Cyclic olefin copolymer, cyclic olefin copolymer composition, varnish, crosslinked product, film or sheet, laminate, circuit board, electronic device, and prepreg

Abstract

This cyclic olefin-based copolymer contains: (A) structural units (A) derived from one or more olefins represented by general formula (I); (B) structural units (B) derived from one or more cyclic non-conjugated dienes represented by general formula (II); and (C) structural units (C) derived from one or more cyclic olefins represented by general formula (III). If the total number of moles of structural units (A), structural units (B) and structural units (C) in the cyclic olefin-based copolymer is taken to be 100 mol%, the sum total of the content of structural units (B) derived from cyclic non-conjugated dienes and the content of structural units (C) derived from cyclic olefins is 40.0-50.0 mol%. The number average molecular weight Mn of the cyclic olefin-based copolymer is 3000-16,000.

Description

[Technical Field]

[0001] The present invention relates to a cyclic olefin copolymer, a cyclic olefin copolymer composition, a varnish, a crosslinked product, a film or sheet, a laminate, a circuit board, an electronic device, and a prepreg. [Background technology]

[0002] Recently, the use of high-frequency bands has become more common due to an increase in wireless communication devices and faster communication speeds. This has led to a demand for circuit board materials with high insulation properties and small dielectric loss tangents to minimize transmission loss at high frequencies.

[0003] Examples of resin materials used for such circuit boards include cyclic olefin copolymers copolymerized with dienes, as described in Patent Documents 1 and 2.

[0004] Patent Documents 1 and 2 disclose that a sheet obtained by crosslinking a cyclic olefin copolymer copolymerized with a specific diene compound with an organic peroxide or the like exhibits excellent dielectric properties. Furthermore, Patent Documents 3 and 4 disclose crosslinkable resin molded articles containing crosslinkable cycloolefin polymers, which have excellent fluidity when heated and solvent solubility. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2010-100843 [Patent Document 2] International Publication No. 2012 / 046443 [Patent Document 3] Japanese Patent Application Publication No. 2019-081898 [Patent Document 4] International Publication No. 2021 / 149713 Summary of the Invention [Problem to be solved by the invention]

[0006] According to the investigations of the present inventors, it has become clear that there is room for further improvement in the solvent solubility of the cyclic olefin copolymers having crosslinkable groups as described in Patent Document 1 and Patent Document 2. If the solvent solubility can be improved, it is believed that the impregnation into the fiber substrate during the production of a circuit board can be further improved. Furthermore, although the cyclic olefin copolymers having crosslinkable groups described in Patent Documents 3 and 4 show improvements in fluidity and solubility, it has become clear that there is room for further improvement in the viscosity of varnish produced when the varnish contains a large amount of cyclic olefin copolymer (high solid content).If the viscosity of varnish at high solid content can be improved, it is believed that the impregnation of fiber substrates during circuit board production can be further improved. From the above, there is room for further improvement in cyclic olefin copolymers having crosslinkable groups in terms of improving solvent solubility while maintaining excellent dielectric properties and reducing the viscosity of varnish when varnish is produced containing a large amount of cyclic olefin copolymer.

[0007] The present invention has been made in view of the above circumstances, and provides a cyclic olefin copolymer and a cyclic olefin copolymer composition which are capable of producing a crosslinked product having excellent dielectric properties in the high frequency range suitable for circuit boards and the like, and which also produce a varnish with low viscosity even when the varnish contains a large amount of the cyclic olefin copolymer. [Means for solving the problem]

[0008] According to the present invention, there are provided the following cyclic olefin copolymers, cyclic olefin copolymer compositions, varnishes, crosslinked products, films or sheets, laminates, circuit boards, electronic devices, and prepregs.

[0009] [1] (A) one or more olefin-derived structural units (A) represented by the following general formula (I), (B) one or more structural units (B) derived from a cyclic non-conjugated diene represented by the following general formula (II), (C) one or more structural units (C) derived from cyclic olefins represented by the following general formula (III), A cyclic olefin copolymer comprising: When the total number of moles of the structural units (A), (B), and (C) in the cyclic olefin copolymer is taken as 100 mol%, the total content of the structural unit (B) derived from the cyclic non-conjugated diene and the structural unit (C) derived from the cyclic olefin is in the range of 40.0 mol% or more and 50.0 mol% or less; A cyclic olefin copolymer having a number average molecular weight Mn of 3,000 or more and 16,000 or less. [ka] (In general formula (I), R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. [ka] (In the general formula (II), u is 0 or 1, v is 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. [ka] (In general formula (III), R 1 ~R 8 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 4 or less carbon atoms, and R 5 ~R 8 may be bonded to each other to form a monocyclic ring, and the monocyclic ring may have a double bond, and R 5 and R 6 and, or R 7 and R 8 and may form an alkylidene group.) [2] In the cyclic olefin copolymer described in [1] above, When the total number of moles of the structural unit (A), the structural unit (B), and the structural unit (C) in the cyclic olefin copolymer is taken as 100 mol%, A cyclic olefin copolymer having a content of the structural unit (B) derived from the cyclic non-conjugated diene of 5 mol % or more and 20 mol % or less. [3] In the cyclic olefin copolymer according to the above [1] or [2], The cyclic olefin copolymer contains 5-vinyl-2-norbornene as the cyclic non-conjugated diene constituting the structural unit (B) derived from the cyclic non-conjugated diene. [4] In the cyclic olefin copolymer according to any one of the above [1] to [3], A cyclic olefin copolymer in which the cyclic olefin constituting the structural unit (C) derived from the cyclic olefin contains bicyclo[2.2.1]-2-heptene. [5] A cyclic olefin copolymer composition comprising the cyclic olefin copolymer according to any one of the above [1] to [4]. [6] A varnish containing the cyclic olefin copolymer composition according to [5] above and a solvent. [7] A crosslinked product obtained by crosslinking the cyclic olefin copolymer composition described in [5] above. [8] A film or sheet comprising the crosslinked product according to [7] above. [9] A laminate comprising the crosslinked product according to [7] above.

[10] A circuit board comprising an electrical insulating layer containing the crosslinked body according to [7] above, and a conductor layer provided on the electrical insulating layer.

[11] An electronic device comprising the circuit board described in

[10] above.

[12] A prepreg comprising the cyclic olefin copolymer according to any one of the above [1] to [4] and a sheet-like fiber base material. [Effects of the Invention]

[0010] According to the present invention, it is possible to obtain a crosslinked product having excellent dielectric properties in the high frequency range suitable for circuit boards and the like, and it is also possible to provide a cyclic olefin copolymer and a cyclic olefin copolymer composition which produce a varnish with low viscosity even when the varnish contains a large amount of the cyclic olefin copolymer. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, the present invention will be described based on the embodiments. In the present embodiments, "A to B" indicating a numerical range means A or more and B or less unless otherwise specified.

[0012] [Cyclic olefin copolymer (m)] The cyclic olefin copolymer (m) according to this embodiment is (A) one or more olefin-derived structural units (A) represented by the following general formula (I), (B) one or more structural units (B) derived from a cyclic non-conjugated diene represented by the following general formula (II), (C) one or more structural units (C) derived from cyclic olefins represented by the following general formula (III), When the total number of moles of the structural units (A), (B) and (C) in the cyclic olefin copolymer is taken as 100 mol %, the total content of the structural units (B) derived from the cyclic non-conjugated diene and the structural units (C) derived from the cyclic olefin is in the range of 40.0 mol % or more and 50.0 mol % or less, and the number average molecular weight Mn is 3,000 or more and 16,000 or less.

[0013] [ka]

[0014] In the above general formula (I), R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.

[0015] [ka]

[0016] In the above general formula (II), 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.

[0017] [ka]

[0018] In the above general formula (III), R 1 ~R 8 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 4 or less carbon atoms, and R 5 ~R 8 may be bonded to each other to form a monocyclic ring, and the monocyclic ring may have a double bond, and R 5 and R 6 and, or R 7 and R 8 may form an alkylidene group.

[0019] In the cyclic olefin copolymer (m) according to the present embodiment, when the total number of moles of the structural units (A), (B) and (C) in the cyclic olefin copolymer (m) is taken as 100 mol %, the total content of the structural unit (B) derived from the cyclic non-conjugated diene and the structural unit (C) derived from the cyclic olefin is 40.0 mol % or more and 50.0 mol % or less. The cyclic olefin copolymer (m) according to this embodiment contains the structural unit (A), the structural unit (B), and the structural unit (C), and the total content of the structural unit (B) and the structural unit (C) is within the above range, so that the crosslinked product (Q) obtained from the cyclic olefin copolymer (m) has excellent dielectric properties, and furthermore, the solubility of the cyclic olefin copolymer (m) in solvents is further improved, resulting in good moldability and improved product yield. In other words, this embodiment can provide a cyclic olefin copolymer (m) and a cyclic olefin resin composition that maintain excellent dielectric properties and have excellent solubility when a varnish containing a large amount of the cyclic olefin copolymer is prepared. In this case, the lower limit of the total content of the structural units (B) derived from the cyclic non-conjugated diene and the structural units (C) derived from the cyclic olefin is preferably 40.5 mol% or more, more preferably 41.0 mol% or more, from the viewpoint of further improving the performance balance between the dielectric properties and solubility. Also, the upper limit of the total content of the structural units (B) derived from the cyclic non-conjugated diene and the structural units (C) derived from the cyclic olefin is preferably 49.0 mol% or less, more preferably 48.0 mol% or less, even more preferably 47.5 mol% or less, still more preferably 47.0 mol% or less, even more preferably 46.0 mol% or less, still more preferably 45.0 mol% or less, still more preferably 44.0 mol% or less, and even more preferably 43.5 mol% or less, from the viewpoint of further improving the performance balance between the dielectric properties and solubility.

[0020] Furthermore, the cyclic olefin copolymer (m) according to this embodiment has a number average molecular weight Mn of 3,000 or more and 16,000 or less. The cyclic olefin copolymer (m) according to this embodiment has a number average molecular weight Mn within the above range, so that the crosslinked product (Q) obtained from the cyclic olefin copolymer (m) has excellent dielectric properties, and furthermore, the solubility of the cyclic olefin copolymer (m) in solvents is further improved, resulting in good moldability and improved product yield. In other words, this embodiment can provide a cyclic olefin copolymer (m) and a cyclic olefin resin composition that maintain excellent dielectric properties and have excellent solubility when a varnish is prepared containing a large amount of the cyclic olefin copolymer. In this case, the lower limit of the number average molecular weight Mn is preferably at least 4,000, more preferably at least 5,000, even more preferably at least 6,000, even more preferably at least 7,000, and even more preferably at least 7,300. When the number average molecular weight Mn of the cyclic olefin copolymer (m) is at least the above-mentioned lower limit, the dielectric properties, heat resistance, and mechanical properties of the crosslinked product (Q) obtained by crosslinking the cyclic olefin copolymer (m) or the cyclic olefin copolymer composition according to this embodiment can be made better. The upper limit of the number average molecular weight Mn is preferably 15,000 or less, more preferably 12,000 or less, even more preferably 11,500 or less, and even more preferably 11,200 or less. When the number average molecular weight Mn of the cyclic olefin copolymer (m) is the above upper limit or less, the cyclic olefin copolymer (m) or the cyclic olefin copolymer composition according to this embodiment can have good moldability, such as impregnation ability into a fiber substrate and wiring embeddability, when producing a circuit board.

[0021] <Structural unit (A)> In the above general formula (I), R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. Examples of olefin monomers for forming the structural unit (A) include 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, and 1-eicosene. Among these, ethylene or propylene is preferred, and ethylene is more preferred, from the viewpoint of obtaining a crosslinked product having better heat resistance, mechanical properties, dielectric properties, transparency, and gas barrier properties. The olefin monomer for forming the structural unit (A) may be used alone or in combination of two or more.

[0022] In the cyclic olefin copolymer (m) according to this embodiment, when the total number of moles of the structural units (A), (B) and (C) in the cyclic olefin copolymer (m) is taken as 100 mole%, the content of the structural unit (A) is preferably 20 mole% or more and 60 mole% or less, more preferably 30 mole% or more and 60 mole% or less, even more preferably 40 mole% or more and 59 mole% or less, even more preferably 45 mole% or more and 59 mole% or less, even more preferably 50 mole% or more and 58 mole% or less, and even more preferably 52 mole% or more and 57 mole% or less. By having the content of the structural unit (A) within the above numerical range, the solubility of the cyclic olefin copolymer according to this embodiment in solvents is further improved. Furthermore, in the cyclic olefin copolymer (m) according to this embodiment, when the total number of moles of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (m) is taken as 100 mol%, the lower limit of the content of the structural unit (A) is preferably 20 mol% or more, more preferably 30 mol% or more, even more preferably 40 mol% or more, even more preferably 45 mol% or more, even more preferably 50 mol% or more, and even more preferably 52 mol% or more, from the viewpoint of further improving the solubility of the cyclic olefin copolymer according to this embodiment in a solvent. Furthermore, from the viewpoint of further improving the solubility of the cyclic olefin copolymer according to this embodiment in a solvent, the upper limit of the content of the structural unit (A) is preferably 60 mol% or less, more preferably 59 mol% or less, even more preferably 58 mol% or less, and even more preferably 57 mol% or less. The content of the structural unit (A) is 1 It can be measured by H-NMR.

[0023] <Structural unit (B)> The cyclic non-conjugated diene monomer, which is the copolymerization raw material for the cyclic olefin copolymer (m) according to this embodiment, undergoes addition copolymerization to form the structural unit represented by the above formula (II). Specifically, a cyclic non-conjugated diene represented by the following general formula (IIa) corresponding to the above general formula (II) is used.

[0024] [ka]

[0025] In the above general formula (IIa), u is 0 or 1, v is 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.

[0026] The cyclic non-conjugated diene represented by the above general formula (IIa) is not particularly limited, but examples thereof include cyclic non-conjugated dienes represented by the following chemical formula: Among these, 5-vinyl-2-norbornene and 8-vinyl-9-methyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene is preferred, and 5-vinyl-2-norbornene is more preferred.

[0027] [ka]

[0028] [ka]

[0029] The cyclic non-conjugated diene represented by the above general formula (IIa) can also be specifically represented by the following general formula (IIb).

[0030] [ka]

[0031] In the general formula (IIb), n is an integer of 0 to 10, and R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0032] The cyclic olefin copolymer (m) according to this embodiment is characterized in that it contains a structural unit derived from a cyclic non-conjugated diene represented by general formula (II) and thus has a double bond in a side chain portion, i.e., a portion other than the main chain of the copolymer.

[0033] In the cyclic olefin copolymer (m) according to this embodiment, when the total number of moles of structural units in the cyclic olefin copolymer (m) is taken as 100 mol%, the content of the structural unit (B) is preferably 1 mol% to 40 mol%, more preferably 1 mol% to 35 mol%, even more preferably 3 mol% to 30 mol%, even more preferably 3 mol% to 25 mol%, even more preferably 5 mol% to 20 mol%, even more preferably 7 mol% to 17 mol%, and even more preferably 10 mol% to 15 mol%. By having the content of the structural unit (B) within the above numerical range, the solubility of the cyclic olefin copolymer according to this embodiment in solvents is further improved. Furthermore, in the cyclic olefin copolymer (m) according to this embodiment, when the total number of moles of structural units in the cyclic olefin copolymer (m) is taken as 100 mol%, the lower limit of the content of the structural unit (B) is preferably 1 mol% or more, more preferably 3 mol% or more, even more preferably 5 mol% or more, even more preferably 7 mol% or more, and even more preferably 10 mol% or more, from the viewpoint of further improving the solubility of the cyclic olefin copolymer according to this embodiment in a solvent. Furthermore, from the viewpoint of further improving the solubility of the cyclic olefin copolymer according to this embodiment in a solvent, the upper limit of the content of the structural unit (B) is preferably 40 mol% or less, preferably 35 mol% or less, more preferably 30 mol% or less, even more preferably 25 mol% or less, even more preferably 20 mol% or less, even more preferably 17 mol% or less, and even more preferably 15 mol% or less. The content of the structural unit (B) is 1 It can be measured by H-NMR.

[0034] <Structural unit (C)> In the above general formula (III), R 1 ~R 8 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 4 or less carbon atoms. Here, the halogen atom is a fluorine atom, chlorine atom, bromine atom, or iodine atom. Examples of hydrocarbon groups having 4 or less carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl and isobutyl groups, and cycloalkyl groups such as cyclopropyl groups. Also R 5 ~R 8 may be bonded to each other to form a monocyclic ring, and the monocyclic ring may have a double bond, and R 5 and R 6 and, or R 7 and R 8 may form an alkylidene group. Examples of the monocyclic ring formed here are shown below.

[0035] [ka]

[0036] In the above monocyclic ring, the carbon atom numbered 1 or 2 corresponds to R 5 (R 6 ) or R 7 (R 8 ) is a carbon atom forming an alicyclic structure to which is bonded. Specific examples of the alkylidene group include an ethylidene group, a propylidene group, and an isopropylidene group.

[0037] Examples of cyclic olefin monomers for forming the structural unit (C) include bicyclo[2.2.1]-2-heptene (also called 2-norbornene) and its alkyl and / or alkylidene substituted derivatives, such as 5-methyl-2-norbornene, 5-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, and 5-ethylidene-2-norbornene; polar group substituted derivatives thereof, such as halogen; dicyclopentadiene, 2,3-dihydrodicyclopentadiene; dimethanooctahydronaphthalene, and its alkyl and / or alkylidene substituted derivatives. alkyl and / or alkylidene substituents, and polar group substituents such as halogen, carboxyl group, and cyano group, for example, 6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene, 6-ethyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene, 6-ethylidene-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene, 6-chloro-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene, cyclopentadiene, 6-chloro-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene, 6-cyano-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene, 6-pyridyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene, 6-methoxycarbonyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene, etc.; adducts of cyclopentadiene with tetrahydroindene, etc.; 3-4 monomers, such as 4,9:5,8-dimethano-3a,4,4a,5,8,8a,9,9a-octahydro-1H-benzoindene, 4,11:5,10:6,9-trimethano-3a,4,4a,5,5a,6,9,9a,10,10a,11,11a-dodecahydro-1H-cyclopentaanthracene, 5-carboxymethylbicyclo[2.2.1]hept-2-ene, 5-methyl-5-carboxymethylbicyclo[2.2.1]hept-2-ene, 5-cyanobicyclo[2.2.1]hept-2-ene, 8-carboxymethyltetracyclo[4.4.0.1]hept-2-ene,2,5 .1 7,10 ]-3-dodecene, 8-carboxyethyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-carboxy n-propyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-carboxyisopropyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-carboxy n-butyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-todecene, 8-methyl-8-carboxymethyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-methyl-8-carboxyethyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-methyl-8-carboxy n-propyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-methyl-8-carboxyisopropyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-methyl-8-carboxy n-butyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene; etc. Among these, bicyclo[2.2.1]-2-heptene is preferred. The cyclic olefin monomer for forming the structural unit (C) may be used alone or in combination of two or more kinds.

[0038] In the cyclic olefin copolymer (m) according to this embodiment, when the total number of moles of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (m) is taken as 100 mole%, the content of the structural unit (C) is preferably 5 mole% or more and 40 mole% or less, more preferably 10 mole% or more and 38 mole% or less, even more preferably 13 mole% or more and 38 mole% or less, even more preferably 15 mole% or more and 35 mole% or less, even more preferably 20 mole% or more and 35 mole% or less, and even more preferably 21 mole% or more and 35 mole% or less. By having the content of the structural unit (C) within the above numerical range, the solubility of the cyclic olefin copolymer according to this embodiment in solvents is further improved. Furthermore, in the cyclic olefin copolymer (m) according to this embodiment, when the total number of moles of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (m) is taken as 100 mol%, the lower limit of the content of the structural unit (C) is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 13 mol% or more, even more preferably 15 mol% or more, even more preferably 20 mol% or more, and even more preferably 21 mol% or more, from the viewpoint of further improving the solubility of the cyclic olefin copolymer according to this embodiment in a solvent. Furthermore, from the viewpoint of further improving the solubility of the cyclic olefin copolymer according to this embodiment in a solvent, the upper limit of the content of the structural unit (C) is preferably 40 mol% or less, more preferably 39 mol% or less, even more preferably 38 mol% or less, even more preferably 37 mol% or less, and even more preferably 35 mol% or less. The content of the structural unit (C) is: 1 It can be measured by H-NMR.

[0039] <Structural unit (D)> The cyclic olefin copolymer (m) according to this embodiment may further contain one or more structural units derived from cyclic olefins represented by the following general formula (V).

[0040] [ka]

[0041] In the above general 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, u+v is 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.

[0042] Specifically, a cyclic olefin monomer represented by the following general formula (Va) corresponding to the above general formula (V) is used.

[0043] [ka]

[0044] In the above general 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, u+v is a positive integer, w is 0 or 1, 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.

[0045] Specific examples of the cyclic olefin represented by the above general formula (Va) include the compounds described in WO 2006 / 118261. The cyclic olefin represented by the general formula (Va) includes tetracyclo[4.4.0.1 2,5 .1 7,10 Tetracyclododecene has the advantage that the modulus of elasticity of the copolymer and crosslinked product is easily maintained due to its rigid ring structure, and crosslinking can be easily controlled due to the absence of a heterogeneous double bond structure.

[0046] In the cyclic olefin copolymer (m) according to this embodiment, when the total number of moles of the structural units (A), (B) and (C) in the cyclic olefin copolymer is taken as 100 mole %, the content of the structural unit (D) is preferably 1 mole % or more and 35 mole % or less, more preferably 3 mole % or more and 25 mole % or less, and even more preferably 5 mole % or more and 15 mole % or less. When the content of the structural unit (D) is within the above numerical range, the solubility of the cyclic olefin copolymer according to this embodiment in a solvent is further improved. The content of the structural unit (D) is 1 It can be measured by H-NMR.

[0047] From the viewpoint of further improving the performance balance between dielectric properties and solubility, the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (m) according to this embodiment is preferably 65 mol% or more, more preferably 75 mol% or more, even more preferably 85 mol% or more, even more preferably 95 mol% or more, even more preferably 97 mol% or more, even more preferably 99 mol% or more, and preferably 100 mol% or less, when the total number of moles of all structural units in the cyclic olefin copolymer (m) is taken as 100 mol%,

[0048] [Method for producing cyclic olefin copolymer (m)] The cyclic olefin copolymer (m) according to 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.

[0049] [Cyclic olefin resin composition] The cyclic olefin resin composition according to this embodiment contains the cyclic olefin copolymer (m) according to this embodiment. Furthermore, various additives may be added to the cyclic olefin resin composition according to the present embodiment depending on the purpose. The amount of the additive added is appropriately selected depending on the application within a range that does not impair the object of the present invention. Examples of the additives include one or more additives selected from the group consisting of radical polymerization initiators, elastomers, heat stabilizers, weather stabilizers, radiation-resistant agents, plasticizers, lubricants, mold release agents, nucleating agents, friction and wear improvers, flame retardants, foaming agents, antistatic agents, colorants, antifogging agents, antiblocking agents, impact resistance agents, surface wetting improvers, fillers, hydrochloric acid absorbers, and metal deactivators.

[0050] The cyclic olefin resin composition according to this embodiment can be prepared, for example, by mixing the cyclic olefin copolymer (m) with various additives as required. Examples of the mixing method include melt blending using an extruder or solution blending in an appropriate solvent, such as saturated hydrocarbons such as heptane, hexane, decane, and cyclohexane, or aromatic hydrocarbons such as toluene, benzene, and xylene.

[0051] The cyclic olefin resin composition according to this embodiment can be made into a varnish by mixing it with a solvent. The solvent for preparing the varnish-like cyclic olefin resin composition is not particularly limited as long as it does not impair the solubility or affinity of the cyclic olefin copolymer (m).Preferably used solvents include saturated hydrocarbons such as heptane, hexane, octane, and decane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and decahydronaphthalene; aromatic hydrocarbons such as toluene, benzene, xylene, mesitylene, and pseudocumene; alcohols such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, and phenol; ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, and acetophenone; cellosolves such as methyl cellosolve and ethyl cellosolve; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, and butyl formate; and halogenated hydrocarbons such as trichloroethylene, dichloroethylene, and chlorobenzene. Preferably, heptane, decane, cyclohexane, methylcyclohexane, decahydronaphthalene, toluene, benzene, xylene, mesitylene, and pseudocumene are used. These solvents can be used alone or in combination of two or more in any proportion.

[0052] In this embodiment, the method for preparing a varnish-like cyclic olefin resin composition may be carried out by any method, but typically includes a step of mixing the cyclic olefin copolymer (m) with a solvent. The order in which the components are mixed is not limited, and the components may be mixed in any manner, such as all at once or in portions. The apparatus for preparing the varnish is also not limited, and any apparatus capable of stirring and mixing, such as a batch type or a continuous type, may be used. The temperature at which the varnish is prepared may be selected from the range of room temperature to the boiling point of the solvent. The varnish may be prepared by using the reaction solution obtained when the cyclic olefin copolymer (m) is obtained as it is as a solvent.

[0053] [Crosslinked product (Q)] The crosslinked product (Q) according to this embodiment can be obtained by crosslinking the cyclic olefin copolymer (m) according to this embodiment or the cyclic olefin resin composition according to this embodiment. The method for crosslinking the cyclic olefin copolymer (m) according to this embodiment or the cyclic olefin resin composition according to this embodiment is not particularly limited, and examples include a method of crosslinking the cyclic olefin copolymer (m) according to this embodiment or the cyclic olefin resin composition according to this embodiment while molding into a desired shape or after molding using a radical polymerization initiator, sulfur, a hydrosilyl group-containing compound, an electron beam or other radiation.

[0054] Crosslinking using a radical polymerization initiator can be performed using the same crosslinking method as that used for polyolefins. Specifically, a radical polymerization initiator such as dicumyl peroxide is blended with the cyclic olefin copolymer (m) or the cyclic olefin resin composition, followed by heating and crosslinking. The content of the radical polymerization initiator is not particularly limited, but is typically 0.02 to 20 parts by mass, preferably 0.05 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, even more preferably 1.0 to 5 parts by mass, even more preferably 1.5 to 3 parts by mass, and even more preferably 2.0 to 2.5 parts by mass per 100 parts by mass of the cyclic olefin copolymer (m). When the content of the radical polymerization initiator is below the upper limit, the dielectric properties of the crosslinked product (Q) are improved. When the content is above the lower limit, the heat resistance and mechanical properties of the crosslinked product (Q) are improved. Furthermore, from the viewpoint of further improving the dielectric properties of the crosslinked body (Q), the upper limit of the content of the radical polymerization initiator is preferably 0.02 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, even more preferably 0.5 parts by mass or more, even more preferably 1.0 part by mass or more, even more preferably 1.5 parts by mass or more, and even more preferably 2.0 parts by mass or more per 100 parts by mass of the cyclic olefin copolymer (m). Furthermore, from the viewpoint of further improving the performance balance between the heat resistance and mechanical properties of the crosslinked body (Q), the lower limit of the content of the radical polymerization initiator is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and even more preferably 2.5 parts by mass or less.

[0055] The radical polymerization initiator may be a known thermal radical polymerization initiator, a photoradical polymerization initiator, or a combination of these. When a thermal radical polymerization initiator is used, the radical polymerization initiator has a 10-hour half-life temperature of usually 80° C. or higher, preferably 120° C. or higher, from the viewpoint of further improving storage stability. Examples of such thermal radical polymerization initiators include dialkyl peroxides such as dicumyl peroxide, t-butylcumyl peroxide, 2,5-bis(t-butylperoxy)2,5-dimethylhexane, 2,5-bis(t-butylperoxy)2,5-dimethylhexyne-3, di-t-butyl peroxide, isopropylcumyl-t-butyl peroxide, and bis(α-t-butylperoxyisopropyl)benzene; 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl-4,4-bis(t-butylperoxy)valerate, and ethyl-3,3-bis(t-butylperoxy). peroxyketals such as bis(t-butylperoxy)butyrate and 3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxycyclononane; peroxyesters such as bis(t-butylperoxy)isophthalate, t-butylperoxybenzoate and t-butylperoxyacetate; hydroperoxides such as t-butyl hydroperoxide, t-hexyl hydroperoxide, cumin hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide and p-menthane hydroperoxide; bibenzyl compounds such as 2,3-dimethyl-2,3-diphenylbutane; and 3,3,5,7,7-pentamethyl-1,2,4-trioxepane. Commercially available thermal radical polymerization initiators include, for example, "Percumyl P," "Percumyl D," "Perbutyl C," "Perbutyl A," "Perbutyl P," "Perbutyl L," "Perbutyl O," "Perbutyl ND," and "Perbutyl Z," manufactured by NOF Corporation.

[0056] Among radical polymerization initiators, specific examples of photoradical polymerization initiators include benzoin alkyl ether, benzil dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, methylbenzoyl formate, isopropyl thioxanthone, and mixtures of two or more of these. Sensitizers can also be used in conjunction with these photoradical polymerization initiators. Examples of sensitizers include carbonyl compounds such as anthraquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, benzanthrone, p,p'-tetramethyldiaminobenzophenone, and chloranil; nitro compounds such as nitrobenzene, p-dinitrobenzene, and 2-nitrofluorene; aromatic hydrocarbons such as anthracene and chrysene; sulfur compounds such as diphenyl disulfide; and nitrogen compounds such as nitroaniline, 2-chloro-4-nitroaniline, 5-nitro-2-aminotoluene, and tetracyanoethylene.

[0057] When crosslinking with sulfur or the like, a sulfur-based compound, and optionally a vulcanization accelerator and a vulcanization accelerator aid, are blended with the cyclic olefin resin composition and heated to carry out the crosslinking reaction. The amount of sulfur-based compound is not particularly limited, but it is typically used in the range of 0.1 to 10 parts by mass, preferably 0.3 to 5 parts by mass, per 100 parts by mass of the cyclic olefin copolymer (m) in order to efficiently proceed with the crosslinking reaction and to improve the physical properties of the resulting crosslinked product and from the standpoint of economic efficiency. When a vulcanization accelerator or a vulcanization accelerator aid is used in combination, it is typically used in the range of 0.1 to 20 parts by mass, preferably 0.2 to 10 parts by mass. Various known sulfur-based compounds can be used to cause the crosslinking reaction, and examples include sulfur, sulfur monochloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dimethyldithiocarbamate. Various vulcanization accelerators can also be used, including thiazole-based accelerators such as N-cyclohexyl-2-benzothiazole-sulfenamide, N-oxydiethylene-2-benzothiazole-sulfenamide, N,N-diisopropyl-2-benzothiazole-sulfenamide, 2-mercaptobenzothiazole, 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-diethyl-4-morpholinothio)benzothiazole, and benzothiazyl-disulfide; guanidine-based accelerators such as diphenylguanidine, triphenylguanidine, di-ortho-tolylguanidine, ortho-tolylbiguanide, and diphenylguanidine phthalate; acetaldehyde-aniline reaction products; butyraldehyde-aniline condensates; aldehyde amines such as hexamethylenetetramine and acetaldehyde ammonia; and aldehyde-aniline compounds. ammonium-based compounds; imidazoline-based compounds such as 2-mercaptoimidazoline; thiourea-based compounds such as thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, and diorthothylthiourea; thiuram-based compounds such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, and dipentamethylenethiuram tetrasulfide; dithioacid salt-based compounds such as zinc dimethyldithiocarbamate, zinc diethylthiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, and tellurium diethyldithiocarbamate; and xanthate-based compounds such as zinc dibutylxanthogenate.Examples of vulcanization accelerators include metal oxides such as zinc oxide, activated zinc white, zinc carbonate, complex zinc white, magnesium oxide, litharge, red lead, and basic lead carbonate; fatty acid compounds such as stearic acid, oleic acid, lauric acid, and lead stearate; and organic amine / glycol compounds such as triethanolamine and diethylene glycol.

[0058] The temperature at which the cyclic olefin copolymer (m) or the cyclic olefin resin composition is crosslinked with a radical polymerization initiator or sulfur is typically 100 to 300°C, preferably 120 to 250°C, and more preferably 120 to 220°C, and the crosslinking may be carried out by changing the temperature stepwise. At or above the lower limit, the crosslinking can proceed sufficiently. At or below the upper limit, the coloring of the resulting crosslinked product can be suppressed and the process can be simplified. For reference, polybutadiene, a typical double bond-containing polymer, generally cannot be crosslinked under the above conditions and requires crosslinking conditions at a high temperature, such as 300°C.

[0059] The cyclic olefin copolymer (m) or cyclic olefin resin composition according to this embodiment can also be crosslinked using a hydrosilyl group-containing compound having at least two hydrosilyl groups per molecule. Crosslinking using a hydrosilyl group-containing compound can be carried out, for example, according to the method described in JP 2015-193680 A. Details are omitted here.

[0060] The crosslinking method using electron beams or other radiation has the advantage that there are no restrictions on temperature or fluidity during molding, and examples of radiation include electron beams, gamma rays, UV rays, etc.

[0061] In either case of the method using a radical polymerization initiator, sulfur, a hydrosilyl group-containing compound, or the method using radiation, crosslinking can be carried out in the presence of a crosslinking aid.

[0062] The crosslinking aid is not particularly limited, and examples thereof 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; maleimide compounds such as N,N'-m-phenylene bismaleimide and N,N'-(4,4'-methylenediphenylene)dimaleimide; and cyclic non-conjugated dienes such as vinylnorbornene, ethylidenenorbornene, and dicyclopentadiene. These crosslinking aids may be used alone or in combination.

[0063] If necessary, the crosslinked product (Q) according to this embodiment may contain a heat stabilizer, a weather stabilizer, an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, a lubricant, a dye, a pigment, a natural oil, a synthetic oil, a wax, an organic or inorganic filler, and the like, to the extent that the object of the present invention is not impaired, and the content thereof is an appropriate amount. Specific examples of stabilizers that can be added as an optional ingredient include phenolic antioxidants such as tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid alkyl esters, and 2,2'-oxamidobis[ethyl-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate]; fatty acid metal salts such as zinc stearate, calcium stearate, and calcium 12-hydroxystearate; and polyhydric alcohol fatty acid esters such as glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. These may be blended alone or in combination, for example, a combination of tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane with zinc stearate and glycerin monostearate. Commercially available thermal radical polymerization initiators include, for example, Irganox 1010, 1035, 1076, 1098, and 1135 manufactured by BASF Japan Ltd.

[0064] Examples of organic or inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloons, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, and polyamide fiber.

[0065] To mix the crosslinked product (Q) with various additives, a method of melt-blending the cyclic olefin copolymer (m) with various additives using an extruder or the like, or a solution blending method in which the cyclic olefin copolymer (m) and various additives are dissolved or dispersed in an appropriate solvent, for example, a saturated hydrocarbon such as heptane, hexane, decane, or cyclohexane; or an aromatic hydrocarbon such as toluene, benzene, or xylene, can be used.

[0066] The crosslinking reaction can be carried out by melting a mixture of the cyclic olefin resin composition and the above-mentioned radical polymerization initiator, sulfur, hydrosilyl group-containing compound, or the like, or by dissolving or dispersing the mixture in a solvent in a solution state. Alternatively, the mixture can be dissolved in a solvent and the solvent can be evaporated from the solution, and the mixture can be formed into any shape such as a film or coating, after which the crosslinking reaction can be further carried out.

[0067] When the reaction is carried out in a molten state, the mixture of raw materials is melt-kneaded and reacted using a kneading device such as a mixing roll, a Banbury mixer, an extruder, a kneader, a continuous mixer, etc. Alternatively, the crosslinking reaction can be further carried out after molding by any method.

[0068] 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.

[0069] When the crosslinking reaction is carried out using electron beams or other radiation, or UV, the reaction can be carried out after shaping by any method.

[0070] [Molded body] The molded article according to this embodiment includes the crosslinked article (Q) according to this embodiment. The molded article according to this embodiment is, for example, a film or a sheet. Various known methods can be used to form a film or sheet using the cyclic olefin copolymer (m) according to this embodiment or the cyclic olefin resin composition according to this embodiment. 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 heat-treated to crosslink the cyclic olefin copolymer (m) according to this embodiment or the cyclic olefin resin composition according to this embodiment. 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 cyclic olefin copolymer (m) according to this embodiment or the cyclic olefin resin composition according to this embodiment is melt-molded to obtain a film or sheet.

[0071] The film or sheet of this embodiment can be laminated on a substrate to form a laminate, which can be used for various purposes. Various known methods can be used to form the laminate of this embodiment. For example, a laminate can be produced by laminating the film or sheet produced by the above-mentioned method onto a substrate, and, if necessary, heat-curing the laminate by a press or the like. Furthermore, a laminate can also be produced by laminating an electrical insulating layer containing the above-described crosslinked body onto a conductor layer.

[0072] The cyclic olefin copolymer (m) according to this embodiment or the cyclic olefin resin composition according to this embodiment may be formed on the surface layer of various multilayer molded articles or multilayer laminate films. In this case, the resin layer formed by the cyclic olefin copolymer (m) according to this embodiment or the cyclic olefin resin composition according to this embodiment is preferably 100 μm or less. Examples of various multilayer molded articles or multilayer laminated films include a multilayer molded article for an optical lens in which the cyclic olefin copolymer (m) according to this embodiment or the cyclic olefin-based resin composition according to this embodiment is formed on the surface of a resin optical lens, and a multilayer gas barrier film in which the cyclic olefin copolymer (m) according to this embodiment or the cyclic olefin-based resin composition according to this embodiment is formed on the surface of a resin film such as a PET film or a PE film in order to impart gas barrier properties.

[0073] The molded article according to the present embodiment may be, for example, a prepreg. The prepreg according to the present embodiment is formed by combining the cyclic olefin copolymer (m) according to the present embodiment or the cyclic olefin-based resin composition according to the present embodiment with a sheet-like fiber substrate. 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 above-mentioned varnish. The impregnation of the sheet-like fiber substrate with the above-mentioned 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. Furthermore, 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. In this embodiment, after the varnish is impregnated into the sheet-like fiber substrate, the obtained impregnated body is heated to a predetermined temperature, whereby the solvent contained in the varnish evaporates and a prepreg is obtained.

[0074] The fibers constituting the sheet-like fiber substrate according to this embodiment can be inorganic and / or organic fibers, and are not particularly limited. Examples include organic fibers such as PET (polyethylene terephthalate) 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, organic fibers and glass fibers are preferred, with aramid fibers, liquid crystal polyester fibers, and glass fibers being particularly 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 usually in the range of 10 to 90 mass %, preferably 20 to 80 mass %, and more preferably 30 to 70 mass % of the prepreg or laminate. This range is preferable because it provides a high level of balance between the dielectric properties and mechanical strength of the resulting laminate.

[0075] The thickness of the prepreg according to this embodiment is selected appropriately depending on the intended use, but is usually 0.001 to 10 mm, preferably 0.005 to 1 mm, and more preferably 0.01 to 0.5 mm. This range is suitable because it allows for sufficient shaping during lamination and the mechanical strength, toughness, and other properties of the laminate obtained by curing.

[0076] The cyclic olefin copolymer (m) according to this embodiment or the cyclic olefin resin composition according to this embodiment has excellent dielectric properties, heat resistance, mechanical properties, etc., and therefore can be suitably used for circuit boards. The method for producing a circuit board can be generally known and is not particularly limited. For example, the film, sheet, or prepreg produced by the above-mentioned 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 circuit board.

[0077] 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 metal is made into a foil or the like and heat-fused onto the electrical insulating layer, a method in which the metal is made into a 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 metal is formed on the electrical insulating layer by a method such as sputtering, vapor deposition, or plating. The circuit board may be either a single-sided board or a double-sided board.

[0078] Such a circuit board can be used as an electronic device by mounting electronic components such as semiconductor elements, etc. Electronic devices can be manufactured based on 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.

[0079] Furthermore, the cyclic olefin copolymer (m) according to this embodiment or the cyclic olefin resin composition according to this embodiment can be crosslinked and foamed to form a foam. In this case, the above-mentioned foaming agent may be added to the cyclic olefin resin composition.

[0080] [Application] The crosslinked product (Q) according to this embodiment has excellent solvent resistance, heat resistance, mechanical strength, and transparency, and therefore, molded articles made of the crosslinked product (Q) can be used as overcoat materials or interlayer materials for, for example, optical fibers, optical waveguides, optical disk substrates, optical filters, lenses, optical adhesives, optical filters for PDPs, coating materials for organic EL, base film substrates for solar cells in the aerospace field, coating materials for solar cells and thermal control systems, electronic elements such as semiconductor elements, light-emitting diodes, various types of memories, hybrid ICs, MCMs, circuit boards, prepregs and laminates used to form insulating layers for circuit boards, display components, etc. It can be used in applications such as insulating materials, substrates for liquid crystal displays and solar cells, medical instruments, automotive components, release agents, resin modifiers, transparent substrates for displays, lithium ion battery components, semiconductor process components, film capacitors, gas barrier coating materials, electric wire coating materials, automotive components, aerospace components, semiconductor process materials, electric wire coating materials, lithium ion battery components, fuel cell components, capacitor films, flexible display components, anchor coating materials, transparent adhesives, modifiers, crosslinking aids, medical containers, medical catheter components, waterproof sealants, release agents, hard coating materials, and foam modifiers. In particular, since the dielectric properties are excellent in stability over time, and the properties are also excellent in solvent resistance, heat resistance, transparency, mechanical properties, etc., the film can be suitably used for high frequency applications such as high frequency circuit boards, etc. Furthermore, since the film has excellent gas barrier properties, the film can be suitably used as a substrate for liquid crystal displays and a substrate, film, or sheet for solar cells.

[0081] 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 of achieving the object of the present invention are included in the present invention. [Example]

[0082] The present invention will be explained in more detail below by way of synthesis examples and examples, but the present invention is not limited thereto in any way.

[0083] The composition of the cyclic olefin copolymer (m) used in the synthesis examples, working examples, and comparative examples was measured by the method described below.

[0084] [Method for measuring the content of each structural unit constituting a cyclic olefin copolymer] The contents of the structural unit (A), the structural unit (B), the structural unit (C) and the structural unit (D) were measured using a nuclear magnetic resonance spectrometer "EXcalibur270" manufactured by JEOL Ltd. under the following conditions. Number of times accumulated: 16 to 64 times Measurement temperature: room temperature The results obtained from the above measurements 1 From the H-NMR spectrum, the peak intensities were calculated from the peaks derived from hydrogen directly bonded to the double bond carbon and the peaks derived from other hydrogen atoms.

[0085] The number average molecular weight (Mn) of the cyclic olefin copolymer (m) used in the synthesis examples, examples, and comparative examples was measured by GPC and calculated as a standard polystyrene equivalent. The GPC measurement was carried out under the following conditions. Apparatus: GPC HLC-8321 (Tosoh Corporation) Solvent: o-dichlorobenzene Columns: TSKgel GMH6-HT x 2, TSKgel GMH6-HTL x 2 (both manufactured by Tosoh Corporation) Flow rate: 1.0ml / min Sample: 1 mg / mL o-dichlorobenzene solution Temperature: 140℃

[0086] The following raw materials were used in the experiment:

[0087] Transition metal compounds (1): It was synthesized by the method described in JP-A-2004-331965.

[0088] [ka]

[0089] Ethylene (Sumitomo Seika Chemicals) Modified methylaluminoxane (MMAO, manufactured by Tosoh Finechem Co., Ltd.) Toluene (Wako Pure Chemical Industries, Ltd.: Wako Special Grade) 5-vinyl-2-norbornene (Tokyo Chemical Industry Co., Ltd.) 2-Norbornene (Tokyo Chemical Industry Co., Ltd.) Acetone (Wako Pure Chemical Industries, Ltd.: Wako Special Grade) Methanol (Wako Pure Chemical Industries, Ltd.: Wako Special Grade)

[0090] Initiator 1: Percumyl D (manufactured by NOF Corporation) Antioxidant 1: Irganox 1010 (manufactured by BASF)

[0091] Cyclic olefin copolymer (m): [Synthesis Example 1: Cyclic Olefin Copolymer (m-1)] A 1 L stainless steel autoclave was thoroughly purged with nitrogen and charged with 372 mL of toluene, 95 mL of 5-vinyl-2-norbornene (hereinafter referred to as VNB), 33 mL of a 5 M toluene solution of 2-norbornene (hereinafter referred to as NB), 1.5 mmol of a hexane solution of MMAO (calculated as Al), and 1116 mL of hydrogen. Ethylene was then introduced into the system until the total pressure reached 0.78 MPaG. Polymerization was initiated by adding 4 μmol of transition metal compound (1) dissolved in toluene. After reacting for 40 minutes at 35 °C, an additional 4 μmol of transition metal compound (1) was added. This process of adding 4 μmol of transition metal compound (1) every 30 minutes was repeated twice more for a total of 130 minutes. The polymerization was then terminated by adding a small amount of methanol. After polymerization, ion-exchanged water was added to the resulting polymer solution and stirred for 1 hour. The organic layer was then filtered through filter paper. The organic layer was poured into acetone to precipitate the polymer, which was then stirred and filtered through filter paper. The resulting polymer was dried under reduced pressure at 80°C for 10 hours to obtain an ethylene / NB / VNB copolymer. NMR analysis revealed that the NB-derived structure in the polymer was 13 mol% and the VNB-derived structure was 35 mol%. GPC analysis revealed that the number-average molecular weight (Mn) was 11,000.

[0092] [Synthesis Example 2: Cyclic Olefin Copolymer (m-2)] An ethylene / NB / VNB copolymer was obtained in the same manner as in Synthesis Example 1, except that 410 mL of toluene, 50 mL of VNB, and 40 mL of NB (5 M toluene solution) were used. The compositional ratio of NB-derived structures in the polymer determined by NMR was 21 mol%, the compositional ratio of VNB-derived structures was 20 mol%, and the number average molecular weight (Mn) determined by GPC measurement was 10,000.

[0093] [Synthesis Example 3: Cyclic Olefin Copolymer (m-3)] An ethylene / NB / VNB copolymer was obtained in the same manner as in Synthesis Example 1, except that 433 mL of toluene, 15 mL of VNB, 52 mL of NB (5 M toluene solution), and 1488 mL of hydrogen were used. NMR determined the composition ratio of NB-derived structures in the polymer to be 33 mol%, the composition ratio of VNB-derived structures to be 10 mol%, and the number average molecular weight (Mn) determined by GPC measurement to be 7,500.

[0094] [Synthesis Example 4: Cyclic Olefin Copolymer (m-4)] An ethylene / NB / VNB copolymer was obtained in the same manner as in Synthesis Example 1, except that 444 mL of toluene, 7 mL of VNB, and 49 mL of NB (5 M toluene solution) were used. The composition ratio of NB-derived structures in the polymer determined by NMR was 37 mol%, the composition ratio of VNB-derived structures was 6 mol%, and the number average molecular weight (Mn) determined by GPC measurement was 11,100.

[0095] [Synthesis Example 5: Cyclic Olefin Copolymer (m-5)] An ethylene / NB / VNB copolymer was obtained in the same manner as in Synthesis Example 1, except that 460 mL of toluene, 16 mL of VNB, 55 mL of NB (5 M toluene solution), and 744 mL of hydrogen were used. The composition ratio of NB-derived structures in the polymer determined by NMR was 32 mol%, the composition ratio of VNB-derived structures was 9 mol%, and the number average molecular weight (Mn) determined by GPC measurement was 20,000.

[0096] [Synthesis Example 6: Cyclic olefin copolymer (m-6)] In a 1 L stainless steel autoclave that had been thoroughly purged with nitrogen, 410 mL of toluene, 19 mL of VNB, and tetracyclo[4.4.0.1 2,5 .1 7,10After adding 71 ml of ]-3-dodecene (hereinafter also referred to as TD), 1.5 mmol of a toluene solution of MMAO (manufactured by Tosoh Finechem Co., Ltd.) in terms of Al, and 744 ml of hydrogen, ethylene was introduced into the system until the total pressure reached 0.78 MPa. 33 μmol of transition metal compound (1) dissolved in toluene was added, and polymerization was carried out at 35°C for 180 minutes. The polymerization was then terminated by adding a small amount of methanol. After polymerization, ion-exchanged water was added to the resulting polymer solution and stirred for 1 hour. The organic layer was then filtered through filter paper. This organic layer was poured into acetone 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 an ethylene / TD / VNB copolymer. NMR determined the polymer to have a TD-derived structure of 30 mol% and a VNB-derived structure of 12 mol%, and the number-average molecular weight (Mn) determined by GPC measurement was 11,300.

[0097] [Synthesis Example 7: Cyclic olefin copolymer (m-7)] An ethylene / TD / VNB copolymer was obtained in the same manner as in Synthesis Example 6, except that the amount of toluene was 377 mL, the amount of VNB was 73 mL, and the amount of TD was 50 mL. The composition ratio of the TD-derived structure in the polymer determined by NMR was 15 mol%, the composition ratio of the VNB-derived structure was 28 mol%, and the number average molecular weight (Mn) determined by GPC measurement was 10,500.

[0098] [Synthesis Example 8: Cyclic olefin copolymer (m-8)] A 1 L stainless steel autoclave was thoroughly purged with nitrogen and charged with 340 mL of toluene, 35 mL of VNB, 82 mL of NB (5 M toluene solution), 44 mL of TD, a hexane solution of MMAO (2 mmol Al equivalent), and 558 mL of hydrogen. Ethylene was then introduced into the system until the total pressure reached 0.52 MPaG. Polymerization was initiated by adding 4.7 μmol of transition metal compound (1) dissolved in toluene. After 40 minutes of reaction at 35°C, 9.3 μmol of transition metal compound (1) was added, and after another 30 minutes, 9.3 μmol of transition metal compound (1) was added and the reaction was continued for 30 minutes, for a total of 100 minutes. The polymerization was then terminated by adding a small amount of methanol. After polymerization, ion-exchanged water was added to the resulting polymer solution and stirred for 1 hour. The organic layer was then filtered through filter paper. The organic layer was poured into acetone to precipitate the polymer, which was then stirred and filtered through filter paper. The resulting polymer was dried under reduced pressure at 80°C for 10 hours to obtain an ethylene / TD / NB / VNB copolymer. The composition ratio of the TD-derived structure in the polymer determined by NMR was 14 mol%, the composition ratio of the NB-derived structure was 17 mol%, and the composition ratio of the VNB-derived structure was 10 mol%, and the number average molecular weight (Mn) calculated by GPC measurement was 8,400.

[0099] [Example 1] Each varnish was prepared by the method described below and evaluated.

[0100] (Preparation of 45% toluene varnish) To 4.4 g of toluene, 3.6 g of the cyclic olefin copolymer (m-1) obtained in Synthesis Example 1 was added and stirred overnight to obtain a varnish-like cyclic olefin copolymer resin composition (45% toluene varnish).

[0101] (Solvent solubility: measurement of varnish viscosity) The viscosity of the 45% toluene varnish obtained in the above (Preparation of 45% toluene varnish) was measured. It was measured using an E-type viscometer, and the viscosity was calculated from the value at a torque of 20% or the closest rotation speed after preheating. The results are shown in Table 1. The measurements were carried out under the following conditions: Device: TVE-25H (manufactured by Toki Sangyo Co., Ltd.) Measuring cone: 1°34×R24

[0102] Regarding the impregnation of 45% toluene varnish, those with a viscosity of 100 or more but less than 500 (mPa·s) were rated "A," those with a viscosity of 500 or more but less than 1000 (mPa·s) were rated "B," and those with a viscosity of 1000 or more (mPa·s) or those with residual dissolution were rated "C."

[0103] (Preparation of 20% toluene varnish) The cyclic olefin copolymer (m-1) obtained in Synthesis Example 1, initiator 1 (Percumyl D manufactured by NOF Corporation) as a radical polymerization (crosslinking) initiator, antioxidant 1 (Irganox 1010 manufactured by BASF) as an antioxidant, and toluene as a solvent were weighed out according to the contents in Table 1. The weighed sample was stirred until fully dissolved, thereby obtaining a varnish-like cyclic olefin copolymer resin composition (20% toluene varnish). The content of each raw material in Table 1 is expressed in parts by mass.

[0104] (film production) The 20% toluene varnish obtained in the above (Preparation of 20% toluene varnish) according to the content in Table 1 was coated onto a release-treated PET film in the longitudinal direction at a speed of 10 mm / sec, and then dried in a nitrogen gas stream in a blower dryer at 150°C for 4 minutes. Two of the obtained films were stacked, pressurized to 3.5 MPa in a vacuum press, heated from room temperature (25°C) at a constant rate, and held at 180°C for 120 minutes to obtain a laminated film.

[0105] <Dielectric loss tangent> The dielectric loss tangent at 10 GHz of the film obtained in the above (film formation) was measured by the cylindrical cavity resonator method in accordance with JIS R1641. In this case, dielectric loss tangent less than 0.0010 was evaluated as "A", and dielectric loss tangent tangent of 0.0010 or more was evaluated as "B". In addition, those that could not be measured were marked as "C". The results are shown in Table 1.

[0106] [Examples 2 to 4 and Comparative Examples 1 to 4] A 20% toluene varnish, a 45% toluene varnish, and a film were prepared and evaluated in the same manner as in Example 1, except that the content of each component was changed to the content shown in Table 1. The results obtained are shown in Table 1. In Comparative Examples 2 and 3, residual cyclic olefin copolymer remained during the preparation of the 45% toluene varnish, and the 45% toluene varnish could not be obtained. Therefore, for Comparative Examples 2 and 3, it was impossible to measure the viscosity of the varnish using the 45% toluene varnish.

[0107] Furthermore, in Comparative Example 3, a varnish-like cyclic olefin copolymer composition (20% toluene varnish) was obtained, but in Comparative Example 2, a varnish-like cyclic olefin copolymer composition (20% toluene varnish) was not obtained either. For the above reasons, it was not possible to measure the dielectric loss tangent in Comparative Example 2, and therefore the result of Comparative Example 2 in Table 1 is marked as "measurable."

[0108] [Table 1]

[0109] In Examples 1 to 4, it was possible to obtain crosslinked bodies with excellent dielectric properties in the high frequency range, which are suitable for circuit boards, etc., and even when varnishes were prepared containing a large amount of cyclic olefin copolymer, low viscosity was maintained. On the other hand, in Comparative Examples 1 to 4, when varnishes were prepared containing a large amount of cyclic olefin copolymer, the cyclic olefin copolymer did not dissolve completely, or even if it did dissolve, the viscosity was high, resulting in poor impregnation properties.

[0110] This application claims priority based on Japanese Patent Application No. 2022-016604, filed February 4, 2022, the disclosure of which is incorporated herein by reference in its entirety.

Claims

1. (A) one or more olefin-derived structural units (A) represented by the following general formula (I), (B) one or more structural units (B) derived from a cyclic non-conjugated diene represented by the following general formula (II), (C) one or more structural units (C) derived from cyclic olefins represented by the following general formula (III), A cyclic olefin copolymer comprising: When the total number of moles of the structural units (A), (B), and (C) in the cyclic olefin copolymer is taken as 100 mol%, the total content of the structural unit (B) derived from the cyclic non-conjugated diene and the structural unit (C) derived from the cyclic olefin is in the range of 40.0 mol% or more and 49.0 mol% or less; The number average molecular weight Mn is 3,000 or more and 16,000 or less, A cyclic olefin copolymer which does not contain one or more structural units (D) derived from cyclic olefins represented by the following general formula (V): 【Chemistry 1】 (In general 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 general formula (II), u is 0 or 1, v is 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.) 【Transformation 3】 (In general formula (III), R １ ~R ８ are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 4 or less carbon atoms, and R ５ ~R ８ may be bonded to each other to form a single ring, and the single ring may have a double bond, and R ５ and R ６ With or R ７ and R ８ and may form an alkylidene group.) 【Chemistry 4】 (In general formula (V), u is 0 or 1, v is 0 or a positive integer, u+v is 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.

2. The cyclic olefin copolymer according to claim 1, When the total number of moles of the structural unit (A), the structural unit (B), and the structural unit (C) in the cyclic olefin copolymer is taken as 100 mol%, A cyclic olefin copolymer in which the content of the structural unit (B) derived from the cyclic non-conjugated diene is 5 mol % or more and 40 mol % or less.

3. The cyclic olefin copolymer according to claim 1 or 2, The cyclic non-conjugated diene constituting the structural unit (B) derived from the cyclic non-conjugated diene contains 5-vinyl-2-norbornene.

4. The cyclic olefin copolymer according to claim 1 or 2, The cyclic olefin constituting the cyclic olefin-derived structural unit (C) contains bicyclo[2.2.1]-2-heptene.

5. A cyclic olefin copolymer composition comprising the cyclic olefin copolymer according to claim 1 or 2.

6. A varnish comprising the cyclic olefin copolymer composition according to claim 5 and a solvent.

7. A crosslinked product obtained by crosslinking the cyclic olefin copolymer composition according to claim 5.

8. A film or sheet comprising the crosslinked product according to claim 7.

9. A laminate comprising the crosslinked product according to claim 7.

10. A circuit board comprising an electrical insulating layer containing the crosslinked product according to claim 7 and a conductor layer provided on the electrical insulating layer.

11. An electronic device comprising the circuit board according to claim 10.

12. A prepreg comprising the cyclic olefin copolymer according to claim 1 or 2 and a sheet-like fiber substrate.

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