Method for producing varnish-like cyclic olefin copolymer composition, cyclic olefin copolymer composition, crosslinked product, film, or sheet, laminate, circuit board, electronic device, and prepreg

Abstract

A method for producing a varnish-like cyclic olefin copolymer composition containing a cyclic olefin copolymer (m) and an organic solvent, wherein the method for producing a varnish-like cyclic olefin copolymer composition is characterized in that the cyclic olefin copolymer (m) contains (A) one or more repeating units derived from an olefin, (B) one or more repeating units derived from a cyclic unconjugated diene, and (C) one or more repeating units derived from a cyclic olefin; the method includes a polymerization step that copolymerizes the olefin, cyclic unconjugated diene, and cyclic olefin in the presence of a catalyst for olefin polymerization containing a transition metal compound (A) and a compound (B); the transition metal compound (A) contains one or more selected from transition metal compounds (A-1) and transition metal compounds (A-2); and the compound (B) contains one or more selected from the group consisting of organic metal compounds (B-1), organic aluminum oxy compounds (B-2), and compounds (B-3) that react with the transition metal compound (A) to form an ion pair.

Description

Method for producing varnish-like cyclic olefin copolymer composition, cyclic olefin copolymer composition, crosslinked product, film or sheet, laminate, circuit board, electronic device, and prepreg

[0001] The present invention relates to a method for producing a cyclic olefin copolymer composition in the form of a varnish, a cyclic olefin copolymer composition, a crosslinked product, a film or sheet, a laminate, a circuit board, an electronic device, and a prepreg.

[0002] Recently, the number of wireless communication devices using high frequency bands has increased, and the increasing speed of communication has inevitably led to the increased use of higher frequency bands. As a result, there is a demand for circuit boards with a small dielectric loss tangent to minimize transmission loss at high frequencies.

[0003] 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 that exhibit excellent fluidity during heating and solvent solubility.

[0004] JP 2010-100843 A, International Publication No. 2012 / 046443, JP 2019-081898 A, International Publication No. 2021 / 149713

[0005] Incoronata Tritto, Laura Boggioni, Cristina Zampa, and Dino R. Ferro, “Ethylene-Norbornen Copolymers by Cs-Symmetric Metallocenes: Determination of the Copolymerization Parameters and Mechanistic Considerations on the Basis of Tetrad Analysis” Macromolecules, 2005, 38, 9910-9919.

[0006] The inventors' studies have revealed that the cycloolefin copolymers having crosslinkable groups, such as those described in Patent Documents 1 and 2, have room for further improvement in toluene solubility when the cycloolefin copolymer contains a large amount (high solid content). It is believed that improving toluene solubility at high solid content would further improve impregnation into fiber substrates during circuit board production. Furthermore, the cycloolefin copolymers having crosslinkable groups described in Patent Documents 3 and 4 exhibit improved fluidity and solubility, but gelation occurs when dissolved in toluene at a high cycloolefin copolymer content (high solid content) and allowed to stand at room temperature, resulting in impaired fluidity. Impaired fluidity poses problems related to varnish management methods and the impairment of stable impregnation into fiber substrates during circuit board production. That is, the inventors' studies have revealed that the inventions described in Patent Documents 3 and 4 have room for further improvement in terms of maintaining a solution state even in varnishes containing a large amount of cycloolefin copolymers having crosslinkable groups.

[0007] The present invention has been made in view of the above circumstances, and provides a method for producing a varnish-like cyclic olefin copolymer composition that can maintain a solution state for a longer period of time even when it contains a large amount of a cyclic olefin copolymer having a crosslinkable group (high solid content).

[0008] As a result of intensive research to solve the above problems, the present inventors have found that by improving the method for producing a cyclic olefin copolymer, it is possible to prepare a varnish that can maintain a solution state for a longer period of time even when it contains a large amount of a cyclic olefin copolymer having a crosslinkable group (high solids content), and have completed the present invention.

[0009] That is, according to the present invention, there are provided a method for producing a varnish-like cyclic olefin copolymer composition, a cyclic olefin copolymer composition, a crosslinked product, a film or sheet, a laminate, a circuit board, an electronic device, and a prepreg, which are shown below.

[0010] 1. A method for producing a varnish-like cyclic olefin copolymer composition comprising a cyclic olefin copolymer (m) and an organic solvent, wherein the cyclic olefin copolymer (m) comprises: (A) one or more olefin-derived repeating units represented by the following general formula (I), (B) one or more cyclic non-conjugated diene-derived repeating units represented by the following general formula (III), and (C) one or more cyclic olefin-derived repeating units represented by the following general formula (V), [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. [In the above general 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. [In the above general 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 ７８may be bonded to each other to form a monocycle or polycycle.] The method comprises a polymerization step of copolymerizing an olefin, a cyclic non-conjugated diene, and a cyclic olefin in the presence of an olefin polymerization catalyst containing a transition metal compound (A) and a compound (B), wherein the transition metal compound (A) contains one or more selected from the group consisting of a transition metal compound (A-1) represented by the following formula (II), and a transition metal compound (A-2) represented by the following formula (VI), [In the formula (II), M ２ represents a transition metal atom of Group 4 of the periodic table, and n １ represents an integer of 1 to 3; each L independently represents a monovalent anionic ligand having an atom of Group 15 of the periodic table as a coordinating atom; X １ each independently represents a group or atom selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and substitution products thereof; R ５ ~R ９ each independently represents a group or atom selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and a substitution product thereof; R ５ ~R ９ Any two or three of these may be fused to form a ring, and the ring formed may have aromaticity and contain a conjugated double bond.] [In the formula (VI), M ３ represents a transition metal atom of Group 4 of the periodic table, and n ２ represents an integer of 1 to 4, and X ２ each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and substitution products thereof; R １０ ~R １７each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and the group consisting of substituted groups thereof; R １０ ~R １７ adjacent ones of the compounds may be bonded to each other to form a ring, and the ring formed may have aromaticity including a conjugated double bond.] A method for producing a varnish-like cyclic olefin copolymer composition, characterized in that the compound (B) contains one or more compounds selected from the group consisting of an organometallic compound (B-1), an organoaluminum oxy compound (B-2), and a compound (B-3) that reacts with the transition metal compound (A) to form an ion pair. 2. The production method according to 1., wherein the content of the cyclic olefin copolymer (m) in the varnish-like cyclic olefin copolymer composition is 30 mass% or more. 3. The production method according to 1. or 2., wherein the organic solvent contains at least one solvent selected from the group consisting of aromatic hydrocarbon solvents, cyclic hydrocarbon solvents, linear hydrocarbon solvents, and halogenated aromatic hydrocarbon solvents. 4. The production method according to any one of 1. to 3., wherein, when the total number of moles of repeating units in the cyclic olefin copolymer (m) is taken as 100 mol%, the content of the olefin-derived repeating unit (A) is 10 mol% to 90 mol%, the content of the cyclic non-conjugated diene-derived repeating unit (B) is 1 mol% to 40 mol%, and the content of the cyclic olefin-derived repeating unit (C) is 1 mol% to 50 mol%. 5. The production method according to any one of 1. to 4., wherein the cyclic non-conjugated diene constituting the cyclic non-conjugated diene-derived repeating unit (B) includes 5-vinyl-2-norbornene. 6. The production method according to any one of 1. to 4., wherein the cyclic olefin constituting the cyclic olefin-derived structural unit (C) is tetracyclo[4.4.0.1 ２，５ .1 ７，１０7. The method according to any one of 1. to 6., further comprising a catalyst removal step of removing the olefin polymerization catalyst. 8. The method according to any one of 1. to 6., further comprising a step of removing the olefin polymerization catalyst from the cyclic olefin copolymer (m). １３ In the C-NMR spectrum, the integral value of the signal in the range of 43.8 ppm to 45.0 ppm is expressed as X Ｃ , the integral value of the signal in the range of 40.3 ppm to 41.3 ppm is Y Ａ , the integral value of the signal in the range of 38.4 ppm to 39.9 ppm is expressed as X Ｂ , then (X Ｂ -X Ｃ ) / Y Ａ The production method according to any one of 1. to 7., wherein the value of is 0.2 or more and 2.0 or less. 9. The production method according to any one of 1. to 8., wherein the cyclic olefin copolymer (m) has a glass transition temperature of 100°C or more as measured by a differential scanning calorimeter (DSC). 10. A cyclic olefin copolymer composition obtained by the production method according to any one of 1. to 9.. 11. A crosslinked body obtained by crosslinking the cyclic olefin copolymer composition according to 10.. 12. A film or sheet comprising the crosslinked body according to 11.. 13. A laminate obtained by laminating the film or sheet according to 12. on a substrate. 14. A circuit board comprising an electrical insulating layer comprising the crosslinked body according to 11., and a conductor layer provided on the electrical insulating layer. 15. An electronic device comprising the circuit board according to 14.. 16. A prepreg comprising the cyclic olefin copolymer composition according to 10. and a sheet-like fiber substrate. 17. A varnish-like cyclic olefin copolymer composition comprising a cyclic olefin copolymer (m) and an organic solvent, wherein the cyclic olefin copolymer (m) comprises: (A) one or more olefin-derived repeating units represented by the following general formula (I); (B) one or more cyclic non-conjugated diene-derived repeating units represented by the following general formula (III); and (C) one or more cyclic olefin-derived repeating units represented by the following general formula (V): [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. [In the above general 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. [In the above general 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.] １３ In the C-NMR spectrum, the integral value of the signal in the range of 43.8 ppm to 45.0 ppm is expressed as X Ｃ , the integral value of the signal in the range of 40.3 ppm to 41.3 ppm is Y Ａ The sum of the integral values ​​of the signals in the range of 38.4 ppm to 39.9 ppm is X Ｂ , then (X Ｂ -X Ｃ ) / Y Ａ18. The cyclic olefin copolymer composition in the form of a varnish according to 16., wherein the cyclic olefin copolymer (m) has a glass transition temperature of 100°C or higher as measured by a differential scanning calorimeter (DSC). 19. The cyclic olefin copolymer composition in the form of a varnish according to 17. or 18., wherein the content of the cyclic olefin copolymer (m) in the varnish-like cyclic olefin copolymer composition is 30% by mass or higher. 20. The cyclic olefin copolymer composition in the form of a varnish according to any one of 17. to 19., wherein the organic solvent comprises at least one solvent selected from the group consisting of aromatic hydrocarbon solvents, cyclic hydrocarbon solvents, linear hydrocarbon solvents, and halogenated aromatic hydrocarbon solvents. 21. The varnish-like cyclic olefin copolymer composition according to any one of 17. to 20., wherein, when the total number of moles of repeating units in the cyclic olefin copolymer (m) is taken as 100 mol%, the content of the olefin-derived repeating unit (A) is 10 mol% to 90 mol%, the content of the cyclic non-conjugated diene-derived repeating unit (B) is 1 mol% to 40 mol%, and the content of the cyclic olefin-derived repeating unit (C) is 1 mol% to 50 mol%. 22. The varnish-like cyclic olefin copolymer composition according to any one of 17. to 21., wherein the cyclic non-conjugated diene constituting the cyclic non-conjugated diene-derived repeating unit (B) includes 5-vinyl-2-norbornene. 23. The varnish-like cyclic olefin copolymer composition according to any one of 17. to 21., wherein the cyclic olefin constituting the cyclic olefin-derived structural unit (C) is tetracyclo[4.4.0.1 ２，５ .1 ７，１０ 24. The varnish-like cyclic olefin copolymer composition according to any one of 17. to 22., comprising at least one selected from the group consisting of tetracyclo[4.4.0.1]-3-dodecene and bicyclo[2.2.1]-2-heptene. 25. The olefin constituting the olefin-derived repeating unit (A) contains ethylene, the cyclic non-conjugated diene constituting the cyclic non-conjugated diene-derived repeating unit (B) contains 5-vinyl-2-norbornene, and the cyclic olefin constituting the cyclic olefin-derived structural unit (C) is tetracyclo[4.4.0.1]-3-dodecene and bicyclo[2.2.1]-2-heptene. ２，５ .1 ７，１０26. A film or sheet comprising the crosslinked product according to claim 25. 27. A laminate obtained by laminating the film or sheet according to claim 26. on a substrate. 28. A circuit board comprising an electrical insulating layer comprising the crosslinked product according to claim 25., and a conductor layer provided on the electrical insulating layer. 29. An electronic device comprising the circuit board according to claim 28. 30. A prepreg comprising the varnish-form cyclic olefin copolymer composition according to any of claims 17. to 24., and a sheet-like fiber substrate.

[0011] According to the present invention, there can be provided a method for producing a varnish-like cyclic olefin copolymer composition that can maintain a solution state for a longer period of time even when it contains a large amount of a cyclic olefin copolymer having a crosslinkable group (high solid content).

[0012] The present invention will be described below based on embodiments. In the present embodiments, "A to B" indicating a numerical range means A or more and B or less unless otherwise specified. When a numerical range is described in stages, the upper and lower limits of each numerical range can be combined arbitrarily. Each monomer constituting the cyclic olefin copolymer according to the present invention may be a monomer obtained from a fossil raw material, or a monomer obtained from an animal or plant raw material.

[0013] [Method for producing a cyclic olefin copolymer composition in varnish form] Hereinafter, a method for producing a cyclic olefin copolymer composition in varnish form will be described.

[0014] The method for producing a varnish-like cyclic olefin copolymer composition of this embodiment is a method for producing a varnish-like cyclic olefin copolymer composition containing a cyclic olefin copolymer (m) and an organic solvent, and includes a polymerization step of copolymerizing an olefin, a cyclic non-conjugated diene, and a cyclic olefin in the presence of an olefin polymerization catalyst containing a transition metal compound (A) and a compound (B). By carrying out polymerization in the presence of an olefin polymerization catalyst containing a transition metal compound (A) and a compound (B), it is possible to obtain a varnish-like cyclic olefin copolymer composition that can maintain a solution state even when it contains a large amount of a cyclic olefin copolymer having a crosslinkable group (high solids content).

[0015] <Olefin Polymerization Catalyst> The olefin polymerization catalyst contains a transition metal compound (A) and a compound (B).

[0016] <Transition Metal Compound (A)> The transition metal compound (A) contains one or more compounds selected from the group consisting of a transition metal compound (A-1) represented by the following formula (II) and a transition metal compound (A-2) represented by the following formula (VI). The transition metal compound (A) preferably contains a transition metal compound (A-2) represented by the following formula (VI).

[0017] (Transition Metal Compound (A-1)) The transition metal compound (A-1) is represented by the following formula (II).

[0018]

[0019] In the above formula (II), M ２ indicates a transition metal in Group 4 of the periodic table. ２ Examples of M include a titanium atom, a zirconium atom, and a hafnium atom. ２ is preferably a titanium atom or a zirconium atom, and more preferably a titanium atom.

[0020] n １ represents an integer of 1 to 3. １ is M ２ Valence and X １is selected depending on the type of the transition metal compound (A-1) represented by formula (II) so that the entire compound is electrically neutral. １ is preferably 2.

[0021] Each L independently represents a monovalent anionic ligand having an atom of Group 15 of the periodic table as a coordinating atom. L is preferably a monovalent anionic ligand represented by formula (IV).

[0022]

[0023] In the above formula (IV), Y represents an atom of Group 15 of the periodic table. Examples of Y include a nitrogen atom, a phosphorus atom, and an arsenic atom. Y is preferably a nitrogen atom.

[0024] Z represents one type of atom selected from Group 14, Group 15, or Group 16 of the periodic table. Examples of Z include a carbon atom or a silicon atom, etc., which belong to Group 14; a nitrogen atom, a phosphorus atom, or an arsenic atom, etc., which belong to Group 15; and an oxygen atom or a sulfur atom, etc., which belong to Group 16. Z is preferably a carbon atom or a nitrogen atom, and more preferably a carbon atom.

[0025] n ３ represents an integer of 1 to 3. ３ is the valence of Z and R １８ Depending on the type of n, the monovalent anionic ligand represented by formula (IV) is selected so that the entire ligand is electrically neutral. ２ is preferably 1 or 2, and more preferably 2.

[0026] R １８ each independently represents a group or atom selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and the group consisting of substituted groups thereof, and each may be bonded to each other to form a ring, and the formed ring may have aromaticity including a conjugated double bond, or the formed ring may be bonded to a cyclopentadienyl group.

[0027] R １８Examples of the halogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups and aluminum-containing groups represented by R ３ and R ４ Examples of the halogen atom include a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, as well as those exemplified as substituents thereof. １８ Examples of structures in which the groups bond to each other to form a ring and the formed ring is bonded to a cyclopentadienyl group include the following:

[0028]

[0029] R １８ is a group selected from the group consisting of hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups, and aluminum-containing groups, and substitution products thereof; １９ Each of the groups independently preferably has 1 to 20 carbon atoms, and more preferably has 1 to 10 carbon atoms.

[0030] R １８ are each independently preferably an atom or group selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an amide group, an aryl group, an aralkyl group, a silyl group, an alkylamide group, an alkylsilyl group, an arylamide group, a silylamide group, a phosphinoamide group, and a phosphido group, and a substituted product thereof; more preferably an alkyl group, a cycloalkyl group, or an aryl group, or a substituted product thereof; even more preferably a t-butyl group, a tricyclodecane group, or a phenyl group, or a substituted product thereof; and even more preferably a t-butyl group.

[0031] X １each independently represents a group or atom selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and substitution products thereof.

[0032] X １ Examples of the halogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups and aluminum-containing groups represented by R ３ and R ４ Examples of the halogen atom include a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, as well as those exemplified as substitution products thereof.

[0033] X １ is a group selected from the group consisting of hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups, and aluminum-containing groups, and substitution products thereof; １ The number of carbon atoms in each of X is preferably 1 to 20, and more preferably 1 to 10. １ is preferably a halogen atom, more preferably a chlorine atom.

[0034] R ５ ~R ９ each independently represents a group or atom selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and a substitution product thereof; R ５ ~R ９ Any two or three of these may be condensed to form a ring, and the ring formed may have aromaticity containing a conjugated double bond.

[0035] R ５ ~R ９Examples of the halogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups and aluminum-containing groups represented by R ３ and R ４ Examples of the halogen atom include a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, as well as those exemplified as substitution products thereof.

[0036] R ５ ~R ９ is a group selected from the group consisting of hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups, and aluminum-containing groups, and substitution products thereof; ５ ~R ９ The number of carbon atoms in each of R is preferably 1 to 20, and more preferably 1 to 10. ５ ~R ９ is preferably a hydrogen atom.

[0037] (Transition Metal Compound (A-2)) The transition metal compound (A-2) is represented by the following formula (VI).

[0038]

[0039] In the above formula (VI), M ３ indicates a transition metal in Group 4 of the periodic table. ３ Examples of the atom include a titanium atom, a zirconium atom, and a hafnium atom.

[0040] M ３ is preferably a titanium atom or a zirconium atom, and more preferably a titanium atom.

[0041] n ２ represents an integer of 1 to 4. ２ is M ３ Valence and X ２ is selected depending on the type of n so that the transition metal compound (A-2) represented by formula (VI) as a whole is electrically neutral. ２is preferably 2.

[0042] X ２ each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a silicon-containing group, and a boron-containing group, and substitution products thereof.

[0043] X ２ Examples of the halogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups and aluminum-containing groups represented by R ３ and R ４ Examples of the halogen atom include a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, as well as those exemplified as substitution products thereof.

[0044] X ２ is a group selected from the group consisting of hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups, and aluminum-containing groups, and substitution products thereof; ２ The number of carbon atoms in each of X is preferably 1 to 20, and more preferably 1 to 10. ２ is preferably a halogen atom, more preferably a chlorine atom.

[0045] R １０ ~R １７ each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a silicon-containing group, and a boron-containing group, and the group consisting of substituted groups thereof; R １０ ~R １４ Adjacent ones of these may be bonded to each other to form a ring, and the ring formed may have aromaticity containing a conjugated double bond.

[0046] R １０ ~R １７Examples of the halogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups and aluminum-containing groups represented by R ３ and R ４ Examples of the halogen atom include a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, as well as those exemplified as substitution products thereof.

[0047] R １０ ~R １７ is a group selected from the group consisting of hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups, and aluminum-containing groups, and substitution products thereof; １０ ~R １７ Each of the groups independently preferably has 1 to 20 carbon atoms, and more preferably has 1 to 10 carbon atoms.

[0048] R １０ ~R １７ Specific examples of the combination of R １０ ~R １４ and R １７ are each independently an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, and a silicon-containing group, and substitution products thereof, and R １５ and R １６ R is preferably an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, and a substitution product thereof. １０ ~R １４ Adjacent ones of these may be bonded to each other to form a ring, and the ring formed may have aromaticity containing a conjugated double bond.

[0049] R １０ ~R １７ Specific examples of the combination of R １０ ~R １４ and R １７are each independently a hydrogen atom or a hydrocarbon group, and R １５ and R １６ are each independently a hydrogen atom, a hydrocarbon group, or a halogen-containing hydrocarbon group.

[0050] R １０ ~R １７ Specific examples of the combination of R １０ ~R １４ and R １７ are each independently a hydrogen atom, an alkyl group, or a cyclic hydrocarbon group to which two or more substituents are bonded, and R １５ and R １６ and are each independently a hydrogen atom, a hydrocarbon group, or a halogen-containing alkyl group.

[0051] R １０ ~R １７ Specific examples of the combination of R １０ ~R １４ and R １７ are each independently a hydrogen atom or a t-butyl group, and R １５ and R １６ are each independently a hydrogen atom or an isopropyl group.

[0052] R １０ ~R １７ Specific examples of the combination of R １０ ~R １４ are each independently a hydrogen atom, a branched alkyl group, or a cyclic hydrocarbon group to which two or more substituents are bonded, and R １５ and R １６ are each independently hydrogen, a cyclic hydrocarbon group, a branched alkyl group, or a halogen-containing alkyl group, and R １７ is preferably a hydrogen atom, a branched alkyl group or a halogen-containing alkyl group.

[0053] <Compound (B)> Compound (B) contains one or more compounds selected from the group consisting of organometallic compounds (B-1), organoaluminum oxy compounds (B-2), and compounds (B-3) that react with the transition metal compounds represented by formula (II) above or the transition metal compounds represented by formula (VI) above to form an ion pair. Compound (B) preferably contains one or more compounds selected from the group consisting of organoaluminum oxy compounds (B-2) and compounds (B-3) that react with the transition metal compound (A) to form an ion pair, and more preferably contains both the organoaluminum oxy compound (B-2) and the compound (B-3) that reacts with the transition metal compound (A) to form an ion pair.

[0054] (Organometallic Compound (B-1)) Examples of the organometallic compound (B-1) (hereinafter also referred to as "component (B-1)") include organometallic compounds of Groups 1, 2, 12, and 13, such as organoaluminum compounds (B-1a) represented by general formula (B-1a), complex alkyl compounds of Group 1 metals and aluminum (B-1b) represented by general formula (B-1b), and dialkyl compounds of Group 2 or Group 12 metals (B-1c) represented by general formula (B-1c).

[0055] (B-1a): Ra ｍ Al(ORb) ｎ H ｐ X ｑ In formula (B-1a), Ra and Rb each independently represent a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms, X represents a halogen atom, m represents a number satisfying 0<m≦3, n represents a number satisfying 0≦n<3, p represents a number satisfying 0≦p<3, and q represents a number satisfying 0≦q<3, and m+n+p+q=3. Examples of the organoaluminum compound (B-1a) include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, dialkylaluminum hydrides such as diisobutylaluminum hydride, and tricycloalkylaluminums.

[0056] (B-1b): M2AlRa ４In formula (B-1b), M2 is Li, Na or K, and Ra is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Examples of the complex alkyl compound (B-1b) include LiAl(C ２ H ５ ) ４ , LiAl(C ７ H １５ ) ４ Examples include:

[0057] (B-1c): RaRbM3 In formula (B-1c), Ra and Rb each independently represent a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms, and M3 represents Mg, Zn, or Cd. Examples of compound (B-1c) include dimethyl magnesium, diethyl magnesium, di-n-butyl magnesium, ethyl-n-butyl magnesium, diphenyl magnesium, dimethyl zinc, diethyl zinc, di-n-butyl zinc, and diphenyl zinc.

[0058] Among the organometallic compounds (B-1), organoaluminum compounds (B-1a) are preferred.

[0059] (Organoaluminum oxy compound (B-2)) As the organoaluminum oxy compound (B-2) (hereinafter also referred to as "component (B-2)"), conventionally known aluminoxanes can be used as they are. Specific examples include compounds represented by the following general formula [B2-1] and / or the following general formula [B2-2], the benzene-insoluble organoaluminum oxy compounds described in JP-A Nos. 2-78687 and 2-167305, and the aluminoxanes having two or more types of alkyl groups described in JP-A No. 3-103407. In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more.

[0060]

[0061]

[0062] Further, examples of the organoaluminum oxy compound (B-2) include modified methylaluminoxanes represented by the following general formula [B2-3]: In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, and m and n each independently represent an integer of 2 or greater.

[0063]

[0064] This modified methylaluminoxane is prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such compounds are generally called MMAO. Such MMAO can be prepared by the methods described in U.S. Patent Nos. 4,960,878 and 5,041,584.

[0065] Further, the organoaluminum oxy compound (B-2) may also include a boron-containing organoaluminum oxy compound represented by the following general formula [B2-4]: ｃ represents a hydrocarbon group having 1 to 10 carbon atoms. ｄ may be the same or different and represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0066]

[0067] As the organoaluminum oxy compound (B-2), methylaluminoxane, which is a commercially available product and therefore easily available, and MMAO prepared from trimethylaluminum and triisobutylaluminum are preferred. Of these, MMAO, which has improved solubility in various solvents and storage stability, is more preferred.

[0068] (Compound (B-3) that Reacts with Transition Metal Compound (A) to Form an Ion Pair) Examples of the compound (B-3) that reacts with the transition metal compound (A) to form an ion pair (hereinafter also referred to as "ionic compound (B-3)" or "component (B-3)") include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-A Nos. 1-501950, 1-502036, 3-179005, 3-179006, 3-207703, 3-207704, and U.S. Pat. No. 5,321,106. Further examples include heteropoly compounds and isopoly compounds. However, this does not include the aforementioned (B-2) organoaluminum oxy compounds.

[0069] The ionic compound (B-3) is preferably a boron compound represented by the following general formula [B3-1]: ｅ＋ As for H ＋ , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, etc. ｆ From R ｉ may be the same or different and are substituents selected from a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group, and are preferably substituted aryl groups.

[0070]

[0071] Examples of the boron compound represented by the general formula [B3-1] include triphenylcarbenium tetrakis(pentafluorophenyl)borate and those described in paragraphs

[0133] to

[0144] of WO 2015 / 122414.

[0072] The method for producing a cyclic olefin copolymer according to the present embodiment preferably includes a catalyst removal step for removing an olefin polymerization catalyst. By including the catalyst removal step, the catalyst and transition metals in the catalyst can be removed, which may improve the electrical properties of the resulting cyclic olefin copolymer.

[0073] The polymerization reaction solution obtained in the polymerization step is mixed with an acidic aqueous solution such as a dilute hydrochloric acid aqueous solution, or an alkaline aqueous solution such as ion-exchanged water or a sodium hydroxide aqueous solution, and after mixing, the mixture is allowed to stand until the liquid-liquid interface separates, thereby extracting the cyclic olefin copolymer into the organic phase side and the catalyst into the aqueous layer side, and separating the olefin copolymer and the catalyst.

[0074] The olefin polymerization catalyst preferably contains a transition metal compound (A-2) represented by the following formula (VI), and the compound (B) preferably contains one or more compounds selected from the group consisting of an organoaluminum oxy compound (B-2) and a compound (B-3) that reacts with the transition metal compound (A) to form an ion pair.

[0075] <Cyclic Olefin Copolymer (m)> The cyclic olefin copolymer (m) of the present embodiment contains (A) one or more olefin-derived repeating units represented by the following general formula (I), (B) one or more cyclic non-conjugated diene-derived repeating units represented by the following general formula (III), and (C) one or more cyclic olefin-derived repeating units represented by the following general formula (V).

[0076]

[0077] 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.

[0078]

[0079] In the above general 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.

[0080]

[0081] In the 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, w is 0 or 1, and R ６１ ~R ７８ 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 ７５ ~R ７８ may be bonded to each other to form a monocyclic or polycyclic ring.

[0082] In the cyclic olefin copolymer (m), when the total number of moles of repeating units in the cyclic olefin copolymer (m) is taken as 100 mol%, the content of the olefin-derived repeating unit (A) is preferably 10 mol% to 90 mol%, more preferably 15 mol% to 85 mol%, even more preferably 20 mol% to 80 mol%, even more preferably 30 mol% to 80 mol%, even more preferably 35 mol% to 70 mol%, and even more preferably 40 mol% to 65 mol%. The content of the cyclic non-conjugated diene-derived repeating unit (B) is preferably 1 mol% to 40 mol%, more preferably 2 mol% to 35 mol%, even more preferably 3 mol% to 25 mol%, and even more preferably 5 mol% to 20 mol%. The content of the cyclic olefin-derived repeating unit (C) is preferably 1 mol% to 50 mol%, more preferably 5 mol% to 48 mol%, even more preferably 10 mol% to 45 mol%, and even more preferably 15 mol% to 43 mol%. When the content of each repeating unit in the cyclic olefin copolymer (m) is within the above range, the crosslinked product obtained from the cyclic olefin copolymer composition has excellent stability of dielectric properties over time and excellent heat resistance. Furthermore, a crosslinked product (Q) having excellent mechanical properties, dielectric properties, transparency, and gas barrier properties can be obtained. In other words, a crosslinked product (Q) having an excellent balance of these physical properties can be obtained.

[0083] The olefin monomer, which is one of the copolymerization raw materials for the cyclic olefin copolymer (m), is a monomer that provides the skeleton represented by the above formula (I) upon addition copolymerization, and is an olefin represented by the following general formula (Ia).

[0084]

[0085] In the above general formula (Ia), R ３００ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. Examples of the olefin represented by general formula (Ia) 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. From the viewpoint of obtaining a crosslinked product (Q) having better heat resistance, mechanical properties, dielectric properties, transparency, and gas barrier properties, among these, ethylene and propylene are preferred, and ethylene is more preferred. Two or more types of olefin monomers represented by the above formula (Ia) may be used.

[0086] The cyclic non-conjugated diene monomer, which is one of the copolymerization raw materials for the cyclic olefin copolymer (m), undergoes addition copolymerization to form the constituent unit represented by the above formula (III). Specifically, a cyclic non-conjugated diene represented by the following general formula (IIIa), which corresponds to the above general formula (III), is used.

[0087]

[0088] In the above general formula (IIIa), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, w is 0 or 1, and R ６１ ~R ７６ and R ａ１ and R ｂ１ may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; R １０４ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, and R ７５ and R ７６may be bonded to each other to form a monocyclic or polycyclic ring.

[0089] The cyclic non-conjugated diene represented by the general formula (IIIa) is not particularly limited, but examples thereof include cyclic non-conjugated dienes represented by the following chemical formulas: 5-vinyl-2-norbornene, 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.

[0090]

[0091]

[0092] The cyclic non-conjugated diene represented by the above general formula (IIIa) can also be specifically represented by the following general formula (IIIb).

[0093]

[0094] In general formula (IIIb), 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.

[0095] The cyclic olefin copolymer (m) of the present embodiment is characterized in that it contains a structural unit derived from a cyclic non-conjugated diene represented by general formula (III) and thus has a double bond in a side chain portion, i.e., a portion other than the main chain of the copolymer.

[0096] The cyclic olefin monomer, which is one of the copolymerization raw materials for the cyclic olefin copolymer (m), undergoes addition copolymerization to form a constituent unit represented by the above formula (V). Specifically, a cyclic olefin monomer represented by the following general formula (Va) corresponding to the above general formula (V) is used.

[0097]

[0098] 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, w is 0 or 1, and R６１ ~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.

[0099] Specific examples of the cyclic olefin represented by the general formula (Va) include the compounds described in WO 2006 / 118261. Examples of the cyclic olefin represented by the general formula (Va) include bicyclo[2.2.1]-2-heptene (also called norbornene) and tetracyclo[4.4.0.1]-2-heptene. ２，５ .1 ７，１０ ]-3-dodecene (also called tetracyclododecene), and at least one selected from the group consisting of tetracyclo[4.4.0.1 ２，５ .1 ７，１０ These cyclic olefins have the advantage that the modulus of elasticity of the copolymer and crosslinked product is easily maintained because they have a rigid ring structure, and crosslinking can be easily controlled because they do not contain a heterogeneous double bond structure.

[0100] By using the olefin monomer represented by the general formula (Ia) and the cyclic olefin represented by the general formula (Va) as the copolymerization components, the solubility of the cyclic olefin copolymer (m) in a solvent is further improved, resulting in good moldability and an improved product yield.

[0101] In the cyclic olefin copolymer (m), the olefin constituting the olefin-derived repeating unit (A) contains ethylene, the cyclic non-conjugated diene constituting the cyclic non-conjugated diene-derived repeating unit (B) contains 5-vinyl-2-norbornene, and the cyclic olefin constituting the cyclic olefin-derived structural unit (C) contains tetracyclo[4.4.0.1 ２，５ .1 ７，１０]-3-dodecene, which further improves the stability of the cyclic olefin copolymer (m) when made into a varnish.

[0102] The cyclic olefin copolymer (m) may be composed of (A) one or more olefin-derived repeating units represented by general formula (I), (B) one or more cyclic non-conjugated diene-derived repeating units represented by general formula (III), and (C) one or more cyclic olefin-derived repeating units represented by general formula (V), as well as repeating units derived from the cyclic non-conjugated diene represented by general formula (III) and a cyclic olefin other than the cyclic olefin represented by general formula (V), and / or a chain polyene. In this case, as the copolymerization raw materials for the cyclic olefin copolymer (m), in addition to the olefin monomer represented by general formula (Ia), the cyclic non-conjugated diene monomer represented by general formula (IIIa), and the cyclic olefin monomer represented by general formula (Va), the cyclic non-conjugated diene monomer represented by general formula (IIIa) and the cyclic olefin monomer other than the cyclic olefin monomer represented by general formula (Va), and / or a chain polyene monomer can be used. Such cyclic olefin monomers and linear polyene monomers are cyclic olefins represented by the following general formula (VIa) or (VIIa), or linear polyenes represented by the following general formula (VIIIa): Two or more different types of these cyclic olefins or linear polyenes may be used.

[0103]

[0104] In general formula (VIa), x and d each represent an integer of 0 or 1 or more, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, y and z each represent 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 a carbon atom to which R ９３ or the carbon atom to which R９１ may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y=z=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.

[0105]

[0106] In general 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 1≦f≦18.

[0107]

[0108] In general 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.

[0109] Specific examples of the cyclic olefins represented by general formula (VIa) and general formula (VIIa) include the compounds described in paragraphs 0037 to 0063 of WO 2006 / 118261.

[0110] Specific examples of the chain polyene represented by general 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.

[0111] When the cyclic olefin copolymer (m) contains a structural unit derived from a chain polyene represented by the general formula (VIIIa) above, or a structural unit derived from a cyclic olefin other than the cyclic non-conjugated diene represented by the general formula (III) and the cyclic olefin represented by the general formula (V) [for example, general formula (VIa) or general formula (VIIa)], the content of the structural unit is usually 0.1 to 100 mol %, preferably 0.1 to 50 mol %, based on the total molar number of repeating units derived from one or more olefins represented by the general formula (I) above, repeating units derived from one or more cyclic non-conjugated dienes represented by the general formula (III) above, and repeating units derived from one or more cyclic olefins represented by the general formula (V) above.

[0112] By using the olefin monomer represented by the general formula (I), the cyclic olefin represented by the general formula (VIa) or (VIIa), and the chain polyene represented by the general formula (VIIIa) as copolymerization components, the solubility of the cyclic olefin copolymer (m) in solvents is further improved, resulting in good moldability and improved product yield. Among these, the cyclic olefin represented by the general formula (VIa) or (VIIa) is preferred. These cyclic olefins have a rigid ring structure, which makes it easy to maintain the elastic modulus of the copolymer and crosslinked product, and they have the advantage of not containing heterogeneous double bond structures, making it easy to control crosslinking.

[0113] The comonomer content and glass transition temperature (Tg) of the cyclic olefin copolymer (m) can be controlled by adjusting the monomer charging ratio depending on the intended application. The Tg of the cyclic olefin copolymer (m) is preferably 300°C or less, more preferably 250°C or less, even more preferably 200°C or less, even more preferably 170°C or less, and even more preferably 150°C or less. When the Tg is below the upper limit, the melt moldability of the cyclic olefin copolymer (m) and its solubility in solvents when varnishing are improved. From the viewpoint of improving heat resistance, the Tg of the cyclic olefin copolymer (m) is preferably 100°C or more, more preferably 110°C or more, even more preferably 120°C or more, even more preferably 125°C or more, and even more preferably 130°C or more. From the viewpoint of improving the balance between melt moldability, solubility in solvents, and heat resistance, the Tg of the cyclic olefin copolymer (m) is preferably 100°C or more and 300°C or less, more preferably 110°C or more and 250°C or less, even more preferably 120°C or more and 200°C or less, even more preferably 125°C or more and 170°C or less, and still more preferably 130°C or more and 150°C or less.

[0114] The intrinsic viscosity [η] of the cyclic olefin copolymer (m) measured in decahydronaphthalene at 135°C is, for example, in the range of 0.05 to 5 dl / g, preferably 0.07 to 1 dl / g, and more preferably 0.08 to 0.5 dl / g. When the intrinsic viscosity [η] is equal to or less than the upper limit, moldability is improved. When the intrinsic viscosity [η] is equal to or more than the lower limit, the heat resistance and mechanical properties of the crosslinked product (Q) obtained by crosslinking the cyclic olefin copolymer composition are improved. The intrinsic viscosity [η] of the cyclic olefin copolymer (m) depends on the amount of the polymerization catalyst, co-catalyst, H ２ It can be controlled by adjusting the polymerization conditions such as the amount added and the polymerization temperature.

[0115] The number average molecular weight (Mn) of the cyclic olefin copolymer (m) determined by GPC measurement is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 5,000 or more, even more preferably 7,000 or more, and preferably 100,000 or less, more preferably 70,000 or less, even more preferably 50,000 or less, even more preferably 25,000 or less, and preferably 1,000 or more and 100,000 or less, more preferably 2,000 or more and 70,000 or less, even more preferably 5,000 or more and 50,000 or less, even more preferably 7,000 or more and 25,000 or less. This further improves the stability of the cyclic olefin copolymer (m) when it is made into a varnish. In other words, when the varnish is prepared and stored, the occurrence of precipitates and gelation is further suppressed.

[0116] <Stereoregularity> The cyclic olefin copolymer (m) according to this embodiment is believed to have a specific stereoregularity. Specifically, the cyclic olefin copolymer (m) is believed to have a certain range of ratio of mesostructure to racemostructure in the chain structure of repeating unit (C)-repeating unit (A)-repeating unit (C). This further improves the stability of the cyclic olefin copolymer (m) when it is made into a varnish.

[0117] The stereoregularity of the cyclic olefin copolymer (m) according to this embodiment is １３ It is measured by C-NMR. １３ The C-NMR signal positions and signal measurement methods will be explained.

[0118] First, the specific stereoregularity according to this embodiment will be described using as an example a polymer having a structure represented by the following general formula: The mesostructure in the repeating unit (C)-repeating unit (A)-repeating unit (C) chain refers to the structure shown as αβm in Figure 5 of Non-Patent Document 1. The racemostructure refers to the structure shown as αβr in the same figure. (Quoted from Non-Patent Document 1, page 9913, Figure 5)

[0119] Figure 5 in Non-Patent Document 1 shows an example, which shows a structure in which norbornene and ethylene are linked together. A structure in which the stereochemical orientation of the asymmetric carbons of adjacent norbornenes sandwiching ethylene is the same is called a mesostructure, and a structure in which the orientation is different is called a racemostructure. Figure 5 in Non-Patent Document 1 shows norbornene as an example of a cyclic olefin forming the repeating unit (C), but it is not clear whether the cyclic olefin forming the repeating unit (C) is tetracyclo[4.4.0.1]. ２，５ .1 ７，１０ The same applies when the cyclic olefin forming the repeating unit (C) is a monomer other than these.

[0120] In the cyclic olefin copolymer (m) according to this embodiment, (X Ｂ -X Ｃ ) / Y Ａ It is preferable that the value of (X Ｂ -X Ｃ ) / Y Ａ The value of (X) is considered to correspond to the ratio of mesostructure to racemostructure in the chain structure of repeating unit (C)-repeating unit (A)-repeating unit (C). Ｂ -X Ｃ ) / Y Ａ The lower limit of (X) is not particularly limited, but is preferably 0.2 or more, more preferably 0.3 or more, even more preferably 0.4 or more, even more preferably 0.5 or more, even more preferably 0.6 or more, even more preferably 0.7 or more, and even more preferably 0.8 or more. Ｂ -X Ｃ ) / Y Ａ The upper limit of (X) is not particularly limited, but is preferably 2.0 or less, more preferably 1.8 or less, even more preferably 1.6 or less, even more preferably 1.5 or less, even more preferably 1.3 or less, even more preferably 1.1 or less, and even more preferably 1.0 or less. Ｂ -X Ｃ ) / Y ＡThe numerical range of is not particularly limited, but can be, for example, 0.2 or more and 2.0 or less, 0.3 or more and 1.8 or less, 0.4 or more and 1.6 or less, 0.5 or more and 1.5 or less, 0.6 or more and 1.3 or less, 0.7 or more and 1.1 or less, or 0.8 or more and 1.0 or less. (X Ｂ -X Ｃ ) / Y Ａ When the value of is within the above range, the stability of the cyclic olefin copolymer (m) when made into a varnish is improved. The stereoregularity can be appropriately adjusted by selecting the polymerization method, the catalyst used, the composition, etc.

[0121] (X Ｂ -X Ｃ ) / Y Ａ The value of is determined as follows. １３ In the C-NMR spectrum, the integral value of the signal in the range of 43.8 to 45.0 ppm is expressed as X Ｃ , the integral value of the signal in the range of 40.3 to 41.3 ppm is Y Ａ The sum of the integral values ​​of the signals in the range of 38.4 to 39.9 ppm is X Ｂ When Ｂ -X Ｃ ) / Y Ａ Here, we obtain the value of X Ｃ is the integral value of the signal derived from the repeating unit (B), and Y Ａ is the integral value of the signal derived from the repeating unit (C), and X Ｂ is the sum of the integral of the signal derived from repeating unit (B) and the integral of the signal derived from repeating unit (C). １３ In principle, the C-NMR spectrum is measured under the measurement conditions described in the Examples.

[0122] <Cyclic Olefin Copolymer Composition in Varnish> Hereinafter, the cyclic olefin copolymer composition in varnish form will be described.

[0123] The varnish-like cyclic olefin copolymer composition of the present embodiment is a varnish-like cyclic olefin copolymer composition comprising a cyclic olefin copolymer (m) and an organic solvent, wherein the cyclic olefin copolymer (m) comprises (A) one or more olefin-derived repeating units represented by the following general formula (I), (B) one or more cyclic non-conjugated diene-derived repeating units represented by the following general formula (III), and (C) one or more cyclic olefin-derived repeating units represented by the following general formula (V): [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. [In the above general 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. [In the above general 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.] １３In the C-NMR spectrum, the integral value of the signal in the range of 43.8 ppm to 45.0 ppm is expressed as R Ｂ , the integral value of the signal in the range of 40.3 ppm to 41.3 ppm is M Ｃ , the sum of the integral values ​​of the signals in the range of 38.4 ppm to 39.9 ppm is R Ｂ＋Ｃ , then (R Ｂ＋Ｃ -R Ｂ ) / M Ｃ It is preferable that the value of is 0.2 or more and 2.0 or less.

[0124] The content of the cyclic olefin copolymer (m) in the varnish-like cyclic olefin copolymer composition is not particularly limited, but is preferably 30% by mass to 70% by mass, more preferably 30% by mass to 60% by mass, and even more preferably 30% by mass to 55% by mass. If the content is within this range, the varnish-like cyclic olefin copolymer composition can more effectively maintain a solution state.

[0125] <Organic Solvent> The solvent for preparing the varnish-like cyclic olefin copolymer composition is not particularly limited as long as it does not impair the solubility or affinity of the cyclic olefin copolymer (m).

[0126] The organic solvent preferably comprises at least one selected from the group consisting of aromatic hydrocarbon solvents, cyclic hydrocarbon solvents, linear hydrocarbon solvents, and halogenated aromatic hydrocarbon solvents, more preferably at least one selected from the group consisting of aromatic hydrocarbon solvents such as toluene, benzene, xylene, mesitylene, and pseudocumene; cyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and decahydronaphthalene; linear hydrocarbon solvents such as butane, hexane, octane, and decane; and halogenated hydrocarbon solvents such as trichloroethylene, dichloroethylene, and chlorobenzene, even more preferably at least one selected from the group consisting of aromatic hydrocarbon solvents and cyclic hydrocarbon solvents, even more preferably at least one selected from the group consisting of toluene and cyclohexane, and even more preferably toluene. These solvents may be used alone or in combination of two or more in any desired ratio.

[0127] The method for producing a varnish-like cyclic olefin copolymer composition of the present embodiment may include other steps such as a precipitation step of precipitating the obtained polymer.

[0128] <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 copolymer composition according to this embodiment. The method for crosslinking the cyclic olefin copolymer (m) according to this embodiment or the cyclic olefin copolymer composition according to this embodiment is not particularly limited, and examples thereof include a method of crosslinking the cyclic olefin copolymer (m) according to this embodiment or the cyclic olefin copolymer 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.

[0129] 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 a cyclic olefin copolymer composition, followed by heating and crosslinking. The blending ratio 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, and more preferably 0.5 to 10 parts by mass per 100 parts by mass of the cyclic olefin copolymer (m). When the blending ratio of the radical polymerization initiator is below the upper limit, the dielectric properties of the crosslinked product (Q) are improved, while when the blending ratio is above the lower limit, the heat resistance and mechanical properties of the crosslinked product (Q) are improved.

[0130] 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, it should have a 10-hour half-life temperature of usually 80° C. or higher, preferably 120° C. or higher, from the viewpoint of storage stability. Examples of such 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)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.

[0131] 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.

[0132] 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 copolymer composition, and the mixture is heated to carry out the crosslinking reaction. While there are no particular limitations on the amount of sulfur-based compound blended, 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, improve the physical properties of the resulting crosslinked product, and from the standpoint of economy, etc. 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 induce 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. 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 the vulcanization accelerator aid 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 aids such as stearic acid, oleic acid, lauric acid, and lead stearate; and organic amine / glycol aids such as triethanolamine and diethylene glycol.

[0133] The temperature at which the cyclic olefin copolymer (m) or the cyclic olefin copolymer 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, crosslinking can be sufficiently carried out. At or below the upper limit, discoloration 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.

[0134] The cyclic olefin copolymer (m) or cyclic olefin copolymer 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-A-2015-193680. Details are omitted here.

[0135] The crosslinking method using electron beams or other radiation has the advantage that there are no restrictions on the temperature or fluidity during molding, and examples of radiation include electron beams, gamma rays, UV rays, and the like.

[0136] 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.

[0137] 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 vinyl norbornene, ethylidene norbornene, and dicyclopentadiene. These crosslinking aids may be used alone or in combination.

[0138] 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 blending ratio of the filler is an appropriate amount. Specific examples of the stabilizer that may be added as an optional component 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 ester, 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.

[0139] 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.

[0140] 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.

[0141] The crosslinking reaction can be carried out by using a mixture of the cyclic olefin copolymer composition and the above-mentioned radical polymerization initiator, sulfur, hydrosilyl group-containing compound, or the like in a molten state, or by using the mixture in a solution state in which the mixture is dissolved or dispersed in a solvent, or by volatilizing the solvent from the solution state in which the mixture is dissolved in a solvent, forming the mixture into any desired shape such as a film or coating, and then allowing the crosslinking reaction to proceed further.

[0142] 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.

[0143] 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.

[0144] 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.

[0145] <Molded Article> 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 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 copolymer 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 copolymer 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 can be a method in which the cyclic olefin copolymer (m) according to this embodiment or the cyclic olefin copolymer composition according to this embodiment is melt-molded to obtain a film or sheet.

[0146] The film or sheet of this embodiment can be laminated on a substrate and used as a laminate 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-described method on 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 crosslinked product described above on a conductor layer.

[0147] The cyclic olefin copolymer (m) according to this embodiment or the cyclic olefin copolymer composition according to this embodiment may be formed on the surface layer of various multilayer molded articles or multilayer laminated films. In this case, the resin layer formed by the cyclic olefin copolymer (m) according to this embodiment or the cyclic olefin copolymer composition according to this embodiment is preferably 100 μm or less. Examples of various multilayer molded articles or multilayer laminated films include multilayer molded articles for optical lenses in which the cyclic olefin copolymer (m) according to this embodiment or the cyclic olefin copolymer composition according to this embodiment is formed on the surface of a resin optical lens, and multilayer gas barrier films in which the cyclic olefin copolymer (m) according to this embodiment or the cyclic olefin copolymer composition according to 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.

[0148] The prepreg of this embodiment is formed by combining the cyclic olefin copolymer (m) of this embodiment or the cyclic olefin copolymer composition of this 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, a method including the steps of impregnating a sheet-like fiber substrate with the above-described varnish to obtain an impregnated body and heating the obtained impregnated body to dry the solvent contained in the varnish can be used. 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 then, if necessary, placing a protective film on top of the varnish and pressing it from above with a roller or the like. The step of heating the impregnated body and drying the solvent contained in the varnish is not particularly limited, and examples thereof include drying in air or nitrogen using a blower dryer in a batch process, or drying by passing the impregnated body through a heating furnace in a continuous process. 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.

[0149] 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, and aramid fibers, liquid crystal polyester fibers, and glass fibers are 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 varnish is carried out, for example, by immersion and application. 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. Within this range, the dielectric properties and mechanical strength of the resulting laminate are well balanced, which is preferable.

[0150] 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.

[0151] The cyclic olefin copolymer (m) according to this embodiment or the cyclic olefin copolymer composition according to this embodiment has excellent dielectric properties, heat resistance, mechanical properties, etc., and therefore can be suitably used for circuit boards. A generally known method can be used as a method for producing a circuit board, and is not particularly limited. For example, a 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.

[0152] 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.

[0153] Such circuit boards can be used as electronic devices by mounting electronic components such as semiconductor elements. Electronic devices 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, wireless base station antennas, millimeter-wave antennas, and RFID antennas; communication devices such as mobile phones, smartphones, PHS phones, 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 test equipment, high-frequency measurement equipment, and the like.

[0154] Furthermore, the cyclic olefin copolymer (m) according to this embodiment or the cyclic olefin copolymer 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 copolymer composition.

[0155] <Applications> The crosslinked product (Q) according to this embodiment has excellent solvent resistance, heat resistance, mechanical strength, and transparency, and therefore, a molded article made of the crosslinked product (Q) can be used as an overcoat material or interlayer material 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. The compound can be used in applications such as insulating materials, substrates for liquid crystal displays and solar cells, medical instruments, automotive components, mold release agents, resin modifiers, transparent display substrates, 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, mold release materials, hard coating materials, and foam modifiers. In particular, because of its excellent stability over time in dielectric properties, as well as excellent solvent resistance, heat resistance, transparency, and mechanical properties, it can be suitably used in high-frequency applications such as high-frequency circuit boards. Furthermore, because of its excellent gas barrier properties, it can be suitably used as substrates, films, or sheets for liquid crystal displays and solar cell substrates.

[0156] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations may be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention.

[0157] The present invention will be explained in more detail below with reference to Synthesis Examples and Examples, but the present invention is not limited thereto in any way.

[0158] 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.

[0159] [Method for measuring the content of each structural unit constituting the cyclic olefin copolymer] The contents of the structural unit (A), the structural unit (B), and the structural unit (C) were measured using a nuclear magnetic resonance spectrometer "EXcalibur 270" manufactured by JEOL Ltd. under the following conditions: Number of accumulations: 16 to 64 Measurement temperature: Room temperature １ From the H-NMR spectrum, the intensity of the signal derived from hydrogen directly bonded to the double bond carbon and the signal derived from other hydrogen were calculated.

[0160] 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 (manufactured by Tosoh Corporation) Solvent: o-dichlorobenzene Column: TSKgel GMH6-HT x 2, TSKgel GMH6-HTL x 2 (both manufactured by Tosoh Corporation) Flow rate: 1.0 ml / min Sample: 1 mg / mL o-dichlorobenzene solution Temperature: 140°C

[0161] [Glass transition temperature Tg (°C)] Measured using a DSC-6220 manufactured by Shimadzu Science Co., Ltd. ２ The glass transition temperature (Tg) of the cyclic olefin copolymer was measured under a nitrogen atmosphere. The cyclic olefin copolymer was heated from room temperature to 200°C at a heating rate of 10°C / min, held at that temperature for 5 minutes, and then cooled to -20°C at a heating rate of 10°C / min, held at that temperature for 5 minutes. The glass transition temperature (Tg) of the cyclic olefin copolymer was determined from the endothermic curve obtained when the temperature was raised to 200°C at a heating rate of 10°C / min.

[0162] [ １３ C-NMR measurement] １３The C-NMR measurement was carried out under the following conditions: Apparatus: AVANCE III cryo-500 nuclear magnetic resonance, manufactured by Bruker Biospin Measurement nuclei: １３ C (125 MHz) Measurement mode: Single pulse proton (with inverse gate) decoupling Pulse width: 90 degrees Number of points: 64,000 Measurement range: -55 to 195 ppm (total 250 ppm) Repetition time: 12 seconds Number of accumulations: 256 Solvent: 1,1,2,2-tetrachloroethane-d2 Concentration: 10% w / v Temperature: 120°C Chemical shift reference: Tetramethylsilane reference (1,1,2,2-tetrachloroethane-d2: equivalent to 74.2 ppm)

[0163] The following raw materials were used in the experiment:

[0164] Transition metal compound (1): Transition metal compound (1) corresponding to transition metal compound (A) was synthesized by the method described in Macromolecules 2011, 44, 1986.

[0165] [During the ceremony, ｔ Bu is a tert-butyl group; ｉ Pr is an isopropyl group.

[0166] Transition metal compound (2): A transition metal compound (2) not corresponding to the transition metal compound (A) was synthesized by the method described in JP-A-2004-331965.

[0167]

[0168] Transition metal compound (3): A transition metal compound (3) not corresponding to the transition metal compound (A) was synthesized by the method described in J. Organomet. Chem., 1997, 527, 297-300.

[0169]

[0170] Ethylene (manufactured by Sumitomo Seika Chemicals Co., Ltd.) Organoaluminum oxy compound (B-2): Modified methylaluminoxane (MMAO, manufactured by Tosoh Finechem Corporation) Compound (B-3) that reacts with transition metal compound (A) to form an ion pair: Triphenylcarbenium tetrakis(pentafluorophenyl)borate (manufactured by AGC) Toluene (manufactured by Wako Pure Chemical Industries, Ltd.: Wako special grade) 5-vinyl-2-norbornene (manufactured by Tokyo Chemical Industry Co., Ltd.) 2-Norbornene (manufactured by Tokyo Chemical Industry Co., Ltd.) Acetone (manufactured by Wako Pure Chemical Industries, Ltd.: Wako special grade) Methanol (manufactured by Wako Pure Chemical Industries, Ltd.: Wako special grade)

[0171] Cyclic olefin copolymer (m):

[0172] Synthesis Example 1 Cyclic Olefin Copolymer (m-1) Into a 1 L stainless steel autoclave that had been thoroughly purged with nitrogen, 339 mL of toluene, 65 mL of 5-vinyl-2-norbornene (hereinafter also referred to as VNB), tetracyclo[4.4.0.1 ２，５ .1 ７，１０After adding 96 ml of ]-3-dodecene (hereinafter also referred to as TD), 1.5 mmol of MMAO hexane solution in terms of Al, and 93 ml of hydrogen, ethylene was introduced into the system until the total pressure reached 0.75 MPa. 2.5 μmol of transition metal compound (1) dissolved in toluene and 10 μmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate dissolved in toluene were added and the reaction was allowed to proceed at 35°C for 30 minutes. 2.5 μmol of transition metal compound (1) and 10 μmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were then added. After a further 30 minutes, 2.5 μmol of transition metal compound (1) and 10 μmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were added. Polymerization was allowed to proceed for a total of 100 minutes, after which the polymerization was terminated by the addition of a small amount of methanol. After polymerization was completed, ion-exchanged water was added to the resulting polymer solution and the mixture was stirred for 1 hour. The organic layer was then filtered through filter paper to remove the catalyst. The organic layer was poured into acetone to precipitate the polymer, which was stirred and filtered through a filter paper. The resulting polymer was dried under reduced pressure at 80°C for 10 hours to obtain an ethylene / TD / VNB copolymer. The compositional ratio of the TD-derived structure in the polymer determined by NMR was 30 mol%, the compositional ratio of the VNB-derived structure was 16 mol%, and the number average molecular weight (Mn) determined by GPC measurement was 21,000.

[0173] Synthesis Example 2 Cyclic Olefin Copolymer (m-2) Into a 1 L SUS autoclave that had been thoroughly purged with nitrogen, 425 mL of toluene, 23 mL of VNB, 52 mL of a 5 M toluene solution of 2-norbornene (hereinafter also referred to as NB), 1.5 mmol in terms of Al of a hexane solution of MMAO, and 124 mL of hydrogen were placed, and then ethylene was introduced into the system until the total pressure reached 0.75 MPa. 2.5 μmol of transition metal compound (1) dissolved in toluene and 10 μmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate dissolved in toluene were added, and the mixture was allowed to react at 35° C. for 30 minutes. Then, 2.5 μmol of transition metal compound (1) and 10 μmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were added. After another 30 minutes, 2.5 μmol of transition metal compound (1) and 10 μmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were added. Polymerization was continued for a total of 100 minutes, and then a small amount of methanol was added to terminate the polymerization. After polymerization was completed, ion-exchanged water was added to the resulting polymer solution and stirred for 1 hour. The organic layer was then filtered through filter paper to remove the catalyst. This organic layer was poured into acetone to precipitate a 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 / NB / VNB copolymer. The composition ratio of the NB-derived structure in the polymer determined by NMR was 40 mol %, the composition ratio of the VNB-derived structure was 10 mol %, and the number average molecular weight (Mn) determined by GPC measurement was 8,000.

[0174] Synthesis Example 3: Cyclic Olefin Copolymer (m-3) Into a 1 L SUS autoclave that had been thoroughly purged with nitrogen, 410 mL of toluene, 19 mL of VNB, 71 mL of TD, 1.5 mmol of a toluene solution of MMAO (calculated as Al), and 744 mL of hydrogen were charged, and ethylene was then introduced into the system until the total pressure reached 0.78 MPa. 40 μmol of transition metal compound (2) dissolved in toluene was added, and polymerization was carried out at 35°C for 180 minutes, after which the polymerization was terminated by adding a small amount of methanol. After completion of polymerization, ion-exchanged water was added to the resulting polymer solution and stirred for 1 hour, and the organic layer was filtered through filter paper to remove the catalyst. This organic layer was poured into acetone to precipitate a 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. The composition ratio of the TD-derived structure in the polymer determined by NMR was 30 mol %, the composition ratio of the VNB-derived structure was 12 mol %, and the number average molecular weight (Mn) determined by GPC measurement was 11,000.

[0175] Synthesis Example 4: Cyclic Olefin Copolymer (m-4) A 1 L SUS autoclave that had been thoroughly purged with nitrogen was charged with 433 mL of toluene, 15 mL of VNB, 52 mL of a 5 M toluene solution of NB, 1.5 mmol of a hexane solution of MMAO (calculated as Al), and 1,488 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 (2) dissolved in toluene. After reacting for 40 minutes at 35°C, 4 μmol of transition metal compound (2) was added, and this process of adding 4 μmol of transition metal compound (2) every 30 minutes was repeated two more times, allowing polymerization to continue for a total of 130 minutes. Polymerization was then terminated by adding a small amount of methanol. After polymerization was completed, ion-exchanged water was added to the resulting polymer solution and stirred for 1 hour. The organic layer was then filtered through filter paper to remove the catalyst. This organic layer was poured into acetone to precipitate a 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. The compositional ratio of the NB-derived structure in the polymer determined by NMR was 33 mol%, the compositional ratio of the VNB-derived structure in the polymer was 10 mol%, and the number average molecular weight (Mn) determined by GPC measurement was 7,500.

[0176] Synthesis Example 5: Cyclic Olefin Copolymer (m-5) Into a 1 L SUS autoclave that had been thoroughly purged with nitrogen, 340 mL of toluene, 35 mL of VNB, 82 mL of a 5 M toluene solution of NB, 44 mL of TD, 2 mmol of a hexane solution of MMAO (calculated as Al), and 558 mL of hydrogen were charged, and then ethylene was introduced into the system until the total pressure reached 0.52 MPaG. 4.7 μmol of transition metal compound (2) dissolved in toluene was added to initiate polymerization. After reacting for 40 minutes at 35°C, 9.3 μmol of transition metal compound (2) was added, and after another 30 minutes, 9.3 μmol of transition metal compound (2) was added, followed by another 30 minutes of reaction, for a total of 100 minutes of polymerization. Thereafter, the polymerization was terminated by adding a small amount of methanol. After polymerization was completed, ion-exchanged water was added to the resulting polymer solution and stirred for 1 hour. The organic layer was then filtered through filter paper to remove the catalyst. This organic layer was poured into acetone to precipitate a 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. NMR determined the compositional ratio of the TD-derived structure in the polymer to be 14 mol%, the compositional ratio of the NB-derived structure to be 17 mol%, and the compositional ratio of the VNB-derived structure to be 10 mol%, and the number average molecular weight (Mn) determined by GPC measurement to be 8,400.

[0177] Synthesis Example 6: Cyclic Olefin Copolymer (m-6) Into a 1 L SUS autoclave that had been thoroughly purged with nitrogen, 378 mL of toluene, 79 mL of VNB, 43 mL of TD, 1.5 mmol (calculated as Al) of a toluene solution of MMAO, and 744 mL of hydrogen were charged, and then ethylene was introduced into the system until the total pressure reached 0.78 MPa. 40 μmol of transition metal compound (2) dissolved in toluene was added, and polymerization was carried out at 35°C for 180 minutes, after which the polymerization was terminated by adding a small amount of methanol. After completion of polymerization, ion-exchanged water was added to the obtained polymer solution and stirred for 1 hour, and the organic layer was filtered through filter paper to remove the catalyst. This organic layer was poured into acetone to precipitate a polymer, which was stirred and then filtered through filter paper. The obtained polymer was dried under reduced pressure at 80°C for 10 hours to obtain an ethylene / TD / VNB copolymer. The composition ratio of the TD-derived structure in the polymer determined by NMR was 13 mol %, the composition ratio of the VNB-derived structure was 30 mol %, and the number average molecular weight (Mn) determined by GPC measurement was 11,000.

[0178] Synthesis Example 7 Cyclic Olefin Copolymer (m-7) Into a 1 L SUS autoclave that had been thoroughly purged with nitrogen, 225 mL of toluene, 65 mL of VNB, 180 mL of TD, 1.5 mmol in terms of Al of a toluene solution of triisobutylaluminum, and 93 mL of hydrogen were placed, and then ethylene was introduced into the system until the total pressure reached 0.75 MPa. 2.5 μmol of transition metal compound (3) dissolved in toluene and 10 μmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate dissolved in toluene were added, and the mixture was allowed to react at 35° C. for 30 minutes. Then, 2.5 μmol of transition metal compound (1) and 10 μmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were added. After another 30 minutes, 2.5 μmol of transition metal compound (1) and 10 μmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were added. Polymerization was continued for a total of 100 minutes, and then a small amount of methanol was added to terminate the polymerization. After polymerization was completed, ion-exchanged water was added to the resulting polymer solution and stirred for 1 hour. The organic layer was then filtered through filter paper to remove the catalyst. This organic layer was poured into acetone to precipitate a 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. The composition ratio of the TD-derived structure in the polymer determined by NMR was 30 mol %, the composition ratio of the VNB-derived structure was 10 mol %, and the number average molecular weight (Mn) determined by GPC measurement was 9,000.

[0179] [Examples 1 to 4, Comparative Examples 1 to 5] Each varnish was prepared by the method described below and evaluated.

[0180] (Preparation of Varnish) Cyclic olefin copolymer (m) and cyclohexane or toluene were mixed in the amounts (unit: parts by mass) shown in Table 1 and stirred overnight to obtain a cyclic olefin copolymer resin composition in the form of a varnish.

[0181] (stereoregularity) １３ C-NMR measurement was performed, and the integrated value of the signal in the range of 43.8 ppm to 45.0 ppm was calculated as X Ｃ , the integral value of the signal in the range of 40.3 ppm to 41.3 ppm is Y Ａ, the sum of the integral values ​​of the signals in the range of 38.4 ppm to 39.9 ppm is X Ｂ When Ｂ -X Ｃ ) / Y Ａ The value was calculated.

[0182] The stability of the varnishes was evaluated as follows: A varnish that showed no precipitates or gelation after being left standing for two weeks in an environment with a temperature of 22 to 27°C and a humidity of 30 to 70% was rated "A," a varnish that showed no precipitates but gelation after being left standing for two weeks in the above environment was rated "B," and a varnish that had residual residue after stirring overnight or that had precipitates after being left standing for two weeks in the above environment was rated "C."

[0183]

[0184] In Table 1, "-" in the stereoregularity column means (X Ｂ -X Ｃ ) / Y Ａ indicates that the value could not be measured.

[0185] This application claims priority based on Japanese Patent Application No. 2022-102901, filed on June 27, 2022, the disclosure of which is incorporated herein by reference in its entirety.

Claims

1. A cyclic olefin copolymer (m); Organic solvent A method for producing a varnish-like cyclic olefin copolymer composition, comprising: The cyclic olefin copolymer (m) is (A) one or more olefin-derived repeating units represented by the following general formula (I), (B) one or more repeating units derived from a cyclic non-conjugated diene represented by the following general formula (III), (C) one or more repeating units derived from a cyclic olefin represented by the following general formula (V), 【Chemistry 1】 [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. 【Chemistry 2】 [In the above general 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 each is 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 are bonded to each other may form a monocyclic or polycyclic ring.] 【Chemistry 3】 [In the above general formula (V), u is 0 or 1, v is 0 or 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 each is 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. The method further comprising: The method includes a polymerization step of copolymerizing an olefin, a cyclic non-conjugated diene, and a cyclic olefin in the presence of an olefin polymerization catalyst containing a transition metal compound (A) and a compound (B), The transition metal compound (A) is A transition metal compound (A-1) represented by the following formula (II), and The transition metal compound (A-2) contains one or more transition metal compounds represented by the following formula (VI): 【Chemistry 4】 [In the above formula (II), M ２ represents a transition metal atom of Group 4 of the periodic table, n １ represents an integer from 1 to 3, Each L independently represents a monovalent anionic ligand having an atom of Group 15 of the periodic table as a coordinating atom; X １ each independently represents a group or atom selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and substitution products thereof; R ５ ~R ９ each independently represents a group or atom selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and a substitution product thereof; R ５ ~R ９ Any two or three of these may be condensed to form a ring, and the ring formed may have aromaticity including a conjugated double bond. 【Chemistry 5】 [In the above formula (VI), M ３ represents a transition metal atom of Group 4 of the periodic table, n ２ represents an integer from 1 to 4, X ２ each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and substitution products thereof; R １０ ~R １７ each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and a substitution product thereof; R １０ ~R １７ Adjacent ones of may be bonded to each other to form a ring, and the ring formed may have aromaticity including a conjugated double bond. The compound (B) is organometallic compound (B-1), Organoaluminum oxy compound (B-2), and The compound (B-3) contains one or more compounds selected from the group consisting of:

1. A method for producing a cyclic olefin copolymer composition in a varnish form, comprising:

2. The method according to claim 1, wherein the content of the cyclic olefin copolymer (m) in the varnish-like cyclic olefin copolymer composition is 30 mass% or more.

3. 3. The method according to claim 1, wherein the organic solvent comprises at least one selected from the group consisting of aromatic hydrocarbon solvents, cyclic hydrocarbon solvents, linear hydrocarbon solvents, and halogenated aromatic hydrocarbon solvents.

4. 3. The method according to claim 1 or 2, wherein, when the total number of moles of repeating units in the cyclic olefin copolymer (m) is taken as 100 mol%, the content of the repeating unit (A) derived from the olefin is 10 mol% or more and 90 mol% or less, the content of the repeating unit (B) derived from the cyclic non-conjugated diene is 1 mol% or more and 40 mol% or less, and the content of the repeating unit (C) derived from the cyclic olefin is 1 mol% or more and 50 mol% or less.

5. The method according to claim 1 or 2, wherein the cyclic non-conjugated diene constituting the repeating unit (B) derived from the cyclic non-conjugated diene includes 5-vinyl-2-norbornene.

6. The cyclic olefin constituting the cyclic olefin-derived structural unit (C) is tetracyclo[4.4.0.1 ２，５ .1 ７，１０ 3. The method according to claim 1, wherein the compound is at least one selected from the group consisting of bicyclo[2.2.1]-3-dodecene and bicyclo[2.2.1]-2-heptene.

7. The process according to claim 1 or 2, further comprising a catalyst removal step of removing the olefin polymerization catalyst.

8. The cyclic olefin copolymer (m) １３ In the C-NMR spectrum, The integral value of the signal in the range of 43.8 ppm to 45.0 ppm is expressed as X Ｃ , The integral value of the signal in the range of 40.3 ppm to 41.3 ppm is Y Ａ , The integral value of the signal in the range of 38.4 ppm to 39.9 ppm is X Ｂ , Then, (X Ｂ -X Ｃ ) / Y Ａ The method according to claim 1 or 2, wherein the value of is 0.2 or more and 2.0 or less.

9. The process according to claim 1 or 2, wherein the cyclic olefin copolymer (m) has a glass transition temperature of 100° C. or higher as measured by a differential scanning calorimeter (DSC).

10. A cyclic olefin copolymer composition obtained by the process according to claim 1 or 2.

11. A crosslinked body obtained by crosslinking the cyclic olefin copolymer composition according to claim 10.

12. A film or sheet comprising the crosslinked product according to claim 11.

13. A laminate comprising the film or sheet according to claim 12 laminated on a substrate.

14. A circuit board comprising: an electrical insulating layer containing the crosslinked body according to claim 11; and a conductor layer provided on the electrical insulating layer.

15. An electronic device comprising the circuit board according to claim 14.

16. A prepreg comprising the cyclic olefin copolymer composition according to claim 10 and a sheet-like fiber substrate.

17. A cyclic olefin copolymer (m); Organic solvent A varnish-like cyclic olefin copolymer composition comprising: The cyclic olefin copolymer (m) is (A) one or more olefin-derived repeating units represented by the following general formula (I), (B) one or more repeating units derived from a cyclic non-conjugated diene represented by the following general formula (III), (C) one or more repeating units derived from a cyclic olefin represented by the following general formula (V), 【Chemistry 6】 [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. 【Chemistry 7】 [In the above general 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 each is 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 are bonded to each other may form a monocyclic or polycyclic ring.] 【Chemistry 8】 [In the above general formula (V), u is 0 or 1, v is 0 or 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 each is 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. The cyclic olefin copolymer (m) １３ In the C-NMR spectrum, The integral value of the signal in the range of 43.8 ppm to 45.0 ppm is expressed as X Ｃ , The integral value of the signal in the range of 40.3 ppm to 41.3 ppm is Y Ａ , The sum of the integral values ​​of the signals in the range from 38.4 ppm to 39.9 ppm is X Ｂ , Then, (X Ｂ -X Ｃ ) / Y Ａ The cyclic olefin copolymer composition in a varnish form, wherein the value of is 0.2 or more and 2.0 or less.

18. The varnish-like cyclic olefin copolymer composition according to claim 17, wherein the cyclic olefin copolymer (m) has a glass transition temperature of 100°C or higher as measured by a differential scanning calorimeter (DSC).

19. The varnish-like cyclic olefin copolymer composition according to claim 17 or 18, wherein the content of the cyclic olefin copolymer (m) in the varnish-like cyclic olefin copolymer composition is 30 mass% or more.

20. The varnish-like cyclic olefin copolymer composition according to claim 17 or 18, wherein the organic solvent comprises at least one selected from the group consisting of aromatic hydrocarbon solvents, cyclic hydrocarbon solvents, linear hydrocarbon solvents and halogenated aromatic hydrocarbon solvents.

21. 19. The varnish-like cyclic olefin copolymer composition according to claim 17 or 18, wherein, when the total number of moles of repeating units in the cyclic olefin copolymer (m) is taken as 100 mol%, the content of the repeating unit (A) derived from the olefin is 10 mol% or more and 90 mol% or less, the content of the repeating unit (B) derived from the cyclic non-conjugated diene is 1 mol% or more and 40 mol% or less, and the content of the repeating unit (C) derived from the cyclic olefin is 1 mol% or more and 50 mol% or less.

22. The varnish-like cyclic olefin copolymer composition according to claim 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.

23. The cyclic olefin constituting the cyclic olefin-derived structural unit (C) is tetracyclo[4.4.0.1 ２，５ .1 ７，１０ 19. The varnish-like cyclic olefin copolymer composition according to claim 17 or 18, comprising at least one member selected from the group consisting of bicyclo[2.2.1]-3-dodecene and bicyclo[2.2.1]-2-heptene.

24. The olefin constituting the olefin-derived repeating unit (A) contains ethylene, The cyclic non-conjugated diene constituting the repeating unit (B) derived from the cyclic non-conjugated diene contains 5-vinyl-2-norbornene, The cyclic olefin constituting the cyclic olefin-derived structural unit (C) is tetracyclo[4.4.0.1 ２，５ .1 ７，１０ 19. The varnish-like cyclic olefin copolymer composition according to claim 17 or 18, comprising 1-(2-methyl-1,2-dioxanediol)-3-dodecene.

25. A crosslinked product obtained by crosslinking the varnish-like cyclic olefin copolymer composition according to claim 17 or 18.

26. A film or sheet comprising the crosslinked product according to claim 25.

27. A laminate comprising the film or sheet according to claim 26 laminated onto a substrate.

28. A circuit board comprising an electrical insulating layer containing the crosslinked body according to claim 25 and a conductor layer provided on the electrical insulating layer.

29. An electronic device comprising the circuit board according to claim 28.

30. A prepreg comprising the varnish-like cyclic olefin copolymer composition according to claim 17 or 18 and a sheet-like fiber substrate.

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