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, which is a method for producing a varnish-like cyclic olefin copolymer composition that contains a cyclic olefin copolymer (m) and an organic solvent, 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 non-conjugated diene, and (C) one or more repeating units derived from a cyclic olefin. The method comprises a polymerization step for 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) containing one or more compounds selected from the group consisting of transition metal compounds (A-1) and transition metal compounds (A-2); the compound (B) contains one or more compounds selected from the group consisting of an organic metal compound (B-1), an organic aluminum oxide compound (B-2), and a compound (B-3) that reacts with the transition metal compound (A) to form an ion pair.

Description

Technical Field

[0001] The present invention relates to a method for producing a varnish-like cyclic olefin copolymer composition, a cyclic olefin copolymer composition, a crosslinked body, a film or sheet, a laminate, a circuit board, an electronic device and a prepreg. Background Art

[0002] Recently, in addition to the increase in wireless communication devices using high frequency bands, the use of high frequency bands has inevitably increased due to the increase in communication speeds. In order to reduce the transmission loss at high frequencies to the maximum, circuit boards with low dielectric loss tangent are required.

[0003] Patent Documents 1 and 2 disclose that a sheet obtained by crosslinking a cyclic olefin copolymer obtained by copolymerizing a specific diene compound with an organic peroxide or the like exhibits excellent dielectric properties.

[0004] Patent Documents 3 and 4 disclose cross-linkable resin shaped articles containing a cross-linkable cycloolefin polymer, which have excellent fluidity during heating and solvent solubility.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2010-100843

[0008] Patent Document 2: International Publication No. 2012 / 046443

[0009] Patent Document 3: Japanese Patent Application Publication No. 2019-081898

[0010] Patent Document 4: International Publication No. 2021 / 149713

[0011] Non-patent literature

[0012] Non-patent document 1: Incoronata Tritto, Laura Boggioni, Cristina Zampa and Dino R. Ferro, "Ethylene-Norbornen Copolymers by Cs-Symmetric Metallocenes: Determination of the Copolymerization Parameters and MechanisticConsiderations on the Basis of Tetrad Analysis" Macromolecules, 2005, 38, 9910-9919. Summary of the invention

[0013] Problems to be solved by the invention

[0014] According to the research of the present inventors, there is room for further improvement in the toluene solubility of the cyclic olefin copolymers having crosslinkable groups as described in Patent Documents 1 and 2 in a state containing a large amount of the cyclic olefin copolymer (high solid content). It is believed that if the toluene solubility at a high solid content can be improved, the impregnation property of the fiber base material during the production of the circuit board can be further improved.

[0015] It is also known that although the cyclic olefin copolymers having crosslinkable groups described in Patent Documents 3 and 4 have improved fluidity and solubility, when dissolved in toluene in a state containing a large amount of the cyclic olefin copolymer (high solid content), gelation is observed when left at room temperature, and fluidity is impaired.

[0016] When the fluidity is impaired, the management method of the varnish and the stable impregnation of the varnish into the fiber base material during the production of the circuit board are impaired, which becomes a problem.

[0017] That is, according to the studies of the present inventors, the inventions described in Patent Documents 3 and 4 have room for further improvement in that a solution state is maintained even in a varnish state containing a large amount of a cyclic olefin copolymer having a crosslinkable group.

[0018] 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 which can maintain a solution state for a longer period of time even in a state containing a large amount of cyclic olefin copolymers having crosslinkable groups (high solid content).

[0019] Means for solving problems

[0020] The present inventors have conducted intensive studies to solve the above-mentioned problems and have found that by improving the method for producing cyclic olefin copolymers, it is possible to prepare a varnish that can maintain a solution state for a longer period of time even in a state containing a large amount of cyclic olefin copolymers having crosslinkable groups (high solid content), thereby completing the present invention.

[0021] Specifically, the present invention provides 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 as described below.

[0022] 1. A method for producing a varnish-like cyclic olefin copolymer composition, which is a method for producing a varnish-like cyclic olefin copolymer composition comprising a cyclic olefin copolymer (m) and an organic solvent, characterized in that:

[0023] The cyclic olefin copolymer (m) comprises: (A) one or more repeating units derived from olefins represented by the following general formula (I), (B) one or more repeating units derived from cyclic non-conjugated dienes represented by the following general formula (III), and (C) one or more repeating units derived from cyclic olefins represented by the following general formula (V).

[0024] [Chemistry 1]

[0025]

[0026] [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.

[0027] [Chemistry 2]

[0028]

[0029] [In the above general formula (III), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R 61 ~R 76 and R a1 and R b1 may be the same as or different from each other, 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 from 0 to 10, R 75 and R 76 They may be bonded to each other to form a single ring or multiple rings.

[0030] [Chemistry 3]

[0031]

[0032] [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 as or different from each other, 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 78They may be bonded to each other to form a single ring or multiple rings.

[0033] 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);

[0034] 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),

[0035] [Chemistry 4]

[0036]

[0037] [In the above formula (II),

[0038] M 2 represents a transition metal atom of Group 4 of the periodic table,

[0039] n 1 represents an integer from 1 to 3,

[0040] L each independently represents a monovalent anionic ligand in which an atom of Group 15 of the periodic table serves as a coordinating atom,

[0041] 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 substituents thereof,

[0042] 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 substituents thereof, and R 5 ~R 9 Any two or three of them may be condensed to form a ring, and the formed ring may be an aromatic ring containing a conjugated double bond.

[0043] [Chemistry 5]

[0044]

[0045] [In the above formula (VI),

[0046] M 3 represents a transition metal atom of Group 4 of the periodic table,

[0047] n 2 represents an integer from 1 to 4,

[0048] 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 substituents thereof,

[0049] 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 substituents thereof, and R 10 ~R 17 Adjacent groups in the group may be bonded to each other to form a ring, and the formed ring may be an aromatic ring containing a conjugated double bond.

[0050] The compound (B) contains one or more 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.

[0051] 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% by mass or more.

[0052] 3. The production method according to 1. or 2., 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.

[0053] 4. The production method according to any one of 1. to 3., wherein, when the total molar number of repeating units in the cyclic olefin-based copolymer (m) is set to 100 mol%, the content of the repeating units (A) derived from olefins is 10 mol% or more and 90 mol% or less, the content of the repeating units (B) derived from cyclic non-conjugated dienes is 1 mol% or more and 40 mol% or less, and the content of the repeating units (C) derived from cyclic olefins is 1 mol% or more and 50 mol% or less.

[0054] 5. The production method according to any one of 1. to 4., wherein the cyclic non-conjugated diene constituting the repeating unit (B) derived from a cyclic non-conjugated diene comprises 5-vinyl-2-norbornene.

[0055] 6. The production method according to any one of 1. to 5., wherein the cyclic olefin constituting the structural unit (C) derived from the cyclic olefin comprises a tetracyclic [4.4.0.1 2,5 .1 7,10 At least one member selected from the group consisting of 1-3-dodecene and bicyclo[2.2.1]-2-heptene.

[0056] 7. The production method according to any one of 1. to 6., further comprising: a catalyst removal step of removing the olefin polymerization catalyst.

[0057] 8. The production method according to any one of 1. to 7., wherein 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 defined as X. C , the integral value of the signal in the range of 40.3ppm and below 41.3ppm is set to Y A , the integral value of the signal in the range of 38.4 ppm to 39.9 ppm is set to X B When (X B -X C ) / Y A The value of is 0.2 or more and 2.0 or less.

[0058] 9. The production method according to any one of 1. to 8., wherein the cyclic olefin-based copolymer (m) has a glass transition temperature of 100° C. or higher as measured by a differential scanning calorimeter (DSC).

[0059] 10. A cyclic olefin-based copolymer composition obtained by the production method described in any one of 1. to 9.

[0060] 11. A crosslinked product obtained by crosslinking the cyclic olefin copolymer composition according to 10.

[0061] 12. A film or sheet comprising the cross-linked body described in 11.

[0062] 13. A laminated body, comprising the film or sheet according to 12. laminated on a substrate.

[0063] 14. A circuit board comprising: an electrical insulating layer comprising the crosslinked body according to 11; and a conductive layer provided on the electrical insulating layer.

[0064] 15. An electronic device comprising the circuit substrate according to 14.

[0065] 16. A prepreg comprising the cyclic olefin copolymer composition according to 10. and a sheet-like fiber base material.

[0066] 17. A varnish-like cyclic olefin copolymer composition comprising a cyclic olefin copolymer (m) and an organic solvent,

[0067] The cyclic olefin copolymer (m) comprises: (A) one or more repeating units derived from olefins represented by the following general formula (I), (B) one or more repeating units derived from cyclic non-conjugated dienes represented by the following general formula (III), and (C) one or more repeating units derived from cyclic olefins represented by the following general formula (V).

[0068] [Chemistry 6]

[0069]

[0070] [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.

[0071] [Chemistry 7]

[0072]

[0073] [In the above general formula (III), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R 61 ~R 76 and R a1 and R b1 may be the same as or different from each other, 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 from 0 to 10, R 75 and R 76 They may be bonded to each other to form a single ring or multiple rings.

[0074] [Chemistry 8]

[0075]

[0076] [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 as or different from each other, 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, R75 ~R 78 They may be bonded to each other to form a single ring or multiple rings.

[0077] In the above-mentioned 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 defined as X. C , the integral value of the signal in the range of 40.3ppm and below 41.3ppm is set to Y A , the total integrated value of the signal in the range of 38.4 ppm or more and 39.9 ppm or less is set to X B When (X B -X C ) / Y A The value of is 0.2 or more and 2.0 or less.

[0078] 18. The varnish-like cyclic olefin copolymer composition 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).

[0079] 19. The varnish-like cyclic olefin copolymer composition 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 more.

[0080] 20. The varnish-like cyclic olefin copolymer composition according to any one of 17. to 19., 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.

[0081] 21. A varnish-like cyclic olefin copolymer composition according to any one of 17. to 20., wherein, when the total molar number of repeating units in the aforementioned cyclic olefin copolymer (m) is set to 100 mol%, the content of the aforementioned repeating units (A) derived from olefins is 10 mol% or more and 90 mol% or less, the content of the aforementioned repeating units (B) derived from cyclic non-conjugated dienes is 1 mol% or more and 40 mol% or less, and the content of the aforementioned repeating units (C) derived from cyclic olefins is 1 mol% or more and 50 mol% or less.

[0082] 22. The varnish-like cyclic olefin-based copolymer composition according to any one of 17. to 21., wherein the cyclic non-conjugated diene constituting the repeating unit (B) derived from the cyclic non-conjugated diene comprises 5-vinyl-2-norbornene.

[0083] 23. The varnish-like cyclic olefin copolymer composition according to any one of 17. to 22., wherein the cyclic olefin constituting the structural unit (C) derived from the cyclic olefin comprises a tetracyclic [4.4.0.1 2,5 .1 7,10 At least one member selected from the group consisting of 1-3-dodecene and bicyclo[2.2.1]-2-heptene.

[0084] 24. The varnish-like cyclic olefin copolymer composition according to any one of 17. to 23., wherein the olefin constituting the repeating unit (A) derived from olefin comprises ethylene, the cyclic non-conjugated diene constituting the repeating unit (B) derived from cyclic non-conjugated diene comprises 5-vinyl-2-norbornene, and the cyclic olefin constituting the structural unit (C) derived from cyclic olefin comprises tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene.

[0085] 25. A cross-linked product obtained by cross-linking the varnish-like cyclic olefin copolymer composition according to any one of 17. to 24.

[0086] 26. A film or sheet comprising the cross-linked body described in 25.

[0087] 27. A laminated body, comprising the film or sheet according to 26. laminated on a substrate.

[0088] 28. A circuit board comprising: an electrical insulating layer comprising the crosslinked body according to 25., and a conductive layer provided on the electrical insulating layer.

[0089] 29. An electronic device comprising the circuit substrate described in 28.

[0090] 30. A prepreg comprising the varnish-like cyclic olefin-based copolymer composition according to any one of 17. to 24. and a sheet-like fiber base material.

[0091] Effects of the Invention

[0092] According to the present invention, there can be provided a method for producing a varnish-like cyclic olefin copolymer composition which can maintain a solution state for a longer period of time even in a state containing a large amount of cyclic olefin copolymer having a crosslinkable group (high solid content). DETAILED DESCRIPTION

[0093] Hereinafter, the present invention will be described based on the embodiment. In addition, in the present embodiment, "A to B" indicating a numerical range means A or more and B or less unless otherwise specified.

[0094] When a numerical range is described in stages, the upper limit and the lower limit of each numerical range can be arbitrarily combined.

[0095] Each monomer constituting the cyclic olefin-based copolymer of the present invention may be a monomer obtained from a fossil raw material or a monomer obtained from an animal or plant raw material.

[0096] [Method for producing varnish-like cyclic olefin copolymer composition]

[0097] Hereinafter, a method for producing a varnish-like cyclic olefin-based copolymer composition will be described.

[0098] The method for producing a varnish-like cyclic olefin copolymer composition of the present embodiment is a method for producing a varnish-like cyclic olefin copolymer composition comprising a cyclic olefin copolymer (m) and an organic solvent, comprising: 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).

[0099] By carrying out polymerization in the presence of an olefin polymerization catalyst containing a transition metal compound (A) and a compound (B), a varnish-like cyclic olefin copolymer composition can be obtained which can maintain a solution state even in a state containing a large amount of cyclic olefin copolymers having crosslinkable groups (high solid content).

[0100] <Olefin Polymerization Catalyst>

[0101] The olefin polymerization catalyst contains a transition metal compound (A) and a compound (B).

[0102] <Transition Metal Compound (A)>

[0103] The transition metal compound (A) contains one or two 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).

[0104] The transition metal compound (A) preferably contains a transition metal compound (A-2) represented by the following formula (VI).

[0105] (Transition Metal Compound (A-1))

[0106] The transition metal compound (A-1) is represented by the following formula (II).

[0107] [Chemistry 9]

[0108]

[0109] In the above formula (II), M 2It represents a transition metal of Group 4 of the periodic table.

[0110] As M 2 , titanium atom, zirconium atom or hafnium atom etc. can be exemplified. 2 Preferred is a titanium atom or a zirconium atom, and more preferred is a titanium atom.

[0111] n 1 Indicates an integer from 1 to 3. n 1 According to M 2 The valence and X 1 The type is selected so that the transition metal compound (A-1) represented by the formula (II) becomes electrically neutral as a whole. 1 Preferred is 2.

[0112] L each independently represents a monovalent anionic ligand in which an atom of Group 15 of the periodic table serves as a coordinating atom.

[0113] L is preferably a monovalent anionic ligand represented by formula (IV).

[0114] [Chemistry 10]

[0115]

[0116] 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.

[0117] Z represents an atom selected from Group 14, Group 15 or Group 16 of the periodic table. Examples of Z include a carbon atom or silicon atom of Group 14, a nitrogen atom, a phosphorus atom or an arsenic atom of Group 15, and an oxygen atom or sulfur atom of Group 16.

[0118] Z is preferably a carbon atom or a nitrogen atom, more preferably a carbon atom.

[0119] n 3 Indicates an integer from 1 to 3. n 3 According to the valence of Z and R 18 The type is selected so that the monovalent anionic ligand represented by formula (IV) becomes electrically neutral as a whole.

[0120] n 2 It is preferably 1 or 2, and more preferably 2.

[0121] R 18Each 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 group consisting of substituents thereof, and each can be bonded to each other to form a ring, and the formed ring can be an aromatic ring containing a conjugated double bond, and the formed ring can also be bonded to a cyclopentadienyl group.

[0122] As R 18 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 shown in the figure, and their substituents can be exemplified as R 3 and R 4 The groups exemplified are 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 shown in the figure, and substituents thereof.

[0123] As R 18 As examples of the structure in which the groups are bonded to each other to form a ring, and the formed ring is bonded to a cyclopentadienyl group, the following structures can be exemplified.

[0124] [Chemistry 11]

[0125]

[0126] R 18 When R is a group selected from the group consisting of 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 substituents thereof, 19 The number of carbon atoms in each independently is preferably 1-20, more preferably 1-10.

[0127] R 18 Preferably, each is independently 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 phosphamide group and a phosphino group, and a substituent thereof, and an atom or group selected from the group consisting of alkyl group, cycloalkyl group or aryl group, or a substituent thereof, further preferably a tert-butyl group, a tricyclodecyl group or a phenyl group, or a substituent thereof, and further preferably a tert-butyl group.

[0128] 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 substituents thereof.

[0129] As X 1 The halogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, silicon-containing group, boron-containing group and aluminum-containing group represented by R and their substituents are exemplified as follows: 3 and R 4 The groups exemplified are 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 the above-mentioned group, and substituents thereof.

[0130] In X 1 When X is a group selected from the group consisting of 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 substituent thereof, 1 The number of carbon atoms in each independently is preferably 1-20, more preferably 1-10.

[0131] X 1 A halogen atom is preferred, and a chlorine atom is more preferred.

[0132] 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 substituents thereof, and R 5 ~R 9 Any two or three of them may be condensed to form a ring, and the formed ring may be an aromatic ring containing a conjugated double bond.

[0133] As R 5 ~R 9 The halogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, silicon-containing group, boron-containing group and aluminum-containing group represented by R and their substituents are exemplified as follows: 3 and R 4 The groups exemplified are 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 the above-mentioned group, and substituents thereof.

[0134] In R 5 ~R 9 When R is a group selected from the group consisting of 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 substituents thereof, 5 ~R 9The number of carbon atoms in each independently is preferably 1-20, more preferably 1-10.

[0135] R 5 ~R 9 Preferred is a hydrogen atom.

[0136] (Transition Metal Compound (A-2))

[0137] The transition metal compound (A-2) is represented by the following formula (VI).

[0138] [Chemistry 12]

[0139]

[0140] In the above formula (VI), M 3 It represents a transition metal of Group 4 of the periodic table.

[0141] As M 3 , a titanium atom, a zirconium atom or a hafnium atom can be exemplified.

[0142] M 3 Preferred is a titanium atom or a zirconium atom, and more preferred is a titanium atom.

[0143] n 2 Indicates an integer from 1 to 4.

[0144] n 2 According to M 3 The valence and X 2 The type is selected so that the transition metal compound (A-2) represented by the formula (VI) becomes electrically neutral as a whole.

[0145] n 2 Preferred is 2.

[0146] 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 substituents thereof.

[0147] As X 2 The halogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, silicon-containing group, boron-containing group and aluminum-containing group represented by R and their substituents are exemplified as follows: 3 and R 4 The groups exemplified are 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 the above-mentioned group, and substituents thereof.

[0148] In X 2When X is a group selected from the group consisting of 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 substituent thereof, 2 The number of carbon atoms in each independently is preferably 1-20, more preferably 1-10.

[0149] X 2 A halogen atom is preferred, and a chlorine atom is more preferred.

[0150] 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 substituents thereof, and R 10 ~R 14 Adjacent groups in the group may be bonded to each other to form a ring, and the formed ring may be an aromatic ring containing a conjugated double bond.

[0151] As R 10 ~R 17 The halogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, silicon-containing group, boron-containing group and aluminum-containing group represented by R and their substituents are exemplified as follows: 3 and R 4 The groups exemplified are 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 the above-mentioned group, and substituents thereof.

[0152] In R 10 ~R 17 In the case where R is a group selected from the group consisting of 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, an aluminum-containing group, and substituents thereof, 10 ~R 17 The number of carbon atoms in each independently is preferably 1-20, more preferably 1-10.

[0153] As R 10 ~R 17 A specific example of the combination of is preferably 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 substituents thereof, and R 15 and R 16Each is independently an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, and a substituent thereof.

[0154] R 10 ~R 14 Adjacent groups in the group may be bonded to each other to form a ring, and the formed ring may be an aromatic ring containing a conjugated double bond.

[0155] As R 10 ~R 17 A specific example of the combination of 10 ~R 14 and R 17 are independently a hydrogen atom or a hydrocarbon group, and R 15 and R 16 Each is independently a hydrogen atom, a hydrocarbon group, or a halogen-containing hydrocarbon group.

[0156] As R 10 ~R 17 A specific example of the combination of is more preferably 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 Each is independently a hydrogen atom, a hydrocarbon group or a halogen-containing alkyl group.

[0157] As R 10 ~R 17 A specific example of the combination of is more preferably R 10 ~R 14 and R 17 are independently a hydrogen atom or a tert-butyl group, and R 15 and R 16 are each independently a hydrogen atom or an isopropyl group.

[0158] As R 10 ~R 17 A specific example of the combination of 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 independently hydrogen, a cyclic hydrocarbon group, a branched alkyl group or a halogen-containing alkyl group, and R 17 It is a hydrogen atom, a branched alkyl group or a halogen-containing alkyl group.

[0159] <Compound (B)>

[0160] Compound (B) contains one or more selected from the group consisting of an organometallic compound (B-1), an organoaluminum oxide compound (B-2), and a compound (B-3) that forms an ion pair by reacting with the transition metal compound represented by the above formula (II) or the transition metal compound represented by the above formula (VI).

[0161] Compound (B) preferably contains one or more selected from the group consisting of an organoaluminum oxide compound (B-2) and a compound (B-3) that forms an ion pair by reacting with the transition metal compound (A), and more preferably contains both the organoaluminum oxide compound (B-2) and the compound (B-3) that forms an ion pair by reacting with the transition metal compound (A).

[0162] (Organometallic compound (B-1))

[0163] Examples of the organometallic compound (B-1) (hereinafter also referred to as "component (B-1)") include organoaluminum compounds (B-1a) represented by the general formula (B-1a), complex alkyl compounds of Group 1 metals and aluminum (B-1b) represented by the general formula (B-1b), and dialkyl compounds of Group 2 or Group 12 metals (B-1c) represented by the general formula (B-1c), etc., which are organometallic compounds of Group 1, Group 2, Group 12, and Group 13.

[0164] (B-1a): Ra m Al(ORb) n H p X q

[0165] In the formula (B-1a), Ra and Rb are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X is a halogen atom, m is a number satisfying 0 < m ≤ 3, n is a number satisfying 0 ≤ n < 3, p is a number satisfying 0 ≤ p < 3, q is 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, dialkylhydroaluminums such as diisobutylaluminum hydride, and tricycloalkylaluminum.

[0166] (B-1b): M2AlRa4

[0167] In the 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 alkyl complex (B-1b) include LiAl(C2H5)4 and LiAl(C7H 15 )4.

[0168] (B-1c): RaRbM3

[0169] In formula (B-1c), Ra and Rb are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M3 is 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.

[0170] Among the organometallic compounds (B-1), organoaluminum compounds (B-1a) are preferred.

[0171] (Organoaluminum oxy-compound (B-2))

[0172] As the organoaluminum oxy-compound (B-2) (hereinafter also referred to as “component (B-2)”), a conventionally known aluminoxane can be used as it is.

[0173] Specifically, examples include compounds represented by the following general formula [B2-1] and / or the following general formula [B2-2], benzene-insoluble organic aluminum oxide compounds described in JP-A-2-78687 and JP-A-2-167305, and aluminoxanes having two or more alkyl groups described in JP-A-3-103407.

[0174] In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more.

[0175] [Chemistry 13]

[0176]

[0177] [Chemistry 14]

[0178]

[0179] In addition, examples of the organoaluminum oxy-compound (B-2) include modified methylaluminoxane represented by the following general formula [B2-3].

[0180] 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 more.

[0181] [Chemistry 15]

[0182]

[0183] The modified methylaluminoxane is prepared using trimethylaluminum and alkylaluminum other than trimethylaluminum. Such a compound is generally referred to as MMAO. Such MMAO can be prepared by the methods listed in the specification of U.S. Patent No. 4,960,878 and the specification of U.S. Patent No. 5,041,584.

[0184] Furthermore, examples of the organoaluminum oxy-compound (B-2) include boron-containing organoaluminum oxy-compounds represented by the following general formula [B2-4].

[0185] In the formula, R c represents a hydrocarbon group having 1 to 10 carbon atoms. d They may be the same as or different from each other and represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0186] [Chemistry 16]

[0187]

[0188] As the organoaluminum oxy-compound (B-2), methylaluminoxane, which is commercially available and thus easily available, and MMAO prepared using trimethylaluminum and triisobutylaluminum are preferred. Among them, MMAO having improved solubility in various solvents and storage stability is more preferred.

[0189] (Compound (B-3) that reacts with the transition metal compound (A) to form an ion pair)

[0190] 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 Japanese Patent Application Publication No. 1-501950, Japanese Patent Application Publication No. 1-502036, Japanese Patent Application Publication No. 3-179005, Japanese Patent Application Publication No. 3-179006, Japanese Patent Application Publication No. 3-207703, Japanese Patent Application Publication No. 3-207704, and USP No. 5321106. Furthermore, heteropoly compounds and isopoly compounds may also be mentioned. However, the aforementioned (B-2) organoaluminum oxide compound is not included.

[0191] As the ionic compound (B-3), preferably, a boron compound represented by the following general formula [B3-1] is used.

[0192] In the formula, as R e+ , for example H + , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptatrienyl cation, ferrocenium cation with transition metal, etc. f To R i They may be the same as or different from each other and are substituents selected from the group consisting of hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups, and are preferably substituted aryl groups.

[0193] [Chemistry 17]

[0194]

[0195] Examples of the boron compound represented by the general formula [B3-1] include triphenylcarbonium tetrakis(pentafluorophenyl)borate and the boron compounds described in

[0133] to

[0144] of International Publication No. 2015 / 122414.

[0196] The method for producing a cyclic olefin copolymer of the present embodiment preferably includes a catalyst removal step of removing the olefin polymerization catalyst. By including the catalyst removal step, the catalyst and the transition metal in the catalyst can be removed, and thus the electrical properties of the obtained cyclic olefin copolymer may be improved.

[0197] The polymerization reaction solution obtained in the polymerization step is mixed with an acidic aqueous solution such as a dilute hydrochloric acid aqueous solution, an alkaline aqueous solution such as ion exchange water or a sodium hydroxide aqueous solution, and after mixing, it is allowed to stand until the liquid-liquid interface separates, thereby extracting the cyclic olefin copolymer on the organic phase side and the catalyst on the water layer side, respectively, to separate the olefin copolymer from the catalyst.

[0198] The olefin polymerization catalyst contains a transition metal compound (A-2) represented by the following formula (VI), and the compound (B) preferably contains one or more selected from the group consisting of an organic aluminum oxide compound (B-2) and a compound (B-3) that reacts with the transition metal compound (A) to form an ion pair.

[0199] <Cyclic olefin copolymer (m)>

[0200] The cyclic olefin-based copolymer (m) of the present embodiment comprises: (A) one or more repeating units derived from olefins represented by the following general formula (I), (B) one or more repeating units derived from cyclic non-conjugated dienes represented by the following general formula (III), and (C) one or more repeating units derived from cyclic olefins represented by the following general formula (V).

[0201] [Chemistry 18]

[0202]

[0203] In the above general formula (I), R 300 It represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.

[0204] [Chemistry 19]

[0205]

[0206] 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 ~R76 and R a1 and R b1 may be the same as or different from each other, 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 from 0 to 10, R 75 and R 76 They may be bonded to each other to form a single ring or multiple rings.

[0207] [Chemistry 20]

[0208]

[0209] In the above general formula (V), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, w is 0 or 1, and R 61 ~R 78 and R a1 and R b1 may be the same as or different from each other, 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 They may be bonded to each other to form a single ring or multiple rings.

[0210] In the cyclic olefin copolymer (m), when the total molar number of repeating units in the cyclic olefin copolymer (m) is set to 100 mol%, the content of the repeating units (A) derived from olefin is preferably 10 mol% or more and 90 mol% or less, more preferably 15 mol% or more and 85 mol% or less, further preferably 20 mol% or more and 80 mol% or less, further preferably 30 mol% or more and 80 mol% or less, further preferably 35 mol% or more and 70 mol% or less, further preferably 40 mol% or more and 65 mol% or less; ... The content of the repeating unit (B) of the non-conjugated diene is preferably from 1 mol% to 40 mol%, more preferably from 2 mol% to 35 mol%, further preferably from 3 mol% to 25 mol%, further preferably from 5 mol% to 20 mol%; the content of the repeating unit (C) derived from the cyclic olefin is preferably from 1 mol% to 50 mol%, more preferably from 5 mol% to 48 mol%, further preferably from 10 mol% to 45 mol%, further preferably from 15 mol% to 43 mol%.

[0211] When the contents of the repeating units in the cyclic olefin copolymer (m) are within the above ranges, the crosslinked product obtained from the cyclic olefin copolymer composition has excellent stability over time in dielectric properties 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 properties can be obtained.

[0212] The olefin monomer as one of the copolymerization raw materials of the cyclic olefin-based copolymer (m) is a monomer which provides the skeleton represented by the above formula (I) by addition copolymerization, and is an olefin represented by the following general formula (Ia).

[0213] [Chemistry 21]

[0214]

[0215] 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. As the olefin represented by the general formula (Ia), for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. From the viewpoint of obtaining a crosslinked body (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 olefin monomers represented by the above formula (Ia) can be used.

[0216] The cyclic non-conjugated diene monomer as one of the copolymerization raw materials of the cyclic olefin copolymer (m) is a monomer which forms the structural unit represented by the above formula (III) by addition copolymerization. Specifically, a cyclic non-conjugated diene represented by the following general formula (IIIa) corresponding to the above general formula (III) is used.

[0217] [Chemistry 22]

[0218]

[0219] 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 b1may be the same as or different from each other, 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 from 0 to 10, R 75 and R 76 They may be bonded to each other to form a single ring or multiple rings.

[0220] The cyclic non-conjugated diene represented by the general formula (IIIa) is not particularly limited, and examples thereof include cyclic non-conjugated dienes represented by the following chemical formulas. Among them, 5-vinyl-2-norbornene, 8-vinyl-9-methyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, more preferably 5-vinyl-2-norbornene.

[0221] [Chemistry 23]

[0222]

[0223] [Chemistry 24]

[0224]

[0225] The cyclic non-conjugated diene represented by the above general formula (IIIa) can also be specifically represented by the following general formula (IIIb).

[0226] [Chemistry 25]

[0227]

[0228] In the general formula (IIIb), n is an integer of 0 to 10, R1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0229] The cyclic olefin-based copolymer (m) of the present embodiment is characterized in that it contains a structural unit derived from a cyclic non-conjugated diene represented by the general formula (III) and thus has a double bond in a side chain portion, that is, in a portion other than a copolymerized main chain.

[0230] The cyclic olefin monomer as one of the copolymerization raw materials of the cyclic olefin copolymer (m) is a monomer which forms the structural unit represented by the above formula (V) by addition copolymerization. Specifically, a cyclic olefin monomer represented by the following general formula (Va) corresponding to the above general formula (V) is used.

[0231] [Chemistry 26]

[0232]

[0233] 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 R 61 ~R 78 and R a1 and R b1 may be the same as or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl 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 They may be bonded to each other to form a single ring or multiple rings.

[0234] As specific examples of the cyclic olefin represented by the general formula (Va), compounds described in International Publication No. 2006 / 118261 can be used.

[0235] The cyclic olefin represented by the general formula (Va) is preferably selected from bicyclo[2.2.1]-2-heptene (also called norbornene) and tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene (also called tetracyclododecene), more preferably tetracyclo[4.4.0.1 2,5 .1 7,10 These cyclic olefins have the following advantages: since they have a rigid ring structure, it is easy to maintain the elastic modulus of the copolymer and the crosslinked body, and since they do not contain heterogeneous double bond structures, it is easy to control the crosslinking.

[0236] By using the olefin monomer represented by the general formula (Ia) and the cyclic olefin represented by the general formula (Va) as copolymerization components, the solubility of the cyclic olefin copolymer (m) in the solvent is further improved, so that the moldability becomes good and the product yield is improved.

[0237] In the cyclic olefin copolymer (m), it is preferred that the olefin constituting the olefin-derived repeating unit (A) comprises ethylene, the cyclic non-conjugated diene constituting the cyclic non-conjugated diene-derived repeating unit (B) comprises 5-vinyl-2-norbornene, and the cyclic olefin constituting the cyclic olefin-derived structural unit (C) comprises tetracyclo[4.4.0.1 2,5 .1 7,10 Thus, the stability of the cyclic olefin copolymer (m) when it is made into a varnish is further improved.

[0238] The cyclic olefin-based copolymer (m) may also be composed of (A) one or more repeating units derived from olefins represented by the general formula (I), (B) repeating units derived from cyclic non-conjugated dienes represented by the general formula (III), and (C) one or more repeating units derived from cyclic olefins represented by the general formula (V), and repeating units derived from cyclic olefins other than the cyclic non-conjugated dienes represented by the general formula (III) and the cyclic olefins represented by the general formula (V), and / or chain polyenes.

[0239] At this time, as the copolymerization raw material of the cyclic olefin-based copolymer (m), in addition to the olefin monomer represented by the general formula (Ia), the cyclic non-conjugated diene monomer represented by the general formula (IIIa), and the cyclic olefin monomer represented by the general formula (Va), a cyclic olefin monomer other than the cyclic non-conjugated diene monomer represented by the general formula (IIIa) and the cyclic olefin monomer represented by the general formula (Va), and / or a chain polyene monomer can also be used.

[0240] Examples of such cyclic olefin monomers and chain polyene monomers include cyclic olefins represented by the following general formula (VIa) or (VIIa), and chain polyenes represented by the following general formula (VIIIa). Two or more different cyclic olefins and chain polyenes may be used.

[0241] [Chemistry 27]

[0242]

[0243] In the general formula (VIa), x and d are integers of 0 or more, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, y and z are 0, 1 or 2, and R 81 ~R 99 may be the same as or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, i.e., an aliphatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group, R 89 and R 90 The carbon atom bonded to R 93 The bonded carbon atom or R 91 The carbon atom to which the bond is attached may be directly bonded or bonded via an alkylene group having 1 to 3 carbon atoms. When y=z=0, R 95 With R 92 or R 95 With R 99 They may be bonded to each other to form a monocyclic or polycyclic aromatic ring.

[0244] [Chemistry 28]

[0245]

[0246] In the general formula (VIIa), R 100 and R101 They may be the same as or different from each other, and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1≤f≤18.

[0247] [Chemistry 29]

[0248]

[0249] In the general formula (VIIIa), R 201 To R 206 They may be the same as or different from each other and are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. P is a linear or branched hydrocarbon group having 1 to 20 carbon atoms and may contain a double bond and / or a triple bond.

[0250] As specific examples of the cyclic olefins represented by the general formula (VIa) and the general formula (VIIa), the compounds described in paragraphs 0037 to 0063 of International Publication No. 2006 / 118261 can be used.

[0251] Specific examples of the chain polyene represented by the 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. In addition, cyclized polyenes obtained by cyclizing polyenes such as 1,3-butadiene and 1,5-hexadiene can also be used.

[0252] When the cyclic olefin copolymer (m) contains a structural unit derived from a chain polyene represented by the general formula (VIIIa) 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, the general formula (VIa) and the general formula (VIIa)], the content of the structural unit is usually 0.1 to 100 mol %, preferably 0.1 to 50 mol % relative to the total molar number of the repeating units derived from one or more olefins represented by the general formula (I), the repeating units derived from one or more cyclic non-conjugated dienes represented by the general formula (III) and the repeating units derived from one or more cyclic olefins represented by the general formula (V).

[0253] By using the olefin monomers shown in the above-mentioned general formula (I), the cyclic olefins shown in the general formula (VIa) or (VIIa) and the chain polyene shown in the general formula (VIIIa) as copolymerization components, the solubility of the cyclic olefin copolymer (m) in the solvent is further improved, so that the moldability becomes good and the yield rate of the product is improved. Among them, the cyclic olefins shown in the general formula (VIa) or (VIIa) are preferred. These cyclic olefins have the following advantages: since they have a rigid ring structure, it is easy to maintain the elastic modulus of the copolymer and the crosslinked body, and since they do not contain heterogeneous double bond structures, it is easy to control crosslinking.

[0254] The comonomer content and glass transition point (Tg) of the cyclic olefin copolymer (m) can be controlled by adjusting the monomer input ratio according to the target application.

[0255] The Tg of the cyclic olefin copolymer (m) is preferably 300° C. or lower, more preferably 250° C. or lower, further preferably 200° C. or lower, further preferably 170° C. or lower, further preferably 150° C. or lower. When Tg is below the above upper limit, the melt moldability of the cyclic olefin copolymer (m) and the solubility in a solvent when it is formed into a varnish are improved.

[0256] From the viewpoint of improving heat resistance, the Tg of the cyclic olefin copolymer (m) is preferably 100°C or higher, more preferably 110°C or higher, further preferably 120°C or higher, further preferably 125°C or higher, further preferably 130°C or higher.

[0257] From the viewpoint of improving the balance among melt moldability, solubility in solvents and heat resistance, the Tg of the cyclic olefin copolymer (m) is preferably 100°C to 300°C, more preferably 110°C to 250°C, further preferably 120°C to 200°C, further preferably 125°C to 170°C, further preferably 130°C to 150°C.

[0258] The intrinsic viscosity [η] of the cyclic olefin copolymer (m) measured in decalin 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 below the above upper limit, the moldability is improved. In addition, when the intrinsic viscosity [η] is above the above lower limit, the heat resistance and mechanical properties of the crosslinked body (Q) obtained by crosslinking the cyclic olefin copolymer composition are improved.

[0259] It should be noted that the intrinsic viscosity [η] of the cyclic olefin copolymer (m) can be controlled by polymerization conditions such as the polymerization catalyst, the co-catalyst, the amount of H2 added, the polymerization temperature, etc.

[0260] The number average molecular weight (Mn) of the cyclic olefin copolymer (m) measured by GPC is preferably 1,000 or more, more preferably 2,000 or more, further preferably 5,000 or more, further preferably 7,000 or more, and preferably 100,000 or less, more preferably 70,000 or less, further preferably 50,000 or less, further 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, further preferably 5,000 or more and 50,000 or less, further preferably 7,000 or more and 25,000 or less. Thus, the stability of the cyclic olefin copolymer (m) when it is made into a varnish is further improved. That is, when preparing and storing a varnish, the generation of precipitates and gelation can be further suppressed.

[0261] <Stereoregularity>

[0262] The cyclic olefin copolymer (m) of the present embodiment is considered to have a specific stereoregularity. Specifically, it is considered that the ratio of the meso structure to the racemic structure in the chain structure of the repeating unit (C)-repeating unit (A)-repeating unit (C) of the cyclic olefin copolymer (m) is within a certain range. Thus, the stability of the cyclic olefin copolymer (m) when it is made into a varnish is further improved.

[0263] The stereoregularity of the cyclic olefin copolymer (m) of the present embodiment can be determined by 13 C-NMR was used for determination. 13 The signal position of C-NMR and the method of measuring the signal are described below.

[0264] First, the specific stereoregularity of the present embodiment will be described by taking a polymer having a structure represented by the following general formula as an example.

[0265] The meso structure in the chain of repeating unit (C)-repeating unit (A)-repeating unit (C) is a structure described as αβm in FIG5 of Non-Patent Document 1. The racemic structure is a structure described as αβr in the figure.

[0266] [Chemistry 30]

[0267]

[0268] (Quoted from Figure 5 on page 9913 of Non-Patent Document 1)

[0269] FIG. 5 of Non-Patent Document 1 is an example showing a structure in which norbornene and ethylene form a chain. A structure in which the asymmetric carbons of adjacent norbornenes sandwiching ethylene have the same stereo orientation is a meso structure, and a structure in which the stereo orientations are different is a racemic structure. FIG. 5 of Non-Patent Document 1 describes an example in which norbornene is a cyclic olefin forming a repeating unit (C), but in the case in which the cyclic olefin forming a repeating unit (C) is a tetracyclic [4.4.0.1 2,5 .1 7,10 The same also applies to the case of -3-dodecene. The same also applies to the case of the cyclic olefin forming the repeating unit (C) being a monomer other than these.

[0270] In the cyclic olefin copolymer (m) of the present embodiment, (X B -X C ) / Y A The value of is preferably 0.2 or more and 2.0 or less. B -X C ) / Y A The value of corresponds to the ratio of the meso structure to the racemic structure in the chain structure of repeating unit (C)-repeating unit (A)-repeating unit (C).

[0271] (X B -X C ) / Y A The lower limit of is not particularly limited, but is preferably 0.2 or more, more preferably 0.3 or more, further preferably 0.4 or more, further preferably 0.5 or more, further preferably 0.6 or more, further preferably 0.7 or more, further preferably 0.8 or more.

[0272] (X B -X C ) / Y A The upper limit of is not particularly limited, but is preferably 2.0 or less, more preferably 1.8 or less, further preferably 1.6 or less, further preferably 1.5 or less, further preferably 1.3 or less, further preferably 1.1 or less, further preferably 1.0 or less.

[0273] (X B -X C ) / Y A The numerical range of is not particularly limited, and can be, for example, 0.2 to 2.0, 0.3 to 1.8, 0.4 to 1.6, 0.5 to 1.5, 0.6 to 1.3, 0.7 to 1.1, or 0.8 to 1.0.

[0274] By making (X B -X C ) / YA When the value of is within the above range, the stability of the cyclic olefin copolymer (m) when it is made into a varnish is improved. The above stereoregularity can be appropriately adjusted by selecting the polymerization method, the catalyst used, the composition, etc.

[0275] (X B -X C ) / Y A The value of is obtained as follows.

[0276] In the cyclic olefin copolymer of this embodiment 13 In the C-NMR spectrum, we obtain:

[0277] The integrated value of the signal in the range of 43.8 to 45.0 ppm is defined as X C ,

[0278] The integrated value of the signal in the range of 40.3 to 41.3 ppm is defined as Y. A ,

[0279] The total integrated value of the signal in the range of 38.4 to 39.9 ppm is defined as X. B When, (X B -X C ) / Y A The value of .

[0280] Here, X C is the integral value of the signal from the repeating unit (B), Y A is the integral value of the signal from the repeating unit (C), X B It is the sum of the integrated value of the signal derived from the repeating unit (B) and the integrated value of the signal derived from the repeating unit (C).

[0281] 13 In principle, the C-NMR spectrum is measured under the measurement conditions described in the Examples.

[0282] <Varnish-like cyclic olefin copolymer composition>

[0283] Hereinafter, the varnish-like cyclic olefin copolymer composition will be described.

[0284] 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 repeating units derived from olefins represented by the following general formula (I), (B) one or more repeating units derived from cyclic non-conjugated dienes represented by the following general formula (III), and (C) one or more repeating units derived from cyclic olefins represented by the following general formula (V).

[0285] [Chemistry 31]

[0286]

[0287] [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.

[0288] [Chemistry 32]

[0289]

[0290] [In the above general formula (III), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R 61 ~R 76 and R a1 and R b1 may be the same as or different from each other, 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 from 0 to 10, R 75 and R 76 They may be bonded to each other to form a single ring or multiple rings.

[0291] [Chemistry 33]

[0292]

[0293] [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 as or different from each other, 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 They may be bonded to each other to form a single ring or multiple rings.

[0294] In the above-mentioned 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 defined as R B , the integral value of the signal in the range of 40.3ppm or more and 41.3ppm or less is set to M C The total integrated value of the signal in the range of 38.4 ppm to 39.9 ppm is defined as R B+C When (R B+C-R B ) / M C The value of is preferably 0.2 or more and 2.0 or less.

[0295] The content of the cyclic olefin copolymer (m) in the varnish-like cyclic olefin copolymer composition is not particularly limited, but is preferably 30% to 70% by mass, more preferably 30% to 60% by mass, and even more preferably 30% to 55% by mass. If the content is within this range, the varnish-like cyclic olefin copolymer composition can further maintain a solution state.

[0296] <Organic Solvents>

[0297] The solvent used for preparing the varnish-like cyclic olefin copolymer composition is not particularly limited as long as it does not impair the solubility or affinity for the cyclic olefin copolymer (m).

[0298] The organic solvent preferably includes at least one selected from the group consisting of aromatic hydrocarbon solvents, cyclic hydrocarbon solvents, straight-chain hydrocarbon solvents and halogenated aromatic hydrocarbon solvents, more preferably includes at least one selected from the group consisting of aromatic hydrocarbon solvents such as toluene, benzene, xylene, mesitylene, and trimethylol; cyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and decahydronaphthalene; straight-chain hydrocarbon solvents such as heptane, hexane, octane, and decane; and halogenated hydrocarbon solvents such as trichloroethylene, dichloroethylene, and chlorobenzene. It is further preferred to include at least one selected from the group consisting of aromatic hydrocarbon solvents and cyclic hydrocarbon solvents, further preferably toluene and cyclohexane. These solvents can be used alone or in any proportion. Mix two or more.

[0299] The method for producing a varnish-like cyclic olefin-based copolymer composition according to the present embodiment may include other steps such as a precipitation step of precipitating the obtained polymer.

[0300] <Crosslinked body (Q)>

[0301] The crosslinked product (Q) of the present embodiment is obtained by crosslinking the cyclic olefin copolymer (m) of the present embodiment or the cyclic olefin copolymer composition of the present embodiment. There is no particular limitation on the crosslinking method of the cyclic olefin copolymer (m) of the present embodiment or the cyclic olefin copolymer composition of the present embodiment, and examples thereof include a method of crosslinking while molding into an arbitrary shape using a free radical polymerization initiator, sulfur, a hydrosilyl-containing compound, an electron beam, or other radiation, or a method of crosslinking after molding.

[0302] The crosslinking using a free radical polymerization initiator can be directly applied to the crosslinking method using a free radical polymerization initiator commonly used in polyolefins. That is, a free radical polymerization initiator such as dicumyl peroxide is added to the cyclic olefin copolymer (m) or the cyclic olefin copolymer composition, and heated and crosslinked. The mixing ratio of the free radical polymerization initiator is not particularly limited, but is generally 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 relative to 100 parts by mass of the cyclic olefin copolymer (m). When the mixing ratio of the free radical polymerization initiator is below the above upper limit, the dielectric properties of the crosslinked body (Q) are improved, and when it is above the above lower limit, the heat resistance and mechanical properties of the crosslinked body (Q) can be improved.

[0303] As the radical polymerization initiator, known thermal radical polymerization initiators, photoradical polymerization initiators, and combinations thereof can be used. Among these radical polymerization initiators, when a thermal radical polymerization initiator is used, the 10-hour half-life temperature is 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 diisopropylbenzene peroxide, tert-butyl cumene peroxide, 2,5-bis(tert-butylperoxy)2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)2,5-dimethylhexyne-3, di-tert-butyl peroxide, isopropylcumyl tert-butyl peroxide, and bis(α-tert-butylperoxyisopropyl)benzene; 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclododecane, n-butyl-4,4-bis(tert-butylperoxy)valerate, and ethyl-3,3 - Peroxy ketals such as bis(tert-butyl peroxy)butyrate and 3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxycyclononane; peroxy esters such as bis(tert-butyl peroxy)isophthalate, tert-butyl peroxybenzoate and tert-butyl peroxyacetate; hydroperoxides such as tert-butyl hydroperoxide, tert-hexyl hydroperoxide, isopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide and p-menthane hydroperoxide; bibenzyl compounds such as 2,3-dimethyl-2,3-diphenylbutane; 3,3,5,7,7-pentamethyl-1,2,4-trioxepane, etc.

[0304] Among the free radical polymerization initiators, specific examples of the photoradical polymerization initiator include benzoin alkyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzophenone, methyl benzoylformate, isopropylthioxanthone, and mixtures of two or more thereof. In addition, a sensitizer may be used together with these photoradical polymerization initiators. Examples of the sensitizer 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, anthracene, Aromatic hydrocarbons such as diphenyl disulfide, sulfur compounds such as nitroaniline, 2-chloro-4-nitroaniline, 5-nitro-2-aminotoluene, tetracyanoethylene and other nitrogen compounds, etc.

[0305] When crosslinking is performed by sulfur or the like, a sulfur compound, and, if necessary, a vulcanization accelerator and a vulcanization accelerator auxiliary are added to the cyclic olefin copolymer composition and heated to perform a crosslinking reaction. The amount of the sulfur compound added is not particularly limited, but from the perspective of making the crosslinking reaction efficient, improving the physical properties of the obtained crosslinked product, and achieving economic efficiency, it is usually used in an amount of 0.1 to 10 parts by mass, preferably 0.3 to 5 parts by mass, relative to 100 parts by mass of the cyclic olefin copolymer (m). When a vulcanization accelerator or a vulcanization accelerator auxiliary is used in combination, it is usually used in an amount of 0.1 to 20 parts by mass, preferably 0.2 to 10 parts by mass.

[0306] As the sulfur compound used to induce the crosslinking reaction, various known sulfur compounds can be used, and examples thereof include sulfur, sulfur monochloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dimethyldithiocarbamate. In addition, various vulcanization accelerators can be used as vulcanization accelerators, including thiazole series such as N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-benzothiazolesulfenamide, N,N-diisopropyl-2-benzothiazolesulfenamide, 2-mercaptobenzothiazole, 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-diethyl-4-morpholinylthio)benzothiazole, and benzothiazolyl disulfide; guanidine series such as diphenylguanidine, triphenylguanidine, di-o-tolylguanidine, o-tolylbiguanide, and diphenylguanidine phthalate; acetaldehyde-aniline reaction products; butyraldehyde-aniline condensation products; aldehyde amines such as hexamethylenetetramine and acetaldehyde ammonia , or aldehyde-ammonia system; imidazoline system such as 2-mercaptoimidazoline; thiourea system such as thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, and di-o-tolylthiourea; thiuram system such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, and dipentamethylenethiuram tetrasulfide; dithioacid salt system such as zinc dimethyldithiocarbamate, zinc diethylthiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, and tellurium diethyldithiocarbamate; xanthate system such as zinc dibutyl xanthate, etc. Examples of the vulcanization accelerator include metal oxides such as zinc oxide, active zinc white, zinc carbonate, composite zinc white, magnesium oxide, yellow lead (Litharge), red lead, and basic lead carbonate; fatty acids such as stearic acid, oleic acid, lauric acid, and lead stearate; and organic amine / diols such as triethanolamine and diethylene glycol.

[0307] The temperature for crosslinking the cyclic olefin copolymer (m) or the cyclic olefin copolymer composition with a free radical polymerization initiator or using sulfur crosslinking is usually 100 to 300°C, preferably 120 to 250°C, and more preferably 120 to 220°C. The temperature can also be changed in stages to perform crosslinking. When it is above the above lower limit, crosslinking can be fully performed. In addition, when it is below the above upper limit, the coloring of the obtained crosslinked body can be suppressed, and the process can be simplified. It should be noted that, for reference, polybutadiene, which is a representative double bond-containing polymer, cannot usually be crosslinked under the above conditions and requires crosslinking conditions at a high temperature such as 300°C.

[0308] The cyclic olefin copolymer (m) or cyclic olefin copolymer composition of the present embodiment may also be crosslinked using a hydrosilyl-containing compound having at least two hydrosilyl groups in one molecule. Crosslinking using a hydrosilyl-containing compound may be performed, for example, according to the method described in Japanese Patent Application Laid-Open No. 2015-193680. Detailed description is omitted here.

[0309] The method of cross-linking using electron beams or other radiation has the advantage that there is no limitation on the temperature or fluidity during molding. Examples of radiation include electron beams, gamma rays, UV rays, and the like.

[0310] In any of the methods of using a radical polymerization initiator, sulfur, a hydrosilyl-containing compound, and the like, and the method of cross-linking using radiation, cross-linking may be performed in combination with a cross-linking aid.

[0311] 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 mixture, and allyl methacrylate; vinyl monomers such as divinylbenzene, vinyltoluene, and vinylpyridine; hexamethylenediallylnadic acid esters; Allyl compounds such as amine, diallyl itaconate, diallyl phthalate, diallyl isophthalate, diallyl monoglycidyl isocyanurate, triallyl cyanurate, triallyl isocyanurate; maleimide compounds such as N,N'-m-phenylene bismaleimide, N,N'-(4,4'-methylenediphenylene) dimaleimide, etc.; cyclic non-conjugated dienes such as vinyl norbornene, ethylidene norbornene, and dicyclopentadiene. These crosslinking aids can be used alone or in combination.

[0312] The crosslinked product (Q) according to the present embodiment may contain a heat stabilizer, a weather stabilizer, an antistatic agent, a slip agent, an anti-blocking agent, an anti-fogging agent, a lubricant, a dye, a pigment, a natural oil, a synthetic oil, a wax, an organic or inorganic filler, etc. as needed to the extent that the purpose of the present invention is not impaired, and the mixing ratio is an appropriate amount. Specific examples of stabilizers that can be added as an optional component include phenolic antioxidants such as tetrakis[methylene-3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate alkyl ester, and 2,2'-oxalamidobis[ethyl-3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; fatty acid metal salts such as zinc stearate, calcium stearate, and calcium 12-hydroxystearate; polyhydric alcohol fatty acid esters such as glycerol monostearate, glycerol monolaurate, glycerol distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. These may be added alone or in combination, and for example, a combination of tetrakis[methylene-3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, zinc stearate, and glycerol monostearate may be mentioned.

[0313] Examples of the organic or inorganic filler include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balls, 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, polyamide fiber, and the like.

[0314] In order to mix the crosslinked product (Q) and various additives, a method of melt blending the cyclic olefin copolymer (m) and 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 and dispersed in an appropriate solvent can be adopted. The solvent is, for example, a saturated hydrocarbon such as heptane, hexane, decane, cyclohexane; an aromatic hydrocarbon such as toluene, benzene, xylene, etc.

[0315] The crosslinking reaction can be carried out by making a mixture of the cyclic olefin copolymer composition and the above-mentioned free radical polymerization initiator, sulfur, hydrosilyl-containing compound and the like into a molten state, or can be carried out in a solution state obtained by dissolving or dispersing the mixture in a solvent, or can be carried out after volatilizing the solution dissolved in a solvent to form it into any form such as a film or a coating and then further carrying out the crosslinking reaction.

[0316] When reacting in a molten state, a mixing device such as a mixing roll, a Banbury mixer, an extruder, a kneader, a continuous mixer, etc. is used to melt and knead the mixture of raw materials to react. In addition, a crosslinking reaction can also be further performed after molding using any method.

[0317] As the solvent used when the reaction is carried out in a solution state, the same solvent as used in the above-mentioned solution mixing method can be used.

[0318] When the cross-linking reaction is carried out using electron beams, other radiation, or UV, the reaction may be carried out after shaping by any method.

[0319] <Molding>

[0320] The molded product of the present embodiment includes the crosslinked product (Q) of the present embodiment.

[0321] The molded product of the present embodiment is, for example, a film or a sheet.

[0322] As a method for forming a film or sheet using the cyclic olefin copolymer (m) of the present embodiment or the cyclic olefin copolymer composition of the present embodiment, various known methods can be applied. For example, the following method can be cited: by applying the above-mentioned varnish on a supporting substrate such as a thermoplastic resin film and drying it, and then performing a heat treatment, etc., so that the cyclic olefin copolymer (m) of the present embodiment or the cyclic olefin copolymer composition of the present embodiment is cross-linked to form it. The coating method for applying the varnish to the supporting substrate is not particularly limited, and for example, coating using a spin coater, coating using a spray coater, coating using a rod coater, etc. can be cited.

[0323] Another example is a method of melt-molding the cyclic olefin copolymer (m) of the present embodiment or the cyclic olefin copolymer composition of the present embodiment to obtain a film or a sheet.

[0324] The film or sheet of the present embodiment can be used in various applications as a laminate by laminating on a substrate. Various known methods can be applied to the method of forming the laminate of the present embodiment.

[0325] For example, a laminate can be produced by laminating a film or sheet produced by the above method on a substrate and, if necessary, heat-curing the laminate by pressing or the like.

[0326] Alternatively, a laminate may be produced by laminating an electrical insulating layer including the crosslinked body described above on a conductor layer.

[0327] The cyclic olefin copolymer (m) of the present embodiment or the cyclic olefin copolymer composition of the present embodiment can also be formed on the surface layer of various multilayer molded bodies or multilayer laminated films. In this case, the resin layer formed by the cyclic olefin copolymer (m) of the present embodiment or the cyclic olefin copolymer composition of the present embodiment is preferably 100 μm or less.

[0328] As various multilayer molded bodies or multilayer laminated films, for example, there can be mentioned a multilayer molded body for an optical lens in which the cyclic olefin copolymer (m) of the present embodiment or the cyclic olefin copolymer composition of the present embodiment is formed on the surface of a resin optical lens, and a multilayer gas barrier film in which the cyclic olefin copolymer (m) of the present embodiment or the cyclic olefin copolymer composition of the present embodiment is formed in order to impart gas barrier properties to the surface of a resin film such as a PET film or a PE film.

[0329] The prepreg of the present embodiment is formed by compositely combining the cyclic olefin copolymer (m) of the present embodiment or the cyclic olefin copolymer composition of the present embodiment with a sheet-like fiber base material.

[0330] The method for producing the prepreg is not particularly limited, and various known methods can be applied. For example, there can be mentioned a method comprising the steps of: impregnating the sheet-like fiber base material with the varnish to obtain an impregnated body; and heating the obtained impregnated body to dry the solvent contained in the varnish.

[0331] The impregnation of the sheet-like fiber substrate with the varnish can be carried out, for example, by applying a predetermined amount of the varnish to the sheet-like fiber substrate by a known method such as spray coating, dip coating, roll coating, curtain coating, die coating, or slit coating, and if necessary, overlaying a protective film thereon, and pressing from the upper side with a roller or the like.

[0332] The step of heating the impregnated body to dry 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 through a heating furnace in a continuous process.

[0333] In the present embodiment, after the sheet-like fiber base material is impregnated with the varnish, the obtained impregnated body is heated to a predetermined temperature, whereby the solvent contained in the varnish evaporates, thereby obtaining a prepreg.

[0334] As the fiber constituting the sheet-like fiber substrate of the present embodiment, inorganic and / or organic fibers can be used, without particular limitation, and examples thereof include organic fibers such as PET (polyethylene terephthalate) fibers, aramid fibers, ultrahigh molecular weight polyethylene fibers, polyamide (nylon) fibers, and liquid crystal polyester fibers; inorganic fibers such as glass fibers, carbon fibers, alumina fibers, tungsten fibers, molybdenum fibers, titanium fibers, steel fibers, boron fibers, silicon carbide fibers, and silicon dioxide fibers. Among them, organic fibers and glass fibers are preferred, and aramid fibers, liquid crystal polyester fibers, and glass fibers are particularly preferred. As glass fibers, E glass, NE glass, S glass, D glass, H glass, and T glass can be cited.

[0335] The impregnation of the sheet-like fiber base material with the varnish is carried out by, for example, dipping or coating. The impregnation can be repeated multiple times as necessary.

[0336] These sheet-like fiber substrates can be used alone or in combination of two or more, and their usage amount can be appropriately selected as needed, usually in the range of 10 to 90% by mass, preferably 20 to 80% by mass, and more preferably 30 to 70% by mass in the prepreg or laminate. Within this range, the dielectric properties and mechanical strength of the obtained laminate are highly balanced, which is preferred.

[0337] The thickness of the prepreg of this embodiment is appropriately selected according to the purpose of use, and is usually 0.001 to 10 mm, preferably 0.005 to 1 mm, and more preferably 0.01 to 0.5 mm. If it is within this range, the shapeability during lamination, the mechanical strength and toughness of the laminate obtained by curing can be fully exerted, so it is preferred.

[0338] The cyclic olefin copolymer (m) of the present embodiment or the cyclic olefin-based copolymer composition of the present embodiment is excellent in dielectric properties, heat resistance, mechanical properties, and the like, and therefore can be suitably used for circuit boards.

[0339] As a method for manufacturing a circuit substrate, a generally known method can be used without particular limitation. For example, the film, sheet or prepreg manufactured by the above method is heated and cured by lamination pressing, etc. to form an electrical insulating layer. Then, a conductor layer is laminated on the obtained electrical insulating layer by a known method to produce a laminate. Then, the conductor layer in the laminate is subjected to circuit processing, etc. to obtain a circuit substrate.

[0340] As the metal that becomes the conductor layer, copper, aluminum, nickel, gold, silver, stainless steel and the like can be used. As the method for forming the conductor layer, for example, there can be mentioned: a method of forming the metal into a foil or the like and heat-melting it on the electrical insulating layer; a method of forming the metal into a foil or the like and attaching it to the electrical insulating layer using an adhesive; or a method of forming a conductor layer formed of the metal on the electrical insulating layer by a method such as sputtering, evaporation, plating, etc. As the form of the circuit board, it can be any of a single-sided board and a double-sided board.

[0341] Such a circuit board can be used as an electronic device by mounting electronic components such as semiconductor elements, for example. The electronic device can be produced based on known information.

[0342] Examples of such electronic devices include ICT infrastructure equipment such as servers, routers, supercomputers, mainframes, and workstations; antennas such as GPS antennas, antennas for wireless base stations, millimeter wave antennas, and RFID antennas; communication equipment such as mobile phones, smart phones, PHS, PDAs, and tablet terminals; digital devices such as personal computers, televisions, digital cameras, digital video cameras, POS terminals, wearable terminals, and digital media players; in-vehicle electronic equipment such as electronic control system devices, in-vehicle communication equipment, car navigation equipment, millimeter wave radars, and in-vehicle camera modules; semiconductor testing equipment, high-frequency measuring equipment, etc.

[0343] In addition, the cyclic olefin copolymer (m) of the present embodiment or the cyclic olefin copolymer composition of the present embodiment can be crosslinked and foamed to form a foam. In this case, the aforementioned foaming agent can be added to the cyclic olefin copolymer composition.

[0344] <Purpose>

[0345] The crosslinked product (Q) of the present embodiment has excellent solvent resistance, heat resistance, mechanical strength, and transparency. Therefore, the molded product formed from the crosslinked product (Q) can be used in, for example, optical fibers, optical waveguides, optical disk substrates, filters, lenses, optical adhesives, PDP filters, organic EL coating materials, base film substrates for solar cells in the aerospace field, coating materials for solar cells or thermal control systems, semiconductor elements, light-emitting diodes, various memory-type electronic components, hybrid ICs, MCMs, circuit boards, prepregs for forming insulating layers of circuit boards, laminates, outer coating materials or interlayer insulating materials for display components, The present invention can be used in the following applications: liquid crystal display, solar cell substrates, medical instruments, automotive components, mold release agents, resin modifiers, transparent substrates for displays, lithium ion battery components, semiconductor process components, thin film capacitors, gas barrier coating materials, wire covering materials, automotive components, aerospace components, semiconductor process materials, wire covering materials, lithium ion battery components, fuel cell components, capacitor films, flexible display components, anchor coating materials, transparent adhesives, modifying materials, crosslinking aids, medical containers, medical catheter components, waterproof sealing materials, mold release materials, hard coating materials, and foaming modifiers.

[0346] In particular, since the dielectric properties are excellent in stability over time, solvent resistance, heat resistance, transparency, mechanical properties, etc. are also excellent, it can be suitably used for high-frequency applications such as high-frequency circuit substrates. Furthermore, since the gas barrier properties are also excellent, it can be suitably used as a substrate for liquid crystal displays, a substrate, film or sheet for solar cells.

[0347] As mentioned above, although embodiment of this invention was described, these are illustrations of this invention, and various structures other than the above-mentioned can also be adopted.

[0348] In addition, the present invention is not limited to the above-mentioned embodiment, and modifications, improvements, etc. within the scope that can achieve the object of the present invention are included in the present invention.

[0349] Example

[0350] Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited thereto.

[0351] In addition, the composition of the cyclic olefin type copolymer (m) used in the synthesis example, the Example, and the comparative example was measured by the following method.

[0352] [Method for measuring the content of each structural unit constituting the cyclic olefin copolymer]

[0353] The contents of the structural unit (A), the structural unit (B), and the structural unit (C) were measured under the following conditions using an "EXcalibur 270" nuclear magnetic resonance apparatus manufactured by JEOL Ltd.

[0354] Cumulative times: 16 to 64 times

[0355] Measuring temperature: room temperature

[0356] The above measurements obtained 1 The H-NMR spectrum is calculated from the intensities of the signal derived from hydrogen directly bonded to the double-bonded carbon and the signal derived from other hydrogen.

[0357] 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 measurement and obtained as a standard polystyrene conversion value. The GPC measurement was performed under the following conditions.

[0358] Device: GPC HLC-8321 (manufactured by Tosoh Corporation)

[0359] Solvent: o-dichlorobenzene

[0360] Column: TSKgel GMH6-HT×2, TSKgel GMH6-HTL×2 (both manufactured by Tosoh Corporation)

[0361] Flow rate: 1.0ml / min

[0362] Sample: 1 mg / mL o-dichlorobenzene solution

[0363] Temperature: 140℃

[0364] [Glass transition temperature Tg (℃)]

[0365] The glass transition temperature Tg of the cyclic olefin copolymer was measured in an N2 (nitrogen) atmosphere using DSC-6220 manufactured by Shimadzu Scientific Corporation. The cyclic olefin copolymer was heated from room temperature to 200°C at a heating rate of 10°C / min and then kept for 5 minutes, then cooled to -20°C at a cooling rate of 10°C / min and then kept for 5 minutes. Then, the glass transition point (Tg) of the cyclic olefin copolymer was obtained from the endothermic curve when the temperature was increased to 200°C at a heating rate of 10°C / min.

[0366] [ 13 C-NMR measurement]

[0367] 13 C-NMR measurement was carried out under the following conditions.

[0368] Equipment: AVANCE III Cryo-500 NMR manufactured by Bruker BioSpin

[0369] Determination of the core: 13 C(125MHz)

[0370] Measurement mode: Single pulse proton (with reverse gate) decoupled

[0371] Pulse width: 90 degrees

[0372] Points: 64000

[0373] Measuring range: -55~195ppm (total 250ppm)

[0374] Repeat time: 12 seconds

[0375] Total times: 256 times

[0376] Solvent: 1,2,2-Tetrachloroethane-d2

[0377] Concentration: 10% w / v

[0378] Temperature: 120℃

[0379] Chemical shift standard: Tetramethylsilyl standard (1,1,2,2-tetrachloroethane-d2: equivalent to 74.2ppm)

[0380] The following raw materials were used in the experiments.

[0381] Transition metal compounds (1):

[0382] A transition metal compound (1) corresponding to the transition metal compound (A) was synthesized by the method described in Macromolecules 2011, 44, 1986.

[0383] [Chemistry 34]

[0384]

[0385] 〔In the formula, t Bu is tert-butyl, i Pr is isopropyl. 〕

[0386] Transition metal compounds (2):

[0387] A transition metal compound (2) which does not belong to the transition metal compound (A) is synthesized by the method described in Japanese Patent Application Laid-Open No. 2004-331965.

[0388] [Chemistry 35]

[0389]

[0390] Transition metal compounds (3):

[0391] The transition metal compound (3) which does not belong to the transition metal compound (A) is synthesized by the method described in J. Organomet. Chem., 1997, 527, 297-300.

[0392] [Chemistry 36]

[0393]

[0394] Ethylene (manufactured by Sumitomo Chemicals Co., Ltd.)

[0395] Organic aluminum oxide compound (B-2): modified methylaluminoxane (MMAO, manufactured by Tosoh Fine Chemicals Co., Ltd.)

[0396] Compound (B-3) that reacts with the transition metal compound (A) to form an ion pair: triphenylcarbonium tetrakis(pentafluorophenyl)borate (manufactured by AGC Corporation)

[0397] Toluene (Wako Pure Chemical Industries, Ltd.: Wako Special Grade)

[0398] 5-vinyl-2-norbornene (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0399] 2-Norbornene (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0400] Acetone (Wako Pure Chemical Industries, Ltd.: Wako Special Grade)

[0401] Methanol (Wako Pure Chemical Industries, Ltd.: Wako Special Grade)

[0402] Cyclic olefin copolymer (m):

[0403] [Synthesis Example 1: Cyclic olefin copolymer (m-1)]

[0404] In a 1 L SUS autoclave fully purged with nitrogen, 339 mL of toluene, 65 mL of 5-vinyl-2-norbornene (hereinafter also referred to as VNB), and tetracyclo[4.4.0.1 2,5 .1 7,10]-3-dodecene (hereinafter also referred to as TD) 96 ml, MMAO hexane solution of 1.5 mmol in terms of Al, and hydrogen 93 ml, 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 triphenylcarbonium tetrakis (pentafluorophenyl) borate dissolved in toluene were added, and the mixture was reacted at 35°C for 30 minutes. Then, 2.5 μmol of transition metal compound (1) and 10 μmol of triphenylcarbonium tetrakis (pentafluorophenyl) borate were added. After further 30 minutes, 2.5 μmol of transition metal compound (1) and 10 μmol of triphenylcarbonium tetrakis (pentafluorophenyl) borate were added. After a total of 100 minutes of polymerization, a small amount of methanol was added to terminate the polymerization. After the polymerization was completed, ion exchange water was added to the obtained polymer solution, and the mixture was stirred for 1 hour. Then, the organic layer was filtered with filter paper to remove the catalyst. The organic layer was put into acetone to precipitate a polymer, and the mixture was stirred and filtered with 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 structure derived from TD in the polymer determined by NMR was 30 mol%, the composition ratio of the structure derived from VNB was 16 mol%, and the number average molecular weight (Mn) determined by GPC measurement was 21,000.

[0405] [Synthesis Example 2: Cyclic olefin copolymer (m-2)]

[0406] To a 1 L SUS autoclave fully 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 of a hexane solution of MMAO in terms of Al, and 124 mL of hydrogen were added, and ethylene was introduced into the system until the total pressure reached 0.75 MPa. 2.5 μmol of a transition metal compound (1) dissolved in toluene and 10 μmol of triphenylcarbonium tetrakis(pentafluorophenyl)borate dissolved in toluene were added, and the mixture was reacted at 35° C. for 30 minutes. Then, 2.5 μmol of a transition metal compound (1) and 10 μmol of triphenylcarbonium tetrakis(pentafluorophenyl)borate were added. After further 30 minutes, 2.5 μmol of a transition metal compound (1) and 10 μmol of triphenylcarbonium tetrakis(pentafluorophenyl)borate were added. After a total of 100 minutes of polymerization, a small amount of methanol was added to terminate the polymerization. After the polymerization, ion exchange water was added to the obtained polymer solution, and after stirring for 1 hour, the organic layer was filtered with filter paper to remove the catalyst. The organic layer was put into acetone to precipitate the polymer, and after stirring, it was filtered with filter paper. The obtained polymer was dried under reduced pressure at 80°C for 10 hours to obtain an ethylene / NB / VNB copolymer. The composition ratio of the structure derived from NB in ​​the polymer determined by NMR was 40 mol%, and the composition ratio of the structure derived from VNB was 10 mol%. The number average molecular weight (Mn) determined by GPC was 8,000.

[0407] [Synthesis Example 3: Cyclic olefin copolymer (m-3)]

[0408] After adding 410 mL of toluene, 19 ml of VNB, 71 ml of TD, a toluene solution of MMAO in an amount of 1.5 mmol in terms of Al, and 744 ml of hydrogen to a SUS autoclave having an internal volume that was fully purged with nitrogen, ethylene was introduced into the system until the total pressure reached 0.78 MPa. 40 μmol of the transition metal compound (2) dissolved in toluene was added, and after polymerization at 35°C for 180 minutes, a small amount of methanol was added to stop the polymerization. After the polymerization was completed, ion exchange water was added to the obtained polymer solution, and after stirring for 1 hour, the organic layer was filtered with filter paper to remove the catalyst. The organic layer was put into acetone to precipitate the polymer, and after stirring, it was filtered with 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 structure derived from TD in the polymer determined by NMR was 30 mol%, and the composition ratio of the structure derived from VNB was 12 mol%. The number average molecular weight (Mn) determined by GPC measurement was 11,000.

[0409] [Synthesis Example 4: Cyclic olefin copolymer (m-4)]

[0410] After adding 433 mL of toluene, 15 mL of VNB, 52 mL of a 5M toluene solution of NB, a hexane solution of MMAO in an amount of 1.5 mmol in terms of Al, and 1488 mL of hydrogen to a SUS autoclave having an internal volume of 1 L which had been fully purged with nitrogen, ethylene was introduced into the system until the total pressure reached 0.78 MPaG. 4 μmol of a transition metal compound (2) dissolved in toluene was added to initiate polymerization. After reacting at 35°C for 40 minutes, 4 μmol of a transition metal compound (2) was added, and the process of further adding 4 μmol of a transition metal compound (2) every 30 minutes was repeated twice, resulting in a total polymerization of 130 minutes. Then, polymerization was terminated by adding a small amount of methanol. After the polymerization was completed, ion exchange water was added to the obtained polymer solution, and after stirring for 1 hour, the organic layer was filtered with filter paper to remove the catalyst. The organic layer was put into acetone to precipitate the polymer, and after stirring, it was filtered with filter paper. The obtained polymer was dried under reduced pressure at 80°C for 10 hours to obtain an ethylene / NB / VNB copolymer. The composition ratio of the structure derived from NB in ​​the polymer determined by NMR was 33 mol %, and the composition ratio of the structure derived from VNB was 10 mol %. The number average molecular weight (Mn) determined by GPC measurement was 7,500.

[0411] [Synthesis Example 5: Cyclic olefin copolymer (m-5)]

[0412] After adding 340 mL of toluene, 35 mL of VNB, 82 mL of a 5M toluene solution of NB, 44 mL of TD, a hexane solution of MMAO in an amount of 2 mmol in terms of Al, and 558 mL of hydrogen to a 1 L SUS autoclave fully purged with nitrogen, ethylene was introduced into the system until the total pressure reached 0.52 MPaG. 4.7 μmol of a transition metal compound (2) dissolved in toluene was added to initiate polymerization. After reacting at 35° C. for 40 minutes, 9.3 μmol of a transition metal compound (2) was added, and after further 30 minutes, 9.3 μmol of a transition metal compound (2) was added and reacted for 30 minutes, for a total of 100 minutes of polymerization. Then, a small amount of methanol was added to stop the polymerization. After the polymerization was completed, ion exchange water was added to the obtained polymer solution, and after stirring for 1 hour, the organic layer was filtered with filter paper to remove the catalyst. The organic layer was put into acetone to precipitate the polymer, and after stirring, it was filtered with filter paper. The obtained polymer was dried under reduced pressure at 80°C for 10 hours to obtain an ethylene / TD / NB / VNB copolymer. The composition ratio of the structure derived from TD in the polymer determined by NMR was 14 mol%, the composition ratio of the structure derived from NB was 17 mol%, and the composition ratio of the structure derived from VNB was 10 mol%. The number average molecular weight (Mn) determined by GPC measurement was 8,400.

[0413] [Synthesis Example 6: Cyclic olefin copolymer (m-6)]

[0414] After adding 378 mL of toluene, 79 ml of VNB, 43 ml of TD, a toluene solution of MMAO in an amount of 1.5 mmol in terms of Al, and 744 ml of hydrogen to a 1 L SUS autoclave fully purged with nitrogen, ethylene was introduced into the system until the total pressure reached 0.78 MPa. 40 μmol of the transition metal compound (2) dissolved in toluene was added, and after polymerization at 35°C for 180 minutes, a small amount of methanol was added to stop the polymerization. After the polymerization was completed, ion exchange water was added to the obtained polymer solution, and after stirring for 1 hour, the organic layer was filtered with filter paper to remove the catalyst. The organic layer was put into acetone to precipitate the polymer, and after stirring, it was filtered with 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 structure derived from TD in the polymer determined by NMR was 13 mol%, and the composition ratio of the structure derived from VNB was 30 mol%, and the number average molecular weight (Mn) determined by GPC measurement was 11,000.

[0415] [Synthesis Example 7: Cyclic olefin copolymer (m-7)]

[0416] After adding 225 mL of toluene, 65 ml of VNB, 180 ml of TD, 1.5 mmol of a toluene solution of triisobutylaluminum in terms of Al, and 93 ml of hydrogen to a SUS autoclave having an internal volume fully purged with nitrogen, ethylene was introduced into the system until the total pressure reached 0.75 MPa. 2.5 μmol of the transition metal compound (3) dissolved in toluene and 10 μmol of triphenylcarbonium tetrakis(pentafluorophenyl)borate dissolved in toluene were added, and the mixture was reacted at 35° C. for 30 minutes. Then, 2.5 μmol of the transition metal compound (1) and 10 μmol of triphenylcarbonium tetrakis(pentafluorophenyl)borate were added. After further 30 minutes, 2.5 μmol of the transition metal compound (1) and 10 μmol of triphenylcarbonium tetrakis(pentafluorophenyl)borate were added. After a total of 100 minutes of polymerization, a small amount of methanol was added to terminate the polymerization. After the polymerization, ion exchange water was added to the obtained polymer solution, and after stirring for 1 hour, the organic layer was filtered with filter paper to remove the catalyst. The organic layer was put into acetone to precipitate the polymer, and after stirring, it was filtered with 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 structure derived from TD in the polymer determined by NMR was 30 mol%, and the composition ratio of the structure derived from VNB was 10 mol%, and the number average molecular weight (Mn) determined by GPC was 9,000.

[0417] [Examples 1 to 4, Comparative Examples 1 to 5]

[0418] Each varnish was prepared by the method shown below and evaluated.

[0419] (Preparation of varnish)

[0420] The cyclic olefin copolymer (m) and cyclohexane or toluene were mixed in the amounts (parts by mass) listed in Table 1 and stirred overnight to obtain a varnish-like cyclic olefin copolymer resin composition.

[0421] (stereoregularity)

[0422] conduct 13 C-NMR measurement, the integral 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 40.3ppm and below 41.3ppm is set to Y A , the total integrated value of the signal in the range of 38.4 ppm or more and 39.9 ppm or less is set to X B When (X B -X C ) / Y A The value of .

[0423] Here, the stability of the varnish was evaluated as follows.

[0424] The varnish having no precipitate and no gelation observed after standing for 2 weeks in an environment of temperature 22°C to 27°C and humidity 30% to 70% was recorded as "A", the varnish having no precipitate but gelation observed after standing for 2 weeks in the above environment was recorded as "B", and the varnish having dissolved residue after stirring overnight or having precipitate after standing for 2 weeks in the above environment was recorded as "C".

[0425] [Table 1]

[0426]

[0427] In Table 1, the “-” in the stereoregularity column indicates that the stereoregularity cannot be determined (X B -X C ) / Y A The value of .

[0428] This application claims the benefit of priority based on Japanese patent application No. 2022-102901, filed on June 27, 2022, the disclosure of which is incorporated herein in its entirety.

Claims

1. A method for producing a varnish-like cyclic olefin copolymer composition, which is a method for producing a varnish-like cyclic olefin copolymer composition comprising a cyclic olefin copolymer (m) and an organic solvent, characterized in that: The cyclic olefin copolymer (m) comprises: (A) one or more repeating units derived from olefins represented by the following general formula (I), (B) one or more repeating units derived from cyclic non-conjugated dienes represented by the following general formula (III), and (C) one or more repeating units derived from cyclic olefins 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, R 61 ~R 76 and R a1 and R b1 may be the same as or different from each other 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 from 0 to 10, R 75 and R 76 They may be bonded to each other to form a single ring or multiple rings, [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 as or different from each other 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 They may be bonded to each other to form a single ring or multiple rings, 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); 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), [Chemistry 4] In the 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, L each independently represents a monovalent anionic ligand in which an atom of Group 15 of the periodic table serves 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 substituents 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 substituents thereof, and R 5 ~R 9 Any two or three of the above may be condensed to form a ring, and the formed ring may be an aromatic ring containing a conjugated double bond. [Chemistry 5] In the 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 substituents 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 substituents thereof, and R 10 ~R 17 The adjacent groups in the formula (A) may be bonded to each other to form a ring, and the formed ring may be an aromatic ring containing a conjugated double bond. The compound (B) contains one or more 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 manufacturing method according to claim 1, wherein: The content of the cyclic olefin copolymer (m) in the varnish-like cyclic olefin copolymer composition is 30% by mass or more.

3. The manufacturing method according to claim 1 or 2, wherein: The organic solvent includes at least one selected from the group consisting of aromatic hydrocarbon solvents, cyclic hydrocarbon solvents, linear hydrocarbon solvents, and halogenated aromatic hydrocarbon solvents.

4. The manufacturing method according to any one of claims 1 to 3, wherein: When the total molar number of repeating units in the cyclic olefin-based copolymer (m) is set to 100 mol%, the content of the repeating units (A) derived from olefin is 10 mol% or more and 90 mol% or less, the content of the repeating units (B) derived from the cyclic non-conjugated diene is 1 mol% or more and 40 mol% or less, and the content of the repeating units (C) derived from the cyclic olefin is 1 mol% or more and 50 mol% or less.

5. The manufacturing method according to any one of claims 1 to 4, wherein: The cyclic non-conjugated diene constituting the repeating unit (B) derived from a cyclic non-conjugated diene includes 5-vinyl-2-norbornene.

6. The manufacturing method according to any one of claims 1 to 5, wherein: The cyclic olefin constituting the structural unit (C) derived from the cyclic olefin includes a cyclic olefin selected from the group consisting of tetracyclic [4.4.0.1 2,5 .1 7,10 At least one member selected from the group consisting of 1-3-dodecene and bicyclo[2.2.1]-2-heptene.

7. The manufacturing method according to any one of claims 1 to 6, wherein: The method further comprises a catalyst removal step of removing the olefin polymerization catalyst.

8. The manufacturing method according to any one of claims 1 to 7, wherein: In 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 defined as X. C , the integral value of the signal in the range of 40.3ppm and below 41.3ppm is set to Y A , the integral value of the signal in the range of 38.4 ppm to 39.9 ppm is set to X B When (X B -X C ) / Y A The value of is 0.2 or more and 2.0 or less.

9. The manufacturing method according to any one of claims 1 to 8, 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-based copolymer composition obtained by the production method according to claim 1 .

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

12. A film or sheet comprising the cross-linked body according to claim 11. 13 . A laminated body comprising the film or sheet according to claim 12 laminated on a substrate.

14. A circuit substrate, comprising: An electrical insulating layer comprising the crosslinked body according to claim 11, and a conductive 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 base material.

17. A varnish-like cyclic olefin copolymer composition comprising a cyclic olefin copolymer (m) and an organic solvent, The cyclic olefin copolymer (m) comprises: (A) one or more repeating units derived from olefins represented by the following general formula (I), (B) one or more repeating units derived from cyclic non-conjugated dienes represented by the following general formula (III), and (C) one or more repeating units derived from cyclic olefins 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, R 61 ~R 76 and R a1 and R b1 may be the same as or different from each other, 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 from 0 to 10, R 75 and R 76 They may be bonded to each other to form a single ring or multiple rings, [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 as or different from each other 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 They may be bonded to each other to form a single ring or multiple rings, In 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 defined as X. C , the integral value of the signal in the range of 40.3ppm and below 41.3ppm is set to Y A , the total integrated value of the signal in the range of 38.4 ppm or more and 39.9 ppm or less is set to X B When (X B -X C ) / Y A The value of is 0.2 or more and 2.0 or less.

18. The varnish-like cyclic olefin copolymer composition according to claim 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 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% by mass or more.

20. The varnish-like cyclic olefin copolymer composition according to any one of claims 17 to 19, wherein The organic solvent includes at least one 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 claims 17 to 20, wherein When the total molar number of repeating units in the cyclic olefin-based copolymer (m) is set to 100 mol%, the content of the repeating units (A) derived from olefin is 10 mol% or more and 90 mol% or less, the content of the repeating units (B) derived from the cyclic non-conjugated diene is 1 mol% or more and 40 mol% or less, and the content of the repeating units (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 any one of claims 17 to 21, wherein The cyclic non-conjugated diene constituting the repeating unit (B) derived from a cyclic non-conjugated diene includes 5-vinyl-2-norbornene.

23. The varnish-like cyclic olefin copolymer composition according to any one of claims 17 to 22, wherein The cyclic olefin constituting the structural unit (C) derived from the cyclic olefin includes a cyclic olefin selected from the group consisting of tetracyclic [4.4.0.1 2,5 .1 7,10 At least one member selected from the group consisting of 1-3-dodecene and bicyclo[2.2.1]-2-heptene.

24. The varnish-like cyclic olefin copolymer composition according to any one of claims 17 to 23, wherein The olefin constituting the olefin-derived repeating unit (A) comprises ethylene, The cyclic non-conjugated diene constituting the repeating unit (B) derived from the cyclic non-conjugated diene comprises 5-vinyl-2-norbornene, The cyclic olefin constituting the structural unit (C) derived from the cyclic olefin includes a tetracyclic [4.4.0.1 2,5 .1 7,10 ]-3-dodecene. 25 . A crosslinked product obtained by crosslinking the varnish-like cyclic olefin copolymer composition according to claim 17 .

26. A film or sheet comprising the cross-linked body according to claim 25.

27. A laminated body comprising the film or sheet according to claim 26 laminated on a substrate.

28. A circuit substrate, comprising: An electrical insulating layer comprising the crosslinked body according to claim 25, and a conductive 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-based copolymer composition according to claim 17 , and a sheet-like fiber base material.

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