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

Abstract

To provide a resin composition that enables production of a cured product exhibiting an improved balance between low dielectric characteristics and low thermal expansion.SOLUTION: Provided is a resin composition containing: a thermosetting cyclic olefin copolymer (A) with a crosslinkable group; an inorganic filler (B); and a radical initiator (C), the inorganic filler (B) including a zirconium compound (B1).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a varnish, a cured product, 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 that has the objective of providing a resin composition that can give a cured product with a low coefficient of thermal expansion and high copper foil peel strength, and that has excellent moldability, and that contains a thermosetting resin, a functional group-modified copolymer, and an inorganic filler, wherein the functional group-modified copolymer has two or more types of alkyl (meth)acrylate units, or one or more types of alkyl (meth)acrylate units and acrylonitrile units, and at least a portion of the alkyl ester groups of the alkyl (meth)acrylate units and / or the cyano groups of the acrylonitrile units have been modified to at least one group selected from the group consisting of epoxy groups, carboxyl groups, and amide groups. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2021-028391 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 low thermal expansion properties. [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 low thermal expansion can be obtained by using a resin composition comprising a thermosetting cyclic olefin copolymer (A) having a crosslinkable group, an inorganic filler (B), and a radical initiator (C), wherein the inorganic filler (B) comprises a zirconium compound (B1), and thus have completed the present invention.

[0007] [1] a thermosetting cyclic olefin copolymer (A) having a crosslinkable group; an inorganic filler (B); a radical initiator (C); Including, The resin composition, wherein the inorganic filler (B) contains a zirconium compound (B1). [2] The resin composition according to [1], wherein the content of the inorganic filler (B) in the resin composition is 10 parts by mass or more and 600 parts by mass or less, relative to 100 parts by mass of the thermosetting cyclic olefin copolymer (A). [3] The resin composition according to [1] or [2], wherein the content of the zirconium compound (B1) in the resin composition is 10 parts by mass or more and 100 parts by mass or less, relative to 100 parts by mass of the content of the inorganic filler (B). [4] The specific surface area of the zirconium compound (B1) is 0.5 m when measured by the BET method in accordance with JIS Z8830:2013. 2 / g or more 30.0m 2 The resin composition according to any one of [1] to [3] above, wherein the viscosity is 1 / g or less. [5] The resin composition according to any one of the above [1] to [4], wherein the thermal expansion coefficient of the zirconium compound (B1) in the range of 50°C to 250°C is 0.0 ppm / K or less. [6] The zirconium compound (B1) has an average particle diameter D at which the cumulative value reaches 50% in the volume frequency particle size distribution measured by a laser diffraction scattering method. 50The resin composition according to any one of the above [1] to [5], wherein the particle size is 0.01 μm or more and 50 μm or less. [7] The true density ρ of the zirconium compound (B1) is 1.0 g / cm 3 More than 10.0g / cm 3 The resin composition according to any one of the above [1] to [6], which is: [8] The resin composition according to any one of [1] to [7] above, which has an average coefficient of thermal expansion in the range of 25° C. to 90° C., as measured by the following method, of 60.0 ppm / K or less. (method) A cured film having a thickness of 40±20 μm is prepared from the resin composition, The cured film is cut into a test piece having a length of 20 mm, a width of 4 mm, and a thickness of 40±20 μm, and thermomechanical measurements are carried out on the cured film at a temperature increase rate of 5°C / min in a nitrogen atmosphere in the range of 25°C to 90°C, using a test load of 5.0 gf and measurement mode: film extension mode. [9] The resin composition according to any one of [1] to [8] above, which has an average coefficient of thermal expansion in the range of 190°C to 220°C of 140.0 ppm / K or less, as measured by the following method. (method) A cured film having a thickness of 40±20 μm is prepared from the resin composition, The cured film is cut into a test piece having a length of 20 mm, a width of 4 mm, and a thickness of 40±20 μm, and thermomechanical measurements of the cured film are carried out at a temperature increase rate of 5°C / min in a nitrogen atmosphere in the range of 190°C to 220°C, using a test load of 5.0 gf and measurement mode: film elongation mode.

[10] The resin composition according to any one of the above [1] to [9], wherein the zirconium compound (B1) contains elemental tungsten.

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

[10] above, wherein the zirconium compound (B1) comprises one or more compounds selected from the group consisting of zirconium tungstate phosphate, zirconium tungstate, and zirconium phosphate.

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

[11] , wherein the zirconium compound (B1) contains a silane coupling agent having a crosslinkable group on the surface thereof.

[13] The resin composition according to

[12] above, wherein the crosslinkable group includes a vinyl group.

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

[13] , wherein the radical initiator (C) includes a non-peroxide radical initiator.

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

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

[16]

[16] The resin composition according to

[15] , wherein the content of the antioxidant (D) in the resin composition is 0.001 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).

[17] 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

[16] , 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 ~R 76 and R a1 and R b1may 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 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.

[18] The resin composition according to

[17] above, wherein the olefin constituting the olefin-derived repeating unit (a) contains ethylene.

[19] The resin composition according to

[17] or

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

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

[17] to

[19] above, which contains one or two members selected from the group consisting of cyclo[2.2.1]-3-dodecene and bicyclo[2.2.1]-2-heptene. [twenty one] The resin composition according to any one of

[17] to

[20] 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. [twenty two] The resin composition according to any one of [1] to

[21] , wherein the content of the radical initiator (C) in the resin composition 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). [twenty three] The resin composition according to any one of [1] to

[22] , wherein the total content of the thermosetting cyclic olefin copolymer (A), the inorganic filler (B), and the radical initiator (C) in the resin composition is 20% by mass or more and 100% by mass or less, when the total amount of solids in the resin composition is 100% by mass. [twenty four] The resin composition according to any one of the above [1] to

[23] , which is in an uncured state or a semi-cured state. [twenty five] The resin composition according to any one of the above [1] to

[24] , which has a dielectric loss tangent Df of 0.0016 or less as measured by the following method. (method) A cured film having a thickness of 40±20 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 40±20 μm, and the dielectric loss tangent Df is measured at 23±2° C., 50±5% RH and 10 GHz using a cylindrical cavity resonator.

[26] A varnish comprising the resin composition according to any one of the above [1] to

[25] and a solvent.

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

[25] .

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

[25] or the cured product according to the above

[27] .

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

[28] .

[30] The laminate according to

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

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

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

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

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

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

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

[32] . [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 low thermal expansion properties. 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. 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 may be 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, an inorganic filler (B), and a radical initiator (C). The inorganic filler (B) contains a zirconium compound (B1). The resin composition of the present embodiment has the above-described structure, and thus can provide a cured product with an improved balance of low dielectric properties and low thermal expansion properties.

[0011] For example, resin compositions used in high-frequency printed wiring boards and the like are required to have low dielectric properties in the cured product thereof in order to reduce transmission loss, while resin compositions used in semiconductor package substrates and the like are required to have low thermal expansion properties in the cured product thereof in order to improve the reliability of wiring patterns.

[0012] The resin composition of this embodiment can provide a cured product with an improved balance of low dielectric properties and low thermal expansion. 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 low thermal expansion.

[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) having a crosslinkable group and the zirconium compound (B1) contained as the inorganic filler (B) can improve the performance balance of low dielectric properties and low thermal expansion compared to when the thermosetting cyclic olefin copolymer (A) is used alone.

[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 (A)"). 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 has a crosslinkable group, from the viewpoint of improving the heat resistance of the resulting cured product. The crosslinkable group includes 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 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 300 represents 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, more preferably 15 mol% or more, even more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 35 mol% or more, even more preferably 40 mol% or more, even more preferably 45 mol% or more, even more preferably 50 mol% or more, even more preferably 55 mol% or more, and preferably 80 mol% or less, more preferably 75 mol% or less, even more preferably 72 mol% or less, even more preferably 68 mol% or less, even more preferably 65 mol% or less.

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

[0025] Furthermore, the content of repeating units (c) derived from cyclic olefins is preferably 1 mol% or more, more preferably 3 mol% or more, even more preferably 5 mol% or more, even more preferably 8 mol% or more, even more preferably 10 mol% or more, and preferably 40 mol% or less, more preferably 37 mol% or less, even more preferably 33 mol% or less, even more preferably 30 mol% or less, even more preferably 20 mol% or less, even more preferably 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 formula (Ia), R 300represents 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 at least one selected from the group consisting of ethylene and propylene, more preferably ethylene. Two or more types of olefin 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 ~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.

[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 two cyclic olefins 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 elastic modulus of the thermosetting cyclic olefin copolymer (A) and the cured product is easily maintained because they contain a rigid ring structure, and that the absence of heterogeneous double bond structures makes it easy to control crosslinking. The cyclic olefin represented by formula (Va) may contain structural units 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 moldability and improved product yield.

[0045] The thermosetting cyclic olefin copolymer (A) may further contain at least one repeating unit 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) other than repeating units (a) derived from one or more olefins represented by formula (I), repeating units (b) derived from a cyclic non-conjugated diene represented by formula (III), and repeating units derived from a chain polyene. 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 91 may 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 formula (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 formula (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) in terms of polystyrene, as measured by gel permeation chromatography (GPC), is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 3,000 or more, and even more preferably 4,000 or more, from the viewpoint of further improving the performance balance between low dielectric properties and heat resistance. The number average molecular weight (Mn) of the thermosetting cyclic olefin copolymer (A) measured by gel permeation chromatography (GPC) in terms of polystyrene is preferably 100,000 or less, more preferably 80,000 or less, even more preferably 60,000 or less, even more preferably 50,000 or less, even more preferably 40,000 or less, and even more preferably 30,000 or less, from the viewpoint of further improving moldability such as impregnation into a fiber substrate and wiring embedding ability during the production of a printed wiring board. 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 uncured thermosetting cyclic olefin copolymer (A) is, for example, 300°C or less, preferably 280°C or less, more preferably 260°C or less, even more preferably 240°C or less, even more preferably 220°C or less, even more preferably 200°C or less, even more preferably 180°C or less, and even more preferably 160°C or less. When the Tg is below the upper limit, the processability of the thermosetting cyclic olefin copolymer (A) and its solubility in solvents when forming a varnish are improved.

[0058] The intrinsic viscosity [η] of the thermosetting cyclic olefin copolymer (A) measured in decalin at 135°C is, for example, 0.10 dL / g or more, preferably 0.15 dL / g or more, and for example, 15 dL / g or less, preferably 5 dL / g or less, more preferably 3 dL / g or less. When the intrinsic viscosity [η] is equal to or less than the upper limit, processability can be further improved. On the other hand, when the intrinsic viscosity [η] is equal to or greater 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] From the viewpoint of further improving the performance balance of the heat resistance, mechanical properties, and low dielectric properties of the cured product, the content of the thermosetting cyclic olefin copolymer (A) in the resin composition of this embodiment is preferably 1% by mass or more and 95% by mass or less, more preferably 2% by mass or more and 90% by mass or less, even more preferably 4% by mass or more and 80% by mass or less, even more preferably 6% by mass or more and 70% by mass or less, even more preferably 8% by mass or more and 65% by mass or less, and even more preferably 10% by mass or more and 60% 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.

[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] <Inorganic filler (B)> The resin composition of this embodiment contains an inorganic filler (B), which may include, for example, one or more compounds selected from the group consisting of glass, bismuth-nickel-iron oxide (Bi-Ni-Fe-O compound), manganese-tin-zinc nitride (Mn-Sn-Zn-N compound), copper-zinc-vanadium oxide (Cu-Zn-VO compound), and zirconium compound (B1). When the resin composition of this embodiment is used in a copper-clad laminate, the inorganic filler (B) preferably does not contain a continuous fiber woven fabric. The continuous fiber woven fabric is, for example, glass cloth. In this case, the inorganic filler (B) is, for example, a powdery or particulate substance containing one or more selected from the group consisting of glass, bismuth-nickel-iron oxide (Bi-Ni-Fe-O compound), manganese-tin-zinc nitride (Mn-Sn-Zn-N compound), copper-zinc-vanadium oxide (Cu-Zn-VO compound), and zirconium compound (B1).

[0062] In the resin composition of this embodiment, the inorganic filler (B) includes a zirconium compound (B1). The zirconium compound (B1) preferably includes elemental tungsten. The zirconium compound (B1) more preferably includes one or more compounds selected from the group consisting of zirconium tungstate phosphate, zirconium tungstate, and zirconium phosphate, and even more preferably includes zirconium tungstate phosphate.

[0063] In the resin composition of this embodiment, the zirconium compound (B1) may contain a silane coupling agent having a crosslinkable group on its surface. That is, in the resin composition of this embodiment, the zirconium compound (B1) is preferably surface-treated with a silane coupling agent. The silane coupling agent includes one or more selected from known silane coupling agents, such as various silane-based compounds, including epoxy silane, mercapto silane, phenylamino silane, and other amino silanes, alkyl silane, ureido silane, vinyl silane, and methacryl silane. The silane coupling agent preferably contains a vinyl group in the crosslinkable group, specifically, a vinyl silane having a vinyl group.

[0064] The vinyl silane preferably includes one or two selected from the group consisting of 7-octenyltrimethoxysilane, 6-heptenyltriethoxysilane, 6-heptenyltrimethoxysilane, 5-hexenyltriethoxysilane, 5-hexenyltrimethoxysilane, 4-pentenyltriethoxysilane, 4-pentenyltrimethoxysilane, 3-butenyltriethoxysilane, 3-butenyltrimethoxysilane, 2-propenyltriethoxysilane, 2-propenyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane having a long-chain alkyl group, branched alkyl group, or branched alkoxy group having up to 16 carbon atoms, vinyltrimethoxysilane, p-styryltrimethoxysilane, and p-styryltriethoxysilane, and more preferably includes 7-octenyltrimethoxysilane.

[0065] By treating the surface of the zirconium compound (B1) with a silane coupling agent, the adhesion to the resin interface can be improved, and the thermal expansion of the resin composition can be further reduced. Furthermore, by performing the surface treatment with vinylsilane, the zirconium compound (B1) and the thermosetting cyclic olefin copolymer (A) can be directly chemically bonded to each other, thereby improving the dispersibility of the zirconium compound (B1) in the thermosetting cyclic olefin copolymer (A).

[0066] The method for surface-treating the zirconium compound (B1) with a silane coupling agent is not limited, and known methods can be used. Examples of methods for surface-treating the zirconium compound (B1) with a silane coupling agent include a dry method. For example, in a dry method for surface-treating the zirconium compound (B1) with a silane coupling agent, 2 parts by mass of the silane coupling agent are directly added dropwise to 100 parts by mass of the zirconium compound (B1), and the mixture is stirred at 2000 rpm for 60 seconds at room temperature and atmospheric pressure using a planetary mixer. The mixture is then dried under reduced pressure at 100°C for 3 minutes to obtain a zirconium compound (B1) surface-treated with the silane coupling agent.

[0067] From the viewpoint of further improving the performance balance between low thermal expansion and low dielectric properties, the content of the inorganic filler (B) in the resin composition of this embodiment is preferably 600 parts by mass or less, more preferably 450 parts by mass or less, even 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, even more preferably 280 parts by mass or less, and even more preferably 250 parts by mass or less, relative to 100 parts by mass of the thermosetting cyclic olefin copolymer (A). There is no particular lower limit to the content of the inorganic filler (B) in the resin composition of this embodiment, but for example, when the content of the thermosetting cyclic olefin copolymer (A) is taken as 100 parts by mass, it is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 30 parts by mass or more, even more preferably 40 parts by mass or more, even more preferably 50 parts by mass or more, even more preferably 70 parts by mass or more, even more preferably 90 parts by mass or more, even more preferably 100 parts by mass or more, even more preferably 120 parts by mass or more, even more preferably 140 parts by mass or more, and even more preferably 160 parts by mass or more. The content of the inorganic filler (B) in the resin composition of this embodiment, relative to 100 parts by mass of the thermosetting cyclic olefin copolymer (A), is preferably 10 parts by mass or more and 600 parts by mass or less, more preferably 20 parts by mass or more and 450 parts by mass or less, even more preferably 30 parts by mass or more and 400 parts by mass or less, even more preferably 40 parts by mass or more and 350 parts by mass or less, even more preferably 50 parts by mass or more and 300 parts by mass or less, even more preferably 70 parts by mass or more and 300 parts by mass or less, even more preferably 100 parts by mass or more and 300 parts by mass or less, even more preferably 120 parts by mass or more and 250 parts by mass or less, even more preferably 140 parts by mass or more and 250 parts by mass or less, and even more preferably 160 parts by mass or more and 250 parts by mass or less.

[0068] From the viewpoint of further improving the performance balance between low thermal expansion and low dielectric properties, the content of the zirconium compound (B1) in the resin composition of this embodiment is preferably 10 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 70 parts by mass or more, even more preferably 80 parts by mass or more, even more preferably 90 parts by mass or more, even more preferably 95 parts by mass or more, and even more preferably 98 parts by mass or more, relative to 100 parts by mass of the inorganic filler (B). The content of the zirconium compound (B1) in the resin composition of this embodiment is not limited to an upper limit, but may be, for example, 100 parts by mass or less when the content of the inorganic filler (B) is 100 parts by mass. From the viewpoint of further improving the performance balance between low thermal expansion and low dielectric properties, the content of the zirconium compound (B1) in the resin composition of this embodiment is preferably 10 parts by mass or more and 100 parts by mass or less, more preferably 50 parts by mass or more and 100 parts by mass or less, even more preferably 70 parts by mass or more and 100 parts by mass or less, even more preferably 80 parts by mass or more and 100 parts by mass or less, even more preferably 90 parts by mass or more and 100 parts by mass or less, even more preferably 95 parts by mass or more and 100 parts by mass or less, and even more preferably 98 parts by mass or more and 100 parts by mass or less, when the content of the inorganic filler (B) is 100 parts by mass.

[0069] In the resin composition of this embodiment, the specific surface area of the zirconium compound (B1) as measured by the BET method in accordance with JIS Z8830:2013 is preferably 30.0 m from the viewpoint of reducing the viscosity of the varnish of the resin composition and facilitating coating. 2 / g or less, more preferably 25.0m 2 / g or less, more preferably 20.0m 2 / g or less, more preferably 15.0m 2 / g or less, more preferably 10.0m 2 / g or less. In the resin composition of this embodiment, the specific surface area of the zirconium compound (B1) measured by the BET method in accordance with JIS Z8830:2013 is preferably 0.10 m from the viewpoint of improving low thermal expansion properties through interaction with the thermosetting cyclic olefin copolymer (A). 2 / g or more, more preferably 0.15m 2 / g or more, more preferably 0.20m 2 / g or more, more preferably 0.25m 2 / g or more, more preferably 0.30m 2 / g or more. In the resin composition of this embodiment, the specific surface area of the zirconium compound (B1) is preferably 0.10 m when measured by the BET method in accordance with JIS Z8830:2013. 2 / g or more 30.0m 2 / g or less, more preferably 0.15m 2 / g or more 25.0m 2 / g or less, more preferably 0.20m 2 / g or more 20.0m 2 / g or less, more preferably 0.25m 2 / g or more 15.0m 2 / g or less, more preferably 0.30m 2 / g or more 10.0m 2 / g or less.

[0070] In the resin composition of the present embodiment, the thermal expansion coefficient of the zirconium compound (B1) in the range of 50°C to 250°C is preferably 0.0 ppm / K or less, more preferably -0.25 ppm / K or less, even more preferably -0.5 ppm / K or less, even more preferably -0.7 ppm / K or less, even more preferably -1.0 ppm / K or less, and even more preferably -1.5 ppm / K or less, from the viewpoint of improving the low thermal expansion properties of the cured product of the resin composition. In the resin composition of the present embodiment, the thermal expansion coefficient of the zirconium compound (B1) in the range of 50°C to 250°C has no particular lower limit, but is preferably -200 ppm / K or more, more preferably -150 ppm / K or more, even more preferably -100 ppm / K or more, still more preferably -70 ppm / K or more, even more preferably -40 ppm / K or more, and still more preferably -10 ppm / K or more. In the resin composition of this embodiment, the thermal expansion coefficient of the zirconium compound (B1) in the temperature range of 50°C to 250°C is preferably -200 ppm / K or more and 0.0 ppm / K or less, more preferably -150 ppm / K or more and -0.25 ppm / K or less, even more preferably -100 ppm / K or more and -0.5 ppm / K or less, even more preferably -70 ppm / K or more and -0.7 ppm / K or less, even more preferably -40 ppm / K or more and -1.0 ppm / K or less, and even more preferably -10 ppm / K or more and -1.5 ppm / K or less.

[0071] The thermal expansion coefficient of the zirconium compound (B1) of this embodiment can be measured, for example, by the method described in the Examples.

[0072] In the resin composition of this embodiment, the inorganic filler (B) and the zirconium compound (B1) are preferably spherical in shape, from the viewpoint of being able to suppress an extreme increase in viscosity. In the resin composition of this embodiment, the zirconium compound (B1) has an average particle diameter D at which the cumulative value reaches 50% in the volume frequency particle size distribution measured by a laser diffraction scattering method. 50From the viewpoint of improving dispersibility in a solvent, the particle size is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.10 μm or more, even more preferably 0.50 μm or more, and even more preferably 0.80 μm or more. In the resin composition of this embodiment, the zirconium compound (B1) has an average particle diameter D at which the cumulative value reaches 50% in the volume frequency particle size distribution measured by a laser diffraction scattering method. 50 From the viewpoint of improving the uniformity of the coating of the resin composition varnish, the thickness is preferably 50 μm or less, more preferably 45 μm or less, even more preferably 40 μm or less, even more preferably 35 μm or less, and even more preferably 30 μm or less. In the resin composition of this embodiment, the zirconium compound (B1) has an average particle diameter D at which the cumulative value reaches 50% in the volume frequency particle size distribution measured by a laser diffraction scattering method. 50 is preferably 0.01 μm or more and 50 μm or less, more preferably 0.05 μm or more and 45 μm or less, even more preferably 0.10 μm or more and 40 μm or less, even more preferably 0.50 μm or more and 35 μm or less, and even more preferably 0.80 μm or more and 30 μm or less.

[0073] In the resin composition of this embodiment, the true density ρ of the zirconium compound (B1) is preferably 1.0 g / cm 3 from the viewpoint of improving the uniformity of the coating of the varnish of the resin composition. 3 More preferably, 1.5 g / cm 3 More preferably, 2.0 g / cm 3 More preferably, 2.3 g / cm 3 More preferably, 2.7 g / cm 3 That's all. In the resin composition of the present embodiment, the true density ρ of the zirconium compound (B1) is preferably 10.0 g / cm 3 from the viewpoint of improving dispersibility in a solvent. 3 or less, more preferably 9.0 g / cm 3 or less, more preferably 8.0 g / cm 3 or less, more preferably 7.0 g / cm 3 More preferably 6.0 g / cm or less 3 The following is the result. In the resin composition of this embodiment, the true density ρ of the zirconium compound (B1) is preferably 1.0 g / cm 3 More than 10.0g / cm 3 or less, more preferably 1.5 g / cm 3 More than 9.0g / cm 3 More preferably 2.0 g / cm or less 3 More than 8.0g / cm 3 More preferably 2.3 g / cm or less 3 More than 7.0g / cm 3 or less, more preferably 2.7 g / cm 3 More than 6.0g / cm 3 The following is the result. Here, the true density ρ of the resin composition of the present embodiment can be measured by the pycnometer method in accordance with JIS R1620:1995.

[0074] <Radical initiator (C)> The resin composition of the present embodiment contains a radical initiator (C). For crosslinking with the radical initiator (C), a crosslinking method using a normal radical initiator, which is applied to polyolefins and the like, can be applied as is.

[0075] The radical initiator (C) may be a known thermal radical initiator, a known photoradical initiator, or a combination of these.

[0076] Examples of such thermal radical initiators include peroxide radical initiators and non-peroxide radical initiators. Among such thermal radical initiators, examples of peroxide radical initiators include 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, bis(α-t-butylperoxyisopropyl)benzene and other dialkyl peroxides; 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) Examples of the radical initiator include peroxyketals such as valerate, ethyl-3,3-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; and 3,3,5,7,7-pentamethyl-1,2,4-trioxepane. Examples of the radical initiator include non-peroxide radical initiators such as dibenzyl compounds such as 2,3-dimethyl-2,3-diphenylbutane.

[0077] Among the radical initiators (C), examples of photoradical 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 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.

[0078] The radical initiator (C) is preferably a non-peroxide radical initiator from the viewpoint of improving the low dielectric properties of the cured product of the resin composition. The non-peroxide radical initiator preferably includes a non-peroxide radical initiator of a bibenzyl compound. The non-peroxide radical initiator of a bibenzyl compound preferably includes 2,3-dimethyl-2,3-diphenylbutane (DMDPB).

[0079] In order to further improve the performance balance between low dielectric properties and heat resistance of the resulting cured product, the content of the radical initiator (C) in the resin composition of this embodiment is preferably 0.10 parts by mass or more and 25.0 parts by mass or less, more preferably 0.50 parts by mass or more and 20.0 parts by mass or less, even 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 2.1 parts by mass or more and 12.0 parts by mass or less, even more preferably 2.4 parts by mass or more and 11.0 parts by mass or less, even more preferably 2.7 parts by mass or more and 10.0 parts by mass or less, and even more preferably 3.0 parts by mass or more and 9.0 parts by mass or less, based on 100 parts by mass of the thermosetting cyclic olefin copolymer (A).

[0080] The total content of the thermosetting cyclic olefin copolymer (A), inorganic filler (B), and radical initiator (C) in the resin composition of this embodiment is preferably 20% by mass or more and 100% by mass or less, more preferably 40% by mass or more and 100% by mass or less, even more preferably 50% by mass or more and 100% by mass or less, even 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, and even more preferably 85% 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.

[0081] 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.

[0082] <Antioxidant (D)> The resin composition of this 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 amine-based antioxidants. These antioxidants may be used alone or in combination. The antioxidant (D) preferably includes a phenolic antioxidant, such as tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionic acid]pentaerythritol manufactured by BASF.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] From the viewpoint of further improving the performance balance between low dielectric properties and low thermal expansion of the resulting cured product, the content of the antioxidant (D) in the resin composition particles 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 3.0 parts by mass, preferably 0.04 to 2.0 parts by mass, preferably 0.05 to 1.0 part by mass, and preferably 0.05 to 0.10 parts by mass, relative to 100 parts by mass of the thermosetting cyclic olefin copolymer (A).

[0088] <Crosslinking agent (E)> The resin composition of this embodiment may further contain a crosslinking agent (E). The crosslinking agent (E) preferably contains a benzocyclobutene structure. Here, the benzocyclobutene structure refers to, for example, a structure represented by the following formula:

[0089] [ka]

[0090] R in the above formula 1 ~R 6may be the same or different, and are preferably 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 having 1 to 20 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, even more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and even more preferably a hydrogen atom. 1 ~R 6 At least one of R represents a bond, and preferably R 1 ~R 6 represents a bond, and more preferably R 1 ~R 4 represents a bond, and more preferably R 2 and R 3 One of these represents a bond.

[0091] The crosslinking agent (E) can be any compound having the above structure in the molecule, and may be, for example, an acrylic acid ester compound, a methacrylic acid ester compound, a maleimide compound, an acrylamide compound, acrylonitrile, maleic anhydride, a styrene compound, a vinyl compound, or the like, each having a benzocyclobutene structure.

[0092] In particular, from the viewpoint of facilitating the formation of a crosslinked structure with the thermosetting cyclic olefin copolymer (A), it is preferable that the crosslinking agent (E) has one or more functional groups (β) that can be used in a crosslinking reaction. Examples of the functional group (β) include crosslinkable functional groups such as 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 the vinyl group is preferred. When the crosslinking agent (E) has a functional group (β), it is preferable that the aromatic ring in the benzocyclobutene structure contains the functional group (β) in order to facilitate the formation of a crosslinked structure with the thermosetting cyclic olefin copolymer (A).

[0093] Examples of the crosslinking agent (E) include 4-vinylbenzocyclobutene, 4-dimethylvinylsilylbenzocyclobutene, 1-dimethylvinylsilylbenzocyclobutene, 4-acrylbenzocyclobutene, and 1-acrylbenzocyclobutene. Since the aromatic ring in the benzocyclobutene structure contains the functional group (β), 4-vinylbenzocyclobutene, 4-dimethylvinylsilylbenzocyclobutene, and 4-acrylbenzocyclobutene are more preferred, and 4-vinylbenzocyclobutene is even more preferred from the viewpoint of reactivity.

[0094] Compounds having a benzocyclobutene structure in the molecule that can be used as the crosslinking agent (E) can be synthesized by known methods such as those reported by Kirchhoff et al. (PCT. Int. Appl. (1987), WO87 / 05303, pp. 113) and Endo et al. (Journal of Polymer Science, Part A: Polymer Chemistry (1995), 33(4), pp. 707-15).

[0095] The content of the crosslinking agent (E) in the resin composition of this embodiment is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 40 parts by mass or less, and even more preferably 10 parts by mass or more and 30 parts by mass or less, based on 100 parts by mass of the thermosetting cyclic olefin copolymer (A). When the content of the crosslinking agent (E) is equal to or more than the above-mentioned lower limit, the low thermal expansion property of the resin composition can be further improved. On the other hand, when the content of the crosslinking agent (E) is equal to or less than the above-mentioned upper limit, the crosslinkability of the resin composition can be improved, and as a result, the heat resistance can be improved.

[0096] <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 at least one additive selected from the group consisting of organic fillers, heat stabilizers, weather stabilizers, radiation resistant agents, plasticizers, lubricants, release agents, nucleating agents, friction and wear improvers, flame retardants, foaming agents, antistatic agents, colorants, antifogging agents, antiblocking agents, impact resistance agents, surface wetting improvers, hydrochloric acid absorbers, and metal deactivators.

[0097] The resin composition of this embodiment may contain, in addition to the thermosetting cyclic olefin copolymer (A), other resins other than the thermosetting cyclic olefin copolymer (A). The other resins are not particularly limited and may be known resins. The other resins may be, for example, at least one or two resins selected from the group consisting of polyphenylene ether resins, modified polyphenylene ether resins, oligophenylene ether resins, modified oligophenylene ether resins, polydivinylbenzene resins, oligodivinylbenzene resins, maleimide resins, bismaleimide triazine resins, liquid crystal polymers, epoxy resins, and polystyrene resins.

[0098] When the resin composition of the present embodiment contains a resin other than the thermosetting cyclic olefin copolymer (A), the content of the inorganic filler (B) is, from the viewpoint of further improving the performance balance between low thermal expansion and low dielectric properties, preferably from 10 to 600 parts by mass, more preferably from 20 to 570 parts by mass, even more preferably from 30 to 550 parts by mass, even more preferably from 40 to 530 parts by mass, even more preferably from 100 to 510 parts by mass, even more preferably from 120 to 490 parts by mass, even more preferably from 140 to 470 parts by mass, and even more preferably from 160 to 450 parts by mass, relative to 100 parts by mass of the total content of the thermosetting cyclic olefin copolymer (A) and the other resin.

[0099] <Method for producing resin composition> The resin composition of this embodiment can be prepared by mixing the thermosetting cyclic olefin copolymer (A), the inorganic filler (B), the radical initiator (C), and other components as needed. Examples of a mixing method that can be used include a solution blending method in which the components are dissolved and dispersed in a saturated hydrocarbon such as heptane, hexane, decane, or cyclohexane, or an aromatic hydrocarbon such as toluene, benzene, or xylene.

[0100] <Physical properties of resin composition> Hereinafter, preferred properties of the resin composition of this embodiment will be described.

[0101] The resin composition of the present embodiment is, for example, in an uncured state or a semi-cured state.

[0102] In the present embodiment, the dielectric loss tangent Df measured by the following method is preferably 0.0016 or less, more preferably 0.0015 or less, and even more preferably 0.0014 or less at a frequency of 10 GHz, from the viewpoint of improving the low dielectric properties of the cured product of the resin composition. Furthermore, there is no lower limit for the dielectric loss tangent Df measured by the following method, but it is, for example, 0.0001 or more, or may be 0.0002 or more, or 0.0003 or more, or may be 0.0004 or more. (method) A cured film having a thickness of 40±20 μm is prepared from the resin composition of this embodiment, and the cured film is cut into a test piece having a length of 50 mm, a width of 50 mm, and a thickness of 40±20 μm. 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.

[0103] Here, the dielectric loss tangent Df in this embodiment can be measured by, for example, the method described in the examples.

[0104] In the present embodiment, the average coefficient of thermal expansion in the range of 25°C to 90°C measured by the following method is preferably 60.0 ppm / K or less, more preferably 50.0 ppm / K or less, even more preferably 45.0 ppm / K or less, even more preferably 40.0 ppm / K or less, and even more preferably 35.0 ppm / K or less, from the viewpoint of improving the low thermal expansion properties of the cured product of the resin composition. Furthermore, there is no lower limit to the average thermal expansion coefficient measured by the method described below, but it is preferably 0.0 ppm / K or more, more preferably 1.0 ppm / K or more, even more preferably 2.0 ppm / K or more, even more preferably 3.0 ppm / K or more, and even more preferably 4.0 ppm / K or more. The average thermal expansion coefficient measured by the method described below is, for example, preferably 0.0 ppm / K or more and 60.0 ppm / K or less, more preferably 1.0 ppm / K or more and 50.0 ppm / K or less, even more preferably 2.0 ppm / K or more and 45.0 ppm / K or less, even more preferably 3.0 ppm / K or more and 40.0 ppm / K or less, and even more preferably 4.0 ppm / K or more and 35.0 ppm / K or less. (method) A cured film of the resin composition having a thickness of 40±20 μm is prepared. The cured film is cut into test pieces having a length of 20 mm, a width of 4 mm, and a thickness of 40±20 μm. Thermomechanical measurements of the cured film are performed in a nitrogen atmosphere at a temperature rise rate of 5°C / min in the range of 25°C to 90°C under a test load of 5.0 gf and in the film elongation mode.

[0105] In this embodiment, the average thermal expansion coefficient in the range of 25° C. to 90° C. can be measured by, for example, the method described in the examples.

[0106] In the present embodiment, the average coefficient of thermal expansion in the range of 190°C to 220°C measured by the following method is preferably 140.0 ppm / K or less, more preferably 130.0 ppm / K or less, even more preferably 120.0 ppm / K or less, even more preferably 110.0 ppm / K or less, and even more preferably 100.0 ppm / K or less, from the viewpoint of improving the low thermal expansion properties of the cured product of the resin composition. Furthermore, there is no lower limit to the average thermal expansion coefficient measured by the method described below, but it is preferably 0.0 ppm / K or more, more preferably 1.0 ppm / K or more, even more preferably 2.0 ppm / K or more, even more preferably 3.0 ppm / K or more, and even more preferably 4.0 ppm / K or more. The average thermal expansion coefficient measured by the method described below is, for example, preferably 0.0 ppm / K or more and 140.0 ppm / K or less, more preferably 1.0 ppm / K or more and 130.0 ppm / K or less, even more preferably 2.0 ppm / K or more and 120.0 ppm / K or less, even more preferably 3.0 ppm / K or more and 110.0 ppm / K or less, and even more preferably 4.0 ppm / K or more and 100.0 ppm / K or less. (method) A cured film of the resin composition having a thickness of 40±20 μm is prepared. The cured film is cut into test pieces having a length of 20 mm, a width of 4 mm, and a thickness of 40±20 μm. Thermomechanical measurements of the cured film are performed in a nitrogen atmosphere at a temperature rise rate of 5°C / min in the range of 190°C to 220°C under a test load of 5.0 gf and in the film elongation mode.

[0107] In this embodiment, the average thermal expansion coefficient in the range of 190° C. to 220° C. can be measured by, for example, the method described in the examples.

[0108] [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. The solvent for producing the varnish is not particularly limited, but preferably used are 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 and availability of the resin composition, the solvent more preferably contains one or more selected from the group consisting of heptane, decane, cyclohexane, methylcyclohexane, decahydronaphthalene, toluene, benzene, xylene, mesitylene, and pseudocumene. The solvent further preferably contains toluene.

[0109] The amount of solvent added to the entire resin composition containing components dispersible in the resin is preferably 50 parts by mass or more and 400 parts by mass or less, more preferably 55 parts by mass or more and 300 parts by mass or less, even more preferably 60 parts by mass or more and 200 parts by mass or less, and even more preferably 65 parts by mass or more and 150 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.

[0110] In this embodiment, the method for producing the varnish may be carried out by any method, for example, including a step of mixing a resin composition and a solvent. The order of mixing of the components is not limited, and the components can be mixed in any manner, such as all at once or in portions. The apparatus for producing 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 produced can be selected arbitrarily from room temperature to the boiling point of the solvent. The reaction solution obtained when the thermosetting cyclic olefin copolymer (A) is obtained may be used as a solvent to prepare the varnish.

[0111] [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. The crosslinking temperature in the crosslinking step is preferably 150°C or higher, more preferably 160°C or higher, and even more preferably 170°C or higher, from the viewpoint of further improving the heat resistance of the resulting cured product, and is preferably 250°C or lower, more preferably 240°C or lower, even more preferably 230°C or lower, and even more preferably 220°C or lower, from the viewpoint of suppressing thermal decomposition of the thermosetting cyclic olefin copolymer (A) and the cured product. The degree of vacuum in the crosslinking step is 50 kPa or less, preferably 40 kPa or less, more preferably 30 kPa or less, and even more preferably 20 kPa or less, from the viewpoint of maintaining the low dielectric properties of the resulting cured product.

[0112] The crosslinking step can be carried out with the resin composition of the present embodiment in a molten state, or can be carried out by dissolving the resin composition in a solvent, volatilizing the solvent from the solution, forming the resin composition into any shape such as a film or coating, and then allowing the crosslinking reaction to proceed. 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, 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.

[0113] [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.

[0114] [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.

[0115] [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.

[0116] [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.

[0117] 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 performance characteristics such as low dielectric properties and low thermal expansion. Therefore, the metal clad laminate of this embodiment can be suitably used as an insulating layer material for printed wiring boards.

[0118] [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 method of drying in air or nitrogen using a blower dryer, or a continuous method of drying by passing through a heating furnace. After the varnish is impregnated into the sheet-like fiber substrate, the resulting impregnated body is heated to a predetermined temperature, whereby the solvent contained in the varnish evaporates and a prepreg is obtained.

[0119] 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, at least one fiber selected from the group consisting of organic fibers and glass fibers is preferred, and at least one fiber selected from the group consisting of aramid fibers, liquid crystal polyester fibers, and glass fibers is more preferred. 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, for example, 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and for example, 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, of the prepreg or laminate. If it is in this range, the low dielectric properties and mechanical strength of the obtained laminate are well balanced, which is preferable.

[0120] The thickness of the prepreg is appropriately selected depending on the intended use, but is, for example, 0.005 mm or more, preferably 0.01 mm or more, more preferably 0.02 mm or more, and is, for example, 0.5 mm or less, preferably 0.4 mm or less, more preferably 0.3 mm or less. 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.

[0121] [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.

[0122] 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.

[0123] 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.

[0124] [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 low thermal expansion properties, 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.

[0125] 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]

[0126] 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.

[0127] The materials used in each example are listed. Thermosetting cyclic olefin copolymer 1: Synthesis Example 1 described below Radical initiator 1: 2,3-dimethyl-2,3-diphenylbutane (manufactured by Acros Organics) (hereinafter referred to as DMDPB) Radical initiator 2: Dicumyl Peroxide (product name: Percumyl D, manufactured by NOF Corporation) (hereinafter also referred to as DCP) Inorganic filler 1: Coarse grain zirconium tungstophosphate (product name: Cerafit (coarse grain: D 50 >10μm), manufactured by Nippon Chemical Industry Co., Ltd. Inorganic filler 2: Fine particle zirconium tungstophosphate (product name: Cerafit (fine particle: D 50 <1μm), manufactured by Nippon Chemical Industry Co., Ltd. Inorganic filler 3: Dry silane-treated zirconium tungstate phosphate (prepared by Mitsui Chemicals using Inorganic filler 2) Inorganic filler 4: amorphous silica (product name: ADMAFINE SC2300-SVJ, manufactured by Admatechs Co., Ltd.) Antioxidant: Phenolic antioxidant (tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionic acid]pentaerythritol, manufactured by BASF) Crosslinker: 4-vinylbenzocyclobutene (4-VBCB, Merck) Solvent: Toluene (Fujifilm Wako Pure Chemical Industries, Ltd.: Wako Special Grade)

[0128] The following raw materials were used to synthesize thermosetting cyclic olefin copolymer 1.

[0129] ·Transition metal compounds (1): It was synthesized by the method described in Synthesis Example 1 of JP-A No. 2004-331965.

[0130] [ka]

[0131] 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)

[0132] [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.

[0133] [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.

[0134] 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 H-NMR was 11 mol %, the content of repeating units (b) derived from VNB was 27 mol %, and the content of repeating units (a) derived from ethylene was 62 mol %.

[0135] [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.

[0136] [Example 1] (Preparation of varnish) 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.

[0137] (Preparation of cured film) The obtained varnish was applied to a release-treated PET film under the following coating conditions. Equipment: Automatic film coating machine (product name: PI-1210, manufactured by Tester Sangyo Co., Ltd.) Applicator gap: 200μm Coating speed: 10mm / sec

[0138] The applied varnish was dried by blowing air to obtain a dry film under the following drying conditions. Equipment: Blower dryer (product name: STPH-102M, manufactured by Espec Corporation) ·Drying temperature: 150℃ Drying time: 4 minutes Atmosphere: Nitrogen flow (30L / min)

[0139] The dried film was vacuum pressed to obtain a cured film. The thickness of the cured film was adjusted to 40±20 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. When vacuum pressing was performed at 220°C, the temperature was returned to room temperature after vacuum pressing at 180°C, and the release film was replaced. The vacuum pressing conditions were as follows: Equipment: Vacuum press (product name: KVHCII-press, manufactured by Kitagawa Seiki Co., Ltd.) Pressing temperature / pressure / time (when using DMDPB): 180°C / 3.5 MPa / 60 minutes → 220°C / 3.5 MPa / 120 minutes Pressing temperature / pressure / time (when using DCP): 180°C / 3.5MPa / 120min ·Vacuum degree: 1.2kPa or less

[0140] [Examples 2 to 5 and Comparative Examples 1 to 3] Cured films 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.

[0141] For the cured films obtained in Examples 1 to 5 and Comparative Examples 1 to 3, the dielectric loss tangent Df, the average thermal expansion coefficient in the temperature range from 25°C to 90°C, and the average thermal expansion coefficient in the temperature range from 190°C to 220°C were measured according to the methods described below. The results are shown in Table 1.

[0142] [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 40±20 μm in thickness. The dielectric loss tangent Df of the obtained test piece was then measured using a 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

[0143] [Measurement of the average thermal expansion coefficient in the temperature range from 25°C to 90°C] The cured film of each example was subjected to measurement of the average coefficient of thermal expansion in the temperature range of 25° C. to 90° C. The procedure for measuring the average coefficient of thermal expansion was as follows. The cured film of each example was cut into a test piece measuring 20 mm in length, 4 mm in width, and 40±20 μm in thickness. The test piece was then subjected to thermomechanical measurement (TMA measurement). The measurement conditions were as follows: Measurement equipment: Thermomechanical measurement equipment (product name: TMA7100C, manufactured by Hitachi High-Technologies Corporation) Measurement mode: Film stretch mode Test load: 5.0gf Measurement atmosphere: Nitrogen atmosphere Heating rate: 5℃ / min Measurement temperature range: -30℃~300℃ Average thermal expansion coefficient calculation temperature range: 25℃~90℃ and 190℃~220℃

[0144] [Measurement of the average thermal expansion coefficient in the temperature range from 190°C to 220°C] For each example of cured film, the average coefficient of thermal expansion was measured in the temperature range of 190°C to 220°C. The procedure for measuring the average coefficient of thermal expansion was the same as that for measuring the average coefficient of thermal expansion in the temperature range of 25°C to 90°C, except that the temperature range for calculating the average coefficient of thermal expansion was changed to 190°C to 220°C.

[0145] [Table 1]

Claims

1. a thermosetting cyclic olefin copolymer (A) having a crosslinkable group; an inorganic filler (B); a radical initiator (C); Including, The resin composition, wherein the inorganic filler (B) contains a zirconium compound (B1).

2. 2. The resin composition according to claim 1, wherein the content of the inorganic filler (B) in the resin composition is 10 parts by mass or more and 600 parts by mass or less, relative to 100 parts by mass of the thermosetting cyclic olefin copolymer (A).

3. 2. The resin composition according to claim 1, wherein the content of the zirconium compound (B1) in the resin composition is 10 parts by mass or more and 100 parts by mass or less when the content of the inorganic filler (B) is 100 parts by mass.

4. The specific surface area of the zirconium compound (B1) measured by the BET method in accordance with JIS Z8830:2013 is 0.10 m ２ / g or more 30.0m ２ The resin composition according to claim 1, wherein the viscosity is 1000 kJ / g or less.

5. The resin composition according to claim 1, wherein the zirconium compound (B1) has a thermal expansion coefficient of 0.0 ppm / K or less in the range of 50°C to 250°C.

6. The zirconium compound (B1) has an average particle diameter D at which the cumulative value reaches 50% in the volume frequency particle size distribution measured by a laser diffraction scattering method. ５０ The resin composition according to claim 1, wherein the particle size is 0.01 μm or more and 50 μm or less.

7. The true density ρ of the zirconium compound (B1) is 1.0 g / cm ３ 10.0g / cm or more ３ The resin composition according to claim 1, wherein:

8. 2. The resin composition according to claim 1, wherein the resin composition has an average coefficient of thermal expansion in the range of 25°C to 90°C of 60.0 ppm / K or less, as measured by the following method. (method) A cured film having a thickness of 40±20 μm is prepared from the resin composition, The cured film is cut into a test piece having a length of 20 mm, a width of 4 mm, and a thickness of 40±20 μm, and thermomechanical measurements of the cured film are carried out at a temperature increase rate of 5° C. / min in a nitrogen atmosphere in the range of 25° C. to 90° C. under a test load of 5.0 gf and measurement mode: film elongation mode.

9. The resin composition according to claim 1, having an average thermal expansion coefficient in the range of 190°C to 220°C of 140.0 ppm / K or less, as measured by the following method. (method) A cured film having a thickness of 40±20 μm is prepared from the resin composition, The cured film is cut into a test piece having a length of 20 mm, a width of 4 mm, and a thickness of 40±20 μm, and thermomechanical measurements of the cured film are carried out at a temperature increase rate of 5° C. / min in a nitrogen atmosphere in the range of 190° C. to 220° C. under a test load of 5.0 gf and measurement mode: film elongation mode.

10. The resin composition according to claim 1 , wherein the zirconium compound (B1) contains elemental tungsten.

11. 2. The resin composition according to claim 1, wherein the zirconium compound (B1) comprises one or more compounds selected from the group consisting of zirconium tungstate phosphate, zirconium tungstate, and zirconium phosphate.

12. The resin composition according to claim 1 , wherein the zirconium compound (B1) comprises a silane coupling agent having a crosslinkable group on the surface thereof.

13. The resin composition according to claim 12 , wherein the crosslinkable group comprises a vinyl group.

14. The resin composition according to claim 1 , wherein the radical initiator (C) comprises a non-peroxide radical initiator.

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

16. 16. The resin composition according to claim 15, wherein the content of the antioxidant (D) in the resin composition is 0.001 parts by mass or more and 5.0 parts by mass or less, relative to 100 parts by mass of the thermosetting cyclic olefin-based copolymer (A).

17. 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): 【Chemical 1】 [In the formula (I), R ３００ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. 【Chemistry 2】 [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 3】 [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 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.

18. The resin composition according to claim 17, wherein the olefin constituting the olefin-derived repeating unit (a) contains ethylene.

19. The resin composition according to claim 17, wherein the cyclic non-conjugated diene constituting the repeating unit (b) derived from the cyclic non-conjugated diene includes 5-vinyl-2-norbornene.

20. The cyclic olefin constituting the cyclic olefin-derived repeating unit (c) is tetracyclo[4.4.0.1 ２，５ .1 ７，１０ 18. The resin composition according to claim 17, comprising one or two selected from the group consisting of cyclo[2.2.1]-3-dodecene and bicyclo[2.2.1]-2-heptene.

21. 18. The resin composition according to claim 17, 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.

22. 2. The resin composition according to claim 1, wherein the content of the radical initiator (C) in the resin composition is 0.10 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).

23. 2. The resin composition according to claim 1, wherein a total content of the thermosetting cyclic olefin copolymer (A), the inorganic filler (B), and the radical initiator (C) in the resin composition is 20% by mass or more and 100% by mass or less, when a total amount of solids in the resin composition is 100% by mass.

24. The resin composition according to claim 1 , which is in an uncured state or a semi-cured state.

25. The resin composition according to claim 1, wherein the dielectric loss tangent Df measured by the following method is 0.0016 or less. (method) A cured film having a thickness of 40±20 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 40±20 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.

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

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

28. A film or sheet comprising the resin composition according to claim 1 or the cured product according to claim 27.

29. 29. A laminate comprising the film or sheet of claim 28.

30. 30. The laminate of claim 29, further comprising a metal foil on at least one side.

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

32. A printed wiring board comprising: an insulating layer comprising the cured product according to claim 27 or the cured product of the prepreg according to claim 31; and a conductor layer on the insulating layer.

33. An electronic device comprising the printed wiring board according to claim 32.

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