Composition and cured body

Abstract

This composition includes an olefin-aromatic vinyl compound-aromatic polyene copolymer and a phosphorus-based flame retardant (P1) having a melting point of 150°C or higher.

Description

Composition and cured body

[0001] This invention relates to a composition and a cured product.

[0002] Hydrocarbon resins are known as insulating materials for high-frequency applications. Examples of hydrocarbon resins include those described in Patent Documents 1 and 2.

[0003] Patent Document 1 describes an ethylene-olefin-polyene copolymer characterized by satisfying predetermined conditions. It also states that the post-curing resin composition of Patent Document 1 has excellent moldability, and the resulting cured product has low dielectric constant, low dielectric loss, and excellent heat resistance and impact resistance, making it suitable for use as an electrical insulating material for high-frequency applications.

[0004] Patent Document 2 describes a laminate comprising a resin layer containing an olefin-aromatic vinyl compound-aromatic polyene copolymer that satisfies predetermined conditions, and a metal foil. Furthermore, Patent Document 2 states that the cured product (cured body) of the copolymer or the resin layer containing it and the laminate containing the metal foil has high adhesion to the metal foil, excellent low dielectric properties, and can exhibit high mechanical properties at room temperature and high temperatures.

[0005] Japanese Patent Publication No. 2009-161743, International Publication No. 2021 / 112087

[0006] Conventional hydrocarbon resins have had room for improvement in achieving both low dielectric properties and flame retardancy in the resulting cured product. The present invention provides a composition that can improve the performance balance between low dielectric properties and flame retardancy in the resulting cured product.

[0007] The inventors diligently conducted research to achieve the above objectives. As a result, they discovered that a composition containing an olefin-aromatic vinyl compound-aromatic polyene copolymer and a phosphorus-based flame retardant (P1) having a melting point of 150°C or higher can improve the balance between the low dielectric properties and flame retardancy of the resulting cured product, thus completing the present invention.

[0008] According to the present invention, the following compositions and cured products are provided.

[0009] [1] A composition comprising an olefin-aromatic vinyl compound-aromatic polyene copolymer and a phosphorus-based flame retardant (P1) having a melting point of 150°C or higher. [2] The composition according to [1], wherein the melting point of the phosphorus-based flame retardant (P1) is 500°C or lower. [3] The composition according to [1] or [2], wherein when the content of the olefin-aromatic vinyl compound-aromatic polyene copolymer is 100 parts by mass, the content of the phosphorus-based flame retardant (P1) is 1 part by mass or more and 200 parts by mass or less. [4] The composition according to any one of [1] to [3], wherein the particles of the phosphorus-based flame retardant (P1) are dispersed in the olefin-aromatic vinyl compound-aromatic polyene copolymer. [5] The composition according to any one of [1] to [4], wherein the melting point measured by differential scanning calorimetry is 250°C or higher. [6] The dielectric loss tangent by the following method 1 is 100 × 10 －５The composition described in any of [1] to [5] above, which is as follows: (Method 1) A varnish is obtained by dissolving 100 parts by mass of the composition in 200 parts by mass of an organic solvent. Next, the varnish is placed in a silicone rubber mold on a Teflon (registered trademark) sheet, and after air drying, the varnish is vacuum dried under conditions of a pressure of 10 hPa or less, a temperature of 50°C, and a drying time of 12 hours or more to obtain an uncured sheet. Next, the uncured sheet is placed in a stainless steel mold on a Teflon sheet, and the uncured sheet is heated under a pressure of 4 MPa at 120°C for 30 minutes, 150°C for 30 minutes, and then 200°C for 120 minutes to obtain a cured sheet. Next, the dielectric loss tangent of a sample prepared from the cured sheet is measured at a temperature of 23°C and a frequency of 40 GHz by the split cylinder resonator method. [7] The composition described in any of [1] to [6] above, wherein the relative permittivity by Method 2 below is 3.00 or less. (Method 2) A varnish is obtained by dissolving 100 parts by mass of the composition in 200 parts by mass of an organic solvent. Next, the varnish is placed in a silicone rubber mold on a Teflon® sheet, and after air drying, the varnish is vacuum dried under conditions of a pressure of 10 hPa or less, a temperature of 50°C, and a drying time of 12 hours or more to obtain an uncured sheet. Next, the uncured sheet is placed in a stainless steel mold on a Teflon sheet, and the uncured sheet is heated under a pressure of 4 MPa at 120°C for 30 minutes, 150°C for 30 minutes, and then 200°C for 120 minutes to obtain a cured sheet. Next, the dielectric constant of a sample prepared from the cured sheet is measured at a temperature of 23°C and a frequency of 40 GHz by the split cylinder resonator method. [8] The composition according to any one of [1] to [7] above, wherein the olefin-aromatic vinyl compound-aromatic polyene copolymer satisfies any of the following (1) to (5). (1) The number-average molecular weight of the olefin-aromatic vinyl compound-aromatic polyene copolymer is 500 or more and 50,000 or less. (2) The olefin monomer is an α-olefin having 2 to 30 carbon atoms, and the content of the olefin monomer unit is 5 mol% or more and 95 mol% or less.(3) The aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of aromatic vinyl compound monomer units is 0.1 mol% to 70 mol%. (4) The aromatic polyene monomer is an aromatic polyene having 10 to 20 carbon atoms and having multiple vinyl groups and / or vinylene groups in the molecule, and the content of vinyl groups and / or vinylene groups derived from aromatic polyene monomer units is 2 to 30 per number average molecular weight. (5) The total content of the olefin monomer units, the aromatic vinyl compound monomer units, and the aromatic polyene monomer units is 90 mol% to 100 mol%. [9] The composition according to any one of [1] to [8] above, wherein the glass transition temperature measured by differential scanning calorimetry is -100°C to 100°C.

[10] The phosphorus-based flame retardant (P1) is an aromatic organophosphorus flame retardant (P11) having two or more diphenylphosphinoyl groups in its molecule, and 10-oxo-9,10-dihydro-9-oxa-10λ. ５ A composition according to any one of [1] to [9] above, comprising one or more selected from the group consisting of aromatic organophosphorus flame retardants (P12) having two or more -phosphaphenanthrene-10-yl groups in the molecule.

[11] A cured body of a composition according to any one of [1] to

[10] above.

[12] A cured body according to

[11] above, used in CCL, FCCL, interlayer insulating material, RCC, coverlay, high-frequency transmission circuit, or antenna.

[0010] According to the present invention, it is possible to provide a composition that can improve the balance between the low dielectric properties and flame retardancy of the resulting cured product.

[0011] The present invention will be described below based on embodiments. In these embodiments, unless otherwise specified, "A to B" indicating a numerical range means A or greater and B or less. Furthermore, when numerical ranges are described in steps, the upper and lower limits of each numerical range can be arbitrarily combined. In addition, the description "A and / or B" is a concept that includes the cases of A, B, and both A and B. In these embodiments, the notation "(meth)acryloyl" represents a concept that includes both acryloyl and methacryloyl. The same applies to similar notations such as "(meth)acrylate". In the notation of groups (atomic groups) in these embodiments, notations that do not specify whether they are substituted or unsubstituted include both those that do not contain substituents and those that do. For example, "alkyl group" includes not only alkyl groups that do not contain substituents but also alkyl groups that contain substituents. In these embodiments, the notation "sheet" represents a concept that includes both sheets and films.

[0012] [Composition] The composition of this embodiment comprises an olefin-aromatic vinyl compound-aromatic polyene copolymer and a phosphorus-based flame retardant (P1) having a melting point of 150°C or higher. According to the composition of this embodiment, a cured product can be obtained with an improved balance between low dielectric properties and flame retardancy.

[0013] Next, specific examples of each component of the composition of this embodiment will be given. The composition of this embodiment contains an olefin-aromatic vinyl compound-aromatic polyene copolymer (hereinafter also referred to as the copolymer) and a phosphorus-based flame retardant (P1).

[0014] <Copolymer> The composition of this embodiment comprises an olefin-aromatic vinyl compound-aromatic polyene copolymer. The copolymer of this embodiment has olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units. The copolymer may be composed of olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units, and may further have other monomer units.

[0015] The copolymer of this embodiment includes, for example, one or more selected from the group consisting of ethylene-styrene-divinylbenzene copolymer, ethylene-ethylvinylbenzene-divinylbenzene copolymer, ethylene-propylene-styrene-divinylbenzene copolymer, ethylene-1-octene-styrene-divinylbenzene copolymer, and propylene-styrene-divinylbenzene copolymer. The copolymer of this embodiment includes, for example, one or more selected from the group consisting of norbornene-ethylvinylbenzene-divinylbenzene copolymer, norbornene-styrene-ethylvinylbenzene-divinylbenzene copolymer, dimethanooctahydronaphthalene-styrene-ethylvinylbenzene-divinylbenzene copolymer, acenaphthylene-p-methylstyrene-ethylvinylbenzene-divinylbenzene copolymer, norbornene-styrene-divinylbenzene copolymer, dimethanooctahydronaphthalene-styrene-divinylbenzene copolymer, acenaphthylene-styrene-divinylbenzene copolymer, dimethanooctahydronaphthalene-ethylvinylbenzene-divinylbenzene copolymer, acenaphthylene-ethylvinylbenzene-divinylbenzene copolymer, acenaphthylene-styrene-ethylvinylbenzene-divinylbenzene copolymer, norbornene-p-methylstyrene-ethylvinylbenzene-divinylbenzene copolymer, and dimethanooctahydronaphthalene-p-methylstyrene-ethylvinylbenzene-divinylbenzene copolymer.

[0016] The number-average molecular weight of the copolymer in this embodiment is preferably 500 to 50,000, more preferably 1,000 to 30,000, even more preferably 3,000 to 15,000, even more preferably 5,000 to 12,000, and even more preferably 7,000 to 10,000, from the viewpoint of improving the moldability of the composition. The method for measuring the number-average molecular weight of the copolymer can be, for example, the method described in the examples.

[0017] An olefin monomer unit is a repeating unit in a copolymer composed of olefin monomers. The olefin monomer preferably includes α-olefins having 2 to 30 carbon atoms. The olefin monomer includes, for example, one or more selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, and 3,5,5-trimethyl-1-hexene.

[0018] The olefin monomer may be a single α-olefin having 2 to 30 carbon atoms, or a combination of different α-olefins having 2 to 30 carbon atoms. Preferably, the olefin monomer contains one or more selected from the group consisting of ethylene and α-olefins having 3 to 30 carbon atoms, and more preferably contains ethylene.

[0019] The olefin monomer may be one or more selected from the group consisting of, for example, α-olefins having 2 to 30 carbon atoms and cyclic olefin monomers. In this case, the olefin monomer unit may be a repeating unit in the copolymer composed of cyclic olefin monomers. The cyclic olefin monomer preferably includes a cyclic olefin having 7 to 30 carbon atoms, an alicyclic structure, and polymerizable vinyl groups, vinylene groups, or vinylidene groups. The cyclic olefin monomer may include one or more selected from the group consisting of, for example, norbornene, dimethanooctahydronaphthalene, trimetanododecahydroanthracene, phenylnorbornene, indanylnorbornene, methylphenylnorbornene, and acenaphthylene.

[0020] In the copolymer of this embodiment, the content of olefin monomer units is preferably 5 mol% to 95 mol%, more preferably 25 mol% to 90 mol%, even more preferably 50 mol% to 85 mol%, and even more preferably 75 mol% to 83 mol%, when the total content of monomer units in the copolymer is taken as 100 mol%.

[0021] Aromatic vinyl compound monomer units are repeating units in copolymers composed of aromatic vinyl compound monomers. The aromatic vinyl compound monomers preferably include aromatic vinyl compounds having 8 to 20 carbon atoms. For example, the aromatic vinyl compound monomers include one or more selected from the group consisting of benzenes having vinyl groups such as styrene, p-methylstyrene, ethylvinylbenzene, and p-isobutylstyrene; naphthalenes having vinyl groups; and anthracenes having vinyl groups.

[0022] In the copolymer of this embodiment, the content of aromatic vinyl compound monomer units is preferably 0.1 mol% to 70 mol%, more preferably 1 mol% to 50 mol%, even more preferably 10 mol% to 30 mol%, and even more preferably 15 mol% to 25 mol%, when the total content of monomer units in the copolymer is 100 mol%.

[0023] Aromatic polyene monomer units are repeating units in copolymers composed of aromatic polyene monomers. The aromatic polyene monomers preferably include aromatic polyenes having 10 to 20 carbon atoms and containing multiple vinyl and / or vinylene groups within the molecule. For example, the aromatic polyene monomers include one or more selected from the group consisting of divinylbenzene, divinylnaphthalene, divinylanthracene, p-2-propenylstyrene, p-3-butenylstyrene, and 1,2-bis(vinylphenyl)ethane.

[0024] From the viewpoint of improving the crosslinking efficiency of the copolymer, the aromatic polyene monomer preferably comprises one or more selected from the group consisting of o-divinylbenzene, m-divinylbenzene, and p-divinylbenzene, and more preferably comprises one or more selected from the group consisting of m-divinylbenzene and p-divinylbenzene.

[0025] In the copolymer of this embodiment, the content of aromatic polyene monomer units is preferably 0.1 mol% to 10 mol%, more preferably 0.5 mol% to 5 mol%, even more preferably 1 mol% to 3 mol%, and even more preferably 1.5 mol% to 2.5 mol%, when the total content of monomer units in the copolymer is 100 mol%.

[0026] In the copolymer of this embodiment, the content of vinyl groups and / or vinylene groups derived from aromatic polyene monomer units is preferably 2 to 30, more preferably 2 to 20, even more preferably 3 to 10, and even more preferably 3 to 5 per number average molecular weight.

[0027] The copolymer of this embodiment is a ternary system consisting of olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units. In addition to α-olefins having 2 to 30 carbon atoms, the copolymer may also contain cyclic olefin monomer units. Cyclic olefin monomer units are repeating units in the copolymer, composed of cyclic olefin monomers. The cyclic olefin monomers preferably include cyclic olefins having 7 to 30 carbon atoms, an alicyclic structure, and polymerizable vinyl groups, vinylene groups, or vinylidene groups. The cyclic olefin monomers include, for example, one or more selected from the group consisting of norbornene, dimethanooctahydronaphthalene, trimetanododecahydroanthracene, phenylnorbornene, indanylnorbornene, methylphenylnorbornene, and acenaphthylene.

[0028] In the copolymer of the present embodiment, when the total content of all monomer units in the copolymer is taken as 100 mol%, the total content of the olefin monomer unit, the aromatic vinyl compound monomer unit, and the aromatic polyene monomer unit is preferably 50 mol% or more and 100 mol% or less, more preferably 75 mol% or more and 100 mol% or less, still more preferably 90 mol% or more and 100 mol% or less, still more preferably 95 mol% or more and 100 mol% or less, still more preferably 97 mol% or more and 100 mol% or less, still more preferably 99 mol% or more and 100 mol% or less, and even more preferably 100 mol%.

[0029] In the composition of the present embodiment, when the total amount of solid contents (the total amount of components remaining as solid contents when formed into a cured product) in the composition of the present embodiment is taken as 100% by mass, the content of the copolymer of the present embodiment is preferably 1% by mass or more and 99% by mass or less, more preferably 5% by mass or more and 95% by mass or less, still more preferably 8% by mass or more and 50% by mass or less, further preferably 10% by mass or more and 30% by mass or less, and even more preferably 10% by mass or more and 20% by mass or less.

[0030] The copolymer of this embodiment preferably satisfies any of the following (1) to (5), more preferably satisfies two or more of the following (1) to (5), even more preferably satisfies three or more of the following (1) to (5), even more preferably satisfies four or more of the following (1) to (5), and even more preferably satisfies all of the following (1) to (5). (1) The number average molecular weight of the copolymer is 500 or more and 50,000 or less. (2) The olefin monomer is an α-olefin having 2 to 30 carbon atoms, and the content of the olefin monomer unit is 5 mol% or more and 95 mol% or less. (3) The aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of the aromatic vinyl compound monomer unit is 0.1 mol% or more and 70 mol% or less. (4) The aromatic polyene monomer is an aromatic polyene having 10 to 20 carbon atoms and having multiple vinyl and / or vinylene groups in its molecule, and the content of vinyl and / or vinylene groups derived from the aromatic polyene monomer unit is 2 to 30 per number average molecular weight. (5) The total content of olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units is 90 mol% to 100 mol%.

[0031] In this embodiment, the copolymer preferably satisfies any one of the following (1') to (5'), more preferably satisfies two or more of the following (1') to (5'), still more preferably satisfies three or more of the following (1') to (5'), still more preferably satisfies four or more of the following (1') to (5'), and even more preferably satisfies all of the following (1') to (5'). (1') The number average molecular weight of the copolymer is 500 or more and 50,000 or less. (2') The olefin monomer is one or more selected from the group consisting of α-olefins having 2 to 30 carbon atoms and cyclic olefin monomers, and the content of olefin monomer units is 5 mol% or more and 95 mol% or less. (3') The aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of aromatic vinyl compound monomer units is 0.1 mol% or more and 70 mol% or less. (4') The aromatic polyene monomer is an aromatic polyene having 10 to 20 carbon atoms and having a plurality of vinyl groups and / or vinylene groups in the molecule, and the content of vinyl groups and / or vinylene groups derived from aromatic polyene monomer units is 2 or more and 30 or less per number average molecular weight. (5') The total content of olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units is 90 mol% or more and 100 mol% or less.

[0032] <Method for Producing the Copolymer of the Present Embodiment> The copolymer of the present embodiment can be produced by copolymerizing an olefin monomer, an aromatic vinyl compound monomer, an aromatic polyene monomer, and optionally other monomers through coordination polymerization. In the method for producing the copolymer of the present embodiment, from the viewpoint of improving the efficiency of copolymer production, a single-site coordination polymerization catalyst composed of a transition metal compound and a co-catalyst is preferably used. As the single-site coordination polymerization catalyst, for example, those described in JP-A-2009-161743, JP-A-2010-280771, WO 00 / 37517, and the like can be employed.

[0033] <Phosphorus-based flame retardant (P1)> The composition of this embodiment contains a phosphorus-based flame retardant (P1) having a melting point of 150°C or higher. The phosphorus-based flame retardant (P1) is a flame retardant containing phosphorus. From the viewpoint of further improving the flame retardancy of the resulting cured product, the phosphorus-based flame retardant (P1) is preferably an aromatic organophosphorus flame retardant (P11) having two or more diphenylphosphinoyl groups in its molecule; 10-oxo-9,10-dihydro-9-oxa-10λ ５ -Phosphaphenanthrene-10-yl group (10-oxo-9,10-dihydro-9-oxa-10λ) ５ The product comprises one or more selected from the group consisting of: an aromatic organophosphorus flame retardant (P12) having two or more -phosphophenanthren-10-yl groups (hereinafter also called DOPO groups) in its molecule; an aromatic organophosphorus flame retardant (P13) other than aromatic organophosphorus flame retardants (P11) and aromatic organophosphorus flame retardants (P12); organophosphorus flame retardants such as phosphate esters or condensates thereof; and inorganic phosphorus flame retardants such as red phosphorus. More preferably, it comprises one or more selected from the group consisting of aromatic organophosphorus flame retardants (P11) and aromatic organophosphorus flame retardants (P12). The diphenylphosphinoyl group is a functional group represented by the following formula (p1). The DOPO group is a functional group represented by the following formula (p2).

[0034]

[0035] In the above equation (p1), * indicates a coupling.

[0036]

[0037] In the above equation (p2), * indicates a bond.

[0038] The aromatic organophosphorus flame retardant (P11) may have a structure in which, for example, two diphenylphosphinol groups are bonded via a hydrocarbon group R. In this case, the hydrocarbon group R is, for example, a polycyclic aromatic group such as an alkylene group having 2 to 30 carbon atoms, an arylene group having 6 to 20 carbon atoms, a naphthylene group, anthrylene group, or a hydrocarbon group that is a combination of these.Aromatic organophosphorus flame retardants (P11) include, for example, 1,4-bis[(diphenylphosphinoyl)methyl]benzene, 1,4-bis(diphenylphosphinoyl)benzene, 1,2-bis(diphenylphosphinoyl)ethane, 2,5-dimethyl-1,4-bis(diphenylphosphinoyl)benzene, 2,5-dimethyl-1,4-bis[(diphenylphosphinoyl)methyl]benzene, 4,4'-bis(diphenylphosphinoyl)biphenyl, and 4,4'-bis[(diphenylphosphinoyl) [Diphenylphosphinoyl]methyl biphenyl, 1,4-bis(diphenylphosphinoyl)naphthalene, 1,5-bis(diphenylphosphinoyl)naphthalene, 2,6-bis(diphenylphosphinoyl)naphthalene, 2,7-bis(diphenylphosphinoyl)naphthalene, 1,4-bis(diphenylphosphinoyl)anthracene, 1,5-bis(diphenylphosphinoyl)anthracene, 2,6-bis(diphenylphosphinoyl)anthracene, 2,7-bis(diphenylphosphinoyl) Anthracene, 9,10-bis(diphenylphosphinoyl)anthracene, 1,4-bis[(diphenylphosphinoyl)methyl]naphthalene, 1,5-bis[(diphenylphosphinoyl)methyl]naphthalene, 2,6-bis[(diphenylphosphinoyl)methyl]naphthalene, 2,7-bis[(diphenylphosphinoyl)methyl]naphthalene, 1,4-bis[(diphenylphosphinoyl)methyl]anthracene, 1,5-bis[(diphenylphosphinoyl)methyl] It comprises one or more compounds selected from the group consisting of anthracene, 2,6-bis[(diphenylphosphinoyl)methyl]anthracene, 2,7-bis[(diphenylphosphinoyl)methyl]anthracene, 9,10-bis[(diphenylphosphinoyl)methyl]anthracene, 4,4'-bis(diphenylphosphinoyl)diphenyl ether, 4,4'-bis[(diphenylphosphinoyl)methyl]diphenyl ether, and compounds having the structure shown in formula (I) below.

[0039]

[0040] In the above formula (I), R １represents a covalent bond, a methylene group, a 1,4-naphthylene group, a biphenyl-4,4'-diyl group, a 4,4'-oxybis(phenylene) group, or an organic group represented by the following formula (II). Also, * indicates a bond.

[0041]

[0042] In the above formula (II), R ２ ~R ５ Each of these independently represents a hydrogen atom, an alkyl group, or an organic group represented by the following formula (III) ((diphenylphosphinoyl)methyl group). Also, * indicates a bond.

[0043]

[0044] In the above equation (III), * indicates a bond.

[0045] From the viewpoint of further improving the flame retardancy of the resulting cured product, the aromatic organophosphorus flame retardant (P11) preferably includes one or more selected from the group consisting of 1,4-bis[(diphenylphosphinoyl)methyl]benzene and 1,4-bis(diphenylphosphinoyl)benzene.

[0046] Aromatic organophosphorus flame retardants (P12) may have a structure in which, for example, two DOPO groups are bonded via a hydrocarbon group R. In this case, the hydrocarbon group R is, for example, an alkylene group having 2 to 30 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a hydrocarbon group combining these. Examples of aromatic organophosphorus flame retardants (P12) include 1,4-bis[(DOPO)methyl]benzene, 1,4-bis(DOPO)benzene, 1,2-bis(DOPO)ethane, 2,5-dimethyl-1,4-bis(DOPO)benzene, 2,5-dimethyl-1,4-bis[(DOPO)methyl]benzene, 4,4'-bis(DOPO)biphenyl, and 4,4'-bi S[(DOPO)methyl]biphenyl, 1,4-bis(DOPO)naphthalene, 1,5-bis(DOPO)naphthalene, 2,6-bis(DOPO)naphthalene, 2,7-bis(DOPO)naphthalene, 1,4-bis(DOPO)anthracene, 1,5-bis(DOPO)anthracene, 2,6-bis(DOPO)anthracene, 2,7-bis(DOPO) It comprises one or more substances selected from the group consisting of anthracene, 9,10-bis(DOPO)anthracene, 1,4-bis[(DOPO)methyl]naphthalene, 1,5-bis[(DOPO)methyl]naphthalene, 2,6-bis[(DOPO)methyl]naphthalene, 2,7-bis[(DOPO)methyl]naphthalene, 1,4-bis[(DOPO)methyl]anthracene, 1,5-bis[(DOPO)methyl]anthracene, 2,6-bis[(DOPO)methyl]anthracene, 2,7-bis[(DOPO)methyl]anthracene, 9,10-bis[(DOPO)methyl]anthracene, 4,4'-bis(DOPO)diphenyl ether, and 4,4'-bis[(DOPO)methyl]diphenyl ether. The aromatic organophosphorus flame retardant (P12) preferably contains 4,4'-bis[(DOPO)methyl]biphenyl from the viewpoint of further improving the flame retardancy of the resulting cured product. However, in this paragraph, DOPO is defined as "10-oxo-9,10-dihydro-9-oxa-10λ". ５ This indicates "-phosphaphenanthrene-10-yl".

[0047] The aromatic organophosphorus flame retardant (P13) includes, for example, one or more selected from the group consisting of tris(4-methoxyphenyl)phosphine oxide, diphenylphosphine oxide, and triphenylphosphine oxide.

[0048] The melting point of the phosphorus-based flame retardant (P1) is 150°C or higher, preferably 175°C or higher, more preferably 200°C or higher, even more preferably 215°C or higher, even more preferably 240°C or higher, even more preferably 270°C or higher, even more preferably 300°C or higher, and even more preferably 320°C or higher, from the viewpoint of improving the balance between the low dielectric properties and flame retardancy of the resulting cured material. The upper limit of the melting point of the phosphorus-based flame retardant (P1) is not particularly limited, but for example it may be 500°C or lower, 450°C or lower, 400°C or lower, or 350°C or lower. From the viewpoint of further improving the balance between the low dielectric properties and flame retardancy of the resulting cured material, the melting point of the phosphorus-based flame retardant (P1) is preferably 150°C to 500°C, more preferably 175°C to 500°C, even more preferably 200°C to 450°C, even more preferably 215°C to 450°C, even more preferably 240°C to 400°C, even more preferably 270°C to 400°C, even more preferably 300°C to 350°C, and even more preferably 320°C to 350°C.

[0049] In the composition of this embodiment, from the viewpoint of further improving the balance between the low dielectric properties and flame retardancy of the resulting cured body, it is preferable that particles of the phosphorus-based flame retardant (P1) are dispersed in the copolymer. Furthermore, in the cured body of the composition of this embodiment, it is preferable that the phosphorus-based flame retardant (P1) phase and the copolymer phase are separated.

[0050] In the composition of this embodiment, the content of the phosphorus-based flame retardant (P1) is preferably 1 to 200 parts by mass, more preferably 5 to 150 parts by mass, even more preferably 10 to 100 parts by mass, even more preferably 20 to 90 parts by mass, even more preferably 30 to 80 parts by mass, and even more preferably 40 to 75 parts by mass, when the content of the copolymer of this embodiment is 100 parts by mass, from the viewpoint of further improving the balance between the low dielectric properties and flame retardancy of the resulting cured body.

[0051] The total amount of the copolymer of this embodiment and the phosphorus-based flame retardant (P1) in the composition of this embodiment is preferably 1% by mass or more and 100% by mass or less, more preferably 5% by mass or more and 100% by mass or less, even more preferably 10% by mass or more and 70% by mass or less, even more preferably 10% by mass or more and 50% by mass or less, even more preferably 13% by mass or more and 40% by mass or less, and even more preferably 15% by mass or more and 30% by mass or less, when the total amount of solids in the composition of this embodiment (total amount of components remaining as solids when cured) is taken as 100% by mass.

[0052] <Other Components> The composition of this embodiment may further contain, for example, polyether resins, curing agents, fillers, solvents, flame retardants other than phosphorus-based flame retardants (P1), flame retardant aids, surface modifiers, hydrocarbon elastomers, aromatic polyene resins, monomers, copolymers of monomer combinations other than those described above, etc. The composition of this embodiment may also further contain, for example, silane coupling agents, titanate coupling agents, anti-aging agents, stabilizers, ultraviolet absorbers, lubricants, surface modifiers, antioxidants, weathering agents, compatibilizers, antistatic agents, and other additives.

[0053] <Polyether Resin> The composition of this embodiment preferably further comprises a polyether resin. The polyether resin comprises, for example, one or more selected from the group consisting of polyphenylene ether and polyether, and preferably includes polyphenylene ether. The number average molecular weight of the polyphenylene ether is preferably 500 to 10,000, more preferably 1,000 to 4,500, and even more preferably 2,000 to 2,500, from the viewpoint of improving the moldability of the composition.

[0054] From the viewpoint of promoting the curing of the composition, polyphenylene ethers preferably have multiple functional groups within a single molecule. In this case, the functional groups preferably include radically polymerizable functional groups, more preferably include vinyl groups, even more preferably include one or more selected from the group consisting of allyl groups, (meth)acryloyl groups, and aromatic vinyl groups, even more preferably include one or more selected from the group consisting of (meth)acryloyl groups and aromatic vinyl groups, and even more preferably include aromatic vinyl groups. Furthermore, from the viewpoint of promoting the curing of the composition, polyphenylene ethers preferably include polyphenylene ethers modified with radically polymerizable functional groups, and more preferably include bifunctional polyphenylene ethers in which both ends of the molecular chain are modified with radically polymerizable functional groups. Examples of polyphenylene ether products include the Noryl® series (SABIC Corporation), OPE-2St (Mitsubishi Gas Chemical Company, Inc.), Elpac® HC-F series, and Elpac HC-G series (all from JSR Corporation).

[0055] From the viewpoint of improving the flame retardancy of the resulting cured product, the polyether resin content in the composition of this embodiment is preferably 50 parts by mass or more and 500 parts by mass or less, more preferably 100 parts by mass or more and 400 parts by mass or less, even more preferably 150 parts by mass or more and 300 parts by mass or less, and even more preferably 200 parts by mass or more and 250 parts by mass or less, when the copolymer content of this embodiment is 100 parts by mass.

[0056] <Curing Agent> The composition of this embodiment preferably further comprises a curing agent. The curing agent of this embodiment is not particularly limited as long as it is a curing agent that can be used for polymerization of aromatic vinyl compounds or aromatic polyenes. The curing agent of this embodiment comprises, for example, one or more selected from the group consisting of thermal polymerization initiators and photopolymerization initiators.

[0057] The thermal polymerization initiator includes, for example, one or more selected from the group consisting of thermal radical polymerization initiators, thermal cationic polymerization initiators, and thermal anionic polymerization initiators. The photopolymerization initiator includes, for example, one or more selected from the group consisting of photoradical polymerization initiators, photocationic polymerization initiators, and photoanionic polymerization initiators. The photopolymerization initiator includes, for example, one or more selected from the group consisting of benzoin compounds, triphenylphosphonium salts, and triphenylcarbenium salts.

[0058] The curing agent of this embodiment preferably comprises a radical polymerization initiator, more preferably one or more selected from the group consisting of organic peroxides; azo initiators such as 2,2'-azobis(2,4,4-trimethylpentane); hydrocarbon radical polymerization initiators such as 2,3-dimethyl-2,3-diphenylbutane; azo compounds such as azobisisobutyronitrile; persulfates such as potassium persulfate; and inorganic peroxides such as hydrogen peroxide, and even more preferably an organic peroxide.

[0059] If the composition of this embodiment does not contain a polyphenylene ether modified with a radically polymerizable functional group (hereinafter also referred to as a modified polyphenylene ether), the content of the curing agent of this embodiment in the composition of this embodiment is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.3 parts by mass or more and 5 parts by mass or less, even more preferably 0.4 parts by mass or more and 2 parts by mass or less, and even more preferably 0.5 parts by mass or more and 1 part by mass or less, when the content of the copolymer of this embodiment is 100 parts by mass, from the viewpoint of further improving the balance between the low dielectric properties and flame retardancy of the resulting cured product.

[0060] When the composition of this embodiment contains a modified polyphenylene ether, the content of the curing agent of this embodiment in the composition of this embodiment is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.3 parts by mass or more and 5 parts by mass or less, even more preferably 0.4 parts by mass or more and 2 parts by mass or less, and even more preferably 0.5 parts by mass or more and 1 part by mass or less, when the total content of the modified polyphenylene ether and the copolymer of this embodiment is 100 parts by mass, from the viewpoint of further improving the balance between the low dielectric properties and flame retardancy of the resulting cured product.

[0061] <Fillers> The composition of this embodiment preferably further comprises a filler. The filler of this embodiment comprises one or more selected from the group consisting of, for example, inorganic fillers and organic fillers. The inorganic filler comprises one or more selected from the group consisting of, for example, silica such as fused silica and detonation silica; boron nitride; and high dielectric constant fillers such as barium titanate and strontium titanate. The organic filler comprises one or more selected from the group consisting of, for example, high molecular weight polyethylene particles; ultra-high molecular weight polyethylene particles; polystyrene particles; styrene-divinylbenzene copolymer particles; and fluororesin particles such as polytetrafluoroethylene and perfluoroalkoxyalkanes. Examples of fluororesin particle products include Fluon+ (registered trademark) EA-2000 (AGC Inc.).

[0062] The filler of this embodiment preferably contains one or more selected from the group consisting of silica, boron nitride, high molecular weight polyethylene particles, ultra-high molecular weight polyethylene particles, polystyrene particles, styrene-divinylbenzene copolymer particles, and fluororesin particles, and more preferably contains silica, from the viewpoint of improving the low dielectric properties of the resulting cured product.

[0063] From the viewpoint of improving the low dielectric properties of the resulting cured body, the content of the filler of this embodiment in the composition of this embodiment is preferably 50 parts by mass or more and 1000 parts by mass or less, more preferably 100 parts by mass or more and 500 parts by mass or less, even more preferably 200 parts by mass or more and 400 parts by mass or less, and even more preferably 250 parts by mass or more and 350 parts by mass or less, when the content of the copolymer of this embodiment is 100 parts by mass.

[0064] <Flame retardants and flame retardant aids other than phosphorus-based flame retardants (P1)> The composition of this embodiment may further contain one or more selected from the group consisting of flame retardants other than phosphorus-based flame retardants (P1) and flame retardant aids. Flame retardants other than phosphorus-based flame retardants (P1) include, for example, brominated flame retardants. Flame retardant aids include, for example, antimony compounds such as antimony trioxide, antimony tetroxide, antimony pentoxide, and sodium antimonate; and one or more selected from the group consisting of nitrogen-containing compounds such as melamine, 2,4,6-triallyloxy-1,3,5-triazine, 1,3,5-trialyl-1,3,5-triazine-2,3,4-(1H,3H,5H)-trione.

[0065] <Hydrogen-based elastomers> The composition of this embodiment may further contain hydrocarbon-based elastomers. Hydrocarbon-based elastomers include, for example, one or more selected from the group consisting of ethylene-based elastomers; propylene-based elastomers; conjugated diene polymers; and aromatic vinyl compound-conjugated diene block copolymers or random copolymers, and their hydrides (hydrogenated products). Ethylene-based elastomers include, for example, one or more selected from the group consisting of ethylene-α-olefin copolymers such as ethylene-octene copolymer and ethylene-1-hexene copolymer; ethylene-propylene random copolymer; and ethylene-propylene-diene monomer copolymer. Propylene-based elastomers include, for example, one or more selected from the group consisting of atactic polypropylene; low stereoregularity polypropylene; and propylene-α-olefin copolymers such as propylene-1-butene copolymer. Conjugated diene polymers include, for example, one or more selected from the group consisting of polybutadiene and 1,2-polybutadiene. Examples of these products include B-1000, B-2000, B-3000 (all from Nippon Soda Co., Ltd.), Ricon 100 (TOTAL CRAY VALLEY, Inc.), etc. Aromatic vinyl compound-conjugated diene block copolymers or random copolymers, and their hydrides (hydrogenated products) include, for example, one or more selected from the group consisting of styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, hydrogenated styrene-ethylene-butadiene-styrene, hydrogenated styrene-ethylene-propylene-styrene, hydrogenated styrene-ethylene-ethylene-propylene-styrene, and hydrogenated styrene-ethylene-ethylbenzene-styrene, etc. Examples of these products include the ToughTec® series (Asahi Kasei Corporation), S.O.E. Examples include the (Registered Trademark) series (Asahi Kasei Corporation), the Septon (Registered Trademark) series (Kuraray Co., Ltd.), and the Kraton (Registered Trademark) series (Kraton Inc.).

[0066] <Aromatic Polyene Resin> The composition of this embodiment may further contain an aromatic polyene resin. The aromatic polyene resin includes, for example, divinylbenzene copolymers such as divinylbenzene copolymers having a highly branched structure. Examples of divinylbenzene copolymer products include the ODV series (Nippon Steel Chemical & Material Co., Ltd.).

[0067] <Monomers> The composition of this embodiment may further contain monomers. The monomers include, for example, one or more selected from the group consisting of radically polymerizable monomers, cationically polymerizable monomers, and anionicly polymerizable monomers, and preferably include radically polymerizable monomers. The monomers include, for example, one or more selected from the group consisting of olefin monomers, aromatic vinyl compound monomers, aromatic polyene monomers, and polar monomers.

[0068] In this embodiment, the polar monomer is a monomer having one or more atoms selected from the group consisting of oxygen, nitrogen, phosphorus, and sulfur in its molecule. The polar monomer includes, for example, one or more selected from the group consisting of maleimides, bismaleimides such as polyaminobismaleimide compounds, maleic anhydride, glycidyl (meth)acrylate, triallyl isocyanurate, tri(meth)acryloyl isocyanurate, and trimethylolpropane tri(meth)acrylate. Examples of bismaleimide products include the SLK series (Shin-Etsu Chemical Co., Ltd.), MIR-3000, and MIR-5000 (both from Nippon Kayaku Co., Ltd.).

[0069] <Characteristics of the Composition> The characteristics of the composition of this embodiment will be described below.

[0070] From the perspective of improving the heat resistance of the obtained cured product, the melting point of the composition of the present embodiment measured by differential scanning calorimetry is preferably 250°C or higher, more preferably 260°C or higher, still more preferably 265°C or higher, and even more preferably 270°C or higher. The upper limit of the melting point of the composition of the present embodiment measured by differential scanning calorimetry is not particularly limited, and is, for example, 500°C or lower, may be 400°C or lower, may be 350°C or lower, or may be 300°C or lower. From the perspective of improving the heat resistance of the obtained cured product, the melting point of the composition of the present embodiment measured by differential scanning calorimetry is preferably 250°C or higher and 500°C or lower, more preferably 260°C or higher and 400°C or lower, still more preferably 265°C or higher and 350°C or lower, and even more preferably 270°C or higher and 300°C or lower.

[0071] From the perspective of improving the heat resistance of the obtained cured product, the glass transition temperature of the composition of the present embodiment measured by differential scanning calorimetry is preferably -100°C or higher, more preferably -50°C or higher, still more preferably -40°C or higher, and even more preferably -30°C or higher. The upper limit of the glass transition temperature of the composition of the present embodiment measured by differential scanning calorimetry is not particularly limited, and is, for example, 100°C or lower, may be 90°C or lower, may be 80°C or lower, or may be 70°C or lower. From the perspective of improving the heat resistance of the obtained cured product, the glass transition temperature of the composition of the present embodiment measured by differential scanning calorimetry is preferably -100°C or higher and 100°C or lower, more preferably -50°C or higher and 90°C or lower, still more preferably -40°C or higher and 80°C or lower, and even more preferably -30°C or higher and 70°C or lower.

[0072] From the perspective of improving the low dielectric properties of the obtained cured product, the dielectric loss tangent of the composition of the present embodiment measured by the following method 1 is preferably 100×10 －５ or less, more preferably 95×10 －５ or less, still more preferably 92×10 －５ or less, even more preferably 90×10 －５ or less, and even more preferably 85×10 －５The following applies. The lower limit of the dielectric loss tangent of the composition of this embodiment by method 1 below is not particularly limited, but for example, 1 × 10 －５ That's all. 10 x 10 －５ It may be more than 20 x 10 －５ It may be more than 30 x 10 －５ It may be greater than or equal to 45 x 10 －５ It may be greater than or equal to 60 x 10 －５ The above values ​​may also be used. The dielectric loss tangent of the composition of this embodiment, according to method 1 below, is preferably 1 × 10⁻⁶ from the viewpoint of improving the low dielectric properties of the resulting cured body. －５ The above 100 x 10 －５ The following, more preferably 10 × 10 －５ The above 95 x 10 －５ The following, and more preferably 20 × 10 －５ The above 92 x 10 －５ The following, and more preferably 30 × 10 －５ The above 90 x 10 －５ More preferably 45 × 10 －５ The above 85 x 10 －５ More preferably, 60 x 10 －５ The above 85 x 10 －５ The following applies:

[0073] (Method 1) A varnish is obtained by dissolving 100 parts by mass of the composition of this embodiment in 200 parts by mass of an organic solvent. Next, the varnish is placed in a silicone rubber mold on a Teflon® sheet, and after air drying, the varnish is vacuum dried under conditions of a pressure of 10 hPa or less, a temperature of 50°C, and a drying time of 12 hours or more to obtain an uncured sheet. Next, the uncured sheet is placed in a stainless steel mold on a Teflon sheet, and the uncured sheet is heated under a pressure of 4 MPa at 120°C for 30 minutes, 150°C for 30 minutes, and then 200°C for 120 minutes to obtain a cured sheet. Next, the dielectric loss tangent of a sample prepared from the cured sheet is measured at a temperature of 23°C and a frequency of 40 GHz using the split cylinder resonator method.

[0074] The dielectric constant of the composition of this embodiment, obtained by method 2 below, is preferably 3.00 or less, more preferably 2.90 or less, even more preferably 2.80 or less, even more preferably 2.70 or less, even more preferably 2.60 or less, and even more preferably 2.55 or less, from the viewpoint of improving the low dielectric properties of the resulting cured body. The lower limit of the dielectric constant of the composition of this embodiment, obtained by method 2 below, is not particularly limited, but may be, for example, 0.00 or more, 0.10 or more, 0.50 or more, 1.00 or more, 1.50 or more, or 2.00 or more. The dielectric constant of the composition of this embodiment, obtained by method 2 below, is preferably 0.00 to 3.00, more preferably 0.10 to 2.90, even more preferably 0.50 to 2.80, even more preferably 1.00 to 2.70, even more preferably 1.50 to 2.60, and even more preferably 2.00 to 2.55, from the viewpoint of improving the low dielectric properties of the resulting cured body.

[0075] (Method 2) A varnish is obtained by dissolving 100 parts by mass of the composition of this embodiment in 200 parts by mass of an organic solvent. Next, the varnish is placed in a silicone rubber mold on a Teflon® sheet, and after air drying, the varnish is vacuum dried under conditions of a pressure of 10 hPa or less, a temperature of 50°C, and a drying time of 12 hours or more to obtain an uncured sheet. Next, the uncured sheet is placed in a stainless steel mold on a Teflon sheet, and the uncured sheet is heated under a pressure of 4 MPa at 120°C for 30 minutes, 150°C for 30 minutes, and then 200°C for 120 minutes to obtain a cured sheet. Next, the dielectric constant of a sample prepared from the cured sheet is measured at a temperature of 23°C and a frequency of 40 GHz using the split cylinder resonator method.

[0076] The composition of this embodiment preferably has a flame retardancy class of V-1 or V-0, more preferably V-0, as classified by the UL94 vertical combustion test.

[0077] Furthermore, for the composition of this embodiment, the methods for measuring the melting point, glass transition temperature, dielectric loss tangent, relative permittivity, and flame retardancy class as classified by the UL94 vertical combustion test can be, more specifically, those described in the examples.

[0078] <Method for Producing the Composition> The composition of this embodiment is obtained by mixing, dissolving, or melting the copolymer of this embodiment, a phosphorus-based flame retardant (P1), and other components as needed. The method of mixing, etc., is not particularly limited, but known methods such as a twin-screw kneader, various rolls, or various kneaders can be used.

[0079] The composition of this embodiment may be in an uncured state or a semi-cured state.

[0080] <Applications of the Composition> The applications of the composition of this embodiment are not particularly limited, and the composition of this embodiment can be applied to a variety of applications. The composition of this embodiment can improve the balance between the low dielectric properties and flame retardancy of the resulting cured material, and can therefore be applied to, for example, CCL (Copper Clad Laminate), FCCL (Flexible Copper Clad Laminate), interlayer insulating materials, RCC (Resin Coated Copper), coverlays, high-frequency transmission circuits, or antennas.

[0081] <Varnish> The varnish of this embodiment comprises the composition of this embodiment and a solvent. The solvent used in the varnish of this embodiment preferably includes an organic solvent, and more preferably includes one or more selected from the group consisting of toluene, anisole, cyclohexane, methylcyclohexane, cyclohexanone, methyl ethyl ketone, xylene, mesitylene, tetralin, acetone, ethylbenzene, limonene, ethylene glycol methyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, isopropanol, mixed alkanes, and mixed aromatic solvents.

[0082] The content of the solvent of this embodiment in the varnish of this embodiment is preferably 10 parts by mass or more and 2000 parts by mass or less, more preferably 50 parts by mass or more and 1000 parts by mass or less, even more preferably 100 parts by mass or more and 500 parts by mass or less, and even more preferably 150 parts by mass or more and 250 parts by mass or less, when the content of the composition of this embodiment is 100 parts by mass.

[0083] <Molded Article> The molded article of this embodiment is formed by molding the composition of this embodiment. The shape of the molded article of this embodiment may be, for example, a sheet, a tube, or a pellet. The method for molding the molded article of this embodiment is not particularly limited, but for example, extrusion molding, injection molding, press molding, inflation molding, or extrusion lamination can be used.

[0084] <Cured Body> The cured body of this embodiment is obtained by curing the composition of this embodiment. The cured body of this embodiment may also be obtained by curing the molded body of this embodiment.

[0085] The cured body of this embodiment is obtained by heating and curing the composition or molded body of this embodiment. The heating temperature for curing is preferably 100°C to 250°C, and more preferably 100°C to 200°C. The heating time for curing is not particularly limited, but for example, it is 3 minutes to 180 minutes. More specifically, the curing conditions for the cured body of this embodiment can be those described in the examples.

[0086] The cured body of this embodiment is not particularly limited in its applications and can be used in a variety of applications. Because the cured body of this embodiment has an improved balance of low dielectric properties and flame retardancy, it can be used, for example, in CCL, FCCL, interlayer insulating materials, RCC, coverlays, high-frequency transmission circuits, or antennas.

[0087] Although embodiments of the present invention have been described above, these are merely examples, and various other configurations can be adopted. Furthermore, the present invention is not limited to the embodiments described above, and modifications, improvements, etc., that do not impair the effects of the present invention are included in the present invention.

[0088] This embodiment will be described in detail below with reference to examples and other relevant information. However, this embodiment is not limited in any way to the descriptions of these examples.

[0089] First, the raw materials used in each example will be explained. • Olefin-Aromatic Vinyl Compound-Aromatic Polyene Copolymer Copolymer 1: Copolymer obtained in Synthesis Example 1 described later (ethylene:styrene:divinylbenzene = 79.0 mol%:18.9 mol%:2.1 mol%, number average molecular weight: 8,500) • Resin 1: Modified polyphenylene ether resin (Noryl ＴＭ SA9000 resin (manufactured by SHPP Japan LLC) ・Filler 1: Molten spherical silica (GT130MC, manufactured by Denka Co., Ltd.) ・Hardening agent 1: α,α'-di(t-butylperoxy)diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) ・Phosphorus-based flame retardant Flame retardant 1: PQ-60 (melting point 336℃, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Flame retardant 2: Mosaflam 562 (melting point 225℃, CAS number: 3141-62-6, manufactured by UFC CORPORATION) Flame retardant 3: Mosaflam 585 (melting point 279℃, CAS number: 2010980-10-4, manufactured by UFC CORPORATION) Flame retardant 4: SR-3000 (melting point 95°C, manufactured by Daihachi Chemical Industry Co., Ltd.) Flame retardant 5: PX-200 (melting point 92°C, CAS number: 139189-30-3, manufactured by Daihachi Chemical Industry Co., Ltd.) Flame retardant 6: ADEKA stub FP-900L (melting point 25°C or less, CAS number: 1003300-73-9, manufactured by ADEKA Corporation) Flame retardant 7: ADEKA stub FP-T80 (melting point 25°C or less, CAS number: 705257-84-7, manufactured by ADEKA Corporation)

[0090] Flame retardant 1 is a compound represented by the following formula (1).

[0091]

[0092] Furthermore, flame retardant 2 is a compound represented by the following formula (2).

[0093]

[0094] Furthermore, flame retardant 3 is a compound represented by the following formula (3).

[0095]

[0096] [Synthesis Example 1] Copolymer 1 was synthesized using the following raw materials based on the manufacturing methods described in Japanese Patent Publication No. 2009-161743 and Japanese Patent Publication No. 2010-280771: • Monomer ethylene (hereinafter also referred to as Et) • Styrene (hereinafter also referred to as St) • Divinylbenzene (DVB-810, manufactured by Nippon Steel Chemical & Material Co., Ltd.) (hereinafter also referred to as DVB) • Catalyst: Metallocene catalyst (dimethylmethylenebis(cyclopentadienyl)zirconium dichloride) • Co-catalyst: Modified methylaluminoxane (manufactured by Tosoh Finechem Co., Ltd.) (hereinafter also referred to as MMAO) • Solvent: Toluene

[0097] The composition ratio of Et, St, and DVB in copolymer 1 is: １ The peak area intensities assigned to each component were calculated using 1H-NMR measurements. The measurements were performed in a heavy 1,1,2,2-tetrachloroethane solvent at a temperature of 23°C.

[0098] The number-average molecular weight of copolymer 1 was determined by GPC (gel permeation chromatography) measurement, using the number-average molecular weight in terms of standard polystyrene. The measurement was performed under the following conditions: Column: Four TSK-GEL MultiporeHXL-M φ7.8 × 300 mm columns (manufactured by Tosoh Corporation) connected in series were used. Column temperature: 40°C Solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Detector: RI detector

[0099] Next, the manufacturing methods for each example composition will be described.

[0100] [Examples 1-6, Comparative Examples 1-9] The compositions of Examples 1-6 and Comparative Examples 1-9 were prepared by weighing and mixing copolymer 1 and other materials according to the compositions in Table 1.

[0101] <Preparation of Cured Sheets> Cured sheets of the compositions of Examples 1 to 6 and Comparative Examples 1 to 9 were prepared by the following method. Varnish was obtained by dissolving 100 parts by mass of the composition of each example in 200 parts by mass of toluene. Next, the varnish was placed in a silicone rubber mold (frame length 15 mm x width 15 mm x thickness 2 mm) on a Teflon® sheet, and after air drying, the varnish was vacuum dried under the conditions of a pressure of 10 hPa or less, a temperature of 50°C, and a drying time of 12 hours to obtain an uncured sheet. Next, the uncured sheet was placed in a stainless steel mold (frame length 15 mm x width 15 mm x thickness 0.2 mm) on a Teflon sheet, and the uncured sheet was heated under a pressure of 4 MPa at 120°C for 30 minutes, 150°C for 30 minutes, and then at 200°C for 120 minutes to obtain a cured sheet.

[0102] [Examples 7-9, Comparative Examples 10-14] Copolymer 1 and other materials were weighed and mixed according to the compositions in Table 2 to produce the compositions of Examples 7-9 and Comparative Examples 10-14, respectively. Cured sheets of the compositions of Examples 7-9 and Comparative Examples 10-14 were also prepared in the same manner as described in <Preparation of Cured Sheets> above.

[0103] Measurements or evaluations were performed for each example according to the method described below. The results obtained are shown in Table 1 or Table 2.

[0104] <Measurement of Glass Transition Temperature and Melting Point> For the compositions of Examples 1 to 6 and Comparative Examples 1 to 9, the glass transition temperature and melting point were determined by DSC measurement using a DSC measuring device (DSC6200, manufactured by Seiko Electronics Co., Ltd.) under the following conditions. Sample amount: 10 mg Reference: 10 mg alumina Pan: Aluminum pan Atmosphere: Nitrogen Heating / cooling conditions: The temperature was raised from 23°C to 120°C at a heating rate of 10°C / min. Then, the temperature was cooled from 120°C to 23°C at a cooling rate of 20°C / min. Then, the temperature was raised from 23°C to 300°C at a heating rate of 10°C / min.

[0105] <Measurement of Dielectric Loss Tangent and Relative Permittivity> Measurement samples measuring 30 mm in length, 25 mm in width, and 0.2 mm in thickness were cut from the cured sheets of Examples 1 to 6 and Comparative Examples 1 to 9. Then, the dielectric loss tangent and relative permittivity were measured for each measurement sample using the split-cylinder resonator method in accordance with IPC-TM650 2.5.5.13, at a temperature of 23°C and a frequency of 40 GHz, using a split-cylinder resonator (CR-740, manufactured by EM Lab Co., Ltd.) and analyzers (N5222B, N5292A, manufactured by Keysight Technologies).

[0106] <Evaluation of Flame Retardancy> Measurement samples measuring 125 mm in length, 13 mm in width, and 0.2 mm in thickness were cut from the cured sheets of Examples 7-9 and Comparative Examples 10-14. Then, the flame retardancy of each measurement sample was evaluated in accordance with the UL94 vertical combustion test. Flame retardancy was evaluated as follows: A for flame retardancy class V-0, B for V-1, and C for all other cases as classified by the UL94 vertical combustion test.

[0107]

[0108]

[0109] This application claims priority based on Japanese Patent Application No. 2025-053385, filed on 27 March 2025, and incorporates all of its disclosures herein.

Claims

1. A composition comprising an olefin-aromatic vinyl compound-aromatic polyene copolymer and a phosphorus-based flame retardant (P1) having a melting point of 150°C or higher.

2. The composition according to claim 1, wherein the melting point of the phosphorus-based flame retardant (P1) is 500°C or less.

3. The composition according to claim 1, wherein when the content of the olefin-aromatic vinyl compound-aromatic polyene copolymer is 100 parts by mass, the content of the phosphorus-based flame retardant (P1) is 1 part by mass or more and 200 parts by mass or less.

4. The composition according to claim 1, wherein the particles of the phosphorus-based flame retardant (P1) are dispersed in the olefin-aromatic vinyl compound-aromatic polyene copolymer.

5. The composition according to claim 1, wherein the melting point measured by differential scanning calorimetry is 250°C or higher.

6. The dielectric loss tangent by method 1 below is 100 × 10 －５ The composition according to claim 1 is as follows: (Method 1) A varnish is obtained by dissolving 100 parts by mass of the composition in 200 parts by mass of an organic solvent. Next, the varnish is placed in a silicone rubber mold on a Teflon® sheet, and after air drying, the varnish is vacuum dried under conditions of a pressure of 10 hPa or less, a temperature of 50°C, and a drying time of 12 hours or more to obtain an uncured sheet. Next, the uncured sheet is placed in a stainless steel mold on a Teflon sheet, and the uncured sheet is heated under a pressure of 4 MPa at 120°C for 30 minutes, 150°C for 30 minutes, and then 200°C for 120 minutes to obtain a cured sheet. Next, the dielectric loss tangent of a sample prepared from the cured sheet is measured at a temperature of 23°C and a frequency of 40 GHz using the split cylinder resonator method.

7. The composition according to claim 1, wherein the dielectric constant obtained by method 2 below is 3.00 or less. (Method 2) A varnish is obtained by dissolving 100 parts by mass of the composition in 200 parts by mass of an organic solvent. Next, the varnish is placed in a silicone rubber mold on a Teflon® sheet, and after air drying, the varnish is vacuum dried under conditions of a pressure of 10 hPa or less, a temperature of 50°C, and a drying time of 12 hours or more to obtain an uncured sheet. Next, the uncured sheet is placed in a stainless steel mold on a Teflon sheet, and the uncured sheet is heated under a pressure of 4 MPa at 120°C for 30 minutes, 150°C for 30 minutes, and then 200°C for 120 minutes to obtain a cured sheet. Next, the dielectric constant of a sample prepared from the cured sheet is measured at a temperature of 23°C and a frequency of 40 GHz by the split cylinder resonator method.

8. The composition according to claim 1, wherein the olefin-aromatic vinyl compound-aromatic polyene copolymer satisfies any of the following (1) to (5): (1) The number average molecular weight of the olefin-aromatic vinyl compound-aromatic polyene copolymer is 500 or more and 50,000 or less. (2) The olefin monomer is an α-olefin having 2 to 30 carbon atoms, and the content of olefin monomer units is 5 mol% or more and 95 mol% or less. (3) The aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of aromatic vinyl compound monomer units is 0.1 mol% or more and 70 mol% or less. (4) The aromatic polyene monomer is an aromatic polyene having 10 to 20 carbon atoms having a plurality of vinyl groups and / or vinylene groups in the molecule, and the content of vinyl groups and / or vinylene groups derived from aromatic polyene monomer units is 2 to 30 per number average molecular weight. (5) The total content of the olefin monomer units, the aromatic vinyl compound monomer units, and the aromatic polyene monomer units is 90 mol% or more and 100 mol% or less.

9. The composition according to claim 1, wherein the glass transition temperature measured by differential scanning calorimetry is -100°C or higher and 100°C or lower.

10. The phosphorus-based flame retardant (P1) is an aromatic organophosphorus flame retardant (P11) having two or more diphenylphosphinoyl groups in its molecule, and 10-oxo-9,10-dihydro-9-oxa-10λ ５ The composition according to claim 1, comprising one or more selected from the group consisting of aromatic organophosphorus flame retardants (P12) having two or more -phosphaphenanthrene-10-yl groups in the molecule.

11. A cured body of the composition according to any one of claims 1 to 10.

12. The cured body according to claim 11, used in CCL, FCCL, interlayer insulating material, RCC, coverlay, high-frequency transmission circuit, or antenna.

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