11), organic group example (X-12), organic group example (X-13), organic group example (X-14), organic group example (X-15), organic group example (X-16), organic group example (X-17), organic group example (X-18), organic group example (X-19), organic group example (X-20), and organic group example (X-21). However, the organic group having a divalent aromatic ring is not limited to these examples.

[0077] Organic group example (X-1):

[0078] Organic group example (X-2):

[0079] Organic group example (X-3):

[0080] Organic group example (X-4):

[0081] Organic group example (X-5):

[0082] Organic group example (X-6):

[0083] Organic group example (X-7):

[0084] Organic group example (X-8):

[0085] Organic group example (X-9):

[0086] Organic group example (X-10):

[0087] Organic group example (X-11):

[0088] Organic group example (X-12):

[0089] Organic group example (X-13):

[0090] Organic group example (X-14):

[0091] Organic group example (X-15):

[0092] Organic group example (X-16):

[0093] Organic group example (X-17):

[0094] Organic group example (X-18):

[0095] Organic group example (X-19):

[0096] Organic group example (X-20):

[0097] Organic group example (X-21):

[0098] Among these, X １ is preferably a structure represented by the following formula (3).

[0099]

[0100] In formula (3), R ３ is a single bond, -O-, -S-, -SO ２ represents -, -C(=O)-, -C(=O)O- or a divalent organic group.

[0101] In formula (3), R ４ and R ５ each independently represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. The linear or branched alkyl group having 1 to 20 carbon atoms, the cycloalkyl group having 5 to 20 carbon atoms, the linear or branched alkenyl group having 1 to 20 carbon atoms, and the aryl group having 6 to 20 carbon atoms may have a substituent.

[0102] In formula (3), m and n each independently represent an integer of 0 to 4. When m and n each represent 2 or more, a plurality of R ４ and R５ may be the same or different from one another and may be bonded in any combination to form part of a ring structure.

[0103] R in formula (3) ４ and R ５Examples of the linear or branched alkyl group having 1 to 20 carbon atoms in the formula (I) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, and an n-icosyl group; Methyl ethyl group, methyl propyl group, methyl butyl group, methyl pentyl group, methyl hexyl group, methyl heptyl group, methyl octyl group, methyl nonyl group, methyl decyl group, methyl undecyl group, methyl dodecyl group, methyl tridecyl group, methyl tetradecyl group, methyl pentadecyl group, methyl hexadecyl group, methyl heptadecyl group, methyl octadecyl group, methyl nonadecyl group; dimethyl ethyl group, dimethyl propyl group, dimethyl butyl group, dimethyl pentyl group, dimethyl hexyl group, dimethyl heptyl group, dimethyl octyl group, dimethyl nonyl group, dimethyl decyl group, dimethyl undecyl group, dimethyl dodecyl group, dimethyl tridecyl group, dimethyl tetradecyl group, dimethyl pentadecyl group, dimethyl hexadecyl group, dimethyl heptadecyl group, dimethyl octadecyl group; trimethylbutyl group, trimethylpentyl group, trimethylhexyl group, trimethylheptyl group, trimethyloctyl group, trimethylnonyl group, trimethyldecyl group, trimethylundecyl group, trimethyldodecyl group, trimethyltridecyl group, trimethyltetradecyl group, trimethylpentadecyl group, trimethylhexadecyl group, trimethylheptadecyl group; ethylpentyl group, ethylhexyl group, ethylheptyl group, ethyloctyl group, ethylnonyl group, ethyldecyl group, ethylundecyl group, ethyldodecyl group, ethyltridecyl group, ethyltetradecyl group, ethylpentadecyl group, ethylhexadecyl group, ethylheptadecyl group, ethyloctadecyl group; propylhexyl group, propylheptyl group, propyloctyl group, propylnonyl group, propyldecyl group, propylundecyl group, propyldodecyl group, propyltridecyl group, propyltetradecyl group, propylpentadecyl group, propylhexadecyl group, propylheptadecyl group;butylhexyl group, butylheptyl group, butyloctyl group, butylnonyl group, butyldecyl group, butylundecyl group, butyldodecyl group, butyltridecyl group, butyltetradecyl group, butylpentadecyl group, and butylhexadecyl group;

[0104] R in the above formula (3) ４ and R ５ Examples of the cycloalkyl group having 5 to 20 carbon atoms in the formula include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a bicyclo[2,2,1]heptyl group, a cyclooctyl group, and an adamantyl group.

[0105] R in the above formula (3) ４ and R ５ In the formula (I), examples of the linear or branched alkenyl group having 1 to 20 carbon atoms include a vinyl group, an allyl group, a propenyl group, a dimethylpropenyl group, a butenyl group, a dimethylbutenyl group, an ethylpentenyl group, a diethylhexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, and a dodecenyl group.

[0106] R ４ and R ５Examples of the aryl group in the formula (I) include a phenyl group, a tolyl group, a 4-methylphenyl group, a 3-methylphenyl group, a 4-ethylphenyl group, a 2-ethylphenyl group, a 2,6-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,3-dimethylphenyl group, a 3,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,4,6-trimethylphenyl group, a 2,3,6-trimethylphenyl group, a 4-butylphenyl group, a 2-tert-butylphenyl group, a 4-tert-butylphenyl group, a 3-tert-butylphenyl group, a 4-sec-butylphenyl group, a 4-isopropylphenyl group, a 2-isopropylphenyl group, a 4-amylphenyl group, a 4-tert-amylphenyl group, a 4-hexylphenyl group, a 4-methoxyphenyl group, a 2-methylphenyl group, a 4 ... Examples thereof include an ethoxyphenyl group, a 3-methoxyphenyl group, a 3,5-dimethoxyphenyl group, a 2,6-dimethoxyphenyl group, a 3,4-dimethoxyphenyl group, a 4-ethoxyphenyl group, a 4-(N,N-dimethylamino)phenyl group, a 4-(N,N-diethylamino)phenyl group, a 2-(N,N-dimethylamino)phenyl group, a 2-(N,N-dimethylamino)phenyl group, a 3-(N,N-dimethylamino)phenyl group, a 3-(N,N-diethylamino)phenyl group, a 4-(methylthio)phenyl group, a benzylphenyl group, a 4-(trifluoromethoxy)phenyl group, a 4-α-cumylphenyl group, a 4-acetylphenyl group, a 4-fluorophenyl group, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-phenoxyphenyl group, and a naphthyl group.

[0107] When the aromatic heterocyclic compound (B) is used, it is easy to exhibit the various properties of the compound, such as heat resistance, low linear thermal expansion coefficient, and low dielectric properties. ４ and R ５ is preferably a methyl group, an allyl group, a phenyl group or a naphthyl group, more preferably a methyl group, an allyl group or a phenyl group.

[0108] Examples of the structure represented by formula (3) include the above-mentioned organic group example (X-3), organic group example (X-4), organic group example (X-5), organic group example (X-6), organic group example (X-7), organic group example (X-8), organic group example (X-9), organic group example (X-10), organic group example (X-11), organic group example (X-12), organic group example (X-13), organic group example (X-14), organic group example (X-15), organic group example (X-16), organic group example (X-17), organic group example (X-18), organic group example (X-19), organic group example (X-20), and organic group example (X-21).

[0109] The structure represented by the formula (3) is preferably a structure represented by the following formula (4) in terms of solubility, processability, etc.

[0110]

[0111] In formula (4), R ３ , R ４ and R ５ are R in the formula (3), respectively. ３ , R ４ and R ５ is synonymous with.

[0112] Examples of the structure represented by formula (4) include the above-mentioned organic group example (X-3), organic group example (X-5), organic group example (X-7), organic group example (X-9), organic group example (X-11), organic group example (X-13), organic group example (X-15), organic group example (X-16), organic group example (X-18), organic group example (X-19), organic group example (X-20), and organic group example (X-21).

[0113] Among these, from the viewpoint of the impact resistance and heat resistance of the aromatic heterocyclic compound (B), R ３ is preferably a structure represented by the following formula (5):

[0114]

[0115] In formula (5), R ６ and R ７ R each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen atom, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group. ６and R ７ may be bonded to each other to form a ring.

[0116] R ３ is a divalent organic group represented by the formula (5), R ６ and R ７ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0117] R ６ and R ７Examples of the unsubstituted alkyl group having 1 to 20 carbon atoms in the above formula include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, and an n-icosyl group; Methyl ethyl group, methyl propyl group, methyl butyl group, methyl pentyl group, methyl hexyl group, methyl heptyl group, methyl octyl group, methyl nonyl group, methyl decyl group, methyl undecyl group, methyl dodecyl group, methyl tridecyl group, methyl tetradecyl group, methyl pentadecyl group, methyl hexadecyl group, methyl heptadecyl group, methyl octadecyl group, methyl nonadecyl group; dimethyl ethyl group, dimethyl propyl group, dimethyl butyl group, dimethyl pentyl group, dimethyl hexyl group, dimethyl heptyl group, dimethyl octyl group, dimethyl nonyl group, dimethyl decyl group, dimethyl undecyl group, dimethyl dodecyl group, dimethyl tridecyl group, dimethyl tetradecyl group, dimethyl pentadecyl group, dimethyl hexadecyl group, dimethyl heptadecyl group, dimethyl octadecyl group; trimethylbutyl group, trimethylpentyl group, trimethylhexyl group, trimethylheptyl group, trimethyloctyl group, trimethylnonyl group, trimethyldecyl group, trimethylundecyl group, trimethyldodecyl group, trimethyltridecyl group, trimethyltetradecyl group, trimethylpentadecyl group, trimethylhexadecyl group, trimethylheptadecyl group; ethylpentyl group, ethylhexyl group, ethylheptyl group, ethyloctyl group, ethylnonyl group, ethyldecyl group, ethylundecyl group, ethyldodecyl group, ethyltridecyl group, ethyltetradecyl group, ethylpentadecyl group, ethylhexadecyl group, ethylheptadecyl group, ethyloctadecyl group; propylhexyl group, propylheptyl group, propyloctyl group, propylnonyl group, propyldecyl group, propylundecyl group, propyldodecyl group, propyltridecyl group, propyltetradecyl group, propylpentadecyl group, propylhexadecyl group, propylheptadecyl group;butylhexyl group, butylheptyl group, butyloctyl group, butylnonyl group, butyldecyl group, butylundecyl group, butyldodecyl group, butyltridecyl group, butyltetradecyl group, butylpentadecyl group, and butylhexadecyl group;

[0118] R ６ and R ７ Examples of the substituted or unsubstituted aryl group in the above formula include a phenyl group, a tolyl group, a 4-methylphenyl group, a 3-methylphenyl group, a 4-ethylphenyl group, a 2-ethylphenyl group, a 2,6-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,3-dimethylphenyl group, a 3,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,4,6-trimethylphenyl group, a 2,3,6-trimethylphenyl group, a 4-butylphenyl group, a 2-tert-butylphenyl group, a 4-tert-butylphenyl group, a 3-tert-butylphenyl group, a 4-sec-butylphenyl group, a 4-isopropylphenyl group, a 2-isopropylphenyl group, a 4-amylphenyl group, a 4-tert-amylphenyl group, a 4-hexylphenyl group, and a 4-methoxyphenyl group. group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 3,5-dimethoxyphenyl group, a 2,6-dimethoxyphenyl group, a 3,4-dimethoxyphenyl group, a 4-ethoxyphenyl group, a 4-(N,N-dimethylamino)phenyl group, a 4-(N,N-diethylamino)phenyl group, a 2-(N,N-dimethylamino)phenyl group, a 2-(N,N-dimethylamino)phenyl group, a 3-(N,N-dimethylamino)phenyl group, a 3-(N,N-diethylamino)phenyl group, a 4-(methylthio)phenyl group, a benzylphenyl group, a 4-(trifluoromethoxy)phenyl group, a 4-α-cumylphenyl group, a 4-acetylphenyl group, a 4-fluorophenyl group, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-phenoxyphenyl group, and a naphthyl group.

[0119] R ６ and R ７When they are bonded to each other to form a ring which may have a substituent, examples of the ring-forming group include a cyclohexylidene group, a 2-methylcyclohexylidene group, a 2-ethylcyclohexylidene group, a 3-methylcyclohexylidene group, a 3-propylcyclohexylidene group, a 4-methylcyclohexylidene group, a 4-butylcyclohexylidene group, a 2,6-dimethylcyclohexylidene group, a 3,5-dimethylcyclohexylidene group, a 3,3,5-trimethylcyclohexylidene group, a 2,6-dimethylcyclohexylidene group, a 3,5-trimethylcyclohexylidene group, a 2,6-dimethylcyclohexylidene group, a 3,5-trimethylcyclohexylidene group, a 2,6-dimethylcyclohexylidene group, a 2,6 ... Examples of such alkyl groups include a cyclohexylidene group, a 3-methyl-5-ethylcyclohexylidene group, a 3,3,5,5-tetramethylcyclohexylidene group, a cyclopentylidene group, a 2-methylcyclopentylidene group, a 3,5-dimethylcyclopentylidene group, a cycloheptylidene group, a cyclooctylidene group, a cyclononylidene group, a cyclodecylidene group, a cycloundecylidene group, a cyclododecylidene group, a fluorenylidene group, and a xanthonylidene group.

[0120] Among these, when used as the aromatic heterocyclic compound (B), the formula (4) is more likely to exhibit various properties such as heat resistance and dielectric properties derived from this compound, and therefore the following formula (7a), the following formula (7b), the following formula (7c), the following formula (7d), the following formula (7e), the following formula (7f), the following formula (7g), the following formula (7h), the following formula (7i), the following formula (7j), the following formula (7k), the following formula (7l), the following formula (7m), the following formula (7n), the following formula (7o), the following formula (7p), the following formula (7q), the following formula (7r), the following formula (7s), the following formula (7t), the following formula (7u), the following formula (7v), the following formula (7w ...i), the following formula (7i), the following formula (7j), the following formula (7k), the following formula (7l), the following formula (7m), the following formula (7n), the following formula (7o), the following formula (7p), the following formula (7q), the following formula (7r), the following formula (7s), the following formula (7t), the following The structures represented by the following formula (7x), the following formula (7y), the following formula (7z), the following formula (7aa), and the following formula (7ab) are more preferred, and in particular, structures into which a methyl group, a trifluoromethyl group, a phenyl group, or the like is introduced, such as formula (7b), formula (7d), formula (7f), formula (7n), formula (7p), formula (7r), and formula (7ab), are more preferred in terms of excellent dielectric properties, formula (7o) and formula (7p) having a fluorene skeleton are more preferred in terms of heat resistance and a low linear thermal expansion coefficient in addition to dielectric properties, and structures into which an alicyclic structure, such as formula (7i) and formula (7n), is introduced are more preferred in terms of excellent heat resistance and solubility.

[0121]

[0122] When methyl groups are introduced, the number of methyl groups introduced is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more, from the viewpoint of obtaining the above-mentioned effects. From the viewpoint of a well-balanced and excellent dielectric properties, heat resistance, low linear thermal expansion coefficient, and solubility, formulas (7d), (7i), and (7p) are particularly preferred. It is also particularly preferred to copolymerize formulas (7b), (7d), and (7f), which have favorable dielectric properties, with any two of formulas (7i), (7n), (7o), and (7p), which have excellent heat resistance, low linear thermal expansion coefficient, and solubility.

[0123] X １ From the viewpoint of reducing the linear thermal expansion coefficient, it is preferable that the structure contains a divalent organic group represented by the following formula (6).

[0124]

[0125] In formula (6), R ４ represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. The linear or branched alkyl group having 1 to 20 carbon atoms, the cycloalkyl group having 5 to 20 carbon atoms, and the aryl group having 6 to 20 carbon atoms may be substituted with a halogen atom or a substituent having an ethylenically unsaturated double bond.

[0126] m is an integer of 0 to 4. When m is 2 or more, a plurality of R ４ may be the same or different and may be bonded in any combination to form part of a ring structure.

[0127] R in formula (6) ４ is R in the formula (3). ４ Specific examples of the structure represented by formula (6) include the above-mentioned example divalent organic group (X-1) containing an aromatic ring.

[0128] Examples of the organic group having a divalent aliphatic ring include groups represented by the following formulas (12a), (12b), (12c), (12d), (12e), (12f), and (12g), and divalent aliphatic groups having a substituted aromatic ring structure, such as those represented by the following formulas (13) and (14).

[0129]

[0130] In formula (13), R １７ , R １８ and R １９ are each independently a direct bond or an alkylene group having 1 to 4 carbon atoms which may have a substituent. ２０ , R ２１ , R ２２ , R ２３ , R ２４ , and R ２５ are each independently a hydrogen atom, an alkyl group of 1 to 10 carbon atoms which may have a substituent, an aryl group of 4 to 10 carbon atoms which may have a substituent, an acyl group of 1 to 10 carbon atoms which may have a substituent, an alkoxy group of 1 to 10 carbon atoms which may have a substituent, an aryloxy group of 4 to 10 carbon atoms which may have a substituent, an acyloxy group of 1 to 10 carbon atoms which may have a substituent, an amino group which may have a substituent, an alkenyl group of 2 to 10 carbon atoms which may have a substituent, an alkynyl group of 2 to 10 carbon atoms which may have a substituent, a sulfur atom which has a substituent, a silicon atom which has a substituent, a halogen atom, a nitro group, or a cyano group. ２０ , R ２１ , R ２２ , R ２３ , R ２４ , and R ２５ At least two adjacent groups among these may be bonded to each other to form a ring.

[0131] In formula (14), R ２６ , R ２７ , R ２８ , and R ２９ represents a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. ３０ , R ３１ , R ３２ , R ３３ , R ３４ , R ３５ , R ３６ , R ３７each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. m and n each independently represent an integer of 0 to 5.

[0132] The divalent organic groups described above may be used singly or in any combination and ratio of two or more. Using a combination of two or more divalent organic groups is preferred in that it facilitates adjustment of various physical properties such as dielectric properties, solubility, linear thermal expansion coefficient, and glass transition temperature.

[0133] (Y １ ) In formula (1), Y １ is a divalent unsubstituted or substituted nitrogen-containing aromatic heterocycle, and examples of the nitrogen-containing aromatic heterocycle include the nitrogen-containing ring structures in the aromatic heterocyclic groups described above. Among these, one or more divalent unsubstituted or substituted nitrogen-containing aromatic heterocycles selected from the group consisting of the following formulae (2-1), (2-2), (2-3), and (2-4) are preferred.

[0134]

[0135] In formula (2-1), R １ is a group selected from the group consisting of a hydrogen atom, a fluorine atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, the substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, the substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, or the halogenated hydrocarbon group, which is partially substituted with at least one atom selected from oxygen atoms and sulfur atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms.

[0136] In formula (2-2), formula (2-3) and formula (2-4), R ２are each independently a group selected from the group consisting of a hydrogen atom, a fluorine atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms. In formulas (2-2), (2-3), and (2-4), 1 is each independently an integer of 0 to 2. When 1 is 2, multiple R ２ may be the same or different and may be bonded in any combination to form part of a ring structure.

[0137] Substituent R in the nitrogen-containing aromatic heterocycle represented by formula (2-1) １ is a group selected from the group consisting of a hydrogen atom, a fluorine atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, the substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, the substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, or the halogenated hydrocarbon group, which is partially substituted with at least one atom selected from oxygen atoms and sulfur atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms.

[0138] The above-mentioned R １ Examples of the substituent in each functional group include alkyl groups such as methyl, ethyl, propyl, butyl, and pentyl groups, aryl groups such as phenyl, tolyl, and naphthyl groups, aralkyl groups such as benzyl groups, alkoxy groups such as methoxy groups, amino groups such as diethylamino groups, and halogen atoms such as F, Cl, and Br.

[0139] R １Examples of the substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms in the above formula include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, and an n-icosyl group; Methyl ethyl group, methyl propyl group, methyl butyl group, methyl pentyl group, methyl hexyl group, methyl heptyl group, methyl octyl group, methyl nonyl group, methyl decyl group, methyl undecyl group, methyl dodecyl group, methyl tridecyl group, methyl tetradecyl group, methyl pentadecyl group, methyl hexadecyl group, methyl heptadecyl group, methyl octadecyl group, methyl nonadecyl group; dimethyl ethyl group, dimethyl propyl group, dimethyl butyl group, dimethyl pentyl group, dimethyl hexyl group, dimethyl heptyl group, dimethyl octyl group, dimethyl nonyl group, dimethyl decyl group, dimethyl undecyl group, dimethyl dodecyl group, dimethyl tridecyl group, dimethyl tetradecyl group, dimethyl pentadecyl group, dimethyl hexadecyl group, dimethyl heptadecyl group, dimethyl octadecyl group; trimethylbutyl group, trimethylpentyl group, trimethylhexyl group, trimethylheptyl group, trimethyloctyl group, trimethylnonyl group, trimethyldecyl group, trimethylundecyl group, trimethyldodecyl group, trimethyltridecyl group, trimethyltetradecyl group, trimethylpentadecyl group, trimethylhexadecyl group, trimethylheptadecyl group; ethylpentyl group, ethylhexyl group, ethylheptyl group, ethyloctyl group, ethylnonyl group, ethyldecyl group, ethylundecyl group, ethyldodecyl group, ethyltridecyl group, ethyltetradecyl group, ethylpentadecyl group, ethylhexadecyl group, ethylheptadecyl group, ethyloctadecyl group; propylhexyl group, propylheptyl group, propyloctyl group, propylnonyl group, propyldecyl group, propylundecyl group, propyldodecyl group, propyltridecyl group, propyltetradecyl group, propylpentadecyl group, propylhexadecyl group, propylheptadecyl group;butylhexyl group, butylheptyl group, butyloctyl group, butylnonyl group, butyldecyl group, butylundecyl group, butyldodecyl group, butyltridecyl group, butyltetradecyl group, butylpentadecyl group, and butylhexadecyl group;

[0140] Among these, methyl and ethyl groups are preferred in that they are more likely to exhibit the properties such as heat resistance and dielectric properties derived from the aromatic heterocyclic compound (B).

[0141] R １ Examples of the substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms in the formula (I) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a bicyclo[2,2,1]heptyl group, a cyclooctyl group, and an adamantyl group.

[0142] R １Examples of the substituted or unsubstituted aryl group having 6 to 20 carbon atoms in the above formula include a phenyl group, a 2-methylphenyltolyl group, a 4-methylphenyl group, a 3-methylphenyl group, a 4-ethylphenyl group, a 2-ethylphenyl group, a 2,6-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,3-dimethylphenyl group, a 3,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,4,6-trimethylphenyl group, a 2,3,6-trimethylphenyl group, a 4-butylphenyl group, a 2-tert-butylphenyl group, a 4-tert-butylphenyl group, a 3-tert-butylphenyl group, a 4-sec-butylphenyl group, a 4-isopropylphenyl group, a 2-isopropylphenyl group, a 4-amylphenyl group, a 4-tert-amylphenyl group, a 4-hexylphenyl group, a 4- Examples thereof include a methoxyphenyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 3,5-dimethoxyphenyl group, a 2,6-dimethoxyphenyl group, a 3,4-dimethoxyphenyl group, a 4-ethoxyphenyl group, a 4-(N,N-dimethylamino)phenyl group, a 4-(N,N-diethylamino)phenyl group, a 2-(N,N-dimethylamino)phenyl group, a 2-(N,N-dimethylamino)phenyl group, a 3-(N,N-dimethylamino)phenyl group, a 3-(N,N-diethylamino)phenyl group, a 4-(methylthio)phenyl group, a benzylphenyl group, a 4-(trifluoromethoxy)phenyl group, a 4-α-cumylphenyl group, a 4-acetylphenyl group, a 4-fluorophenyl group, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-phenoxyphenyl group, and a naphthyl group.

[0143] Among these, a phenyl group, a methylphenyl group such as a 2-methylphenyl group, a methoxyphenyl group such as a 2-methoxyphenyl group, and a naphthyl group are preferred in that they are more likely to exhibit various properties such as heat resistance and dielectric properties derived from the aromatic heterocyclic compound (B).

[0144] R １ Examples of the substituted or unsubstituted aralkyl group in the formula (I) include a benzyl group and a phenylethyl group.

[0145] R １The amino group in the formula (15) can be exemplified by an amino group represented by the following formula (15):

[0146]

[0147] In formula (15), R ３８ and R ３９ R each independently represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. These organic groups may have any substituent. ３８ and R ３９ may be bonded to each other to form a ring. The * mark in the formula (15) indicates the bonding site to the nitrogen-containing aromatic heterocycle. The same applies to the chemical structural formulas shown below.

[0148] R ３８ and R ３９ Examples of the organic group having 1 to 20 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. １ These are the same as the examples of the alkyl group, cycloalkyl group, aryl group and aralkyl group in the above.

[0149] R ３８ and R ３９ When these are bonded to each other to form a ring, examples of the amino group include those represented by the following substituent group (16).

[0150]

[0151] Among these, the amino group R ３８ and R ３９ is a methyl group, R ３８ and R ３９ is an ethyl group, R ３８ is a methyl group and R ３９ is a combination of phenyl groups, R ３８ is an ethyl group and R ３９ is a combination of phenyl groups, R ３８ and R ３９ An amino group of formula (15) is preferred, which is a piperidinyl group in which the groups are bonded to each other to form a 6-membered ring.

[0152] R １The alkoxy group in the formula (17) includes an alkoxy group represented by the following formula (17).

[0153]

[0154] In formula (17), R ５０ is selected from the group consisting of a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted aralkyl group. ５０ is an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, ５０ Specific examples of R １ The specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group are the same as those in the above.

[0155] R １Specific examples of the substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms in the above formula include, for example, a phenoxy group, a 2-methylphenoxy group, a 4-methylphenoxy group, a 3-methylphenoxy group, a 4-ethylphenoxy group, a 2-ethylphenoxy group, a 2,6-dimethylphenoxy group, a 2,4-dimethylphenoxy group, a 2,3-dimethylphenoxy group, a 3,4-dimethylphenoxy group, a 2,5-dimethylphenoxy group, a 2 , 4,6-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 4-butylphenoxy group, 2-tert-butylphenoxy group, 4-tert-butylphenoxy group, 3-tert-butylphenoxy group, 4-sec-butylphenoxy group, 4-isopropylphenoxy group, 2-isopropylphenoxy group, 4-amylphenoxy group, 4-tert-amylphenoxy group, 4-hexylphenoxy group, 4-methoxyphenoxy group, 2-methoxyphenoxy group, 3-methoxyphenoxy group, 3,5-dimethoxyphenoxy group, 2,6-dimethoxyphenoxy group, 3,4-dimethoxyphenoxy group, 4-ethoxyphenoxy group, 4-(N,N-dimethylamino)phenoxy group, 4-(N,N-diethylamino)phenoxy group, 2-(N,N-dimethylamino)phenoxy group, 2-(N,N-dimethylamino)phenoxy group group, a 3-(N,N-dimethylamino)phenoxy group, a 3-(N,N-diethylamino)phenoxy group, a 4-(methylthio)phenoxy group, a benzylphenoxy group, a 4-(trifluoromethoxy)phenoxy group, a 4-α-cumylphenoxy group, a 4-acetylphenoxy group, a 4-fluorophenoxy group, a 2-fluorophenoxy group, a 3-fluorophenoxy group, a 4-phenoxyphenoxy group, and a naphthoxy group.

[0156] Among these, a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 2-methoxyphenoxy group, a 3-methoxyphenoxy group, a 4-methoxyphenoxy group, and a naphthoxy group are preferred in that they are more likely to exhibit various properties such as heat resistance and dielectric properties derived from the aromatic heterocyclic compound (B).

[0157] From the viewpoint of the thermal stability and the fact that the properties such as heat resistance and dielectric properties derived from the aromatic heterocyclic compound (B) can be more easily exhibited, R１ is preferably selected from the group consisting of a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted amino group, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, and more preferably selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and a substituted amino group.

[0158] Substituent R in the nitrogen-containing aromatic heterocycles represented by formulae (2-2), (2-3) and (2-4) ２ are each independently a group selected from the group consisting of a hydrogen atom, a fluorine atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms. ２ Specific examples of R １ The specific examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group, amino group, alkoxy group, and aryloxy group in the above-mentioned R ２ Specific examples of the substituents corresponding to "substituted" in each functional group are also shown in the above R １ This is similar to the specific example in

[0159] In the formulas (2-2), (2-3), and (2-4), two bonds (L １ and L ２ The position of the bond bonded to (B) is not particularly limited, but is preferably the meta position or the para position from the viewpoint of synthesizing the unit of the aromatic heterocyclic compound (B) with good polymerization reactivity.

[0160] Of these, from the viewpoint of obtaining excellent dielectric properties, nitrogen-containing aromatic heterocycles represented by formula (2-2), formula (2-3), and formula (2-4) are preferred, and among these, the nitrogen-containing aromatic heterocycle represented by formula (2-2) is preferred. Furthermore, of these, from the viewpoint of improving adhesion to a conductor and obtaining excellent dielectric properties, the nitrogen-containing aromatic heterocycle represented by formula (2-1) is preferred. Since the triazine ring has a dipole moment of 0, molecular polarization and dipole rotation are suppressed, and as a result, it is thought that the triazine ring is more likely to exhibit various properties such as a low dielectric constant and a low dielectric dissipation factor than heterocycles with large charge imbalances.

[0161] (Detailed Description of Terminal Group Z) The terminal group of the aromatic heterocyclic compound (B) is represented by the formula (2) above. In formula (2), Z is an alkyl group having 3 to 30 carbon atoms and having an ethylenically unsaturated bond, an aryl group having 6 to 20 carbon atoms and having an ethylenically unsaturated bond, or an aralkyl group having 3 to 30 carbon atoms and having an ethylenically unsaturated bond. The alkyl group having 3 to 30 carbon atoms, the aryl group having 6 to 20 carbon atoms and having an ethylenically unsaturated bond, and the aralkyl group having 3 to 30 carbon atoms and having an ethylenically unsaturated bond may have a substituent. When the alkyl group having 3 to 30 carbon atoms, the aryl group having 6 to 20 carbon atoms and having an ethylenically unsaturated bond, or the aralkyl group having 3 to 30 carbon atoms and having an ethylenically unsaturated bond has a substituent, the substituent is a group other than a hydroxy group.

[0162] The terminal group Y is bonded to the main chain terminal of the aromatic heterocyclic compound (B), and specifically forms a terminal portion of the aromatic heterocyclic compound (B) represented by the following formula (a1) or (a2).

[0163]

[0164] In formula (a1) and formula (a2), L １ , L ２ , X １ , and Y １ is L in the formula (1). １ , L ２ , X １ , and Y １ is synonymous with.

[0165] In order to improve dielectric properties, the terminal group Z is preferably an aromatic or aliphatic hydrocarbon group or a nitrogen-containing heteroaromatic ring, which have low polarization. Furthermore, by including an ethylenically unsaturated double bond, crosslink density can be improved, and therefore heat resistance and curability can be expected.

[0166] Specific examples of Z include aromatic ring-containing groups such as a 3-isopropenylphenyl group, a 4-isopropenylphenyl group, a 2-allylphenyl group, a 2-methoxy-4-allylphenyl group, a 4-(1-propenyl)-2-methoxyphenyl group, a 4-vinylbenzyl group, a 3-vinylbenzyl group, and a 2-vinylbenzyl group, an allyl group, an acryl group, a methacryl group, and a methallyl group.

[0167] When the structure of the aromatic heterocyclic compound (B) contains an ethylenically unsaturated double bond at a site other than the terminal group, the terminal group Z is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms. Specific examples thereof include aryl groups such as a phenyl group, a biphenyl group, a tolyl group, a xylyl group, and a naphthyl group, and aralkyl groups such as a benzyl group, a phenethyl group, a phenylethyl group, and a naphthylmethyl group.

[0168] (Preferred Examples of Aromatic Heterocyclic Compound (B)) Among the above-mentioned aromatic heterocyclic compounds (B), X １ is any one of formula (7b), formula (7d), formula (7f), formula (7i), formula (7n), formula (7o), formula (7p), formula (7r), formula (7u), formula (7z), formula (7aa), and formula (7ab), and Y １ is a nitrogen-containing aromatic heterocycle represented by formula (2-1), and L １ and L ２ is an ether group, and the terminal group Z is any one selected from the group consisting of a 3-isopropenylphenyl group, a 4-isopropenylphenyl group, a 2-allylphenyl group, a 2-methoxy-4-allylphenyl group, a 4-(1-propenyl)-2-methoxyphenyl group, a 4-vinylbenzyl group, a 3-vinylbenzyl group, and a 2-vinylbenzyl group.

[0169]

[0170]

[0171]

[0172] Among the above, X １ However, structures having methyl groups introduced therein, such as those represented by formula (7b), formula (7f), formula (7i), formula (7n), and formula (7ab), are more preferred in terms of excellent dielectric properties. Among these, formulas (7i) and (7n) are more preferred in terms of excellent heat resistance, low linear thermal expansion coefficient, and solubility, since they contain an alicyclic structure.

[0173] (Other Copolymerization Components) The aromatic heterocyclic compound (B) may have a unit having a carbonate bond represented by the following formula (9): That is, the aromatic heterocyclic compound (B) may be a copolymer having a unit represented by the above formula (1) and a unit represented by the following formula (9).

[0174]

[0175] When the aromatic heterocyclic compound (B) has a unit represented by formula (9), it is possible to impart even better heat resistance and dielectric properties.

[0176] In formula (9), X ２ is a divalent organic group.

[0177] X in formula (9) ２ is a divalent organic group. ２ Examples of the formula are X in the formula (1) １ The divalent organic group X in (1) is the same as the example. １ and X in formula (9) ２ may be the same or different. １ and X ２ By freely selecting the above, it is possible to adjust the heat resistance and dielectric properties of the composition, as well as the flowability and surface hardness according to the processability and application.

[0178] When the aromatic heterocyclic compound (B) has a unit represented by the formula (9), the content ratio (molar ratio) of the unit represented by the formula (1) to the unit represented by the formula (9) in the aromatic heterocyclic compound (B) is not limited, but is preferably 1:99 to 99:1, particularly 10:80 to 60:40, especially 20:80 to 55:45, and of these, 35:65 to 50:50.

[0179] The aromatic heterocyclic compound (B) may have a unit having an ester bond represented by the following formula (10). That is, the aromatic heterocyclic compound (B) may be a copolymer having a unit represented by the above formula (1) and a unit represented by the following formula (10). Since the aromatic heterocyclic compound (B) has a unit represented by the following formula (10), it can be imparted with excellent heat resistance and dielectric properties.

[0180]

[0181] In formula (10), X １ and X ３ is a divalent organic group.

[0182] X in formula (10) １ is X in the formula 1 １ It is synonymous with X. ３ is a divalent organic group, and X ３ Examples of the formula are X in the formula (1) １ The same as the example of X １ and X ３ may be the same or different. １ and X ３ By freely selecting the above, it is possible to adjust the heat resistance and dielectric properties of the composition, as well as the flowability and surface hardness according to the processability and application.

[0183] Among them, X １ and X ３ In this case, X preferably has a different structure. １is a divalent organic group selected from the group consisting of the formula (7a), the formula (7b), the formula (7c), the formula (7d), the formula (7e), the formula (7f), the formula (7g), the formula (7h), the formula (7i), the formula (7j), the formula (7k), the formula (7l), the formula (7m), the formula (7n), the formula (7o), the formula (7p), the formula (7q), the formula (7r), the formula (7s), the formula (7t), the formula (7u), the formula (7v), the formula (7w), the formula (7x), the formula (7y), the formula (7z), the following formula (7aa) and the following formula (7ab), ３ It is preferable that the compound (A) contains one or more compounds selected from the group consisting of the following formula (11a), the following formula (11b), the following formula (11c), the following formula (11d), the following formula (11e), and the following formula (11f): In the case of such a structure, an effect of improving compatibility with the thermoplastic resin (A) can be expected.

[0184]

[0185] When the aromatic heterocyclic compound (B) has a unit represented by the formula (10), the content ratio (molar ratio) of the unit represented by the formula (1) to the unit represented by the formula (10) in the aromatic heterocyclic compound (B) is not limited, but is preferably 1:99 to 99:1, particularly 10:80 to 60:40, especially 20:80 to 55:45, and of these, 35:65 to 50:50.

[0186] The method for synthesizing the aromatic heterocyclic compound (B) is not particularly limited, and known methods can be used. １ a monomer serving as a raw material for the portion containing Y １ The monomers that are raw materials for the portion containing X, the monomer for forming the terminal group Z, and, if necessary, the monomers that derive other structural units are mixed with an alkali metal or an alkali metal compound in an organic solvent, and the mixture is stirred at room temperature or stirred while heating. １ a monomer serving as a raw material for the portion containing Y １ After polymerizing the monomers that are the raw materials for the portion containing the monomer, the mixture may be heated and mixed to cause a reaction.

[0187] From the viewpoint of imparting heat resistance and processability to the composition, the glass transition temperature of the aromatic heterocyclic compound (B) is usually 100° C. or higher, preferably 140° C. or higher, more preferably 150° C. or higher, even more preferably 160° C. or higher, particularly preferably 180° C. or higher, and is usually 350° C. or lower, preferably 330° C. or lower, and more preferably 280° C. or lower. When the glass transition temperature is within the above range, good heat resistance and processability during molding can be obtained.

[0188] The glass transition temperature of the aromatic heterocyclic compound (B) can be adjusted by appropriately adjusting the type of aromatic heterocycle and the structure of the substituent, and is not particularly limited. The glass transition temperature of the aromatic heterocyclic compound (B) can be determined using a differential scanning calorimeter (DSC) in accordance with ISO 3146.

[0189] From the viewpoint of heat resistance, the thermal decomposition temperature (5% weight loss temperature, Td5) of the aromatic heterocyclic compound (B) is preferably 400° C. or higher, and more preferably 410° C. or higher. The thermal decomposition temperature (5% weight loss temperature, Td5) of the aromatic heterocyclic compound (B) can be measured using a simultaneous differential scanning calorimeter and thermogravimeter by the method described in the examples.

[0190] The aromatic heterocyclic compound (B) preferably has a relative dielectric constant (εr) of 2.6 or less, more preferably 2.55 or less, and particularly preferably 2.5 or less, measured at a temperature of 23°C and a frequency of 10 GHz. The aromatic heterocyclic compound (B) also has a dielectric loss tangent (tanδ) of 4.5 x 10 －３ Preferably, it is 4.0 × 10 or less. －３ More preferably, it is 3.0 × 10 or less. －３ More preferably, it is 2.5 × 10 or less. －３ It is particularly preferable that the value is 1.5×10 or less. －３ It is particularly preferred that:

[0191] The dielectric constant and the dielectric loss tangent are determined by molding the aromatic heterocyclic compound (B) into a film using a heat press molding machine, conditioning the film at room temperature of 25°C and humidity of 40% for 48 hours, and then measuring the film using a cavity resonator.

[0192] The lower limit of the mass average molecular weight (Mw) of the aromatic heterocyclic compound (B) is preferably 1,000, more preferably 2,000, even more preferably 3,000, particularly preferably 5,000, and the upper limit is preferably 50,000, more preferably 30,000, even more preferably 20,000, particularly preferably 10,000. When the mass average molecular weight (Mw) is within the above numerical range, the solubility, heat resistance, and processability are further improved. The mass average molecular weight (Mw) in the present invention is a value measured by gel permeation chromatography (GPC) using the method described in the Examples.

[0193] From the viewpoint of heat resistance, the content of the aromatic heterocyclic compound (B) in this composition is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and particularly preferably 15% by mass or more, based on the total mass of the solid content of the resin composition. On the other hand, the upper limit is less than 50% by mass, but from the viewpoint of compatibility and the expression of low dielectric properties, it is preferably 45% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, particularly preferably 30% by mass or less, and most preferably 25% by mass or less. The content of the aromatic heterocyclic compound (B) here refers to the content in the solid content excluding the solvent from the resin composition.

[0194] Furthermore, the mass ratio of the content of the aromatic heterocyclic compound (B) to the content of the thermoplastic resin (A) ((B) content / (A) content) is not particularly limited, but from the viewpoint of compatibility, it is preferably 0.8 or less, more preferably 0.75 or less, and even more preferably 0.7 or less. When this mass ratio is below the upper limit, the resin sheet does not become too brittle, and a resin sheet with excellent flexibility and handleability is easily obtained. On the other hand, from the viewpoint of heat resistance, the lower limit of this mass ratio is preferably 0.05 or more, more preferably 0.10 or more, and even more preferably 0.15 or more.

[0195] 3. Cyclic Polyolefin Resin Copolymer (C) The present composition may further contain a cyclic polyolefin resin copolymer (C) for the purposes of improving heat resistance, reducing the linear thermal expansion coefficient, reducing tackiness, etc. The reason why the heat resistance, linear thermal expansion coefficient, tackiness, etc. are improved is not clear, but it is thought that this is because the inclusion of the cyclic polyolefin resin copolymer (C) together with the thermoplastic resin (A) introduces a rigid skeleton into the molecule.

[0196] The cyclic polyolefin resin copolymer (C) is a copolymer having an alicyclic structure, specifically, a copolymer having an alicyclic structure in a side chain of a polyolefin. Suitable examples of the alicyclic structure include cycloalkanes, bicycloalkanes, polycyclic compounds, etc. Among these, cycloalkanes are preferred, and cyclohexane is more preferred. Furthermore, the alicyclic structure is more preferably an alicyclic structure generated by hydrogenation of an aromatic ring contained in a hydrogenated aromatic vinyl polymer block unit described below.

[0197] The cyclic polyolefin resin copolymer (C) preferably has a crystalline melting peak temperature of less than 100° C. The crystalline melting peak temperature of the cyclic polyolefin resin copolymer (C) is preferably 50° C. or higher, more preferably 60° C. or higher, and even more preferably 65° C. or higher. The crystalline melting peak temperature of the cyclic polyolefin resin copolymer is preferably 90° C. or lower, more preferably 85° C. or lower.

[0198] The crystalline melting peak temperature in the present invention is the temperature at which a crystalline melting peak is detected in differential scanning calorimetry (DSC) measured at a heating rate of 10°C / min. The cyclic polyolefin resin copolymer (C) used in the present composition may have a crystalline melting peak at less than 100°C, and may have a crystalline melting peak at two points, for example, less than 100°C and at or above 100°C.

[0199] Known cyclic polyolefins include hydrogenated ring-opening polymers having units derived from monocyclic norbornene-based or polycyclic norbornene-based monomers (e.g., WO 2012 / 046443, WO 2012 / 033076, etc.). These cyclic polyolefins have an alicyclic structure in the polymer main chain, and either do not have a crystalline melting peak temperature below 100°C or are amorphous.

[0200] The crystallinity of a polymer usually varies depending on the regularity of the molecular structure and steric hindrance, and polymers having an alicyclic structure in the side chain or main chain are difficult to crystallize due to the large steric hindrance, and tend to become amorphous. On the other hand, the cyclic polyolefin resin copolymer (C) of the present composition exhibits crystallinity due to the structure of the hydrogenated conjugated diene polymer block unit described below, and the crystalline melting peak temperature can be made to be less than 100°C due to the presence of an alicyclic structure in the side chain of the polyolefin.

[0201] The melt flow rate (MFR) of the cyclic polyolefin resin copolymer (C) is not particularly limited, but is usually 0.1 g / 10 min or more, and from the viewpoint of the molding method and the appearance of the molded product, preferably 0.5 g / 10 min or more. Furthermore, the melt flow rate (MFR) is usually 200 g / 10 min or less, and from the viewpoint of material strength, it is preferably 100 g / 10 min or less, more preferably 90.0 g / 10 min or less. By setting the MFR within the above range, compatibility with the thermoplastic resin (A) is improved. The MFR is determined by measuring in accordance with ISO R1133 under conditions of a measurement temperature of 230°C and a measurement load of 2.16 kg.

[0202] From the viewpoint of low dielectric properties, the cyclic polyolefin resin copolymer (C) used in the present composition is preferably a cyclic polyolefin containing at least one hydrogenated aromatic vinyl polymer block unit and at least one hydrogenated conjugated diene polymer block unit (hereinafter also referred to as "cyclic polyolefin (a)"), or a product modified with at least one of an unsaturated carboxylic acid and an anhydride thereof.

[0203] As used herein, the term "block" refers to a polymeric segment of a copolymer that exhibits microphase separation from structurally or compositionally distinct polymeric segments of the copolymer. Microphase separation occurs due to the immiscibility of polymeric segments in a block copolymer. Microphase separation and block copolymers are extensively discussed in "Block Copolymers - Designer Soft Materials," February 1999 issue of PHYSICS TODAY, pp. 32-38.

[0204] Examples of the cyclic polyolefin (a) include a diblock copolymer composed of a hydrogenated aromatic vinyl polymer block unit (hereinafter also referred to as "block A") and a hydrogenated conjugated diene polymer block unit (hereinafter also referred to as "block B"), a triblock copolymer containing two or more of at least one of block A and block B, a tetrablock copolymer, and a pentablock copolymer. The cyclic polyolefin (a) preferably has at least two or more blocks A, and suitable examples thereof include an A-B-A type, an A-B-A-B type, and an A-B-A-B-A type.

[0205] Furthermore, the cyclic polyolefin (a) preferably has a segment composed of an aromatic vinyl polymer at each end. Therefore, the hydrogenated block copolymer of the present composition preferably has at least two hydrogenated aromatic vinyl polymer block units (blocks A) and at least one hydrogenated conjugated diene polymer block unit (block B) between the two hydrogenated aromatic vinyl polymer block units (blocks A). From these viewpoints, the cyclic polyolefin (a) is more preferably an A-B-A type or an A-B-A-B-A type.

[0206] The content of hydrogenated aromatic vinyl polymer block units (block A) in the cyclic polyolefin (a) is preferably 30 to 99 mol%, more preferably 40 to 90 mol%. It is even more preferably 50 mol% or more, and even more preferably 60 mol% or more. When the ratio of hydrogenated aromatic vinyl polymer block units (block A) is equal to or greater than the lower limit, rigidity is not reduced, and heat resistance and linear thermal expansion coefficient are also improved. On the other hand, when the ratio is equal to or less than the upper limit, flexibility is improved.

[0207] The content of hydrogenated conjugated diene polymer block units (block B) in the cyclic polyolefin (a) is preferably 1 to 70 mol%, more preferably 10 to 60 mol%. It is even more preferably 50 mol% or less, and even more preferably 40 mol% or less. When the ratio of hydrogenated conjugated diene polymer block units (block B) is equal to or greater than the lower limit, flexibility is improved. On the other hand, when the ratio is equal to or less than the upper limit, rigidity is not reduced, and heat resistance and linear thermal expansion coefficient are also improved.

[0208] The hydrogenated aromatic vinyl polymer block units and hydrogenated conjugated diene polymer block units constituting the cyclic polyolefin (a) can be obtained by hydrogenating polymer blocks composed of an aromatic vinyl monomer and a conjugated diene monomer such as 1,3-butadiene, which will be described in detail later. Furthermore, the cyclic polyolefin (a) is preferably a block copolymer having no functional groups. The term "having no functional groups" means that the block copolymer has no functional groups, i.e., no groups containing atoms other than carbon and hydrogen atoms.

[0209] The monomers for forming the aromatic vinyl polymer block unit and the conjugated diene polymer block unit before hydrogenation will be described below.

[0210] (Aromatic Vinyl Monomer) The aromatic vinyl monomer serving as a raw material for the aromatic vinyl polymer block unit before hydrogenation is a monomer represented by the following formula (18).

[0211]

[0212] In formula (18), R is hydrogen or an alkyl group, and Ar is a phenyl group, a halophenyl group, an alkylphenyl group, an alkylhalophenyl group, a naphthyl group, a pyridinyl group, or an anthracenyl group.

[0213] In formula (18), when R is an alkyl group, the number of carbon atoms is preferably 1 to 6, and the alkyl group may be mono- or polysubstituted with functional groups such as halo, nitro, amino, hydroxy, cyano, carbonyl, and carboxyl. Ar is preferably a phenyl group or an alkylphenyl group, more preferably a phenyl group.

[0214] Examples of aromatic vinyl monomers include styrene, α-methylstyrene, vinyltoluene (including all isomers, with p-vinyltoluene being particularly preferred), ethylstyrene, propylstyrene, butylstyrene, vinylbiphenyl, vinylnaphthalene, vinylanthracene (including all isomers), and mixtures thereof. Of these, styrene is preferred.

[0215] (Conjugated Diene Monomer) The conjugated diene monomer used as a raw material for the conjugated diene polymer block unit before hydrogenation is not particularly limited as long as it is a monomer having two conjugated double bonds. Examples of conjugated diene monomers include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2-methyl-1,3-pentadiene and analogous compounds thereof, and mixtures thereof. Among these, 1,3-butadiene is preferred from the viewpoint of obtaining a block having a high structural regularity and being easily crystallized.

[0216] When 1,3-butadiene is used as the conjugated diene monomer, its polymer, polybutadiene, contains 1,4-bond units ([—CH ２ -CH=CH-CH ２ -]) and 1,2-bond units ([-CH ２ -CH(CH=CH ２)-)]), upon hydrogenation, the former gives a structure similar to the repeating unit of polyethylene (ethylene structure), and the latter gives a structure similar to the repeating unit obtained by polymerizing 1-butene (1-butene structure). Therefore, the hydrogenated conjugated diene polymer block in the present composition preferably has at least either an ethylene structure or a 1-butene structure.

[0217] When isoprene is used as the conjugated diene monomer, its polymer, polyisoprene, contains 1,4-bond units ([—CH ２ -C(CH ３ )=CH-CH ２ -]), 3,4-bond unit ([-CH ２ -CH(C(CH ３ ) = CH ２ )-]) and 1,2-bond units ([-CH ２ -C(CH ３ ) (CH=CH ２ )-]) is present, and the resulting copolymer contains at least one of the three types of units obtained by hydrogenation.

[0218] (Block Structure) The cyclic polyolefin (a) is preferably produced by hydrogenation of a multiblock copolymer such as a triblock copolymer, a tetrablock copolymer, or a pentablock copolymer, such as SBS, SBSB, SBSBS, SBSBSB, SIS, SISIS, and SISBS (where S is polystyrene, B is polybutadiene, and I is polyisoprene). The block may be a linear block or may be branched. When branched, the polymerization chain may be bonded at any position along the backbone of the copolymer. In addition to a linear block, the block may be a tapered block or a star block.

[0219] The block copolymer constituting the cyclic polyolefin (a) before hydrogenation may contain one or more additional block units other than the aromatic vinyl polymer block units and the conjugated diene polymer block units. For example, in the case of a triblock copolymer, these additional block units may be bonded to any position on the triblock polymer backbone.

[0220] A preferred example of the hydrogenated aromatic vinyl polymer block unit is hydrogenated polystyrene. A preferred example of the hydrogenated conjugated diene polymer block unit is hydrogenated polybutadiene or hydrogenated polyisoprene. Of the hydrogenated conjugated diene polymer block units, hydrogenated polybutadiene is more preferred.

[0221] Suitable examples of the cyclic polyolefin (a) include hydrogenated triblock and hydrogenated pentablock copolymers of styrene and butadiene, with hydrogenated triblock copolymers being more preferred as the cyclic polyolefin (a).

[0222] (Hydrogenation Level) The cyclic polyolefin (a) is one in which not only the double bonds derived from conjugated dienes such as butadiene but also the aromatic rings derived from styrene etc. are hydrogenated, and is substantially completely hydrogenated. Specifically, it refers to one that has achieved the following hydrogenation levels:

[0223] The hydrogenation level of the hydrogenated aromatic vinyl polymer block unit is preferably 90% or higher, more preferably 95% or higher, even more preferably 98% or higher, and particularly preferably 99.5% or higher. The hydrogenation level of the hydrogenated conjugated diene polymer block unit is preferably 95% or higher, more preferably 99% or higher, and even more preferably 99.5% or higher. Such a high level of hydrogenation can reduce dielectric loss and improve rigidity and heat resistance.

[0224] The hydrogenation level of the hydrogenated aromatic vinyl polymer block unit indicates the proportion of the aromatic vinyl polymer block unit saturated by hydrogenation. The hydrogenation level of the hydrogenated conjugated diene polymer block unit indicates the proportion of the conjugated diene polymer block unit saturated by hydrogenation. The hydrogenation level of each block unit is determined using proton NMR.

[0225] The cyclic polyolefin resin copolymer (C) may be used alone or in combination of two or more. As the cyclic polyolefin resin copolymer (C) in the present composition, commercially available products can be used, and a specific example is TEFABLOC (registered trademark) manufactured by Mitsubishi Chemical Corporation.

[0226] When the present composition further contains a cyclic polyolefin resin copolymer (C), its content is preferably 2% by mass or more, more preferably 4% by mass or more, and even more preferably 6% by mass or more, based on the total mass of the solid content of the resin composition, from the viewpoint of reducing the linear thermal expansion coefficient and reducing tackiness. On the other hand, the upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, from the viewpoint of flexibility and adhesion to the substrate. The content of the cyclic polyolefin resin copolymer (C) here refers to the content in the solid content excluding the solvent from the resin composition.

[0227] When the composition further contains a cyclic polyolefin resin copolymer (C), the content thereof relative to 100 parts by mass of the thermoplastic resin (A) is preferably 6 parts by mass or more, more preferably 8% by mass or more, and even more preferably 10% by mass or more, from the viewpoints of reducing the linear thermal expansion coefficient and reducing tackiness. On the other hand, the upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less, from the viewpoints of flexibility and adhesion to the substrate.

[0228] When the present composition further contains a cyclic polyolefin resin copolymer (C), the mass ratio of the content of the cyclic polyolefin resin copolymer (C) to the content of the thermoplastic resin (A) ((C) content / (A) content) is not particularly limited, but from the viewpoint of heat resistance, it is preferably 0.8 or less, more preferably 0.7 or less, and even more preferably 0.6 or less. On the other hand, the lower limit of this mass ratio is preferably 0.05 or more, more preferably 0.10 or more, and even more preferably 0.15 or more.

[0229] 4. Organic Peroxide (D) The present composition may contain an organic peroxide (D) for the purpose of accelerating the curing reaction. Examples of organic peroxides include those belonging to the groups of hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, and ketone peroxides.

[0230] Specific examples include hydroperoxides such as cumene hydroperoxide and tert-butyl hydroperoxide; dialkyl peroxides such as dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne and α,α-di(tert-butylperoxyisopropyl)benzene; diacyl peroxides such as lauryl peroxide and benzoyl peroxide; peroxy esters such as tert-butyl peroxyacetate, tert-butyl peroxybenzoate and tert-butylperoxyisopropyl carbonate; and ketone peroxides such as cyclohexanone peroxide.

[0231] The content of the organic peroxide (D) in the composition is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 1 part by mass, per 100 parts by mass of the thermoplastic resin (A). When the content of the organic peroxide (D) is within the above range, the curing reaction can be promoted while maintaining low dielectric properties of the cured sheet.

[0232] 5. Solvent (E) When a resin sheet is produced from the present composition through a coating step, the composition may contain a solvent (E). The solvent (E) is not particularly limited as long as it can uniformly dissolve the thermoplastic resin (A) and the aromatic heterocyclic compound (B), and examples of the solvent include toluene, cyclohexane, tetrahydrofuran, and xylene.

[0233] The solvent (E) preferably has a boiling point of 200° C. or less so that it volatilizes when the resin sheet is dried.

[0234] From the viewpoint of film-forming properties, the content of the solvent (E) in the present composition is preferably 100 parts by mass or more and 500 parts by mass or less, and more preferably 200 parts by mass or more and 400 parts by mass or less, per 100 parts by mass of the thermoplastic resin (A).

[0235] 6. Other Components The present composition may further contain, as components other than those described above, a resin component other than the thermoplastic resin (A), a crosslinking agent other than the aromatic heterocyclic compound (B), an ultraviolet absorber, an antistatic agent, an antioxidant, a coupling agent, a plasticizer, a flame retardant, a colorant, a dispersant, an emulsifier, an elasticity reducing agent, a diluent, an antifoaming agent, an ion trapping agent, a thickener, a leveling agent, a curing agent, a curing aid, inorganic particles, organic particles, etc.

[0236] Examples of the resin component other than the thermoplastic resin (A) include thermoplastic elastomers other than the thermoplastic resin (A), as well as polycarbonate resins and polyester resins. In the case of polycarbonate resins, polycarbonate resins having a unit represented by the above formula (9) are particularly preferred from the viewpoint of compatibility. Also, in the case of polyester resins, polyester resins having a unit represented by the above formula (10) are particularly preferred from the same viewpoint.

[0237] Examples of the crosslinking agent other than the aromatic heterocyclic compound (B) include a bismaleimide compound, an epoxy compound, an ethylenically unsaturated bond-containing compound having no aromatic heterocycle, etc. The crosslinking agent other than the aromatic heterocyclic compound (B) may be bifunctional or trifunctional or higher.

[0238] Examples of the epoxy compound include bifunctional fluorine-containing epoxy compounds such as 2,2'-(2,2,3,3,4,4,5,5-octafluorohexane-1,6-diyl)bis(oxirane), aromatic epoxy compounds such as bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol C type epoxy compounds, bisphenol AF type epoxy compounds, naphthalene type epoxy compounds, biphenyl type epoxy compounds, resorcinol type epoxy compounds, phenol novolac type epoxy compounds, and cresol novolac type epoxy compounds, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and the like. diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, cyclohexane diglycidyl ether, dicyclopentadiene diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, diglycidyl hexahydrophthalate Examples of epoxy compounds include aliphatic epoxy compounds such as esters, vinyl(3,4-cyclohexene) dioxide, 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane, and epoxidized polybutadiene, as well as heterocyclic epoxy compounds such as triglycidyl isocyanurate and hydantoin-type epoxy compounds, and polyfunctional epoxy compounds such as halogenated epoxy compounds, glycidylamine-type epoxy compounds, epoxy group-containing rubber compounds, epoxy group-containing polyurethane compounds, and epoxy group-containing acrylic compounds. One or more types of epoxy compounds may be used in combination.

[0239] In order to obtain compatibility and flexibility, a monofunctional epoxy compound may be contained in addition to the above-mentioned epoxy compound.

[0240] By using an epoxy compound as a crosslinking agent other than the aromatic heterocyclic compound (B), it is expected to have the effect of improving dimensional stability and adhesion to the adherend. Among the epoxy compounds, aliphatic epoxy compounds are preferred from the viewpoint of excellent compatibility with the thermoplastic resin (A) in the composition, as well as high adhesion to the adherend and moderate flexibility. Furthermore, among the aliphatic epoxy compounds, alkylene glycol diglycidyl ethers are preferred from the viewpoint of excellent compatibility with the thermoplastic resin (A), and among them, hexanediol diglycidyl ether and tripropylene glycol diglycidyl ether are particularly preferred.

[0241] On the other hand, from the viewpoint of obtaining appropriate hardness and high dimensional stability, epoxy compounds having a cyclic structure are preferred, and among these, aromatic epoxy compounds are preferred because of their excellent compatibility with the aromatic heterocycle (B). Among these, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, tetraphenylethane type epoxy resins, and bixylenol type epoxy resins are particularly preferred.

[0242] From the viewpoint of improving low dielectric properties, fluorine-containing epoxy resins are preferred, and among them, bisphenol AF type epoxy compounds are particularly preferred from the viewpoint of improving adhesion even when the adherend is an insulating material such as PTFE, and also from the viewpoint of excellent dimensional stability.

[0243] The epoxy equivalent of the epoxy compound is preferably 5000 g / eq or less, more preferably 1000 g / eq or less, still more preferably 700 g / eq or less, and particularly preferably 500 g / eq or less, from the viewpoint of compatibility with the thermoplastic resin (A). On the other hand, the lower limit is preferably 10 g / eq or more, more preferably 50 g / eq or more, from the viewpoint of increasing the crosslink density of the cured product and suppressing volatilization of the epoxy compound.

[0244] Among the crosslinking agents other than the aromatic heterocyclic compound (B), examples of the bifunctional crosslinking agent having an ethylenically unsaturated bond include bifunctional aromatic vinyl compounds such as divinylbenzene, divinylnaphthalene, and divinylbiphenyl; ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethoxy bifunctional aliphatic (meth)acrylate compounds such as ethoxylated polypropylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, glycerin di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, and ethoxylated 2-methyl-1,3-propanediol di(meth)acrylate;Cyclohexanedimethanol di(meth)acrylate, ethoxylated cyclohexanedimethanol di(meth)acrylate, propoxylated cyclohexanedimethanol di(meth)acrylate, ethoxylated propoxylated cyclohexanedimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethoxylated tricyclodecane dimethanol di(meth)acrylate, propoxylated tricyclodecane dimethanol di(meth)acrylate, ethoxylated propoxylated tricyclodecane dimethanol di(meth)acrylate bifunctional alicyclic (meth)acrylate compounds such as chlorodecane dimethanol di(meth)acrylate, ethoxylated hydrogenated bisphenol A di(meth)acrylate, propoxylated hydrogenated bisphenol A di(meth)acrylate, ethoxylated propoxylated hydrogenated bisphenol A di(meth)acrylate, ethoxylated hydrogenated bisphenol F di(meth)acrylate, propoxylated hydrogenated bisphenol F di(meth)acrylate, and ethoxylated propoxylated hydrogenated bisphenol F di(meth)acrylate; Ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, ethoxylated propoxylated bisphenol A di(meth)acrylate, ethoxylated bisphenol F di(meth)acrylate, propoxylated bisphenol F di(meth)acrylate, ethoxylated propoxylated bisphenol F di(meth)acrylate, ethoxylated bisphenol AF di(meth)acrylate, propoxylated bisphenol AF di(meth)acrylate, ethoxylated propoxylated bis Examples of the difunctional aromatic (meth)acrylate compounds include phenol AF di(meth)acrylate, ethoxylated fluorene di(meth)acrylate, propoxylated fluorene di(meth)acrylate, and ethoxylated propoxylated fluorene di(meth)acrylate; and difunctional heterocyclic (meth)acrylate compounds such as ethoxylated isocyanuric acid di(meth)acrylate, propoxylated isocyanuric acid di(meth)acrylate, and ethoxylated propoxylated isocyanuric acid di(meth)acrylate.

[0245] Among the crosslinking agents other than the aromatic heterocyclic compound (B), examples of the tri- or higher functional crosslinking agents having an ethylenically unsaturated bond include trialkenyl isocyanurate compounds such as triallyl cyanurate and triallyl isocyanurate; trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, ethoxylated propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, ethoxylated propoxylated pentaerythritol and polyfunctional aliphatic (meth)acrylate compounds such as pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated propoxylated pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetraacrylate, and dipentaerythritol hexa(meth)acrylate; and polyfunctional heterocyclic (meth)acrylate compounds such as ethoxylated isocyanuric acid tri(meth)acrylate, propoxylated isocyanuric acid tri(meth)acrylate, and ethoxylated propoxylated isocyanuric acid tri(meth)acrylate.

[0246] Among these, when a styrene-based thermoplastic elastomer is used as the thermoplastic resin (A), from the viewpoint of obtaining a suitable dispersion structure of the resulting resin composition and cured product, at least one selected from the group consisting of a bifunctional aromatic vinyl compound and a trialkenyl isocyanurate compound is preferred, and among these, divinylbenzene or triallyl isocyanurate is more preferred, and from the viewpoint of low dielectric properties, trialkenyl isocyanurate is even more preferred.

[0247] When the composition contains a crosslinking agent other than the aromatic heterocyclic compound (B), the content thereof is preferably 0.1 to 90 parts by mass, more preferably 0.5 to 70 parts by mass, even more preferably 1 to 50 parts by mass, even more preferably 3 to 25 parts by mass, and particularly preferably 5 to 20 parts by mass, relative to 100 parts by mass of the thermoplastic resin (A). When the content of the crosslinking agent other than the aromatic heterocyclic compound (B) is within the above range, the crosslink density can be increased artificially without decreasing the dielectric properties of the thermoplastic resin (A), and the dielectric properties and heat resistance of the obtained cured sheet are improved.

[0248] When the present composition contains an epoxy compound as a crosslinking agent other than the aromatic heterocyclic compound (B), it is preferable to contain a curing agent that contributes to the crosslinking reaction and / or chain extension reaction between the epoxy groups of the epoxy compound. Examples of the curing agent include phenol-based curing agents, acid anhydride-based curing agents, active ester-based curing agents, amide-based curing agents, and cationic curing agent compounds. One type of curing agent may be used alone, or two or more types may be used in combination.

[0249] Examples of phenol-based curing agents include bisphenols such as bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol AD, bisphenol Z, and tetrabromobisphenol A; biphenols such as 4,4'-biphenol and 3,3',5,5'-tetramethyl-4,4'-biphenol; catechol, resorcinol, hydroquinone, dihydroxynaphthalenes; and compounds in which the hydrogen atoms bonded to the aromatic rings of these compounds are substituted with non-interfering substituents such as halogen groups, alkyl groups, aryl groups, ether groups, ester groups, and organic substituents having a hetero element such as sulfur, phosphorus, or silicon; and novolaks and resols which are polycondensates of the above-mentioned phenols or monofunctional phenols such as phenol, cresol, and alkylphenols with aldehydes.

[0250] Examples of acid anhydride curing agents include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhimic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol tristrimellitate, dodecenyl succinic anhydride, polyazelaic anhydride, and poly(ethyloctadecanedioic)anhydride.

[0251] The active ester curing agent is not particularly limited, but is generally preferably a compound having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, polyarylates, and esters of heterocyclic hydroxy compounds. The active ester curing agent is preferably one obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. From the viewpoint of improving heat resistance in particular, an active ester resin obtained from a carboxylic acid compound or a halide thereof and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound or a halide thereof and a phenol compound and / or a naphthol compound is more preferred.

[0252] Examples of the amide-based curing agent include dicyandiamide and its derivatives, polyamide resins, and the like.

[0253] The cationic polymerization curing agent generates cations when exposed to heat or active energy rays. For example, aromatic onium salts are used. More specifically, SbF ６－ , B.F. ４－ , AsF ６－ , P.F. ６－ , C.F. ３ SO ３ , B(C ６ F ５ ) ４－ and an aromatic cation component having an atom such as iodine, sulfur, nitrogen, or phosphorus.

[0254] From the viewpoint of improving various properties such as heat resistance and adhesiveness, the curing agent is preferably at least one selected from the group consisting of phenol-based curing agents, amine-based curing agents, acid anhydride-based curing agents, and active ester-based curing agents. Among them, acid anhydride-based curing agents and active ester-based curing agents are preferred from the viewpoint of not generating hydroxyl groups in the reaction product with the epoxy compound and making it easier to maintain the low dielectric properties of the cured product.

[0255] The content of the curing agent is preferably 30 to 500 parts by mass, more preferably 40 to 300 parts by mass, and even more preferably 50 to 200 parts by mass, relative to 100 parts by mass of the epoxy compound.

[0256] Furthermore, when the present composition contains the acid anhydride-based curing agent or active ester-based curing agent as a curing agent, it is preferable that a curing aid be further contained in addition to the curing agent. By using a curing aid in combination, the reaction of the epoxy compound proceeds efficiently. Examples of the curing aid include organic phosphine-based curing aids, phosphonium salt-based curing aids, tetraphenylboron salt-based curing aids, metal-based curing aids, imidazole-based curing aids, amine-based curing aids, organic acid dihydrazide curing aids, and boron halide amine complex-based curing aids. These curing aids may be used alone, or two or more may be mixed in any combination and ratio.

[0257] Examples of organic phosphine-based curing aids, phosphonium salt-based curing aids, and tetraphenylboron salt-based curing aids include triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkyl / alkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, and tris(tetraalkoxyphenyl)phosphine. Examples of the organic phosphines include phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, and other organic phosphines; complexes of these organic phosphines with organic borons; and compounds obtained by adding these organic phosphines to maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and other quinone compounds; and diazophenylmethane.

[0258] The metal-based curing aid is not particularly limited. Examples include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organic copper complexes such as copper(II) acetylacetonate, organic zinc complexes such as zinc(II) acetylacetonate, organic iron complexes such as iron(III) acetylacetonate, organic nickel complexes such as nickel(II) acetylacetonate, and organic manganese complexes such as manganese(II) acetylacetonate.

[0259] Examples of organic metal salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. As the metal curing aid, from the viewpoints of curability and solvent solubility, cobalt(II) acetylacetonate, cobalt(III) acetylacetonate, zinc(II) acetylacetonate, zinc naphthenate, and iron(III) acetylacetonate are preferred, with cobalt(III) acetylacetonate and zinc naphthenate being particularly preferred.

[0260] Examples of the imidazole-based curing aid include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, and 1-cyanoethyl-2-methylimidazole. azole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2, 4-Diamino-6-[2'-undecylimidazolyl-(1')]-ethyl s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric-a]benzimidazole, 1-dodecyl Examples of imidazole compounds include 2-phenyl-2-methyl-3-benzylimidazolium carboxylic acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds with epoxy resins.

[0261] Examples of the amine curing aid include trialkylamines such as triethylamine and tributylamine; and amine compounds such as 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene (hereinafter abbreviated as DBU).

[0262] When the composition further contains a curing aid, the content thereof is, from the viewpoint of the progress of the curing reaction, preferably 0.01% by mass or more, more preferably 0.03% by mass or more, even more preferably 0.05% by mass or more, and is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, even more preferably 0.1% by mass or less, relative to 100 parts by mass of the epoxy compound.

[0263] Examples of inorganic particles include calcium carbonate, magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, calcium sulfate, zinc oxide, magnesium oxide, calcium oxide, titanium oxide, aluminum oxide, zinc oxide, alumina, aluminum hydroxide, hydroxyapatite, silica, magnesium silicate, mica, talc, kaolin, clay, glass powder, asbestos powder, zeolite, and clay silicate.

[0264] Examples of organic particles include (meth)acrylate resin particles, styrene resin particles, silicone resin particles, nylon resin particles, polyethylene resin particles, benzoguanamine resin particles, and urethane resin particles.

[0265] When inorganic particles or organic particles are contained, the content thereof is preferably 1 part by mass or more and 200 parts by mass or less, more preferably 5 parts by mass or more and 150 parts by mass or less, and even more preferably 10 parts by mass or more and 100 parts by mass or less, per 100 parts by mass of the resin component of the composition. When the content of inorganic particles or organic particles is equal to or more than the above-mentioned lower limit, the dielectric properties of the cured sheet can be further reduced, and the linear thermal expansion coefficient of the cured sheet can be reduced, making it less likely to peel from the substrate when used as a circuit board material. On the other hand, when the content of inorganic particles or organic particles is equal to or less than the above-mentioned upper limit, the moldability of the cured sheet can be improved.

[0266] [Resin Sheet] A resin sheet according to one embodiment of the present invention (hereinafter also referred to as "the present resin sheet") is obtained by molding the present composition in an uncured state into a sheet shape.

[0267] The thickness of the resin sheet is preferably 10 to 500 μm, more preferably 50 to 400 μm, and even more preferably 100 to 350 μm. When the thickness of the resin sheet is equal to or greater than the lower limit of the above-mentioned numerical range, the resin sheet exhibits good handleability. When the thickness of the resin sheet is equal to or less than the upper limit of the above-mentioned numerical range, the resin sheet exhibits good conformability to uneven surfaces of the substrate when used as a circuit board material. The thickness of the resin sheet can be measured with a micrometer. The thickness of the resin sheet may also be calculated by observing the cross section of the resin sheet using a microscope or the like.

[0268] The weight loss rate of the resin sheet measured by thermogravimetric analysis (TGA) when heated from 35°C to 300°C at a rate of 10°C / min under atmospheric pressure is preferably 12% or less, more preferably 10% or less, even more preferably 8% or less, and even more preferably 7% or less. If the weight loss rate is below the upper limit, foaming of the resin sheet during curing and poor adhesion to the adherend can be reduced. From the above perspective, the lower the weight loss rate, the more preferable, with 0% being most preferable. Since the resin sheet contains the above-mentioned aromatic heterocyclic compound (B) as a crosslinkable component, the crosslinkable component is less likely to volatilize even before curing, making it possible to provide a resin composition with little outgassing.

[0269] The thickness of the resin sheet after curing is preferably 10 to 500 μm, more preferably 50 to 400 μm, and even more preferably 100 to 350 μm. When the thickness of the resin sheet after curing is equal to or greater than the above-mentioned lower limit, handling properties are improved. Furthermore, when the thickness is equal to or less than the above-mentioned upper limit, conformability to unevenness in the substrate is improved when the resin sheet is used as a circuit board material. The thickness is measured with a micrometer on the cured product obtained by heat-pressing the resin sheet at 200°C and 2 MPa for 30 minutes.

[0270] The relative dielectric constant of the resin sheet after curing is preferably 4 or less, more preferably 3 or less, and even more preferably 2.5 or less. On the other hand, there is no particular lower limit to the relative dielectric constant, and it is sufficient if it is 1 or more.

[0271] The dielectric loss tangent of the resin sheet after curing is preferably 0.002 or less, more preferably 0.0018 or less, and even more preferably 0.0015 or less. On the other hand, the lower limit of the dielectric loss tangent is not particularly limited, as long as it is 0 or more. The relative dielectric constant and the dielectric loss tangent are values ​​obtained by measuring the cured product obtained by heat-pressing the resin sheet at 200°C and 2 MPa for 30 minutes as a test piece at a temperature of 23°C and a frequency of 10 GHz in accordance with JIS C2565:1992.

[0272] From the viewpoint of heat resistance, the storage modulus (200°C) of the present resin sheet after curing is preferably 0.01 MPa or more, more preferably 0.05 MPa or more, and even more preferably 0.1 MPa or more. The upper limit of the storage modulus (200°C) is not particularly limited, but is preferably 10 MPa or less, more preferably 5 MPa or less. The storage modulus is a value determined by measuring the dynamic viscoelasticity of a test piece obtained by hot pressing the present resin sheet at 200°C and 2 MPa for 30 minutes.

[0273] From the viewpoint of heat resistance when mounted on a device, the heat resistance temperature of the resin sheet after curing is preferably 200° C. or higher and 500° C. or lower. The heat resistance temperature is a value obtained by reading the temperature just before the resin sheet changes from a rubbery flat region to a viscous liquid state in a graph obtained by measuring the dynamic viscoelasticity of a test piece obtained by heat pressing the resin sheet at 200° C. and 2 MPa for 30 minutes and then curing the test piece.

[0274] The linear thermal expansion coefficient of the resin sheet after curing is preferably 200 ppm / °C or less, more preferably 180 ppm / °C or less, and even more preferably 160 ppm / °C or less. Among these, 150 ppm / °C or less is preferred, 120 ppm / °C or less is more preferred, 110 ppm / °C or less is even more preferred, and 105 ppm / °C or less is even more preferred. The lower limit of the linear thermal expansion coefficient is not particularly limited, but from the viewpoint of preventing peeling or deformation from the conductor when the cured sheet is used as a circuit board material, 10 ppm / °C or more is preferred. The linear thermal expansion coefficient can be measured by thermomechanical analysis using a test piece obtained by heat-pressing the resin sheet at 200°C and 2 MPa for 30 minutes and subjecting the cured product to a method conforming to JIS K7197 (2012). Specifically, a thermal analyzer "TMA 841" (manufactured by Mettler Toledo) was used, and the sample shape was 5 mm wide x 16 mm long. Measurement was started from 30°C, the temperature was raised to 100°C at 5°C / min, and the sample was cooled to 0°C once, and then the temperature was raised again to 150°C. The dimensional change during the reheating process was measured, and based on these results, the average value of the thermal expansion coefficient in the in-plane direction from 0 to 120°C was calculated.

[0275] [Laminate] In order to improve the handling properties of the present resin sheet, a release film may be provided on one or both surfaces to form a laminate.

[0276] The release film may be a resin film whose main component is, for example, a polyolefin such as polyethylene or polypropylene, a polyester such as polyethylene terephthalate or polyethylene naphthalate, a polyimide, or a polycarbonate. The surface of these films may be coated with a silicone resin release agent or the like to adjust the peel strength.

[0277] The thickness of the release film is preferably 1 to 300 μm, more preferably 5 to 200 μm, even more preferably 10 to 150 μm, and even more preferably 20 to 120 μm. The surface of the release film that comes into contact with the resin sheet may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

[0278] The laminate may be wound around a core to form a wound body. In a wound body according to one embodiment of the present invention, the length of the laminate is preferably 10 m or more, more preferably 20 m or more. When the length of the laminate is 10 m or more, for example, when the resin sheet is used as a flexible laminate or a stretchable laminate, it is possible to continuously produce electronic components, and the continuous film production is excellent. The upper limit of the length of the laminate is not particularly limited, but 1000 m or less is preferable.

[0279] The material of the core is not particularly limited, but examples thereof include paper, resin-impregnated paper, acrylonitrile / butadiene / styrene copolymer (ABS resin), fiber-reinforced plastic (FRP), phenolic resin, inorganic-containing resin, etc. An adhesive may be used for the core.

[0280] [Method for Producing Resin Sheet] Hereinafter, a method for producing the resin sheet will be described, but the method for producing the resin sheet is not limited to the following method.

[0281] (First Manufacturing Method) The first manufacturing method of the present resin sheet includes a coating liquid preparation step of preparing a coating liquid comprising a resin composition, and a molding step of molding the coating liquid into a sheet. The first manufacturing method is preferable in that the thermoplastic resin (A) and the aromatic heterocyclic compound (B) are suitably compatible with each other, and an optimal crosslinked structure is easily formed after curing, resulting in good low dielectric properties.

[0282] Coating solution preparation step: In the coating solution preparation step, the thermoplastic resin (A), the aromatic heterocyclic compound (B), and the cyclic polyolefin resin copolymer (C), the organic peroxide (D), the solvent (E), and other components added as needed are stirred and mixed uniformly to obtain a coating solution. For mixing, a general mixing / stirring device such as a mixer, blender, three-roll kneader, ball mill, kneader, single-screw kneader, or twin-screw kneader can be used, and heating may be performed during mixing as needed.

[0283] Molding step: In the molding step, the coating liquid is molded into a sheet to obtain a resin sheet. A known method can be used to mold the coating liquid into a sheet. For example, a doctor blade method, a solvent casting method, or an extrusion film formation method may be used. A preferred molding method includes a method including the following (2-1) coating step and (2-2) drying step.

[0284] Coating step: In the coating step, a coating liquid is applied to the surface of a release film to form a coating film. The coating method may be a common method such as a dip method, a spin coating method, a spray coating method, or a blade method. A coating device such as a spin coater, a slit coater, a die coater, or a blade coater can be used for coating, and this makes it possible to form a coating film of a predetermined thickness uniformly on the release film.

[0285] Drying step: In the drying step, the solvent is removed from the coating film formed above. The drying temperature is not particularly limited, but is usually 10 to 150°C, preferably 25 to 120°C, and more preferably 30 to 110°C. When the drying temperature is equal to or lower than the upper limit, the crosslinking reaction of the aromatic heterocyclic compound (B) in the coating film is suppressed. When the drying temperature is equal to or higher than the lower limit, foaming of the resin sheet is suppressed, the solvent can be effectively removed, and productivity is improved.

[0286] The drying time can be adjusted appropriately depending on the state of the coating film, the drying environment, etc. The drying time is preferably 1 minute or more, more preferably 2 minutes or more, even more preferably 5 minutes or more, still more preferably 10 minutes or more, particularly preferably 20 minutes or more, and most preferably 30 minutes or more. On the other hand, the drying time is preferably 4 hours or less, more preferably 3 hours or less, and even more preferably 2 hours or less. When the drying time is equal to or greater than the above lower limit, the solvent can be sufficiently removed. When the drying time is equal to or less than the above upper limit, productivity can be improved and production costs can be reduced. The solvent in the resin composition can be removed by a known heating method such as a hot plate, a hot air oven, an IR heating oven, a vacuum dryer, or a high-frequency heater.

[0287] From the viewpoint of preventing contamination of the surface of the resin sheet and improving handling properties, a release film may be laminated on the resin sheet after the drying step.

[0288] (Second Manufacturing Method) The second manufacturing method of the present resin sheet includes a film-forming step of extruding a resin composition onto a release film. The second manufacturing method does not require the use of a solvent, and is therefore preferable in terms of cost, ease of multi-layering, and the reduced likelihood of problems caused by residual solvent.

[0289] Film-forming process: In the film-forming process, the thermoplastic resin (A), the aromatic heterocyclic compound (B), and the cyclic polyolefin resin copolymer (C), organic peroxide (D), and other components added as needed are kneaded in a single-screw extruder or a twin-screw extruder, and extruded onto a release film using an extruder or the like under temperature conditions that are equal to or higher than the melting point of the thermoplastic resin (A) and lower than the crosslinking temperature of the aromatic heterocyclic compound (B), to form a film. The extrusion method for the resin composition is not particularly limited, but more specifically, T-die molding can be mentioned.

[0290] [Cured Product] A cured product according to one embodiment of the present invention (hereinafter also referred to as the "cured product") is obtained by curing a resin composition. The curing temperature of the resin composition may be any temperature at which the thermoplastic resin (A) does not flow and at which the crosslinking reaction of the aromatic heterocyclic compound (B) proceeds. Specifically, the curing temperature is preferably 120 to 300°C, more preferably 140 to 250°C, and even more preferably 150 to 220°C. The curing time of the resin sheet is not particularly limited, but is preferably 10 minutes to 1 hour.

[0291] The preferred physical properties of the cured product, such as the relative dielectric constant, dielectric loss tangent, storage modulus, heat resistance temperature, and coefficient of linear thermal expansion, are the same as those of the resin sheet after curing, as described above.

[0292] [Uses of Resin Composition, Resin Sheet, and Cured Product] Uses of the resin composition, resin sheet, and cured product include, but are not limited to, copper foil laminates, stretchable substrates, flexible printed circuit boards, multilayer printed wiring boards, circuit board materials for electric and electronic devices such as capacitors, underfill materials, interchip fills for 3D-LSIs, insulating sheets, vibration damping materials, adhesives, solder resists, semiconductor encapsulants, hole-filling resins, and component-embedding resins.

[0293] [Circuit Board Material] The resin sheet can be used as a circuit board material by laminating it with a conductor.

[0294] The conductor may be a metal foil made of a conductive metal such as copper or aluminum, or an alloy containing such a metal, or a metal layer formed by plating or sputtering.

[0295] When used as a circuit board material for electric and electronic devices, the resin sheet preferably has a thickness of 10 μm or more and 500 μm or less, and the conductor preferably has a thickness of 0.2 μm or more and 70 μm or less.

[0296] In a circuit board material in which a resin layer made of the present resin composition and a conductor are laminated, when the resin layer is sandwiched between two adherends, the distance between the two adherends can also be considered the thickness of the present resin sheet. When the adherends have an uneven portion and a flat portion on the surface in contact with the resin layer, the distance between the flat portions of the two adherends can be considered the thickness of the present resin sheet. When the adherends do not have a flat portion on the surface in contact with the resin sheet, the distance between the two adherends at the widest point can be considered the thickness of the present resin sheet. When only one adherend has a flat portion on the surface in contact with the present resin sheet and the other adherend does not have a flat portion on the surface in contact with the present resin sheet, the distance between the flat portion of one adherend and the other adherend at the widest point can be considered the thickness of the present resin sheet.

[0297] The thickness of the present resin sheet in the circuit board material can be measured with a micrometer after peeling off the adherend. The thickness of the present resin sheet in the circuit board material may also be calculated by observing the cross section of the circuit board material with a microscope or the like.

[0298] (Method for manufacturing circuit board material) The circuit board material can be manufactured, for example, by the following method. In one example, a resin sheet is laminated on a conductor, and then the resin sheet is heat-cured to form an insulating layer. A conductor is further laminated on the insulating layer, and such layers are stacked as many times as necessary.

[0299] The curing temperature of the resin sheet may be any temperature at which the thermoplastic resin (A) does not flow and the crosslinking reaction of the aromatic heterocyclic compound (B) proceeds. Specifically, the curing temperature of the resin sheet is preferably 120 to 300°C, more preferably 140 to 250°C, and even more preferably 150 to 220°C. The curing time is not particularly limited, but is preferably 10 minutes to 1 hour.

[0300] The lamination of the resin sheet and the conductor may be a method of directly overlapping a conductive metal foil such as copper foil on the resin sheet, or a method of bonding the resin sheet and the conductive metal foil such as copper foil using an adhesive. In the circuit board material of this embodiment, when the conductor is laminated, it is preferably directly bonded without an adhesive layer. Alternatively, a method of forming a conductive metal layer by plating or sputtering may be used, or these methods may be combined. Furthermore, the method may include a step of drilling holes in the insulating layer to form via holes, or a step of roughening the surface of the insulating layer.

[0301] Hereinafter, the embodiments will be described in more detail with reference to examples, but the present invention is not limited to the following description in any way.

[0302] [Raw Materials] (Thermoplastic Resin (A)) a-1: Styrene-ethylene-butadiene-styrene block copolymer (SEBS: manufactured by Asahi Kasei Corporation, "Tuftec H1052"), styrene content 20% by mass, storage modulus (24°C) = 6.2 MPa, density = 0.890 g / cm ３a-2: Styrene-ethylene-butadiene-styrene block copolymer (SEBS: manufactured by Asahi Kasei Corporation, "Tuftec H1043"), styrene content 67% by mass, storage modulus (24 ° C) = 1300 MPa, density = 0.970 g / cm ３

[0303] (Aromatic heterocyclic compound (B)) Compounds represented by the following formulae (b-1), (b-2), (b-3), and (b-4) were used. The synthesis procedures for each compound are as follows.

[0304] Synthesis Example 1: Synthesis of Compound Represented by Formula (b-1) 4,6-dichloropyrimidine (2b) (10.0 g, 67.1 mmol) and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (1b) (18.8 g, 60.4 mmol) were weighed into a four-neck flask equipped with a stirrer, and N-methyl-2-pyrrolidone (99.8 g) was added. With stirring, potassium carbonate (19.6 g, 141 mmol) was added, and the mixture was then reacted at 110°C for 4.5 hours under a nitrogen atmosphere. After the reaction solution was cooled to 80°C, a 10% by mass propylene glycol solution of 4-vinylphenol (3b) (12.1 g, 10.1 mmol) was added to the reaction solution, and the mixture was reacted at 110°C for 1 hour. After completion of the reaction, the reaction solution was cooled to room temperature, and the reaction solution was added to 1 L of cooled distilled water to cause crystallization. The precipitated crystals were separated by filtration, then dissolved in 500 mL of dichloromethane, and washed with 150 mL of distilled water. This washing with distilled water was repeated five times. The separated dichloromethane solution was concentrated to half its volume using an evaporator, and the concentrated solution was added to 1.2 L of methanol. The precipitated crystals were collected by filtration and then dried in a vacuum dryer at 80°C to obtain a compound represented by the following formula (b-1) (yield: 20.3 g, yield: 78.0%). The compound represented by formula (b-1) had a mass average molecular weight (Mw) of 5,500, a number average molecular weight (Mn) of 3,700, a glass transition temperature (Tg) of 171°C, and a 5% weight loss temperature (Td5) of 429°C.

[0305]

[0306] Synthesis Example 2: Synthesis of Compound Represented by Formula (b-2) (1) Synthesis of 2,4-dichloro-6-phenyl-1,3,5-triazine (6b) Tetrahydrofuran (2 L) and cyanuric chloride (4b) (200 g, 1.09 mol) were dissolved in a four-neck flask equipped with a stirrer and stirred under a nitrogen atmosphere. To this solution, a 3 mol / L tetrahydrofuran solution of phenylmagnesium bromide (5b) (397.66 mL, 1.19 mol) was added dropwise at 0°C to 5°C. After the addition, the mixture was stirred at 30°C for 12 hours under a nitrogen atmosphere. The reaction mixture was then quenched by slowly adding 100 mL of saturated aqueous ammonium chloride solution at 0°C to 5°C. Next, the tetrahydrofuran was removed under reduced pressure, and the residue was dissolved in ethyl acetate (3 L) and washed with water (2 L, twice). The organic layer was dried over anhydrous sodium sulfate, and the sodium sulfate was filtered off. The filtrate was concentrated to obtain a crude product of 2,4-dichloro-6-phenyl-1,3,5-triazine (6b).

[0307]

[0308] The crude product was added to a mixed solution of petroleum ether and ethyl acetate to cause precipitation, and the precipitate was filtered and dried to obtain 2,4-dichloro-6-phenyl-1,3,5-triazine (6b) (157 g, 694.50 mmol, yield 64.0%, HPLC purity 98.8%) as a light brown solid. １ The 1 H NMR spectrum was consistent with the desired product. １ H NMR (400MHz, CDCl3) δ=8.52 (dd, J=1.2, 8.4Hz, 2H), 7.71-7.62 (m, 1H), 7.58-7.47 (m, 2H)

[0309] (2) Synthesis of Polymer Represented by Formula (b-2) 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (1b) (35.8 g, 115 mmol) was weighed into a four-neck flask equipped with a stirrer, and N-methyl-2-pyrrolidone (132 g) was added. Under stirring, potassium carbonate (38.8 g, 279 mmol) was added, followed by 2,4-dichloro-6-phenyl-1,3,5-triazine (6b) (30.0 g, 133 mmol). The mixture was then reacted at 60°C for 8 hours under a nitrogen atmosphere. Next, 3-vinylphenol (7b) (4.2 g, 35 mmol) was added to the reaction solution, and the mixture was reacted at 60°C for 8 hours. After completion of the reaction, the reaction solution was cooled to room temperature and filtered to remove salts. The resulting filtrate was added dropwise to 1.2 L of distilled water to cause crystallization. The precipitated crystals were filtered off and washed with distilled water. The resulting crystals were added to 500 mL of methanol and stirred for 1 hour. The crystals were then filtered off and collected, followed by drying in a vacuum dryer at 120 ° C. The dried crude crystals were dissolved in 150 g of dichloromethane, the solution was filtered to remove insoluble matter, and the solution was then added to a mixed solution of 600 mL of methanol and 600 mL of acetone to cause crystallization. The precipitated crystals were filtered off and collected, followed by drying in a vacuum dryer at 120 ° C. to obtain a polymer represented by formula (b-2) (yield: 44.8 g, yield: 72.8%). The polymer represented by formula (b-2) had a mass average molecular weight (Mw) of 4,400, a number average molecular weight (Mn) of 2,900, a glass transition temperature (Tg) of 203 ° C., and a 5% weight loss temperature (Td5) of 388 ° C.

[0310]

[0311] Synthesis Example 3: Synthesis of Compound Represented by Formula (b-3) 4,4-(1,1,1,3,3,3-hexafluoropropane-2,2-diyl)biphenol (8b) (47.6 g, 142 mmol) was weighed into a four-neck flask equipped with a stirrer, and N-methyl-2-pyrrolidone (175 g) was added thereto. With stirring, potassium carbonate (51.7 g, 372 mmol) was added thereto, followed by 2,4-dichloro-6-phenyl-1,3,5-triazine (6b) (40.0 g, 177 mmol). The mixture was then reacted at 60°C for 6 hours under a nitrogen atmosphere. Next, 3-vinylphenol (7b) (4.3 g, 35.4 mmol) was added to the reaction solution, and the mixture was reacted at 60°C for 4 hours. After the reaction was completed, the reaction solution was cooled to room temperature, filtered to remove salts, and the resulting filtrate was added dropwise to 1.2 L of distilled water to cause crystallization. The precipitated crystals were filtered off and washed with distilled water. The resulting crystals were added to 500 mL of methanol and stirred for 1 hour. The crystals were then collected by filtration and dried in a vacuum dryer at 120 °C. The dried crude crystals were dissolved in 400 g of dichloromethane, filtered to remove insoluble matter, and then added to a mixed solution of 800 mL of methanol and 400 mL of acetone to cause crystallization. The precipitated crystals were collected by filtration and dried in a vacuum dryer at 120 °C to obtain the compound represented by formula (b-3) (yield: 45.9 g, 53.0%). The compound represented by formula (b-3) had a mass average molecular weight (Mw) of 4,300, a number average molecular weight (Mn) of 3,000, a glass transition temperature (Tg) of 180°C, and a 5% weight loss temperature (Td5) of 382°C.

[0312]

[0313] Synthesis Example 4: Synthesis of Compound Represented by Formula (b-4) 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (1b) (22.0 g, 70.8 mmol) and 2,2-bis(4-hydroxy-3-methylphenyl)propane (9b) (18.1 g, 70.8 mmol) were weighed into a four-neck flask equipped with a stirrer, and N-methyl-2-pyrrolidone (175 g) was added. With stirring, potassium carbonate (51.5 g, 372 mmol) was added, followed by 2,4-dichloro-6-phenyl-1,3,5-triazine (6b) (40.0 g, 177 mmol). The mixture was then reacted at 60°C for 9 hours under a nitrogen atmosphere. Next, 3-vinylphenol (7b) (4.3 g, 35.4 mmol) was added to the reaction solution, and the mixture was reacted at 60°C for 12 hours. After the reaction was completed, the reaction solution was cooled to room temperature, filtered to remove salts, and the resulting filtrate was added dropwise to 1.2 L of distilled water to cause crystallization. The precipitated crystals were filtered off and washed with distilled water. The resulting crystals were added to 500 mL of methanol and stirred for 1 hour. The crystals were then collected by filtration and dried in a vacuum dryer at 120 °C. The dried crude crystals were dissolved in 200 g of dichloromethane, filtered to remove insoluble matter, and then added to a mixed solution of 600 mL of methanol and 200 mL of acetone to cause crystallization. The precipitated crystals were collected by filtration and dried in a vacuum dryer at 120 °C to obtain the compound represented by formula (b-4) (yield: 54.0 g, 70.0%). The compound represented by formula (b-4) had a mass average molecular weight (Mw) of 4,400, a number average molecular weight (Mn) of 2,300, a glass transition temperature (Tg) of 188°C, and a 5% weight loss temperature (Td5) of 383°C.

[0314]

[0315] For use in a comparative example, the following (b'-1), an ethylenically unsaturated bond-containing compound having no aromatic heterocycle, was used: b'-1: triallyl isocyanurate (TAIC: manufactured by Shinryo Corporation), mass average molecular weight (Mw): 250

[0316] (Cyclic Polyolefin Resin Copolymer (C)) c-1: cyclic polyolefin copolymer (HSEBS: Mitsubishi Chemical Corporation, "TEFABLOC CP CP402", hydrogenated aromatic vinyl polymer block unit: content of 67 mol%, hydrogenated polystyrene having a hydrogenation level of 99% or more, hydrogenated conjugated diene polymer block unit: content of 33 mol%, hydrogenated polybutadiene having a hydrogenation level of 99% or more, block structure: pentablock structure, total hydrogenation level: 99% or more, crystalline melting peak temperature: 75°C, MFR (230°C, 2.16 kg): 85 g / 10 min)

[0317] (Organic Peroxide (D)) d-1: 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne (manufactured by NOF Corporation)

[0318] (Solvent (E)) e-1: toluene (content > 99.0 mass%)

[0319] Example 1: The raw materials were blended in the proportions shown in Table 1 and heated to approximately 80°C to completely dissolve the raw materials to prepare a resin composition. The prepared resin composition was spread into a sheet on the release-treated surface of a 50 μm-thick release film (PET film manufactured by Mitsubishi Chemical Corporation) that had been treated with a silicone release agent to obtain a resin sheet. The thickness of the resin sheet was adjusted so that the thickness of the sheet after curing would be approximately 300 μm. The resin sheet spread on the release film was dried in an oven at 100°C for 10 minutes to volatilize the solvent, and then a 50 μm-thick release film (PET film manufactured by Mitsubishi Chemical Corporation) that had been treated with a silicone release agent was laminated on top of the resin sheet with the release-treated surface facing the resin sheet to form a laminate. The laminate was held in a heat press at 200°C for 30 minutes under a pressure of approximately 2 MPa to completely cure the resin sheet, and the release films on both sides were peeled off to obtain a cured sheet. The resulting resin sheet was evaluated for copper foil adhesion. The resulting cured sheets were evaluated for dielectric properties, coefficient of linear thermal expansion, and copper foil adhesion.

[0320] [Examples 2 to 9, Comparative Examples 1 to 5] Resin compositions were prepared in the same manner as in Example 1, except that the raw materials were blended according to the proportions shown in Table 1. Furthermore, resin sheets and cured sheets were produced in the same manner as in Example 1. The obtained resin sheets were evaluated for copper foil adhesion. Furthermore, the obtained cured sheets were evaluated for dielectric properties, linear thermal expansion coefficient, and copper foil adhesion.

[0321] [Compatibility] The compatibility of the resin composition of each example was evaluated visually. The evaluation criteria are as follows: A: The resin composition is uniformly mixed. B: The resin composition is not uniform, and the components are separated. When the compatibility was rated B, a uniform film could not be formed, so the following measurements of copper foil adhesion, dielectric properties, and linear thermal expansion coefficient were not performed.

[0322] [Average Molecular Weight] The mass average molecular weight (Mw) and number average molecular weight (Mw) of the compounds represented by Formula (b-1), Formula (b-2), Formula (b-3), and Formula (b-4) were measured using gel permeation chromatography (GPC) under the following conditions: GPC apparatus: Shimadzu Corporation, SCL-10AVP Column: Four TSKgel SuperHZM-N columns (Tosoh Corporation, particle size 3 μm, inner diameter 4.6 mm, length 15 cm) connected together Mobile phase: Tetrahydrofuran (containing 0.03 vol% of 2,6-di-t-butyl-4-methylphenol as a stabilizer) Detector: Parallax refractive index detector, standard substance: monodisperse polystyrene Flow rate: 0.35 mL / min Sample concentration: 0.1 mass%, sample injection amount: 10 μL Column oven temperature: 40° C. Measurement time: 30 minutes

[0323] [Glass Transition Temperature (Tg)] The glass transition temperatures (Tg) of the compounds represented by Formula (b-1), Formula (b-2), Formula (b-3), and Formula (b-4) were measured by heating approximately 10 mg of a resin sample at a heating rate of 10°C / min using a differential scanning calorimeter (DSC7020 AS-3D manufactured by SII), measuring the calorific value, and determining, in accordance with ISO 3146, the extrapolated glass transition onset temperature, which is the temperature at the intersection of a straight line extending the low-temperature baseline toward the high-temperature side and a tangent drawn at the point where the gradient of the curve of the stepwise change in the glass transition is maximum, and this extrapolated glass transition temperature was taken as the glass transition temperature (Tg).

[0324] [5% Weight Loss Temperature (Td5)] For each of the compounds represented by Formula (b-1), Formula (b-2), Formula (b-3), and Formula (b-4), approximately 5 mg of a sample was heated at a temperature increase rate of 10°C / min using a simultaneous differential scanning calorimeter (TG-DTA EXTER6000, manufactured by SII), and the 5% weight loss temperature (Td5) was measured from the obtained thermal decomposition curve.

[0325] [Thermogravimetric analysis (TGA)] The weight loss rate (%) was measured by thermogravimetric analysis for each of the resin sheets produced in Examples 1 to 9 and Comparative Examples 1 and 3. Specifically, using a thermogravimetric analyzer "NEXTA STA200RV" (manufactured by Hitachi Science Techno Co., Ltd.), approximately 2 mg of the sample was weighed, and the weight change was measured when the temperature was raised from 35°C to 300°C at a rate of 10°C / min, and the weight loss rate (%) was calculated. The results are shown in Table 2.

[0326] [Dielectric Properties] The in-plane dielectric constant and dielectric loss tangent of the cured sheet were measured in TE mode using a cavity resonator (manufactured by AET Co., Ltd.) and a network analyzer MS46 122B (manufactured by Anritsu Co., Ltd.) at a measurement frequency of 10 GHz.

[0327] [Linear thermal expansion coefficient] The linear thermal expansion coefficient of the cured sheet was measured by thermomechanical analysis according to JIS K7197 (2012). Specifically, using a thermal analyzer "TMA 841" (manufactured by Mettler Toledo), the sample shape was 5 mm wide x 16 mm long, and the measurement was started from 30 ° C., heated to 100 ° C. at a rate of 5 ° C. / min, cooled to 0 ° C., and then reheated to 150 ° C. The dimensional change during the reheating process was measured, and the average thermal expansion coefficient in the in-plane direction from 0 to 120 ° C. was calculated based on the results.

[0328] [Copper Foil Adhesion] The release films on both sides of the resin sheet were peeled off, and the resin sheet was bonded to the roughened surface of a low-roughness electrolytic copper foil ("CF-T4X-SV" manufactured by Fukuda Metals Co., Ltd.) having a surface roughness (Rz) of 1.0 μm. An uncured copper foil laminate consisting of copper foil / resin sheet / copper foil was produced. The copper foil laminate was sandwiched between flat metal plates, and a pressure of 2 MPa was applied to the adhesive layer, and the heat press treatment was performed at 200°C for 30 minutes to cure the resin sheet, yielding a cured copper foil laminate. A test piece measuring 1 cm wide x 15 cm long was cut from the cured copper foil laminate, and the peel strength at the interface between the copper foil and the adhesive layer was measured using a universal testing machine "AG-X plus" (manufactured by Shimadzu Corporation) under the following conditions. The adhesion strength to the copper foil was calculated as the average value over a 2 cm section where stable peeling was possible. Peel angle: 180 degrees; Temperature: Room temperature; Peel speed: 50 mm / min

[0329]

[0330]

[0331] In Examples 1 to 9, cured sheets were obtained that had low dielectric properties and excellent adhesion to conductors and heat resistance. In contrast, in Comparative Example 1, a compound having an ethylenically unsaturated bond outside the scope of the aromatic heterocyclic compound (B) was used, resulting in poor dielectric properties. Additionally, as shown in Table 2, the weight loss rate was high and outgassing increased. In Comparative Examples 2 to 5, the resin compositions were separated due to incompatibility between the thermoplastic resin (A) and the aromatic heterocyclic compound (B). Due to poor compatibility, smooth resin sheets could not be produced.

[0332] Although several embodiments of the present invention have been described above, each embodiment is presented as an example and does not limit the scope of the present invention. Each embodiment described in this specification can be modified in various ways within the scope of the effects of the invention and can be combined with features described in other embodiments within the scope of feasibility.

[0333] According to the present invention, there are provided a sheet cured product and a circuit board material having low dielectric properties, excellent conductor adhesion, and heat resistance, as well as a resin composition, a resin sheet, and a laminate from which the sheet cured product and the circuit board material having low dielectric properties and heat resistance can be produced.

Claims

1. A resin composition comprising: at least one thermoplastic resin (A) selected from the group consisting of a styrene-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, and an ethylene-based polymer; and an aromatic heterocyclic compound (B) having two or more ethylenically unsaturated bonds in the molecule, wherein the content of the thermoplastic resin (A) is more than 50% by mass and less than 99% by mass, based on the total mass of the solid content of the resin composition.

2. The resin composition according to claim 1, wherein the thermoplastic resin (A) contains a styrene-based thermoplastic elastomer.

3. The resin composition according to claim 2, wherein the styrene content of the styrene-based thermoplastic elastomer (A) is 10% by mass or more and 70% by mass or less.

4. The resin composition according to claim 1, wherein the aromatic heterocyclic compound (B) has a mass average molecular weight of 1,000 or more and 50,000 or less.

5. The resin composition according to claim 1, wherein the aromatic heterocyclic compound (B) is a compound having a unit represented by the following formula (1) and a terminal group Z represented by the following formula (2). In formula (1), L １ and L ２ are each independently —O— or —S—, and X １ is a divalent organic group, and Y １ is a divalent substituted or unsubstituted nitrogen-containing aromatic heterocycle. In formula (2), Z represents an alkyl group having 3 to 30 carbon atoms and having an ethylenically unsaturated bond, an aryl group having 6 to 20 carbon atoms and having an ethylenically unsaturated bond, or an aralkyl group having 3 to 30 carbon atoms and having an ethylenically unsaturated bond, and the alkyl group having 3 to 30 carbon atoms, the aryl group having 6 to 20 carbon atoms and having an ethylenically unsaturated bond, and the aralkyl group having 3 to 30 carbon atoms and having an ethylenically unsaturated bond may have a substituent, and when the alkyl group having 3 to 30 carbon atoms, the aryl group having 6 to 20 carbon atoms and having an ethylenically unsaturated bond, or the aralkyl group having 3 to 30 carbon atoms and having an ethylenically unsaturated bond has a substituent, the substituent is a group other than a hydroxy group.

6. The above X １ The resin composition according to claim 5 , wherein is a divalent organic group having a substituted or unsubstituted aromatic hydrocarbon ring.

7. The above X １ The resin composition according to claim 5 , wherein is a divalent organic group represented by the following formula (3): In formula (3), R ３ is a single bond, -O-, -S-, -SO ２ represents -, -C(=O)O- or a divalent organic group. ４ and R ５ each independently represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. The linear or branched alkyl group having 1 to 20 carbon atoms, the cycloalkyl group having 5 to 20 carbon atoms, the linear or branched alkenyl group having 1 to 20 carbon atoms, and the aryl group having 6 to 20 carbon atoms may be substituted with a halogen atom or a substituent having an ethylenically unsaturated double bond. m and n each independently represent an integer of 0 to 4. When m and n each are 2 or more, multiple R ４ and R ５ may be the same or different from one another and may be bonded in any combination to form part of a ring structure.

8. The above X １ The resin composition according to claim 7, wherein is a divalent organic group represented by the following formula (4): In formula (4), R ３ , R ４ and R ５ are R in the formula (3), respectively. ３ , R ４ and R ５ is synonymous with.

9. R ３ The resin composition according to claim 7, wherein is a divalent organic group represented by the following formula (5): In formula (5), R ６ and R ７ R each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen atom, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group. ６ and R ７ may be bonded to each other to form a ring.

10. The above X １ The resin composition according to claim 5, wherein the divalent organic group represented by the following formula (6) is contained: In formula (6), R ４ represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. The linear or branched alkyl group having 1 to 20 carbon atoms, the cycloalkyl group having 5 to 20 carbon atoms, and the aryl group having 6 to 20 carbon atoms may be substituted with a halogen atom or a substituent having an ethylenically unsaturated double bond. m is an integer of 0 to 4. When m is 2 or more, multiple R ４ may be the same or different and may be bonded in any combination to form part of a ring structure.

11. The resin composition according to claim 8, wherein the divalent organic group represented by formula (4) comprises one or more divalent organic groups selected from the group consisting of formula (7a), formula (7b), formula (7c), formula (7d), formula (7e), formula (7f), formula (7g), formula (7h), formula (7i), formula (7j), formula (7k), formula (7l), formula (7m), formula (7n), formula (7o), formula (7p), formula (7q), formula (7r), formula (7s), formula (7t), formula (7u), formula (7v), formula (7w), formula (7x), formula (7y), formula (7z), formula (7aa), and formula (7ab):

12. The above Y １ is one or more divalent unsubstituted or substituted nitrogen-containing aromatic heterocycles selected from the group consisting of the following formulas (2-1), (2-2), (2-3), and (2-4): The resin composition according to claim 5. In formula (2-1), R １ is a group selected from the group consisting of a hydrogen atom, a fluorine atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a group in which the substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, the substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, or the halogenated alkyl group having 1 to 20 carbon atoms is partially substituted with at least one atom selected from oxygen atoms and sulfur atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms. ２ are each independently a group selected from the group consisting of a hydrogen atom, a fluorine atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms. In formulas (2-2), (2-3), and (2-4), 1 is each independently an integer of 0 to 2. When 1 is 2, multiple R ２ may be the same or different and may be bonded in any combination to form part of a ring structure.

13. The resin composition according to claim 1, wherein the mass ratio (B / A) of the content of the aromatic heterocyclic compound (B) to the content of the thermoplastic resin (A) is less than 0.

8.

14. The resin composition according to claim 1, further comprising a cyclic polyolefin resin copolymer (C).

15. The resin composition according to claim 14, wherein the cyclic polyolefin resin copolymer (C) is a copolymer having an alicyclic structure in the side chain of the polyolefin.

16. The resin composition according to claim 14, wherein the mass ratio (C / A) of the content of the cyclic polyolefin resin copolymer (C) to the content of the thermoplastic resin (A) is less than 0.

8.

17. A resin sheet comprising the resin composition according to any one of claims 1 to 16.

18. The resin sheet according to claim 17, which exhibits a weight loss rate of 12% or less when heated from 35°C to 300°C at a rate of 10°C / min in the atmosphere, as measured using a thermogravimetric analyzer.

19. A laminate comprising the resin sheet according to claim 17 and a release film provided on one or both surfaces of the resin sheet.

20. A cured product of the resin composition according to any one of claims 1 to 16.

21. The cured product according to claim 20, having a thermal expansion coefficient of 200 ppm / °C or less.

22. The cured product according to claim 20, having a dielectric constant at a frequency of 10 GHz of less than 0.

002.

23. A circuit board material comprising an insulating layer formed by curing the resin composition according to any one of claims 1 to 16 and a conductor laminated together.

24. A resin sheet comprising: (A) at least one thermoplastic resin selected from the group consisting of styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, and ethylene-based polymers; and (B) an aromatic heterocyclic compound having two or more ethylenically unsaturated bonds in the molecule; wherein the resin sheet is heat-pressed at 200°C and 0.2 MPa for 30 minutes to produce a cured product having a dielectric dissipation factor of 0.002 or less, and a storage modulus (200°C) of 0.01 MPa or more.

25. A resin sheet comprising: at least one thermoplastic resin (A) selected from the group consisting of styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, and ethylene-based polymers; and a resin having a unit represented by the following formula (1): wherein the resin sheet is heat-pressed at 200°C and 0.2 MPa for 30 minutes to produce a cured product having a dielectric dissipation factor of 0.002 or less, and a storage modulus (200°C) of 0.01 MPa or more. In formula (1), L １ and L ２ are each independently —O— or —S—, and X １ is a divalent organic group, and Y １ is a divalent substituted or unsubstituted nitrogen-containing aromatic heterocycle.

26. The above Y １ is one or more divalent unsubstituted or substituted nitrogen-containing aromatic heterocycles selected from the group consisting of the following formulas (2-1), (2-2), (2-3), and (2-4): The resin sheet according to claim 25. In formula (2-1), R １ is a group selected from the group consisting of a hydrogen atom, a fluorine atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a group in which the substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, the substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, or the halogenated alkyl group having 1 to 20 carbon atoms is partially substituted with at least one atom selected from oxygen atoms and sulfur atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms. ２ are each independently a group selected from the group consisting of a hydrogen atom, a fluorine atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms. In formulas (2-2), (2-3), and (2-4), 1 is each independently an integer of 0 to 2. When 1 is 2, multiple R ２ may be the same or different and may be bonded in any combination to form part of a ring structure.

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