Resin composition, varnish, cured product of resin composition, film or sheet, laminate, prepreg, printed wiring board, and electronic apparatus

Abstract

To provide a resin composition from which a cured product improved in performance balance between low dielectric characteristics and heat resistance can be obtained.SOLUTION: The resin composition contains a thermosetting cyclic olefinic copolymer (A) having a crosslinkable group, a modified phenylene ether resin (B), and a radical polymerization initiator (C). The modified phenylene ether resin (B) has a biphenyl structure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a varnish, a cured product of the resin composition, a film or sheet, a laminate, a prepreg, a printed wiring board, and an electronic device. [Background technology]

[0002] Resin compositions are used as materials for high-frequency printed wiring boards, etc. Patent Document 1 describes a technique for such resin compositions.

[0003] Patent Document 1 describes a resin composition having a solids concentration of 50.5% by mass or more, which contains a polyphenylene ether derivative (A) containing an N-substituted maleimide structure-containing group and an organic solvent, with the objective of providing a prepreg, a laminate, a multilayer printed wiring board, and a semiconductor package that are capable of exhibiting high adhesion to conductors, excellent heat resistance, a high glass transition temperature, a low thermal expansion coefficient, flame retardancy, and stable and excellent high-frequency characteristics (dielectric characteristics in the high-frequency band). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2023-134512 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides a resin composition that can give a cured product having an improved balance of low dielectric properties and heat resistance. [Means for solving the problem]

[0006] The present inventors have conducted extensive research to achieve the above object, and as a result have found that a cured product having an improved balance of low dielectric properties and heat resistance can be obtained by using a resin composition containing a thermosetting cyclic olefin copolymer (A) having a crosslinkable group, a modified phenylene ether resin (B), and a radical polymerization initiator (C), thereby completing the present invention.

[0007] [1] a thermosetting cyclic olefin copolymer (A) having a crosslinkable group; a modified phenylene ether resin (B); a radical polymerization initiator (C), The modified phenylene ether resin (B) has a biphenyl structure. [2] The resin composition according to [1], wherein the modified phenylene ether resin (B) contains one or more functional groups selected from the group consisting of functional groups containing a carbon-carbon unsaturated double bond and functional groups containing an element other than carbon. [3] The resin composition according to [1] or [2], wherein the modified phenylene ether resin (B) contains one or more functional groups selected from the group consisting of a (meth)acryloyl group, a vinyl group, an allyl group, a maleimide group, and a hydroxy group. [4] The resin composition according to any one of [1] to [3], wherein the modified phenylene ether resin (B) contains a functional group represented by the following formula (2a) or the following formula (2b) at at least one end of the main chain of the modified phenylene ether resin (B): [ka] [ka] [In the formula (2a), R 21 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 22 represents an alkylene group having 1 to 10 carbon atoms or a direct bond. 23represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. [5] The resin composition according to any one of [1] to [4] above, wherein the modified phenylene ether resin (B) contains an ethenylbenzyl group at least on one end of the main chain of the modified phenylene ether resin (B). [6] The resin composition according to any one of [1] to [5] above, wherein the modified phenylene ether resin (B) contains ethenylbenzyl groups at both ends of the main chain of the modified phenylene ether resin (B). [7] The resin composition according to any one of [1] to [6] above, wherein the modified phenylene ether resin (B) has a number average molecular weight of 500 or more and 25,000 or less. [8] The resin composition according to any one of [1] to [7], wherein the content of the modified phenylene ether resin (B) in the resin composition is 10 parts by mass or more and 500 parts by mass or less, relative to 100 parts by mass of the thermosetting cyclic olefin copolymer (A). [9] The thermosetting cyclic olefin copolymer (A) is One or more olefin-derived repeating units (a) represented by the following formula (I); one or more repeating units (b) derived from a cyclic non-conjugated diene represented by the following formula (III); The resin composition according to any one of the above [1] to [8], which contains one or more repeating units (c) derived from cyclic olefins and represented by the following formula (V): [ka] [In the formula (I), R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. [ka] [In the formula (III), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R 61 ~R76 and R a1 and R b1 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; R 104 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, and R 75 and R 76 may be bonded to each other to form a monocyclic or polycyclic ring. [ka] [In the formula (V), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R 61 ~R 78 , R a1 and R b1 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; R 75 ~R 78 may be bonded to each other to form a monocyclic or polycyclic ring.

[10] The resin composition according to [9] above, wherein the olefin constituting the olefin-derived repeating unit (a) contains ethylene.

[11] The resin composition according to [9] or

[10] above, wherein the cyclic non-conjugated diene constituting the repeating unit (b) derived from the cyclic non-conjugated diene includes 5-vinyl-2-norbornene.

[12] The cyclic olefin constituting the cyclic olefin-derived structural unit (c) is a tetracyclo[4.4.0.1 2,5 .1 7,10 The resin composition according to any one of [9] to

[11] above, which contains one or more members selected from the group consisting of cyclo[2.2.1]-3-dodecene and bicyclo[2.2.1]-2-heptene.

[13] The resin composition according to any one of [9] to

[12] above, wherein, when the total number of moles of repeating units in the thermosetting cyclic olefin copolymer (A) is taken as 100 mol %, the content of the olefin-derived repeating units (a) is 10 mol % or more and 80 mol % or less, the content of the cyclic non-conjugated diene-derived repeating units (b) is 1 mol % or more and 40 mol % or less, and the content of the cyclic olefin-derived repeating units (c) is 1 mol % or more and 60 mol % or less.

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

[13] , wherein the content of the radical polymerization initiator (C) is 0.1 parts by mass or more and 25.0 parts by mass or less, relative to 100 parts by mass of the thermosetting cyclic olefin copolymer (A).

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

[14] , wherein the total content of the thermosetting cyclic olefin copolymer (A), the modified phenylene ether resin (B), and the radical polymerization initiator (C) in the resin composition is 50% by mass or more and 100% by mass or less, when the total amount of solids in the resin composition is 100% by mass.

[16] The resin composition according to any one of the above [1] to

[15] , further comprising an antioxidant (D).

[17]

[17] The resin composition according to

[16] , wherein the content of the antioxidant (D) is 0.01 parts by mass or more and 5.0 parts by mass or less, relative to 100 parts by mass of the thermosetting cyclic olefin copolymer (A).

[18] The resin composition according to any one of the above [1 to

[17] , wherein the dielectric loss tangent Df measured by the following method is less than 0.0030. (method) A cured film having a thickness of 30±15 μm is prepared from the resin composition, The cured film is cut into a test piece having a length of 50 mm, a width of 50 mm and a thickness of 30±15 μm, and the dielectric loss tangent Df is measured at 23±2° C., 50±5% RH and 10 GHz using a cylindrical cavity resonator.

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

[18] above, which has two or more peaks in the temperature dispersion of the loss tangent tan δ in dynamic viscoelasticity obtained by the following method. (method) A cured film having a thickness of 30±15 μm is prepared from the resin composition, The cured film is cut into a test piece having a length of 45 mm, a width of 5 mm, and a thickness of 30±15 μm, and the dynamic viscoelasticity of the cured film is measured in a tensile mode under a nitrogen atmosphere at a temperature rise rate of 3°C / min and a frequency of 1 Hz.

[20] The resin composition according to

[19] , wherein the first glass transition temperature corresponding to the peak on the high temperature side in the graph is 200°C or higher. [twenty one] The resin composition according to

[19] or

[20] , wherein the second glass transition temperature corresponding to the low-temperature peak in the graph is lower than 200°C. [twenty two] The resin composition according to any one of

[19] to

[21] above, wherein the value of A represented by the following formula (1) exceeds 1.0. Equation (1): A = (loss tangent value at the peak on the high temperature side) / (loss tangent value at the peak on the low temperature side) [twenty three] The storage modulus at 220°C measured by the following method is 1.0 x 10 7 The resin composition according to any one of the above [1] to

[22] , having a viscosity of 100 Pa or more. (method) A cured film having a thickness of 30±15 μm is prepared from the resin composition, The cured film is cut into a test piece having a length of 45 mm, a width of 5 mm, and a thickness of 30±15 μm, and the dynamic viscoelasticity of the cured film is measured in a tensile mode under a nitrogen atmosphere at a temperature rise rate of 3°C / min and a frequency of 1 Hz. [twenty four] A varnish comprising the resin composition according to any one of the above [1] to

[23] and a solvent. [twenty five] A cured product of the resin composition according to any one of the above [1] to

[23] .

[26] A film or sheet comprising the resin composition according to any one of the above [1] to

[23] or the cured product according to the above

[25] .

[27] A laminate comprising the film or sheet according to

[26] above.

[28] The laminate according to

[27] , further comprising a metal foil on at least one surface.

[29] A prepreg comprising the resin composition according to any one of the above [1] to

[23] and a sheet-like fiber base material.

[30] A printed wiring board comprising an insulating layer containing the cured product according to

[25] above or the cured product of the prepreg according to

[29] above, and a conductor layer on the insulating layer.

[31] An electronic device comprising the printed wiring board according to

[30] . [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a resin composition that can give a cured product having an improved balance of low dielectric properties and heat resistance. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention will be described below based on the embodiments. In this embodiment, "A to B" indicating a numerical range means A or more and B or less unless otherwise specified. Furthermore, when a numerical range is described in stages, the upper and lower limits of each numerical range can be combined arbitrarily. Furthermore, the description "A and / or B" is a concept that includes the case of A, the case of B, and the case of both A and B. In the description of groups (atomic groups) in this specification, when a notation does not specify whether the group is substituted or unsubstituted, it encompasses both groups that do not contain a substituent and groups that contain a substituent. For example, the term "alkyl group" encompasses not only alkyl groups that do not contain a substituent (unsubstituted alkyl groups) but also alkyl groups that contain a substituent (substituted alkyl groups). In this specification, the term "(meth)acrylic" represents a concept that encompasses both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate." Furthermore, each monomer constituting the "thermosetting cyclic olefin copolymer (A) having a crosslinkable group" in this specification may be a monomer obtained from a fossil raw material, or a monomer obtained from an animal or plant raw material.

[0010] The resin composition of the present embodiment contains a thermosetting cyclic olefin copolymer (A) having a crosslinkable group, a modified phenylene ether resin (B), and a radical polymerization initiator (C).

[0011] Resin compositions used in printed wiring boards require, for example, a reflow process, and the cured product obtained by curing the resin composition is required to have improved heat resistance as a basic property. Furthermore, when used in high-frequency printed wiring boards, the cured resin is required to have improved low dielectric properties in order to reduce transmission loss.

[0012] The resin composition of this embodiment can provide a cured product with an improved balance of low dielectric properties and heat resistance. Furthermore, the resin composition of this embodiment can provide a film or sheet, a laminate, a prepreg, a printed wiring board, and an electronic device with an improved balance of low dielectric properties and heat resistance.

[0013] The reasons for this are thought to be as follows. It is believed that the synergistic effect of the thermosetting cyclic olefin copolymer (A) with improved low dielectric properties and the modified phenylene ether resin (B) with improved heat resistance has improved the performance balance of low dielectric properties and heat resistance compared to when the thermosetting cyclic olefin copolymer (A) alone or the modified phenylene ether resin (B) alone is used.

[0014] <Thermosetting cyclic olefin copolymer (A)> The resin composition of the present embodiment contains a thermosetting cyclic olefin copolymer (A) having a crosslinkable group (hereinafter also simply referred to as "copolymer"). The thermosetting cyclic olefin copolymer (A) can be any copolymer that has thermosetting properties and contains repeating units derived from a cyclic olefin, without any particular limitations. The thermosetting cyclic olefin copolymer (A) also contains a crosslinkable group, which improves the heat resistance of the resulting cured product. The crosslinkable group may include one or more crosslinkable functional groups selected from the group consisting of a vinyl group, a vinylidene group, a vinylene group, a vinyl group substituted with an alkyl group, a phenyl group, or an alkylphenyl group, a vinylidene group substituted with an alkyl group, a phenyl group, or an alkylphenyl group, a vinylene group substituted with an alkyl group, a phenyl group, or an alkylphenyl group, a maleimide group, a thiol group, a thienyl group, a silyl group, an epoxy group, an oxazoline group, a (meth)acrylic group, and a carboxyl group, and preferably includes a vinyl group. The crosslinkable group in the thermosetting cyclic olefin copolymer (A) improves compatibility with the modified phenylene ether resin (B) and improves heat resistance. The thermosetting cyclic olefin copolymer (A) will be described in detail below, but the thermosetting cyclic olefin copolymer (A) of this embodiment is not limited to the following aspects.

[0015] From the viewpoint of further improving the performance balance between low dielectric properties and heat resistance of the resulting cured product, the thermosetting cyclic olefin copolymer (A) preferably contains one or more olefin-derived repeating units (a) represented by formula (I), one or more cyclic non-conjugated diene-derived repeating units (b) represented by formula (III), and one or more cyclic olefin-derived repeating units (c) represented by formula (V).

[0016] [ka]

[0017] In formula (I), R 300represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.

[0018] [ka]

[0019] In formula (III), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, w is 0 or 1, and R 61 ~R 76 and R a1 and R b1 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; R 104 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, and R 75 and R 76 may be bonded to each other to form a monocyclic or polycyclic ring.

[0020] [ka]

[0021] In formula (V), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, w is 0 or 1, and R 61 ~R 78 , R a1 and R b1 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; R 75 ~R 78 may be bonded to each other to form a monocyclic or polycyclic ring.

[0022] In the thermosetting cyclic olefin copolymer (A), when the total number of moles of repeating units in the thermosetting cyclic olefin copolymer (A) is taken as 100 mol %, the content of each repeating unit can be as follows.

[0023] The content of the olefin-derived repeating unit (a) is preferably 10 mol% or more and 80 mol% or less, more preferably 15 mol% or more and 77 mol% or less, even more preferably 20 mol% or more and 75 mol% or less, even more preferably 30 mol% or more and 73 mol% or less, even more preferably 40 mol% or more and 71 mol% or less, even more preferably 45 mol% or more and 69 mol% or less, even more preferably 50 mol% or more and 67 mol% or less, and even more preferably 55 mol% or more and 65 mol% or less.

[0024] The content of the repeating unit (b) derived from a cyclic non-conjugated diene is preferably 1 mol% or more and 20 mol% or less, more preferably 3 mol% or more and 25 mol% or less, even more preferably 5 mol% or more and 30 mol% or less, even more preferably 8 mol% or more and 32 mol% or less, even more preferably 10 mol% or more and 34 mol% or less, even more preferably 15 mol% or more and 36 mol% or less, even more preferably 20 mol% or more and 38 mol% or less, and even more preferably 25 mol% or more and 40 mol% or less.

[0025] Furthermore, the content of the repeating unit (c) derived from a cyclic olefin is preferably 1 mol% or more and 40 mol% or less, more preferably 3 mol% or more and 30 mol% or less, even more preferably 5 mol% or more and 25 mol% or less, even more preferably 8 mol% or more and 20 mol% or less, and even more preferably 10 mol% or more and 15 mol% or less.

[0026] When the content of each repeating unit in the thermosetting cyclic olefin copolymer (A) is within the above range, the performance balance of low dielectric properties and heat resistance can be further improved when the copolymer is made into a film. Furthermore, the performance balance of the film's mechanical properties, transparency, and gas barrier properties can be further improved. In other words, a film with an improved balance of these physical properties can be obtained.

[0027] The olefin, which is one of the copolymerization raw materials for the thermosetting cyclic olefin copolymer (A), is a monomer that undergoes addition copolymerization to give the skeleton represented by formula (I), and is an olefin represented by formula (Ia).

[0028] [ka]

[0029] In the above formula (Ia), R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. The olefin represented by formula (Ia), i.e., the olefin constituting the olefin-derived repeating unit (a), includes, for example, one or more olefins selected from ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and the like. From the viewpoint of further improving the balance of low dielectric properties and heat resistance when formed into a film, the olefin represented by formula (Ia), i.e., the olefin constituting the olefin-derived repeating unit (a), preferably contains one or more olefins selected from the group consisting of ethylene and propylene, and more preferably contains ethylene. Two or more olefins represented by formula (Ia) may be used. Furthermore, the olefin may contain at least one biomass-derived monomer (biomass-derived ethylene, biomass-derived propylene, etc.).

[0030] The cyclic non-conjugated diene monomer, which is one of the copolymerization raw materials for the thermosetting cyclic olefin copolymer (A), undergoes addition copolymerization to form a repeating unit represented by formula (III). For example, a cyclic non-conjugated diene represented by formula (IIIa) corresponding to formula (III) is used. The cyclic non-conjugated diene may contain a structural unit derived from a biomass-derived monomer (cyclic non-conjugated diene).

[0031] [ka]

[0032] In formula (IIIa), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, w is 0 or 1, and R 61 ~R 76 and R a1 and R b1 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; R 104 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, and R 75 and R 76 may be bonded to each other to form a monocyclic or polycyclic ring.

[0033] The cyclic non-conjugated diene represented by formula (IIIa), i.e., the cyclic non-conjugated diene constituting the repeating unit (b) derived from a cyclic non-conjugated diene, is not particularly limited, and includes, for example, one or more cyclic non-conjugated dienes selected from the cyclic non-conjugated dienes represented by the following chemical formulas. Among these, the cyclic non-conjugated diene represented by formula (IIIa), i.e., the cyclic non-conjugated diene constituting the repeating unit (b) derived from a cyclic non-conjugated diene, is preferably 5-vinyl-2-norbornene and 8-vinyl-9-methyltetracyclo[4.4.0.1] 2,5 .1 7,10]-3-dodecene, and more preferably 5-vinyl-2-norbornene.

[0034] [ka]

[0035] [ka]

[0036] The cyclic non-conjugated diene represented by formula (IIIa) can also be represented by, for example, formula (IIIb).

[0037] [ka]

[0038] In formula (IIIb), n is an integer of 0 to 10, R1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0039] The thermosetting cyclic olefin copolymer (A) contains a repeating unit derived from a cyclic non-conjugated diene represented by formula (III), and thus can contain double bonds in the side chain portion, i.e., in the portion other than the main chain of the copolymer.

[0040] The cyclic olefin, which is one of the copolymerization raw materials for the thermosetting cyclic olefin copolymer (A), undergoes addition copolymerization to form a repeating unit represented by formula (V). For example, a cyclic olefin represented by formula (Va) corresponding to formula (V) is used.

[0041] [ka]

[0042] In formula (Va), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, w is 0 or 1, and R 61 ~R 78 and R a1 and R b1 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; R 75 ~R 78 may be bonded to each other to form a monocyclic or polycyclic ring.

[0043] Specific examples of the cyclic olefin represented by formula (Va) include the compounds described in WO 2006 / 118261. The cyclic olefin represented by formula (Va), i.e., the cyclic olefin constituting the cyclic olefin-derived structural unit (c), is bicyclo[2.2.1]-2-heptene (also called "norbornene") and tetracyclo[4.4.0.1 2,5 .1 7,10 Preferably, the cyclic olefin contains one or more selected from the group consisting of cyclo[2.2.1]-3-dodecene (also known as "tetracyclododecene"), and more preferably bicyclo[2.2.1]-2-heptene. These cyclic olefins have the advantage that the modulus of elasticity of the copolymer and the cured product is easily maintained because they contain a rigid ring structure, and that crosslinking is easily controlled because they do not contain heterogeneous double bond structures. The cyclic olefin represented by formula (Va) may contain a structural unit derived from a biomass-derived monomer (cyclic olefin).

[0044] By using the olefin represented by formula (Ia) and the cyclic olefin represented by formula (Va) as copolymerization components, the solubility of the thermosetting cyclic olefin copolymer (A) in solvents is further improved, resulting in good processability and improved product yield.

[0045] The thermosetting cyclic olefin copolymer (A) may further contain, in addition to the repeating units (a) derived from one or more olefins represented by formula (I), the repeating units (b) derived from a cyclic non-conjugated diene represented by formula (III), and the repeating units (c) derived from one or more cyclic olefins represented by formula (V), one or more repeating units selected from the group consisting of repeating units derived from cyclic olefins other than the cyclic non-conjugated diene represented by formula (III) and the cyclic olefin represented by formula (V), and repeating units derived from chain polyenes. In this case, as copolymerization raw materials for the thermosetting cyclic olefin copolymer (A), in addition to the olefin represented by formula (Ia), the cyclic non-conjugated diene represented by formula (IIIa), and the cyclic olefin represented by formula (Va), a cyclic olefin other than the cyclic non-conjugated diene represented by formula (IIIa) and the cyclic olefin represented by formula (Va), and / or a chain polyene can be used. Examples of such cyclic olefins and chain polyenes include cyclic olefins represented by formula (VIa), cyclic olefins represented by formula (VIIa), chain polyenes represented by formula (VIIIa), etc. Two or more different types of these cyclic olefins and chain polyenes may be used.

[0046] [ka]

[0047] In formula (VIa), x and d are 0 or an integer of 1 or more, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, y and z are 0, 1, or 2, and R 81 ~R 99 may be the same or different and are a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group which is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group; R 89 and R 90 and the carbon atom to which R is bonded. 93 or the carbon atom to which R is attached 91may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y and z are both 0, R 95 and R 92 or R 95 and R 99 may be bonded to each other to form a monocyclic or polycyclic aromatic ring.

[0048] [ka]

[0049] In formula (VIIa), R 100 and R 101 may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is an integer of 1 or more and 18 or less.

[0050] [ka]

[0051] In formula (VIIIa), R 201 From R 206 may be the same or different and are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and P is a linear or branched hydrocarbon group having 1 to 20 carbon atoms, which may contain a double bond and / or a triple bond.

[0052] Specific examples of the cyclic olefins represented by formula (VIa) and formula (VIIa) that can be used include the compounds described in paragraphs 0037 to 0063 of WO 2006 / 118261.

[0053] Examples of the linear polyene represented by formula (VIIIa) include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, DMDT, 1,3-butadiene, 1,5-hexadiene, etc. Cyclizable polyenes cyclized from polyenes such as 1,3-butadiene and 1,5-hexadiene may also be used.

[0054] When the thermosetting cyclic olefin copolymer (A) contains a repeating unit derived from a chain polyene represented by formula (VIIIa), or a repeating unit derived from a cyclic non-conjugated diene represented by formula (IIIa) and a cyclic olefin other than the cyclic olefin represented by formula (Va) (e.g., formula (VIa) or formula (VIIa)), the content of the repeating units is, for example, 0.1 mol % or more and 100 mol % or less, preferably 0.1 mol % or more and 50 mol % or less, based on the total number of moles of the repeating units derived from one or more olefins represented by formula (I), the repeating units derived from one or more cyclic non-conjugated dienes represented by formula (III), and the repeating units derived from one or more cyclic olefins represented by formula (V).

[0055] By using the olefin represented by formula (Ia), the cyclic olefin represented by formula (VIa) or (VIIa), and the linear polyene represented by formula (VIIIa) as copolymerization components, the effects of this embodiment can be achieved, and the solubility of the thermosetting cyclic olefin copolymer (A) in solvents is further improved, resulting in good moldability and improved product yield. Among these, the cyclic olefin represented by formula (VIa) or (VIIa) is preferred. These cyclic olefins have the advantage that the elastic modulus of the thermosetting cyclic olefin copolymer (A) and film is easily maintained because they contain a rigid ring structure, and the absence of heterogeneous double bond structures makes it easier to control crosslinking.

[0056] The number average molecular weight (Mn) of the thermosetting cyclic olefin copolymer (A) measured by gel permeation chromatography (GPC) in terms of polystyrene, from the viewpoint of further improving the performance balance between low dielectric properties and heat resistance, is preferably 1,000 or more and 100,000 or less, more preferably 3,000 or more and 80,000 or less, even more preferably 4,000 or more and 60,000 or less, even more preferably 5,000 or more and 40,000 or less, even more preferably 5,500 or more and 30,000 or less, and even more preferably 6,000 or more and 10,000 or less, in terms of the content of olefin-derived repeating units (a). The number average molecular weight (Mn) of the thermosetting cyclic olefin copolymer (A) can be controlled by the polymerization conditions such as the polymerization catalyst, co-catalyst, amount of H2 added, and polymerization temperature.

[0057] The comonomer content and glass transition temperature (Tg) of the thermosetting cyclic olefin copolymer (A) can be controlled by adjusting the monomer charging ratio depending on the intended application. The Tg of the film of the thermosetting cyclic olefin copolymer (A) after curing is preferably 110° C. or higher and 300° C. or lower, more preferably 110° C. or higher and 280° C. or lower, even more preferably 110° C. or higher and 260° C. or lower, even more preferably 110° C. or higher and 240° C. or lower, even more preferably 110° C. or higher and 220° C. or lower, even more preferably 110° C. or higher and 200° C. or lower, even more preferably 110° C. or higher and 170° C. or lower, and even more preferably 110° C. or higher and 150° C. When the Tg is within the above range, the melt moldability of the thermosetting cyclic olefin copolymer (A) and its solubility in solvents when made into a varnish are improved.

[0058] The intrinsic viscosity [η] of the thermosetting cyclic olefin copolymer (A) measured in decalin at 135°C is preferably 0.10 dL / g or more and 15 dL / g or less, more preferably 0.12 dL / g or more and 5 dL / g or less, and even more preferably 0.15 dL / g or more and 3 dL / g or less. When the intrinsic viscosity [η] is equal to or less than the upper limit, moldability can be further improved. On the other hand, when the intrinsic viscosity [η] is equal to or more than the lower limit, the heat resistance and mechanical properties of the cured product can be further improved. The intrinsic viscosity [η] of the thermosetting cyclic olefin copolymer (A) can be controlled by the polymerization conditions such as the polymerization catalyst, co-catalyst, amount of H2 added, and polymerization temperature.

[0059] The content of the thermosetting cyclic olefin copolymer (A) in the resin composition of this embodiment, when the entire resin composition is taken as 100% by mass, is preferably 10% by mass or more and 80% by mass or less, more preferably 12% by mass or more and 70% by mass or less, even more preferably 14% by mass or more and 60% by mass or less, even more preferably 15% by mass or more and 55% by mass or less, even more preferably 20% by mass or more and 50% by mass or less, even more preferably 25% by mass or more and 50% by mass or less, and even more preferably 30% by mass or more and 50% by mass or less, from the viewpoint of further improving the performance balance of heat resistance, mechanical properties, and low dielectric properties of the cured product.

[0060] <Method for producing thermosetting cyclic olefin copolymer (A)> The thermosetting cyclic olefin copolymer (A) of this embodiment can be produced, for example, according to the method for producing a cyclic olefin copolymer described in paragraphs 0075 to 0219 of WO 2012 / 046443. Details are omitted here.

[0061] <Modified phenylene ether resin (B)> The modified phenylene ether resin (B) of this embodiment has a biphenyl structure, that is, the modified phenylene ether resin (B) of this embodiment has a structure in which aromatic rings (benzene rings) are directly bonded to each other via single bonds.

[0062] The two aromatic rings in the biphenyl structure may each have a substituent. The substituent on the aromatic ring is not particularly limited, but may include one or more selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, an alkynylcarbonyl group, a (meth)acryloyl group, a vinyl group, an allyl group, a maleimide group, and a hydroxy group.

[0063] It is believed that the biphenyl structure of the modified phenylene ether resin (B) improves the compatibility between the thermosetting cyclic olefin copolymer (A) and the modified phenylene ether resin (B). As a result, it is believed that a synergistic effect between the thermosetting cyclic olefin copolymer (A) with improved low dielectric properties and the modified phenylene ether resin (B) with improved heat resistance can be more easily achieved, resulting in a better balance of low dielectric properties and heat resistance than when the thermosetting cyclic olefin copolymer (A) or the modified phenylene ether resin (B) is used alone.

[0064] The modified phenylene ether resin (B) of the present embodiment preferably contains one or more functional groups selected from the group consisting of a substituent containing a carbon-carbon unsaturated double bond and a functional group containing a polar group, more preferably contains one or more functional groups selected from the group consisting of a (meth)acryloyl group, a vinyl group, an allyl group, a maleimide group, and a hydroxy group, even more preferably contains one or more functional groups selected from the group consisting of a (meth)acryloyl group, a vinyl group, and an allyl group, even more preferably contains one or more functional groups selected from the group consisting of a (meth)acryloyl group and a vinyl group, and even more preferably contains a vinyl group.

[0065] The modified phenylene ether resin (B) preferably contains a modified phenylene ether resin (B) represented by formula (2), from the viewpoint of further improving the balance of low dielectric properties and heat resistance of the resulting cured product.

[0066] [ka]

[0067] In equation (2), R 31 ~R 38 may be the same or different. 31 ~R 38 R represents a functional group containing one or more selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, an alkynylcarbonyl group, a (meth)acryloyl group, a vinyl group, an allyl group, a maleimide group, and a hydroxy group. 11 ~R 18 may be the same or different. 11 ~R 18 represents a functional group containing one or more selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, an alkynylcarbonyl group, a (meth)acryloyl group, a vinyl group, an allyl group, a maleimide group, and a hydroxy group. X1 and X2 may be the same or different and represent a functional group containing one or more selected from the group consisting of a hydrogen atom, a linear, branched, or cyclic hydrocarbon group having 1 to 20 carbon atoms, or a (meth)acryloyl group, a vinyl group, an allyl group, a maleimide group, and a hydroxy group. m1 and m2 each represent a positive integer and may be the same or different. O represents an oxygen atom. R 31 ~R 38 , R 11 ~R 18 At least one of X1 and X2 represents a functional group containing one or more selected from the group consisting of a (meth)acryloyl group, a vinyl group, an allyl group, a maleimide group, and a hydroxy group.

[0068] In formula (2), m1 and m2 may each represent 1 to 50. m1 and m2 may be the same or different. m1 and m2 may each represent 0 to 20. The sum of m1 and m2 may represent 1 to 30.

[0069] In formula (2), the alkyl group is not particularly limited, but is preferably, for example, an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group.

[0070] The alkenyl group is not particularly limited, but is preferably an alkenyl group having 2 to 18 carbon atoms, and more preferably an alkenyl group having 2 to 10 carbon atoms. Specific examples include a vinyl group, an allyl group, and a 3-butenyl group. R in formula (2) 11 ~R 18 By substituting at least one of the above with an alkenyl group, the compatibility between the thermosetting cyclic olefin copolymer (A) and the modified phenylene ether resin (B) can be improved.

[0071] The alkynyl group is not particularly limited, but is preferably an alkynyl group having 2 to 18 carbon atoms, and more preferably an alkynyl group having 2 to 10 carbon atoms. Specific examples include an ethynyl group and a prop-2-yn-1-yl group (propargyl group).

[0072] The alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group, but for example, an alkylcarbonyl group having 2 to 18 carbon atoms is preferred, and an alkylcarbonyl group having 2 to 10 carbon atoms is more preferred. Specific examples include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a hexanoyl group, an octanoyl group, and a cyclohexylcarbonyl group.

[0073] The alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group, but for example, an alkenylcarbonyl group having 3 to 18 carbon atoms is preferred, and an alkenylcarbonyl group having 3 to 10 carbon atoms is more preferred. Specific examples include an acryloyl group, a methacryloyl group, and a crotonoyl group.

[0074] The alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group, but for example, an alkynylcarbonyl group having 3 to 18 carbon atoms is preferred, and an alkynylcarbonyl group having 3 to 10 carbon atoms is more preferred. Specific examples include a propioloyl group.

[0075] The number average molecular weight (Mn) of the modified phenylene ether resin (B) measured by gel permeation chromatography (GPC) in terms of polystyrene is preferably 500 or more, more preferably 750 or more, even more preferably 900 or more, and even more preferably 1,000 or more, from the viewpoint of further improving heat resistance, and is preferably 25,000 or less, more preferably 20,000 or less, even more preferably 15,000 or less, even more preferably 10,000 or less, even more preferably 5,000 or less, even more preferably 4,000 or less, even more preferably 3,000 or less, and even more preferably 2,500 or less, from the viewpoint of further improving low dielectric properties. Furthermore, the number average molecular weight (Mn) of the modified phenylene ether resin (B) measured by gel permeation chromatography (GPC) in terms of polystyrene is preferably 500 or more and 25,000 or less, more preferably 750 or more and 20,000 or less, even more preferably 900 or more and 15,000 or less, even more preferably 1,000 or more and 10,000 or less, even more preferably 1,000 or more and 5,000 or less, even more preferably 1,000 or more and 4,000 or less, even more preferably 1,000 or more and 3,000 or less, and even more preferably 1,000 or more and 2,500, from the viewpoint of further improving the performance balance between low dielectric properties and heat resistance. The number average molecular weight (Mn) of the modified phenylene ether resin (B) can be controlled by the polymerization conditions such as the polymerization catalyst, co-catalyst, and polymerization temperature.

[0076] The content of the modified phenylene ether resin (B) in the resin composition of this embodiment is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, even more preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, even more preferably 30 parts by mass or more, and even more preferably 35 parts by mass or more, per 100 parts by mass of the thermosetting cyclic olefin copolymer (A), from the viewpoint of further improving the heat resistance of the obtained cured product; and is preferably 500 parts by mass or less, more preferably 400 parts by mass or less, even more preferably 350 parts by mass or less, even more preferably 300 parts by mass or less, and even more preferably 280 parts by mass or less, from the viewpoint of further improving the low dielectric properties of the obtained cured product. Furthermore, from the viewpoint of further improving the performance balance between low dielectric properties and heat resistance of the obtained cured product, the content of the modified phenylene ether resin (B) in the resin composition of this embodiment is preferably 10 parts by mass or more and 500 parts by mass or less, more preferably 15 parts by mass or more and 400 parts by mass or less, even more preferably 20 parts by mass or more and 350 parts by mass or less, even more preferably 25 parts by mass or more and 300 parts by mass or less, even more preferably 30 parts by mass or more and 300 parts by mass or less, even more preferably 35 parts by mass or more and 280 parts by mass or less, and even more preferably 35 parts by mass or more and 280 parts by mass or less, per 100 parts by mass of the thermosetting cyclic olefin copolymer (A).

[0077] From the viewpoint of further improving the heat resistance of the resulting cured product, in the formula (2), at least one of X1 and X2 preferably contains a functional group represented by the following formula (2a) or formula (2b).

[0078] [ka]

[0079] In formula (2a), R 21 preferably represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, further preferably represents a hydrogen atom or a methyl group, and further preferably represents a hydrogen atom; R 22represents preferably an alkylene group having 1 to 10 carbon atoms or a direct bond, more preferably an alkylene group having 1 to 4 carbon atoms or a direct bond, and even more preferably an alkylene group having 1 to 2 carbon atoms or a direct bond. The substituent represented by formula (2a) preferably contains one or two vinylbenzyl groups (ethenylbenzyl groups) selected from the group consisting of p-ethenylbenzyl groups, m-ethenylbenzyl groups, and the like.

[0080] [ka]

[0081] In formula (2b), R 23 preferably represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and even more preferably represents a hydrogen atom or a methyl group. Examples of the substituent represented by formula (2b) include a (meth)acryloyl group.

[0082] The modified phenylene ether resin (B) preferably contains a substituent represented by formula (2a) or formula (2b) at at least one end of the main chain of the modified phenylene ether resin (B). More preferably, the modified phenylene ether resin (B) contains a substituent represented by formula (2a) at at least one end of the main chain of the modified phenylene ether resin (B).

[0083] More preferably, the modified phenylene ether resin (B) contains an ethenylbenzyl group at at least one end of the main chain of the modified phenylene ether resin (B). This can improve the compatibility between the thermosetting cyclic olefin copolymer (A) and the modified phenylene ether resin (B). Even more preferably, the modified phenylene ether resin (B) contains an ethenylbenzyl group at both ends of the main chain of the modified phenylene ether resin (B). This can further improve the compatibility between the thermosetting cyclic olefin copolymer (A) and the modified phenylene ether resin (B).

[0084] More specific examples of the modified phenylene ether resin (B) represented by formula (2) include the modified phenylene ether resin (B) shown as "OPE-2St" in ACS Omega 2022,7,26396-26406. Such resins include a resin having ethenylbenzyl groups at both terminal groups (product name: OPE-2st, manufactured by Mitsubishi Gas Chemical Company, Inc.).

[0085] The method for synthesizing the modified phenylene ether resin (B) of the present embodiment is not particularly limited as long as it is possible to synthesize the modified phenylene ether resin (B) having a biphenyl structure.

[0086] <Radical polymerization initiator (C)> The resin composition of the present embodiment contains a radical polymerization initiator (C). Crosslinking with the radical polymerization initiator (C) can be performed by the same method as that used for crosslinking polyolefins, etc. That is, a radical polymerization initiator such as dicumyl peroxide is blended with the thermosetting cyclic olefin copolymer (A), and the mixture is heated to crosslink the copolymer.

[0087] The radical polymerization initiator (C) may be a known thermal radical polymerization initiator, a photoradical polymerization initiator, or a combination of these. When a thermal radical polymerization initiator is used, it should have a 10-hour half-life temperature of, for example, 80°C or higher, preferably 120°C or higher, from the viewpoint of storage stability. Examples of such thermal radical polymerization initiators include dialkyl peroxides such as dicumyl peroxide, t-butylcumyl peroxide, 2,5-bis(t-butylperoxy)2,5-dimethylhexane, 2,5-bis(t-butylperoxy)2,5-dimethylhexyne-3, di-t-butyl peroxide, isopropylcumyl-t-butyl peroxide, and bis(α-t-butylperoxyisopropyl)benzene; 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl-4,4-bis(t-butylperoxy)valerate, and ethyl-3,3-bis(t-butylperoxy). peroxyketals such as bis(t-butylperoxy)butyrate and 3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxycyclononane; peroxyesters such as bis(t-butylperoxy)isophthalate, t-butylperoxybenzoate and t-butylperoxyacetate; hydroperoxides such as t-butyl hydroperoxide, t-hexyl hydroperoxide, cumin hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide and p-menthane hydroperoxide; bibenzyl compounds such as 2,3-dimethyl-2,3-diphenylbutane; and 3,3,5,7,7-pentamethyl-1,2,4-trioxepane.

[0088] As the radical polymerization initiator (C), known thermal radical polymerization initiators, photoradical polymerization initiators, and combinations of these can be used. From the viewpoint of further improving the heat resistance of the resulting cured product, the radical polymerization initiator (C) preferably contains one or more compounds selected from the group consisting of dicumyl peroxide, 2,3-dimethyl-2,3-diphenylbutane, and 2,2'-azobis(2,4,4-trimethylpentane), and more preferably contains dicumyl peroxide.

[0089] Among the radical polymerization initiators (C), examples of photoradical polymerization initiators include benzoin alkyl ether, benzil dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, methylbenzoyl formate, isopropyl thioxanthone, and mixtures of two or more of these. Sensitizers can also be used in conjunction with these photoradical polymerization initiators. Examples of sensitizers include carbonyl compounds such as anthraquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, benzanthrone, p,p'-tetramethyldiaminobenzophenone, and chloranil; nitro compounds such as nitrobenzene, p-dinitrobenzene, and 2-nitrofluorene; aromatic hydrocarbons such as anthracene and chrysene; sulfur compounds such as diphenyl disulfide; and nitrogen compounds such as nitroaniline, 2-chloro-4-nitroaniline, 5-nitro-2-aminotoluene, and tetracyanoethylene.

[0090] The content of the radical polymerization initiator (C) in the resin composition of this embodiment is preferably 0.1 parts by mass or more and 25.0 parts by mass or less, more preferably 0.5 parts by mass or more and 20.0 parts by mass or less, more preferably 1.0 parts by mass or more and 15.0 parts by mass or less, even more preferably 1.5 parts by mass or more and 14.0 parts by mass or less, even more preferably 1.8 parts by mass or more and 13.0 parts by mass or less, even more preferably 2.0 parts by mass or more and 12.0 parts by mass or less, even more preferably 3.0 parts by mass or more and 11.0 parts by mass or less, even more preferably 4.0 parts by mass or more and 11.0 parts by mass or less, and even more preferably 4.5 parts by mass or more and 11.0 parts by mass or less, relative to 100 parts by mass of the thermosetting cyclic olefin copolymer (A), from the viewpoint of further improving the performance balance between low dielectric properties and heat resistance of the obtained cured product.

[0091] The resin composition of this embodiment may further contain a crosslinking aid. There are no limitations on the crosslinking aid, but examples include oximes such as p-quinone dioxime and p,p'-dibenzoylquinone dioxime; acrylates or methacrylates such as ethylene dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, cyclohexyl methacrylate, acrylic acid / zinc oxide mixtures, and allyl methacrylate; vinyl monomers such as divinylbenzene, vinyltoluene, and vinylpyridine; allyl compounds such as hexamethylenediallylnadimide, diaryl itaconate, diallyl phthalate, diallyl isophthalate, diallyl monoglycidyl isocyanurate, triallyl cyanurate, and triallyl isocyanurate; and maleimide compounds such as N,N'-m-phenylene bismaleimide and N,N'-(4,4'-methylenediphenylene)dimaleimide. These crosslinking aids may be used alone or in combination.

[0092] The total content of the thermosetting cyclic olefin copolymer (A), the modified phenylene ether resin (B), and the radical polymerization initiator (C) in the resin composition of this embodiment is preferably 50% by mass or more and 100% by mass or less, more preferably 60% by mass or more and 100% by mass or less, even more preferably 70% by mass or more and 100% by mass or less, even more preferably 80% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, even more preferably 95% by mass or more and 100% by mass or less, and even more preferably 97% by mass or more and 100% by mass or less, when the total amount of solids in the resin composition (the total amount of components remaining as solids when cured) is taken as 100% by mass.

[0093] <Antioxidant (D)> The resin composition of the present embodiment may further contain an antioxidant (D). The antioxidant (D) is not limited, and known antioxidants can be used, such as phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, thioether-based antioxidants, and hindered phenol-based antioxidants.

[0094] Examples of phenolic antioxidants include acrylate-based phenolic compounds described in JP-A-63-179953 and JP-A-1-168643, such as 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate and 2,4-di-t-amyl-6-(1-(3,5-di-t-amyl-2-hydroxyphenyl)ethyl)phenyl acrylate; 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, octadecyl-3-methylphenyl acrylate, and the like. -(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 4,4'-butylidene-bis(6-t-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-t-butylphenol), bis(3-cyclohexyl-2-hydroxy-5-methylphenyl)methane, 3,9-bis(2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetrahydrofuran Alkyl-substituted phenols such as xaspiro[5.5]undecane, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, pentaerythritol tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, triethylene glycol bis(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate), and tocopherol triazine group-containing phenolic compounds such as 6-(4-hydroxy-3,5-di-t-butylanilino)-2,4-bisoctylthio-1,3,5-triazine, 6-(4-hydroxy-3,5-dimethylanilino)-2,4-bisoctylthio-1,3,5-triazine, 6-(4-hydroxy-3-methyl-5-t-butylanilino)-2,4-bisoctylthio-1,3,5-triazine, and 2-octylthio-4,6-bis-(3,5-di-t-butyl-4-oxyanilino)-1,3,5-triazine.Among these, acrylate-based phenol compounds and alkyl-substituted phenol-based compounds are preferred, alkyl-substituted phenol-based compounds are more preferred, and pentaerythritol tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate is even more preferred.

[0095] Examples of phosphorus-based antioxidants include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(2-t-butyl-4-methylphenyl) phosphite, tris(cyclohexylphenyl) phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl) phosphite, monophosphite compounds such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene; 4,4'-butylidene-bis(3-methyl-6-t-butylphenanthren-10-oxide); 4,4'-Isopropylidene-bis(phenyl-di-alkyl(C12-C15) phosphite), 4,4'-Isopropylidene-bis(diphenyl monoalkyl(C12-C15) phosphite), 1,1,3-tris(2-methyl-4-di-tridecylphosphite-5-t-butylphenyl)butane, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene diphosphite, cyclic neo Examples of the diphosphite compounds include pentanetetraylbis(isodecylphosphite), cyclic neopentanetetraylbis(nonylphenylphosphite), cyclic neopentanetetraylbis(2,4-di-t-butylphenylphosphite), cyclic neopentanetetraylbis(2,4-dimethylphenylphosphite), and cyclic neopentanetetraylbis(2,6-di-t-butylphenylphosphite). Among these, monophosphite compounds are preferred, and tris(nonylphenyl)phosphite, tris(dinonylphenyl)phosphite, and tris(2,4-di-t-butylphenyl)phosphite are more preferred.

[0096] Examples of sulfur-based antioxidants include dilauryl 3,3-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3-thiodipropionate, laurylstearyl 3,3-thiodipropionate, pentaerythritol-tetrakis-(β-lauryl-thio-propionate), and 3,9-bis(2-dodecylthioethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane.

[0097] Examples of thioether antioxidants include tetrakis{methylene-3-(laurylthio)propionate}methane, bis[methyl-4-{3-n-alkyl(C12 or C14)thiopropioniodyl}-5-t-butylphenyl]sulfide, and ditridecyl-3,3'-thiodipropionate.

[0098] The content of the antioxidant (D) in the resin composition of this embodiment is preferably 0.01 to 5.0 parts by mass, more preferably 0.02 to 3.0 parts by mass, even more preferably 0.03 to 2.0 parts by mass, even more preferably 0.04 to 1.0 parts by mass, even more preferably 0.05 to 0.5 parts by mass, even more preferably 0.05 to 0.3 parts by mass, and even more preferably 0.05 to 0.2 parts by mass, relative to 100 parts by mass of the thermosetting cyclic olefin copolymer (A), from the viewpoint of further improving the performance balance between low dielectric properties and heat resistance of the resulting cured product.

[0099] <Other ingredients> The resin composition of this embodiment may contain other components as long as the effects of the invention of this embodiment are not impaired. Examples of other components include one or more additives selected from the group consisting of inorganic fillers, organic fillers, heat stabilizers, weather stabilizers, radiation resistant agents, plasticizers, lubricants, mold release agents, nucleating agents, friction and wear improvers, flame retardants, foaming agents, antistatic agents, colorants, antifogging agents, antiblocking agents, impact resistance agents, surface wettability improvers, hydrochloric acid absorbers, and metal deactivators; and resins other than the thermosetting cyclic olefin copolymer (A) and the modified phenylene ether resin (B), such as epoxy resins and polystyrene resins.

[0100] The total amount of solids in the resin composition of this embodiment (the total amount of components that remain as solids when cured) is preferably 70% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, even more preferably 95% by mass or more and 100% by mass or less, and even more preferably 97% by mass or more and 100% by mass or less, when the weight of the resin composition is 100% by mass.

[0101] <Method for preparing resin composition> The resin composition of this embodiment can be prepared by mixing the thermosetting cyclic olefin copolymer (A), the modified phenylene ether resin (B), the radical polymerization initiator (C), and, if necessary, other components such as an antioxidant (D). The mixing method can be a solution blending method in which the components are dissolved or dispersed in a suitable solvent, such as a saturated hydrocarbon such as heptane, hexane, decane, or cyclohexane, or an aromatic hydrocarbon such as toluene, benzene, or xylene.

[0102] Hereinafter, preferred properties of the resin composition of this embodiment will be described.

[0103] From the viewpoint of further improving the balance between low dielectric properties and heat resistance, the dielectric loss tangent Df of the resin composition of this embodiment, measured by the following method, is preferably 0.0001 or more and less than 0.0030, more preferably 0.0002 or more and 0.0028 or less, even more preferably 0.0003 or more and 0.0026 or less, even more preferably 0.0005 or more and 0.0024 or less, even more preferably 0.0008 or more and 0.0021 or less, even more preferably 0.0008 or more and 0.0018 or less, and even more preferably 0.0008 or more and 0.0016 or less at a frequency of 10 GHz. There is no particular restriction on the lower limit of the dielectric loss tangent Df. (method) A cured film of 30±15 μm in thickness is prepared from the resin composition, and a test piece of 50 mm in length, 50 mm in width, and 30±15 μm in thickness is cut out from the cured film. The dielectric loss tangent Df of the test piece is measured using a cylindrical cavity resonator at 23±2°C, 50±5% RH, and 10 GHz.

[0104] In the resin composition of the present embodiment, from the viewpoint of further improving the performance balance between low dielectric properties and heat resistance, it is preferable that when there are two or more peaks in the temperature dispersion of the loss tangent tanδ in dynamic viscoelasticity obtained by the following method, the peak on the high temperature side is larger. (method) A cured film of the resin composition having a thickness of 30±15 μm was prepared. The cured film is cut into test pieces 40 mm long, 3 mm wide, and 30±15 μm thick, and the dynamic viscoelasticity of the cured film is measured in tensile mode under a nitrogen atmosphere at a heating rate of 3°C / min and a frequency of 1 Hz.

[0105] Of two or more peaks, the peak with the greatest peak height is called the main peak, and the peak with the next greatest peak height is called the sub-peak. Furthermore, of the main peak and sub-peak, the peak on the higher temperature side is called the first peak, and the peak on the lower temperature side is called the second peak. The glass transition point corresponding to the first peak is called the first glass transition point, and the glass transition point corresponding to the second peak is called the second glass transition point. The temperature corresponding to the first glass transition point is called the first glass transition temperature Tg1, and the temperature corresponding to the second glass transition point is called the second glass transition temperature Tg2. In other words, the temperature corresponding to the first peak is called the first glass transition temperature Tg1, and the temperature corresponding to the second peak is called the second glass transition temperature Tg2.

[0106] The first glass transition temperature Tg1 is preferably 200° C. or higher and lower than 300° C., more preferably 205° C. or higher and 280° C. or lower, even more preferably 210° C. or higher and 260° C. or lower, even more preferably 215° C. or higher and 250° C. or lower, even more preferably 220° C. or higher and 240° C. or lower, and even more preferably 220° C. or higher and 230° C. There is no particular upper limit to the first glass transition temperature Tg1.

[0107] The second glass transition temperature Tg2 is preferably 50° C. or higher and lower than 200° C., more preferably 80° C. or higher and 195° C. or lower, even more preferably 100° C. or higher and 190° C. or lower, even more preferably 110° C. or higher and 185° C. or lower, even more preferably 120° C. or higher and 180° C. or lower, and even more preferably 120° C. or higher and 175° C. The lower limit of the second glass transition temperature Tg1 is not particularly limited.

[0108] The value of the loss factor tan δ at the first glass transition temperature Tg1 is called tan δ1(Tg1), and the value of the loss factor tan δ at the second glass transition temperature Tg2 is called tan δ2(Tg2). Parameter A, which is the ratio of the loss tangent tan δ1(Tg1) at the first glass transition temperature Tg1 to the loss tangent tan δ2(Tg2) at the second glass transition temperature Tg2, is calculated. Specifically, the value of parameter A is calculated using the following formula (1). Formula (1): A=tanδ1(Tg1) / tanδ2(Tg2)

[0109] When the parameter A is greater than 1.0, this means that the peak at the first glass transition temperature Tg1 on the higher temperature side becomes the main peak. The value of the parameter A is preferably greater than 1.0 and less than 30.0, more preferably greater than 1.1 and less than 25.0, even more preferably greater than 1.5 and less than 20.0, even more preferably greater than 2.0 and less than 15.0, even more preferably greater than 3.0 and less than 12.5, and even more preferably greater than 4.0 and less than 10.0. The upper limit of the parameter A is not particularly limited.

[0110] The storage modulus of the cured product of the resin composition of the present embodiment, as measured by the following method, is preferably 1.0 × 10 at 220°C, from the viewpoint of further improving the performance balance between low dielectric properties and heat resistance. 6 Pa or more 1.0×10 9 Pa or less, preferably 5.0×10 6 Pa or more 8.0×10 9 Pa or less, more preferably 1.0 × 10 7 Pa or more 6.0×10 9 Pa or less, more preferably 2.0 × 10 7 Pa or more 4.0×10 9 Pa or less, more preferably 4.0 × 10 7 Pa or more 2.0×10 9 Pa or less, more preferably 9.0 × 10 7 Pa or more 1.0×10 9 The storage modulus at 220°C is not more than 1 Pa. The upper limit of the storage modulus at 220°C is not particularly limited. (method) A cured film of the resin composition having a thickness of 30±15 μm was prepared. The cured film is cut into test pieces 45 mm long, 5 mm wide, and 30±15 μm thick, and the dynamic viscoelasticity of the cured film is measured in tensile mode under a nitrogen atmosphere at a heating rate of 3°C / min and a frequency of 1 Hz.

[0111] The cured product of the resin composition of the present embodiment used in measuring the above-mentioned various physical properties is produced under the following conditions.

[0112] (conditions) The thermosetting cyclic olefin copolymer (A) of this embodiment is dispersed in 1400 parts by weight of toluene per 100 parts by weight of the thermosetting cyclic olefin copolymer (A) to prepare a raw varnish. Other components, such as a modified phenylene ether resin (B), a radical polymerization initiator (C), and an antioxidant (D), are dispersed in the raw varnish to prepare a varnish. The resulting varnish is applied to a release-treated PET film using an automatic coater at room temperature with an applicator gap of 200 μm and a speed of 10 mm / sec. The resulting varnish is then dried at 150°C for 4 minutes under a nitrogen stream (30 L / min) to form a film. Next, in the case where (C) is 2,3-dimethyl-2,3-diphenylbutane, the mixture is pressurized to 3.5 MPa under conditions of a vacuum of 1.2 kPa or less, heated from 30°C at a rate of 6°C / min, held at 180°C for 60 minutes, and then cooled to room temperature. The PET film was peeled off, sandwiched between polyimide films, and the temperature was raised from 30°C at a rate of 6°C / min, and then held at 220°C for 120 minutes to obtain a cured product with a thickness of 30±15 μm. When (C) was dicumyl peroxide or 2,2'-azobis(2,4,4-trimethylpentane), vacuum pressing was performed only at 180°C for 120 minutes. Note that the release film used during vacuum pressing was PET film at 180°C, and polyimide film (product name: Upilex Film (registered trademark), manufactured by UBE Corporation) at 220°C.

[0113] [varnish] The resin composition of the present embodiment can be mixed with a solvent to form a varnish, that is, the varnish of the present embodiment contains the resin composition and a solvent.

[0114] The solvent for preparing the varnish is not limited as long as it does not impair the solubility or affinity of the thermosetting cyclic olefin copolymer (A), the modified phenylene ether resin (B), the radical polymerization initiator (C), and the antioxidant (D). Preferred solvents include saturated hydrocarbons such as heptane, hexane, octane, and decane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and decahydronaphthalene; aromatic hydrocarbons such as toluene, benzene, xylene, mesitylene, and pseudocumene; alcohols such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, and phenol; ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, and acetophenone; cellosolves such as methyl cellosolve and ethyl cellosolve; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, and butyl formate; and halogenated hydrocarbons such as trichloroethylene, dichloroethylene, and chlorobenzene. From the viewpoint of further improving the solubility of the resin composition and ease of availability, heptane, decane, cyclohexane, methylcyclohexane, decahydronaphthalene, toluene, benzene, xylene, mesitylene, and pseudocumene are more preferably used. These solvents can be used alone or in combination of two or more in any ratio.

[0115] The amount of solvent added to the resin composition is preferably 80 parts by mass or more and 600 parts by mass or less, more preferably 90 parts by mass or more and 500 parts by mass or less, and even more preferably 100 parts by mass or more and 450 parts by mass or less, based on 100 parts by mass of the entire resin composition, from the viewpoint of further improving the handling and coating properties of the varnish.

[0116] The total content of the thermosetting cyclic olefin copolymer (A), the modified phenylene ether resin (B), the radical polymerization initiator (C), and the antioxidant (D) in the varnish is preferably 5% by mass or more and 100% by mass or less, more preferably 10% by mass or more and 100% by mass or less, even more preferably 15% by mass or more and 100% by mass or less, and even more preferably 20% by mass or more and 100% by mass or less.

[0117] In this embodiment, the method for preparing the varnish may be carried out by any method, for example, including a step of mixing a resin composition and a solvent. The order in which the components are mixed is not limited, and the components may be mixed in any manner, such as all at once or in portions. The apparatus for preparing the varnish is also not limited, and any apparatus capable of stirring and mixing, such as a batch type or a continuous type, may be used. The temperature at which the varnish is prepared can be selected arbitrarily from room temperature to the boiling point of the solvent. The varnish may be prepared by using the reaction solution obtained when the thermosetting cyclic olefin copolymer (A) is obtained as it is as a solvent.

[0118] [Cured product] The cured product of this embodiment is a cured product of the resin composition of this embodiment. The cured product of this embodiment can be obtained by crosslinking the thermosetting cyclic olefin copolymer (A) in the resin composition of this embodiment. The crosslinking can be carried out by a crosslinking step in which the resin composition is crosslinked at 150°C or higher under a vacuum of 20 kPa or lower.

[0119] The crosslinking temperature in the crosslinking step is within the following range, from the viewpoint of further improving the heat resistance of the resulting cured product, and from the viewpoint of suppressing thermal decomposition of the thermosetting cyclic olefin copolymer (A) and the cured product: The crosslinking temperature in the crosslinking step is preferably 150°C or higher and 250°C or lower, more preferably 160°C or higher and 230°C or lower, and even more preferably 170°C or higher and 220°C or lower.

[0120] The degree of vacuum in the crosslinking step is preferably 20 kPa or less, more preferably 10 kPa or less, more preferably 5 kPa or less, and even more preferably 2 kPa or less, from the viewpoint of further improving the performance balance between low dielectric properties and heat resistance of the resulting cured product.

[0121] The crosslinking step can be carried out with the resin composition of the present embodiment in a molten state, or with the resin composition in a solution state where it is dissolved or dispersed in a solvent. Alternatively, the crosslinking step can be carried out by volatilizing the solvent from a solution state where the resin composition is dissolved in a solvent, forming the resin composition into any shape such as a film or coating, and then further promoting the crosslinking reaction. When the reaction is carried out in a molten state, the mixture of raw materials is melt-kneaded and reacted using a kneading device such as a mixing roll, a Banbury mixer, an extruder, a kneader, a continuous mixer, etc. Alternatively, the crosslinking reaction can be further carried out after molding by any method. When the reaction is carried out in a solution state, the same solvents as those used in the above solution blending method can be used as the solvent.

[0122] [Film or sheet] The film or sheet of this embodiment contains the resin composition of this embodiment or the cured product of this embodiment. The resin composition of this embodiment or the cured product of this embodiment can be formed into a film or sheet (hereinafter referred to as a film or the like) and used in various applications. Various known methods can be used to form the resin composition of this embodiment or the cured product of this embodiment into a film or the like. For example, a method can be used in which the varnish described above is applied to a support substrate such as a thermoplastic resin film, dried, and then, if necessary, heat-treated to crosslink the resin composition to obtain a cured product, and a film or the like made of the resin composition of this embodiment is formed. Examples of thermoplastic resin films include PET films and polyimide resin films. The method for applying the varnish to the support substrate is not particularly limited, and examples include application using a spin coater, application using a spray coater, and application using a bar coater. Another example is a method in which the resin composition of the present embodiment is melt-molded to obtain a film or the like, and then, if necessary, the resin composition is crosslinked by a heat treatment or the like to form a cured product, thereby forming a film or the like made of the resin composition of the present embodiment.

[0123] [Laminate] The laminate of this embodiment includes the film or sheet of this embodiment. For example, by laminating the film of the present embodiment on a substrate, it can be used as a laminate for various purposes. That is, by laminating the film of the present embodiment on a substrate, it can be used as a laminate for various purposes. For example, it can be used as an organic insulating film that requires low dielectric properties or a curable adhesive sheet for a device that includes an adhesive layer. Various known methods can be applied to form the laminate of this embodiment. For example, a laminate can be produced by laminating a film or the like produced by the above-mentioned method onto a substrate, and, if necessary, heat-curing the laminate using a press or the like. Alternatively, a laminate can be produced by laminating an electrical insulating layer containing the above-mentioned cured product onto a conductor layer.

[0124] [Multi-layer molded body or multi-layer laminated film] The cured product obtained by curing the resin composition of the present embodiment may be formed on the surface layer of various multilayer molded articles or multilayer laminate films. Examples of various multilayer molded articles or multilayer laminated films include a multilayer molded article for an optical lens in which the film of this embodiment is formed on the surface of a resin optical lens, and a multilayer gas barrier film in which the cured product of this embodiment is formed on the surface of a resin film such as a PET film or a PE film to impart gas barrier properties.

[0125] [Prepreg] The prepreg of the present embodiment is formed by combining the resin composition of the present embodiment with a sheet-like fiber base material. That is, the prepreg of the present embodiment includes the resin composition and the sheet-like fiber base material. The method for producing the prepreg is not particularly limited, and various known methods can be applied. For example, there is a method including a step of impregnating a sheet-like fiber substrate with the above-mentioned varnish to obtain an impregnated body, and a step of heating the obtained impregnated body to dry the solvent contained in the varnish. The impregnation of the sheet-like fiber substrate with the varnish can be carried out, for example, by applying a predetermined amount of varnish to the sheet-like fiber substrate by a known method such as spray coating, dip coating, roll coating, curtain coating, die coating, or slit coating, and if necessary, placing a protective film on top of it and pressing it from above with a roller or the like. The process of heating the impregnated body and drying the solvent contained in the varnish is not particularly limited, but examples thereof include a batch process in which the impregnated body is dried in air or nitrogen using a blower dryer, or a continuous process in which the impregnated body is dried by passing it through a heating furnace. After the sheet-like fiber substrate is impregnated with the varnish, the resulting impregnated body is heated to a predetermined temperature, whereby the solvent contained in the varnish evaporates and a prepreg is obtained.

[0126] The fibers constituting the sheet-like fiber substrate can be inorganic or organic, and are not particularly limited. Examples include organic fibers such as PET (polyethylene terephthalate) fibers, polystyrene fibers, aramid fibers, ultra-high molecular weight polyethylene fibers, polyamide (nylon) fibers, and liquid crystal polyester fibers; and inorganic fibers such as glass fibers, carbon fibers, alumina fibers, tungsten fibers, molybdenum fibers, titanium fibers, steel fibers, boron fibers, silicon carbide fibers, and silica fibers. Among these, preferred are one or more types selected from the group consisting of organic fibers and glass fibers, and more preferred are one or more types selected from the group consisting of aramid fibers, liquid crystal polyester fibers, and glass fibers. Examples of glass fibers include E-glass, NE-glass, S-glass, D-glass, H-glass, and T-glass. The impregnation of the sheet-like fiber substrate with the varnish is carried out, for example, by immersion and coating. The impregnation may be repeated multiple times as necessary. These sheet-like fiber substrates can be used alone or in combination of two or more, and the amount used is selected appropriately as desired, but is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and even more preferably 30% by mass to 70% by mass of the prepreg or laminate. Within this range, the low dielectric properties and mechanical strength of the resulting laminate are well balanced, which is preferable.

[0127] The thickness of the prepreg is suitably selected depending on the intended use, but is preferably 0.001 mm to 1 mm, more preferably 0.005 mm to 0.8 mm, and even more preferably 0.01 mm to 0.5 mm. This range is suitable because it allows for sufficient shaping during lamination and the mechanical strength, toughness, and other properties of the laminate obtained by curing.

[0128] [Metal-clad laminate] The laminate of this embodiment may be formed into a metal clad laminate by laminating a metal foil on at least one surface of the laminate of this embodiment and heat-curing the laminate by a lamination press or the like. That is, the laminate of this embodiment may further include a metal foil on at least one surface. The metal foil may be attached to both surfaces of the laminate. Examples of metal foils include copper foil, aluminum foil, nickel foil, gold foil, silver foil, stainless steel foil, etc. From the viewpoints of economy, processability, thermal conductivity, and electrical conductivity, electrolytic copper foil is preferred. As a method for producing the metal clad laminate of this embodiment, various known methods can be applied. For example, a metal clad laminate can be produced by laminating a metal foil on the laminate of this embodiment and, if necessary, heat-curing it by pressing or the like.

[0129] The metal clad laminate of this embodiment contains a cured product of the resin composition of this embodiment, and therefore has an improved balance of low dielectric properties and heat resistance. Therefore, the metal clad laminate of this embodiment can be suitably used as an insulating layer material for printed wiring boards.

[0130] [Printed wiring board] The cured product obtained by curing the resin composition of this embodiment has an improved balance of low dielectric properties and heat resistance, and is therefore suitable for use in printed wiring boards. The printed wiring board of this embodiment includes an insulating layer containing the cured product of this embodiment or a cured product of the prepreg of this embodiment, and a conductor layer on the insulating layer. A commonly known method can be used to manufacture a printed wiring board, and is not particularly limited. For example, a film or laminate manufactured by the above-described method is heat-cured using a lamination press or the like to form an electrical insulating layer. Next, a conductor layer is laminated on the obtained electrical insulating layer using a known method to produce a laminate. Thereafter, the conductor layer in the laminate is subjected to circuit processing or the like to obtain a printed wiring board.

[0131] Examples of metals that can be used for the conductor layer include copper, aluminum, nickel, gold, silver, stainless steel, etc. Methods for forming the conductor layer include, for example, a method in which the above metals are made into foil or the like and heat-fused onto the electrical insulating layer, a method in which the above metals are made into foil or the like and attached to the electrical insulating layer using an adhesive, or a method in which a conductor layer made of the above metals is formed on the electrical insulating layer by a method such as sputtering, vapor deposition, or plating. The printed wiring board may be either a single-sided board or a double-sided board.

[0132] Such a printed wiring board can be used as an electronic device by mounting electronic components such as semiconductor elements on it. That is, the electronic device of this embodiment includes the printed wiring board of this embodiment. The electronic device can be manufactured based on publicly known information. Examples of such electronic devices include ICT infrastructure equipment such as servers, routers, supercomputers, mainframes, and workstations; antennas such as GPS antennas, antennas for wireless base stations, millimeter-wave antennas, and RFID antennas; communication devices such as mobile phones, smartphones, PHS, PDAs, and tablet terminals; digital devices such as personal computers, televisions, digital cameras, digital video cameras, POS terminals, wearable terminals, and digital media players; in-vehicle electronic devices such as electronic control system devices, in-vehicle communication devices, car navigation devices, millimeter-wave radars, and in-vehicle camera modules; semiconductor testing equipment, high-frequency measuring equipment, and the like.

[0133] [Uses of the cured product] The cured product of the resin composition of the present embodiment has a good balance of low dielectric properties and heat resistance, and therefore can be used in applications such as optical fibers, optical waveguides, optical disk substrates, optical filters, lenses, optical adhesives, optical filters for PDPs, coating materials for organic electroluminescence (EL) devices, base film substrates for solar cells in the aerospace field, coating materials for solar cells and thermal control systems, semiconductor elements, light-emitting diodes, electronic elements such as various types of memories, hybrid ICs, MCMs, printed wiring boards, prepregs and laminates used to form insulating layers for printed wiring boards, overcoat materials or interlayer insulating materials for display components, substrates for liquid crystal displays and solar cells, medical instruments, automotive components, resin modifiers, transparent substrates for displays, gas barrier coating materials, wire coating materials, automotive components, aerospace components, semiconductor processing materials, wire coating materials, lithium-ion battery components, fuel cell components, capacitor films, flexible display components, anchor coating materials, transparent adhesives, and hard coating materials. In particular, the cured product obtained by curing the resin composition of the present embodiment has an improved balance of low dielectric properties and heat resistance, and therefore can be suitably used for printed wiring boards, and more suitably used for high-frequency applications such as high-frequency printed wiring boards.

[0134] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations can also be adopted. Furthermore, the present invention is not limited to the above-described embodiment, and modifications and improvements within the scope that do not impair the effects of the present invention are included in the present invention. [Example]

[0135] The present embodiment will be described in detail below with reference to examples, etc. However, the present embodiment is not limited to the descriptions of these examples.

[0136] First, the materials used in each example will be described. Thermosetting cyclic olefin copolymer 1: Synthesis Example 1 described below Modified phenylene ether resin 1: A resin in which both terminal groups are ethenylbenzyl groups, as shown in ACS Omega 2022,7,26396-26406 as "OPE-2St" (product name: OPE-2st-1200, manufactured by Mitsubishi Gas Chemical Company, Inc., number average molecular weight: over 500 and less than 1500). Modified phenylene ether resin 2: A resin in which both terminal groups are ethenylbenzyl groups, as shown in ACS Omega 2022,7,26396-26406 as "OPE-2St" (product name: OPE-2st-2200, manufactured by Mitsubishi Gas Chemical Company, Inc., number average molecular weight: over 1500 and less than 2500). Modified phenylene ether resin 3: Described as "Sabic Noryl SA9000" in U.S. Patent Application Publication No. 2013 / 0199724, this resin has methacryloyl groups at both ends (product name: SA9000, manufactured by SABIC, number average molecular weight: greater than 1500 and less than 2500). Radical polymerization initiator 1: Dicumyl Peroxide (product name: Percumyl D, manufactured by NOF Corporation) Radical polymerization initiator 2: 2,3-Dimethyl-2,3-diphenylbutane (manufactured by Acros Organics) Radical polymerization initiator 3: 2,2'-Azobis(2,4,4-trimethylpentane) (Fujifilm Wako Pure Chemical Industries, Ltd.) Antioxidant: Pentaerythritol tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate (product name: Irganox 1010, manufactured by BASF)

[0137] The following raw materials were used to synthesize thermosetting cyclic olefin copolymer 1.

[0138] ·Transition metal compounds (1): It was synthesized by the method described in Synthesis Example 1 of JP-A No. 2004-331965.

[0139] [ka]

[0140] Modified methylaluminoxane (MMAO, manufactured by Tosoh Finechem Co., Ltd.) Toluene (Fujifilm Wako Pure Chemical Industries, Ltd.: Wako Special Grade) Tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene (hereinafter also referred to as TD) (manufactured by Mitsui Chemicals, Inc.) 5-vinyl-2-norbornene (hereinafter referred to as VNB) (Tokyo Chemical Industry Co., Ltd.) Acetone (Fujifilm Wako Pure Chemical Industries, Ltd.: Wako Special Grade) Methanol (Fujifilm Wako Pure Chemical Industries, Ltd.: Wako Special Grade)

[0141] [Synthesis Example 1: Thermosetting Cyclic Olefin Copolymer 1] A 1 L stainless steel autoclave was thoroughly purged with nitrogen and charged with 455 ml of toluene, 29 ml of VNB, 16 ml of TD, a hexane solution of MMAO (0.8 mmol in terms of aluminum atom), and 446 ml of hydrogen. Ethylene was then introduced into the system until the total pressure reached 0.6 MPa. A toluene solution of 0.028 mmol of transition metal compound (1) was added, and polymerization was carried out at 35°C for 50 minutes. The polymerization was then terminated by injecting 1 ml of methanol. After the polymerization was completed, ion-exchanged water was added to the resulting polymer solution and stirred for 1 hour, after which the organic layer was filtered through filter paper. This organic layer was poured into a mixed solvent of acetone and methanol to precipitate the polymer, which was stirred and then filtered through filter paper. The resulting polymer was dried under reduced pressure at 80°C for 10 hours to obtain the thermosetting cyclic olefin copolymer (A), an ethylene / TD / VNB copolymer.

[0142] [Measurement of the content of each repeating unit in thermosetting cyclic olefin copolymer 1] The contents of repeating units (a), (b) and (c) in the thermosetting cyclic olefin copolymer 1 were measured using a nuclear magnetic resonance spectrometer "EXcalibur270" manufactured by JEOL Ltd. under the following conditions. Number of times: 16 to 64 ·Measurement temperature: room temperature The results obtained from the above measurements 1 From the H-NMR spectrum, the contents of repeating unit (a), repeating unit (b), and repeating unit (c) were calculated based on the intensities of the peaks derived from hydrogen directly bonded to the double bond carbon and the peaks derived from other hydrogen.

[0143] The content of each repeating unit in the thermosetting cyclic olefin copolymer 1 was measured using a nuclear magnetic resonance spectrometer. 1 The content of repeating units (c) derived from TD in copolymer (A) determined by 1 H-NMR was 11 mol %, and the content of repeating units (b) derived from VNB was 26 mol %.

[0144] [Measurement of number average molecular weight (Mn) of thermosetting cyclic olefin copolymer 1] The number average molecular weight (Mn) of the thermosetting cyclic olefin copolymer 1 dissolved in o-dichlorobenzene was measured using gel permeation chromatography (GPC) under the following conditions, calibrating the molecular weight with monodisperse polystyrene standards (manufactured by Tosoh Corporation). Measurement equipment: Tosoh gel permeation chromatograph HLC-8321 GPC / HT type Data processing software: Waters Empower3 Detector: Tosoh Bryce type double-path, dual-flow RI detector (built-in) Column: Tosoh TSKgel GMH6-HT, TSKgel GMH6-HTL Column temperature: 140℃ Sample concentration: 0.1% (w / v) ·Injection volume: 400μL Sampling interval: 0.5 seconds ·Flow rate: 1.0ml / min The number average molecular weight (Mn) of the thermosetting cyclic olefin copolymer 1 determined by GPC measurement was 25,000.

[0145] [Example 1] (Varnish preparation) The thermosetting cyclic olefin copolymer 1 obtained in Synthesis Example 1 and other materials were weighed according to the formulation in Table 1. The weighed sample was stirred in toluene until it was fully dissolved, to obtain a varnish. Note that the blending ratio of each raw material in Table 1 is expressed in parts by mass.

[0146] (Preparation of cured film) The obtained varnish was applied to a release-treated PET film under the following conditions: Equipment: Automatic film coating machine (product name: PI-1210, manufactured by Tester Sangyo Co., Ltd.) Applicator gap: 200μm Coating speed: 10mm / sec

[0147] The applied varnish was dried by blowing air under the following drying conditions to obtain a dry film. Equipment: Blower dryer (product name: STPH-102M, manufactured by Espec Corporation) ·Drying temperature: 150℃ Drying time: 4 minutes Atmosphere: Nitrogen flow (30L / min)

[0148] The dried film was vacuum pressed to obtain a cured film. The thickness of the cured film was adjusted to 30±15 μm. The release film used during vacuum pressing was a PET film at 180°C and a polyimide film (product name: Upilex Film (registered trademark), manufactured by UBE Corporation) at 220°C. The vacuum pressing conditions were as follows: In each example, the vacuum pressing conditions were either Pressing Condition 1 or Pressing Condition 2, as described below, and were selected depending on the type of radical polymerization initiator used. Pressing Condition 1 was applied when Radical Polymerization Initiator 1 (Dicumyl Peroxide) was used as the radical polymerization initiator, and when Radical Polymerization Initiator 3 (2,2'-Azobis(2,4,4-trimethylpentane)) was used as the radical polymerization initiator. Pressing Condition 2 was applied when Radical Polymerization Initiator 2 (2,3-Dimethyl-2,3-Diphenylbutane) was used as the radical polymerization initiator. Equipment: Vacuum press (product name: KVHCII-press, manufactured by Kitagawa Seiki Co., Ltd.) Pressing condition 1: While pressurizing to 3.5 MPa, the temperature was raised from 30°C at a rate of 6°C / min and maintained at 180°C for 120 minutes. Pressing condition 2: While applying a pressure of 3.5 MPa, the sample was heated from 30°C at a rate of 6°C / min to 180°C, held for 60 minutes, then cooled to room temperature and peeled off. The sample was then sandwiched between polyimide films, heated from 30°C at a rate of 6°C / min to 220°C, and held for 120 minutes. ·Vacuum degree: 1.2kPa or less

[0149] [Examples 2 to 6 and Comparative Examples 1 and 2] A varnish and a cured film were prepared in the same manner as in Example 1, except that the blending compositions of the thermosetting cyclic olefin copolymer 1 and other materials were changed to the blending compositions in Table 1.

[0150] The resulting cured film was subjected to measurement of dielectric loss tangent Df and DMA measurement according to the following methods. The results are shown in Table 1.

[0151] [Measurement of dielectric loss tangent Df] The cured film of each example was cut into a test piece measuring 50 mm in length, 50 mm in width, and 30±15 μm in thickness. The dielectric loss tangent Df of the obtained test piece was then measured using the cylindrical cavity resonance method. The measurement conditions were as follows: Measurement equipment: Cylindrical cavity resonator (product name: Synthesized Sweeper 8340B and Network Analyzer 8510B, both manufactured by YHP) Measurement mode: TE011 Frequency: 10GHz Measurement conditions: 23±2°C, 50±5%RH To summarize the above, the dielectric loss tangent Df of a test piece cut from the cured film to a length of 50 mm, width of 50 mm, and thickness of 30±15 μm was measured using a cylindrical cavity resonator at 23±2°C, 50±5% RH, and 10 GHz.

[0152] [DMA measurement] The cured film of each example was cut into a test piece measuring 45 mm in length, 5 mm in width, and 30±15 μm in thickness. DMA measurements were then performed on the resulting test pieces under the following conditions: Measurement equipment: Dynamic viscoelasticity measuring equipment (product name: RSA-III, manufactured by TA-Instruments) Measurement mode: Tensile mode Measurement atmosphere: Nitrogen atmosphere Heating rate: 3℃ / min To summarize the above, test pieces were cut from the cured film to a length of 45 mm, width of 5 mm, and thickness of 30±15 μm. Dynamic viscoelasticity measurements were performed on the cured film in tensile mode under a nitrogen atmosphere at a heating rate of 3°C / min and a frequency of 1 Hz. Dynamic viscoelasticity measurements (DMA measurements) yielded curves (DMA curves) plotted with temperature on the horizontal axis and storage modulus, loss modulus, or loss tangent tanδ on the vertical axis. The storage modulus at 220°C was determined by reading the DMA curve value at 220°C on a curve plotted with temperature on the horizontal axis and storage modulus on the vertical axis. The glass transition temperature (Tg) was determined from the maximum value of the DMA curve with loss tangent tanδ on the vertical axis.

[0153] In Examples 1 to 6, two peaks were observed in the temperature dispersion of the loss tangent tanδ in dynamic viscoelasticity. From the DMA curve graph, a main peak with a large peak height and a sub-peak with a small peak height were confirmed. Furthermore, a first peak on the high-temperature side and a second peak on the low-temperature side were confirmed. A first glass transition point corresponding to the first peak and a second glass transition point corresponding to the second peak were confirmed. A first glass transition temperature Tg1 corresponding to the first glass transition point and a second glass transition temperature Tg2 corresponding to the second glass transition point were determined. The value of the loss factor tanδ at the first glass transition temperature Tg1 was determined as tanδ1(Tg1), and the value of the loss factor tanδ at the second glass transition temperature Tg2 was determined as tanδ2(Tg2). Based on these, the value of parameter A was calculated using the following formula (1). Formula (1): A=tanδ1(Tg1) / tanδ2(Tg2) In each example, the storage modulus value at 220°C was read from a DMA curve with the vertical axis representing the storage modulus and the horizontal axis representing the temperature.

[0154] [Table 1]

Claims

1. a thermosetting cyclic olefin copolymer (A) having a crosslinkable group; a modified phenylene ether resin (B); a radical polymerization initiator (C), The modified phenylene ether resin (B) has a biphenyl structure.

2. The resin composition according to claim 1, wherein the modified phenylene ether resin (B) contains one or more functional groups selected from the group consisting of functional groups containing a carbon-carbon unsaturated double bond and functional groups containing an element other than carbon.

3. 2. The resin composition according to claim 1, wherein the modified phenylene ether resin (B) contains one or more functional groups selected from the group consisting of a (meth)acryloyl group, a vinyl group, an allyl group, a maleimide group, and a hydroxy group.

4. The resin composition according to claim 1, wherein the modified phenylene ether resin (B) contains a functional group represented by the following formula (2a) or the following formula (2b) at at least one end of a main chain of the modified phenylene ether resin (B): 【Chemical 1】 【Chemistry 2】 [In the formula (2a), R ２１ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ２２ represents an alkylene group having 1 to 10 carbon atoms or a direct bond. ２３ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

5. The resin composition according to claim 1 , wherein the modified phenylene ether resin (B) contains an ethenylbenzyl group at at least one end of the main chain of the modified phenylene ether resin (B).

6. The resin composition according to claim 1 , wherein the modified phenylene ether resin (B) contains ethenylbenzyl groups at both ends of the main chain of the modified phenylene ether resin (B).

7. The resin composition according to claim 1, wherein the modified phenylene ether resin (B) has a number average molecular weight of 500 or more and 25,000 or less.

8. 2. The resin composition according to claim 1, wherein the content of the modified phenylene ether resin (B) in the resin composition is 10 parts by mass or more and 500 parts by mass or less, relative to 100 parts by mass of the thermosetting cyclic olefin copolymer (A).

9. The thermosetting cyclic olefin copolymer (A) is one or more olefin-derived repeating units (a) represented by the following formula (I); One or more repeating units (b) derived from a cyclic non-conjugated diene represented by the following formula (III); The resin composition according to claim 1, further comprising one or more repeating units (c) derived from cyclic olefins represented by the following formula (V): 【Chemistry 3】 [In the formula (I), R ３００ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. 【Chemistry 4】 [In the formula (III), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ６１ ~R ７６ and R ａ１ and R ｂ１ may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; R １０４ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, and R ７５ and R ７６ may be bonded to each other to form a monocyclic or polycyclic ring. 【Chemistry 5】 [In the formula (V), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ６１ ~R ７８ , R ａ１ and R ｂ１ may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; R ７５ ~R ７８ may be bonded to each other to form a monocyclic or polycyclic ring.

10. The resin composition according to claim 9, wherein the olefin constituting the olefin-derived repeating unit (a) contains ethylene.

11. The resin composition according to claim 9, wherein the cyclic non-conjugated diene constituting the repeating unit (b) derived from the cyclic non-conjugated diene includes 5-vinyl-2-norbornene.

12. The cyclic olefin constituting the cyclic olefin-derived structural unit (c) is tetracyclo[4.4.0.1 ２，５ .1 ７，１０ 10. The resin composition according to claim 9, comprising one or more selected from the group consisting of cyclo[2.2.1]-3-dodecene and bicyclo[2.2.1]-2-heptene.

13. 10. The resin composition according to claim 9, wherein, when the total number of moles of repeating units in the thermosetting cyclic olefin copolymer (A) is taken as 100 mol%, the content of the olefin-derived repeating unit (a) is 10 mol% or more and 80 mol% or less, the content of the cyclic non-conjugated diene-derived repeating unit (b) is 1 mol% or more and 40 mol% or less, and the content of the cyclic olefin-derived repeating unit (c) is 1 mol% or more and 60 mol% or less.

14. 2. The resin composition according to claim 1, wherein the content of the radical polymerization initiator (C) is 0.1 parts by mass or more and 25.0 parts by mass or less, relative to 100 parts by mass of the thermosetting cyclic olefin copolymer (A).

15. 2. The resin composition according to claim 1, wherein a total content of the thermosetting cyclic olefin copolymer (A), the modified phenylene ether resin (B), and the radical polymerization initiator (C) in the resin composition is 50% by mass or more and 100% by mass or less, when a total amount of solids in the resin composition is 100% by mass.

16. The resin composition according to claim 1 , further comprising an antioxidant (D).

17. 17. The resin composition according to claim 16, wherein the content of the antioxidant (D) is 0.01 parts by mass or more and 5.0 parts by mass or less, relative to 100 parts by mass of the thermosetting cyclic olefin copolymer (A).

18. The resin composition according to claim 1, wherein the dielectric loss tangent Df measured by the following method is less than 0.0030. (method) A cured film having a thickness of 30±15 μm is prepared from the resin composition. The cured film is cut into a test piece having a length of 50 mm, a width of 50 mm and a thickness of 30±15 μm, and the dielectric loss tangent Df of the test piece is measured at 23±2° C., 50±5% RH and 10 GHz using a cylindrical cavity resonator.

19. The resin composition according to claim 1, wherein the temperature dispersion of loss tangent tanδ in dynamic viscoelasticity obtained by the following method has two or more peaks. (method) A cured film having a thickness of 30±15 μm is prepared from the resin composition. The cured film is cut into a test piece having a length of 45 mm, a width of 5 mm, and a thickness of 30±15 μm, and the dynamic viscoelasticity of the cured film is measured in a tensile mode under a nitrogen atmosphere at a temperature increase rate of 3° C. / min and a frequency of 1 Hz.

20. The resin composition according to claim 19, wherein in the graph, a first glass transition temperature corresponding to a peak on the higher temperature side is 200°C or higher.

21. The resin composition according to claim 19, wherein in the graph, a second glass transition temperature corresponding to a peak on the low temperature side is less than 200°C.

22. The resin composition according to claim 19, wherein the value of A represented by the following formula (1) is greater than 1.

0. Equation (1): A = (value of loss tangent at the peak on the high temperature side) / (value of loss tangent at the peak on the low temperature side)

23. The storage modulus at 220°C measured by the following method is 1.0 x 10 ７ The resin composition according to claim 1, wherein the viscosity is 100 Pa or more. (method) A cured film having a thickness of 30±15 μm is prepared from the resin composition. The cured film is cut into a test piece having a length of 45 mm, a width of 5 mm, and a thickness of 30±15 μm, and the dynamic viscoelasticity of the cured film is measured in a tensile mode under a nitrogen atmosphere at a temperature increase rate of 3° C. / min and a frequency of 1 Hz.

24. A varnish comprising the resin composition according to claim 1 and a solvent.

25. A cured product of the resin composition according to claim 1.

26. A film or sheet comprising the resin composition according to claim 1 or the cured product according to claim 25.

27. A laminate comprising the film or sheet of claim 26.

28. 28. The laminate of claim 27, further comprising a metal foil on at least one side.

29. A prepreg comprising the resin composition according to claim 1 and a sheet-like fiber substrate.

30. A printed wiring board comprising an insulating layer comprising the cured product according to claim 25 or the cured product of the prepreg according to claim 29, and a conductor layer on the insulating layer.

31. An electronic device comprising the printed wiring board according to claim 30.

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