Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F236/20—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/20—Diluents or solvents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
  • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
  • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
  • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D145/00—Coating compositions based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Coating compositions based on derivatives of such polymers
  • C09D145/02—Coumarone-indene polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
  • C08J2345/02—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers of coumarone-indene polymers

Definitions

• the present invention relates to cyclic olefin copolymers, cyclic olefin copolymer compositions, varnishes, crosslinked products, films or sheets, laminates, circuit boards, electronic devices and prepregs.
• resin materials used for such circuit boards include cyclic olefin copolymers obtained by copolymerizing dienes described in Patent Document 1 and Patent Document 2.
• 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.
• Patent Documents 3 and 4 disclose a crosslinkable resin molded article containing a crosslinkable cycloolefin polymer which is excellent in fluidity and solvent solubility when heated.
• the varnish viscosity at a high solid content can be improved, it is thought that the impregnation of the fiber base material during the production of the circuit board can be further improved. From the above, it can be concluded that the cyclic olefin copolymer having a crosslinkable group has improved solvent solubility while maintaining excellent dielectric properties, and when a varnish containing a large amount of cyclic olefin copolymer is produced, There was room for further improvement in terms of reducing the varnish viscosity of
• the present invention has been made in view of the above circumstances, and it is possible to obtain a crosslinked product that is suitable for circuit boards and the like and has excellent dielectric properties in a high frequency range.
• the present invention provides a cyclic olefin copolymer and a cyclic olefin copolymer composition which gives a varnish having a low viscosity even when the varnish is produced in a state.
• cyclic olefin copolymers cyclic olefin copolymer compositions, varnishes, crosslinked products, films or sheets, laminates, circuit boards, electronic devices and prepregs are provided.
• A one or more olefin-derived structural units (A) represented by the following general formula (I);
• B a structural unit (B) derived from one or more cyclic non-conjugated dienes represented by the following general formula (II);
• C a structural unit (C) derived from one or more cyclic olefins represented by the following general formula (III);
• a cyclic olefin copolymer comprising When the total number of moles of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer is 100 mol%, the structure derived from the cyclic non-conjugated diene The total content of the unit (B) content and the content of the structural unit (C) derived from the cyclic olefin is in the range of 40.0 mol% or more and 50.0 mol% or less,
• R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.
• u is 0 or 1
• v is 0 or 1
• w is 0 or 1
• R 61 to R 76 and R a1 and R b1 may be the same or different.
• R 104 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
• t is a positive integer of 0 to 10
• R 75 and R 76 are It may form a ring or polycycle.
• R 1 to R 8 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 4 or less carbon atoms
• R 5 to R 8 are bonded to each other to form a monocyclic ring.
• a cyclic olefin copolymer in which the cyclic non-conjugated diene constituting the structural unit (B) derived from the cyclic non-conjugated diene includes 5-vinyl-2-norbornene.
• a cyclic olefin-based copolymer in which the cyclic olefin constituting the structural unit (C) derived from the cyclic olefin includes bicyclo[2.2.1]-2-heptene.
• a cyclic olefin copolymer composition comprising the cyclic olefin copolymer according to any one of [1] to [4] above.
• a crosslinked product obtained by crosslinking the cyclic olefin copolymer composition described in [5] above.
• a film or sheet comprising the crosslinked product according to [7] above.
• a laminate comprising the crosslinked product according to [7] above.
• a circuit board comprising an electrical insulating layer containing the crosslinked product according to [7] above, and a conductor layer provided on the electrical insulating layer.
• An electronic device comprising the circuit board according to [10] above.
• a prepreg comprising the cyclic olefin copolymer according to any one of [1] to [4] above and a sheet-like fiber base material.
• a cyclic olefin copolymer and a cyclic olefin copolymer composition having a low viscosity varnish can be provided.
• the cyclic olefin copolymer (m) is (A) one or more olefin-derived structural units (A) represented by the following general formula (I); (B) a structural unit (B) derived from one or more cyclic non-conjugated dienes represented by the following general formula (II); (C) a structural unit (C) derived from one or more cyclic olefins represented by the following general formula (III); wherein the total number of moles of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer is 100 When expressed as mol%, the total content of the structural unit (B) derived from the cyclic non-conjugated diene and the structural unit (C) derived from the cyclic olefin is 40.0 mol% or more and 50.0 mol% and the number average molecular
• R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.
• 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
• R 61 to R 76 , R a1 and R b1 may be the same or different, and may be 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; It is a positive integer, and R 75 and R 76 may combine with each other to form a monocyclic or polycyclic ring.
• R 1 to R 8 are each independently a hydrogen atom, a halogen atom or a hydrocarbon group having 4 or less carbon atoms, and R 5 to R 8 are bonded to each other to form a monocyclic ring. and the single ring may have a double bond, and R 5 and R 6 or R 7 and R 8 may form an alkylidene group.
• the cyclic olefin copolymer (m) is the total of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (m).
• the total content of the structural unit (B) derived from the cyclic non-conjugated diene and the structural unit (C) derived from the cyclic olefin is 40.0 mol % or more. It is 0 mol % or less.
• the cyclic olefin copolymer (m) includes a structural unit (A), a structural unit (B) and a structural unit (C), and the structural unit (B) and the structural unit (C) is within the above range, the crosslinked product (Q) obtained from the cyclic olefin copolymer (m) has excellent dielectric properties, and furthermore, the solvent for the cyclic olefin copolymer (m) Since the solubility of is further improved, the moldability is improved, and the yield of the product is improved.
• the cyclic olefin copolymer (m) exhibits excellent solubility when a varnish containing a large amount of the cyclic olefin copolymer is produced while maintaining excellent dielectric properties.
• a cyclic olefin resin composition can be provided.
• the lower limit of the total content of the structural unit (B) derived from the cyclic non-conjugated diene and the content of the structural unit (C) derived from the cyclic olefin further improves the performance balance of dielectric properties and solubility.
• the upper limit of the total content of the structural unit (B) derived from the cyclic non-conjugated diene and the content of the structural unit (C) derived from the cyclic olefin further improves the performance balance of dielectric properties and solubility.
• the cyclic olefin copolymer (m) according to the present embodiment has a number average molecular weight Mn of 3,000 or more and 16,000 or less.
• the cyclic olefin copolymer (m) according to the present embodiment has a number average molecular weight Mn within the above range, so that the crosslinked product (Q) obtained from the cyclic olefin copolymer (m) has excellent dielectric properties.
• the solubility of the cyclic olefin copolymer (m) in the solvent is further improved, so the moldability is improved, and the product yield is improved.
• a cyclic olefin copolymer (m) having excellent solubility when a varnish containing a large amount of a cyclic olefin copolymer is produced while maintaining excellent dielectric properties and A cyclic olefin resin composition can be provided.
• the lower limit of the number average molecular weight Mn is preferably 4,000 or more, more preferably 5,000 or more, still more preferably 6,000 or more, still more preferably 7,000 or more, still more preferably 7,300 or more. is.
• the cyclic olefin copolymer (m) or the cyclic olefin copolymer composition according to the present embodiment can be crosslinked. Dielectric properties, heat resistance and mechanical properties of the crosslinked product (Q) obtained by can be improved.
• the upper limit of the number average molecular weight Mn is preferably 15,000 or less, more preferably 12,000 or less, still more preferably 11,500 or less, still more preferably 11,200 or less.
• the cyclic olefin copolymer (m) or the cyclic olefin copolymer composition according to the present embodiment cannot be used to produce a circuit board. Formability such as impregnability into the fiber base material and wiring embedding property can be improved.
• R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.
• olefin monomers for forming the structural unit (A) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3 -ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene , 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like.
• ethylene or propylene is preferred, and ethylene is more preferred, from the viewpoint of obtaining a crosslinked product having superior heat resistance, mechanical properties, dielectric properties, transparency and gas barrier properties.
• One type of olefin monomer for forming the structural unit (A) may be used alone, or two or more types may be used in combination.
• the total number of moles of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (m) is 100 mol%
• the content of the structural unit (A) is preferably 20 mol% or more and 60 mol% or less, more preferably 30 mol% or more and 60 mol% or less, still more preferably 40 mol% or more and 59 mol%.
• the total of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (m) When the number of moles is 100 mol%, the lower limit of the content of the structural unit (A) is preferably 20 from the viewpoint of further improving the solubility in the solvent of the cyclic olefin copolymer according to the present embodiment.
• mol % or more more preferably 30 mol % or more, still more preferably 40 mol % or more, still more preferably 45 mol % or more, still more preferably 50 mol % or more, still more preferably 52 mol % or more.
• the upper limit of the content of the structural unit (A) is preferably 60 mol% or less, more preferably 59 mol % or less, more preferably 58 mol % or less, more preferably 57 mol % or less.
• the content of structural unit (A) can be measured by 1 H-NMR.
• cyclic non-conjugated diene monomer which is the raw material for copolymerization of the cyclic olefin copolymer (m) according to the present embodiment, is subjected to addition copolymerization to form the structural unit represented by the above formula (II). .
• a cyclic non-conjugated diene represented by the following general formula (IIa) corresponding to the above general formula (II) is used.
• u is 0 or 1
• v is 0 or 1
• w is 0 or 1
• R 61 to R 76 and R a1 and R b1 may be the same or different.
• R 104 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
• t is a positive integer of 0 to 10
• R 75 and R 76 are It may form a ring or polycycle.
• the cyclic non-conjugated diene represented by the general formula (IIa) is not particularly limited, but includes, for example, a cyclic non-conjugated diene represented by the following chemical formula.
• a cyclic non-conjugated diene represented by the following chemical formula Of these, 5-vinyl-2-norbornene and 8-vinyl-9-methyltetracyclo[4.4.0.1 2,5 . 1 7,10 ]-3-dodecene is preferred, and 5-vinyl-2-norbornene is more preferred.
• the cyclic non-conjugated diene represented by the above general formula (IIa) can also be specifically represented by the following general formula (IIb).
• n in the general formula (IIb) is an integer of 0 to 10
• R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
• R 2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is.
• the cyclic olefin copolymer (m) contains a structural unit derived from a cyclic non-conjugated diene represented by the general formula (II), so that the side chain portion, that is, other than the main chain of the copolymer It is characterized by having a double bond in the portion of
• the content of the structural unit (B) is Preferably 1 mol% or more and 40 mol% or less, more preferably 1 mol% or more and 35 mol% or less, still more preferably 3 mol% or more and 30 mol% or less, still more preferably 3 mol% or more and 25 mol% or less, still more preferably 5 mol % or more and 20 mol % or less, more preferably 7 mol % or more and 17 mol % or less, further preferably 10 mol % or more and 15 mol % or less.
• the solubility of the cyclic olefin copolymer according to the present embodiment in solvents is further improved.
• the content of the structural unit (B) is is preferably 1 mol% or more, more preferably 3 mol% or more, and still more preferably 5 mol%, from the viewpoint of further improving the solubility of the cyclic olefin copolymer according to the present embodiment in a solvent. Above, more preferably 7 mol % or more, more preferably 10 mol % or more.
• the upper limit of the content of the structural unit (B) is preferably 40 mol% or less, preferably 35 mol. % or less, more preferably 30 mol % or less, still more preferably 25 mol % or less, still more preferably 20 mol % or less, still more preferably 17 mol % or less, still more preferably 15 mol % or less.
• the content of the structural unit (B) can be measured by 1 H-NMR.
• R 1 to R 8 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 4 or less carbon atoms.
• a halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
• Hydrocarbon groups having 4 or less carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group, and cycloalkyl groups such as cyclopropyl group.
• R 5 to R 8 may combine with each other to form a monocyclic ring, and the monocyclic ring may have a double bond, and R 5 and R 6 or R 7 You may form an alkylidene group with R8 .
• the monocyclic ring formed here is exemplified below.
• the carbon atoms numbered 1 or 2 form an alicyclic structure to which R 5 (R 6 ) or R 7 (R 8 ) is bonded in general formula (II).
• R 5 (R 6 ) or R 7 (R 8 ) is bonded in general formula (II).
• the alkylidene group specifically includes an ethylidene group, a propylidene group, and an isopropylidene group.
• Cyclic olefin monomers for forming the structural unit (C) include, for example, bicyclo[2.2.1]-2-heptene (also referred to as 2-norbornene), and alkyl and/or alkylidene substituted products thereof, such as , 5-methyl-2-norbornene, 5-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-2-norbornene, etc.; polar group substitution such as these halogens dicyclopentadiene, 2,3-dihydrodicyclopentadiene, etc.; dimethanooctahydronaphthalene, alkyl and/or alkylidene-substituted products thereof, and polar group-substituted products such as halogen, carboxyl group, cyano group, etc., for example, 6- methyl-1,4:5,8-dime
• the cyclic olefin monomers for forming the structural unit (C) may be used singly or in combination of two or more.
• the total number of moles of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (m) is 100 mol%
• the content of the structural unit (C) is preferably 5 mol% or more and 40 mol% or less, more preferably 10 mol% or more and 38 mol% or less, still more preferably 13 mol% or more and 38 mol%.
• the total of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (m) When the number of moles is 100 mol%, the lower limit of the content of the structural unit (C) is preferably 5 from the viewpoint of further improving the solubility in the solvent of the cyclic olefin copolymer according to the present embodiment.
• mol % or more more preferably 10 mol % or more, still more preferably 13 mol % or more, still more preferably 15 mol % or more, still more preferably 20 mol % or more, still more preferably 21 mol % or more.
• the upper limit of the content of the structural unit (C) is preferably 40 mol% or less, more preferably 39 mol % or less, more preferably 38 mol % or less, still more preferably 37 mol % or less, still more preferably 35 mol % or less.
• the content of structural unit (C) can be measured by 1 H-NMR.
• the cyclic olefin-based copolymer (m) may further contain structural units derived from one or more cyclic olefins represented by general formula (V) below.
• u is 0 or 1
• v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1
• u + v is a positive integer
• w is 0 or 1
• R 61 to R 78 , R a1 and R b1 may be the same or different, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 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; may be formed.
• a cyclic olefin monomer represented by the following general formula (Va) corresponding to the above general formula (V) is used.
• u is 0 or 1
• v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1
• u + v is a positive integer
• w is 0 or 1
• R 61 to R 78 , R a1 and R b1 may be the same or different, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 20 halogenated alkyl group, 3 to 15 carbon atom cycloalkyl group, or 6 to 20 carbon atom aromatic hydrocarbon group; A ring may be formed.
• cyclic olefin represented by the general formula (Va) compounds described in International Publication No. 2006/118261 can be used.
• examples of the cyclic olefin represented by the general formula (Va) include tetracyclo[4.4.0.1 2,5 . 1 7,10 ]-3-dodecene (also called tetracyclododecene) is preferred. Since tetracyclododecene has a rigid ring structure, the elastic modulus of the copolymer and the crosslinked product can be easily maintained, and since it does not contain a heterogeneous double bond structure, there is an advantage that the crosslinkage can be easily controlled.
• the total number of moles of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer is 100 mol. %
• the content of the structural unit (D) is preferably 1 mol% or more and 35 mol% or less, more preferably 3 mol% or more and 25 mol% or less, still more preferably 5 mol% or more and 15 mol% or less.
• the solubility of the cyclic olefin copolymer according to the present embodiment in solvents is further improved.
• the content of the structural unit (D) can be measured by 1 H-NMR.
• the total content of the structural unit (A), the structural unit (B), and the structural unit (C) in the cyclic olefin-based copolymer (m) according to the present embodiment is the performance balance of dielectric properties and solubility. is preferably 65 mol% or more, more preferably 75 mol% or more, and still more preferably is 85 mol % or more, more preferably 95 mol % or more, still more preferably 97 mol % or more, still more preferably 99 mol % or more, and preferably 100 mol % or less.
• the cyclic olefin copolymer (m) can be produced, for example, according to the method for producing a cyclic olefin copolymer described in paragraphs 0075 to 0219 of WO 2012/046443. Details are omitted here.
• the cyclic olefin resin composition according to this embodiment contains the cyclic olefin copolymer (m) according to this embodiment.
• various additives may be added to the cyclic olefin resin composition according to the present embodiment according to the purpose. The amount of the additive to be added is appropriately selected depending on the application within a range that does not impair the purpose of the present invention.
• additives examples include radical polymerization initiators, elastomers, heat stabilizers, weather stabilizers, radiation resistant agents, plasticizers, lubricants, release agents, nucleating agents, friction and abrasion improvers, flame retardants, foaming agents, electrification
• radical polymerization initiators elastomers, heat stabilizers, weather stabilizers, radiation resistant agents, plasticizers, lubricants, release agents, nucleating agents, friction and abrasion improvers, flame retardants, foaming agents, electrification
• additives selected from the group consisting of inhibitors, colorants, antifogging agents, antiblocking agents, impact resistance agents, surface wetting agents, fillers, hydrochloric acid absorbers and metal deactivators is mentioned.
• the cyclic olefin-based resin composition according to the present embodiment can be prepared, for example, by mixing the cyclic olefin copolymer (m) and, if necessary, various additives.
• Mixing methods include a method of melt blending with an extruder or the like, or dissolution in an appropriate solvent such as saturated hydrocarbons such as heptane, hexane, decane and cyclohexane; aromatic hydrocarbons such as toluene, benzene and xylene.
• a solution blending method or the like performed by dispersing can be adopted.
• the cyclic olefin resin composition according to this embodiment can be made into a varnish by mixing with a solvent.
• the solvent for preparing the varnish-like cyclic olefin resin composition is not particularly limited as long as it does not impair the solubility or affinity for the cyclic olefin copolymer (m).
• Solvents preferably used include, for example, saturated hydrocarbons such as heptane, hexane, octane and decane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decahydronaphthalene; aromatics such as toluene, benzene, xylene, mesitylene and pseudocumene.
• hydrocarbons such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, and phenol; ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, and acetophenone; methyl cellosolves such as cellosolve and ethyl cellosolve; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate and butyl formate; halogenated hydrocarbons such as trichlorethylene, dichloroethylene and chlorobenzene, etc.
• alcohols such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, and phenol
• Heptane, decane, cyclohexane, methylcyclohexane, decahydronaphthalene, toluene, benzene, xylene, mesitylene and pseudocumene are preferably used. These solvents can be used singly or as a mixture of two or more at any ratio.
• the varnish-like cyclic olefin-based resin composition may be produced by any method, but usually includes a step of mixing the cyclic olefin copolymer (m) and a solvent. .
• the apparatus for preparing the varnish is not limited, and any batch or continuous apparatus capable of stirring and mixing may be used.
• the temperature for preparing the varnish can be arbitrarily selected within the range from room temperature to the boiling point of the solvent.
• the varnish may be prepared by using the reaction solution in which the cyclic olefin copolymer (m) is obtained as it is as a solvent.
• the crosslinked product (Q) according to this embodiment is obtained by crosslinking the cyclic olefin copolymer (m) according to this embodiment or the cyclic olefin resin composition according to this embodiment.
• the method for crosslinking the cyclic olefin copolymer (m) according to the present embodiment or the cyclic olefin resin composition according to the present embodiment is not particularly limited. and other radiation, while molding into an arbitrary shape, or a method of cross-linking after molding.
• Cross-linking with a radical polymerization initiator can be applied as it is to a cross-linking method with a normal radical polymerization initiator that is applied to polyolefins. That is, the cyclic olefin copolymer (m) or the cyclic olefin resin composition is blended with a radical polymerization initiator such as dicumyl peroxide and heated to crosslink.
• a radical polymerization initiator such as dicumyl peroxide and heated to crosslink.
• the content of the radical polymerization initiator is not particularly limited, it is usually 0.02 to 20 parts by mass, preferably 0.05 to 10 parts by mass, more preferably 0.05 to 10 parts by mass per 100 parts by mass of the cyclic olefin copolymer (m).
• the upper limit of the content of the radical polymerization initiator is preferably 0.02 parts by mass or more per 100 parts by mass of the cyclic olefin copolymer (m) from the viewpoint of further improving the dielectric properties of the crosslinked product (Q).
• the lower limit of the content of the radical polymerization initiator is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, from the viewpoint of further improving the performance balance of the heat resistance and mechanical properties of the crosslinked product (Q). , more preferably 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 2.5 parts by mass or less.
• the radical polymerization initiator known thermal radical polymerization initiators, photoradical polymerization initiators, and these can be used in combination.
• the 10-hour half-life temperature is usually 80° C. or higher, preferably 120° C. or higher, from the viewpoint of further improving storage stability.
• thermal radical polymerization initiators examples include dicumyl peroxide, t-butyl cumyl peroxide, 2,5-bis(t-butylperoxy)2,5-dimethylhexane, 2,5-bis(t -butylperoxy) 2,5-dimethylhexyne-3, di-t-butylperoxide, isopropylcumyl-t-butylperoxide, bis( ⁇ -t-butylperoxyisopropyl)benzene, etc.
• thermal radical polymerization initiators examples include “Perbutyl P”, “Perbutyl D”, “Perbutyl C”, “Perbutyl A”, “Perbutyl P”, “Perbutyl L” and “Perbutyl O”, “Perbutyl ND”, “Perbutyl Z” and the like.
• radical polymerization initiators include benzoin alkyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- one, benzophenone, methylbenzoylformate, isopropylthioxanthone and mixtures of two or more thereof.
• a sensitizer can also be used together with these photoradical polymerization initiators.
• sensitizers include anthraquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, benzanthrone, p,p'-tetramethyldiaminobenzophenone, carbonyl compounds such as chloranil, nitrobenzene, p-dinitrobenzene, 2- Nitro compounds such as nitrofluorene, aromatic hydrocarbons such as anthracene and chrysene, sulfur compounds such as diphenyl disulfide, nitroaniline, 2-chloro-4-nitroaniline, 5-nitro-2-aminotoluene, tetracyanoethylene and the like Nitrogen compounds and the like can be mentioned.
• the cyclic olefin-based resin composition is mixed with a sulfur-based compound and, if necessary, a vulcanization accelerator and a vulcanization accelerator aid, and heated to carry out a cross-linking reaction.
• the content of the sulfur-based compound is not particularly limited, but from the viewpoints of efficient progress of the cross-linking reaction, improvement of the physical properties of the obtained cross-linked product and economic efficiency, etc., it is It is usually used in the range of 0.1 to 10 parts by mass, preferably 0.3 to 5 parts by mass.
• the amount is usually 0.1 to 20 parts by mass, preferably 0.2 to 10 parts by mass.
• sulfur-based compounds can be used for the cross-linking reaction, examples of which include sulfur, sulfur monochloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dimethyldithiocarbamate. etc.
• Various vulcanization accelerators can also be used, such as N-cyclohexyl-2-benzothiazole-sulfenamide, N-oxydiethylene-2-benzothiazole-sulfenamide, N,N-diisopropyl-2-benzothiazole.
• - thiazoles such as sulfenamide, 2-mercaptobenzothiazole, 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-diethyl-4-morpholinothio)benzothiazole, benzothiazyl-disulfide; Guanidines such as diphenylguanidine, triphenylguanidine, di-ortho-tolylguanidine, orthotolylbiguanide, diphenylguanidine phthalate; acetaldehyde-aniline reactants; butyraldehyde-aniline condensates; aldehydes such as hexamethylenetetramine, acetaldehyde ammonia Amine or aldehyde-ammonia series; imidazoline series such as 2-mercaptoimidazoline; thiourea series such as thiocarbanilide, diethylthiourea dibutylthiourea
• the temperature for cross-linking the cyclic olefin copolymer (m) or the cyclic olefin-based resin composition with a radical polymerization initiator or sulfur is usually 100 to 300°C, preferably 120 to 250°C, more preferably 120 to 220°C. and cross-linking may be performed by changing the temperature stepwise. Crosslinking can fully progress as it is more than the said lower limit. Moreover, when it is not more than the above upper limit, coloration of the obtained crosslinked product can be suppressed, or the process can be simplified.
• polybutadiene which is a typical double bond-containing polymer, generally cannot be crosslinked under the conditions described above, and requires crosslinking conditions at a high temperature such as 300°C.
• the cyclic olefin copolymer (m) or cyclic olefin resin composition according to the present embodiment can also be crosslinked using a hydrosilyl group-containing compound having at least two hydrosilyl groups in one molecule.
• Crosslinking using a hydrosilyl group-containing compound can be performed, for example, according to the method described in JP-A-2015-193680. Details are omitted here.
• the cross-linking method using electron beams or other radiation has the advantage that it does not involve restrictions on molding temperature and fluidity. .
• Cross-linking can be carried out in combination with a cross-linking aid in both the method of using a radical polymerization initiator, sulfur, a hydrosilyl group-containing compound, etc., and the method of cross-linking using radiation.
• the cross-linking aid is not particularly limited, and examples include oximes such as p-quinonedioxime and p,p'-dibenzoylquinonedioxime; ethylene dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, cyclohexyl Acrylates or methacrylates such as methacrylates, acrylic acid/zinc oxide mixtures, allyl methacrylate; vinyl monomers such as divinylbenzene, vinyltoluene, vinylpyridine; hexamethylene diallyl nadimide, diallyl itaconate, diallyl phthalate, diallyl isophthalate, diallyl allyl compounds such as monoglycidyl isocyanurate, triallyl cyanurate and triallyl isocyanurate; maleimides such as N,N'-m-phenylenebismaleimide and N,N'-(4,4'-methylenedipheny
• the crosslinked product (Q) may optionally contain a heat stabilizer, a weather stabilizer, an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, a lubricant, a dye, a pigment, a natural oil, Synthetic oils, waxes, organic or inorganic fillers, etc. can be blended to such an extent that the objects of the present invention are not impaired, and the content thereof is an appropriate amount.
• Stabilizers that are blended as optional components include, specifically, tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, ⁇ -(3,5-di-t -Butyl-4-hydroxyphenyl)propionic acid alkyl ester, phenolic antioxidants such as 2,2'-oxamide bis[ethyl-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate]; stearin Fatty acid metal salts such as zinc acid, calcium stearate, calcium 12-hydroxystearate; glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, etc.
• polyhydric alcohol fatty acid esters These may be blended alone or in combination, for example, tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane with zinc stearate and glycerin. A combination with monostearate can be exemplified.
• thermal radical polymerization initiators include Irganox 1010, 1035, 1076, 1098 and 1135 manufactured by BASF Japan.
• Organic or inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, 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, Examples include polypropylene fiber, polyester fiber, and polyamide fiber.
• a method of melt blending the cyclic olefin copolymer (m) and various additives with an extruder or the like, or a method of melt blending the cyclic olefin copolymer (m) and various additives is dissolved or dispersed in a suitable solvent such as saturated hydrocarbons such as heptane, hexane, decane and cyclohexane; aromatic hydrocarbons such as toluene, benzene and xylene.
• the cross-linking reaction can be carried out by melting a mixture of the cyclic olefin-based resin composition and the above-described radical polymerization initiator, sulfur, or compounds such as hydrosilyl group-containing compounds, or by dissolving the mixture in a solvent, or The cross-linking reaction can be carried out in a dispersed solution state, or after the solvent is volatilized from the solution state in a solvent and formed into an arbitrary shape such as a film or coating, and further the crosslinking reaction can proceed.
• the raw material mixture When reacting in a molten state, the raw material mixture is melt-kneaded and reacted using a kneading device such as a mixing roll, Banbury mixer, extruder, kneader, or continuous mixer. Further, the cross-linking reaction can be further advanced after molding by any method.
• a kneading device such as a mixing roll, Banbury mixer, extruder, kneader, or continuous mixer.
• the cross-linking reaction can be further advanced after molding by any method.
• the same solvent as used in the above solution blending method can be used.
• the reaction can be performed after shaping by any method.
• the molded article according to this embodiment includes the crosslinked article (Q) according to this embodiment.
• the molded article according to this embodiment is, for example, a film or a sheet.
• Various known methods can be applied as a method for forming a film or sheet using the cyclic olefin copolymer (m) according to the present embodiment or the cyclic olefin resin composition according to the present embodiment. For example, after applying the above-described varnish on a support substrate such as a thermoplastic resin film and drying it, heat treatment or the like is performed to obtain the cyclic olefin copolymer (m) according to the present embodiment or the cyclic olefin system according to the present embodiment.
• a method of forming by cross-linking a resin composition can be mentioned.
• the method of applying the varnish to the supporting substrate is not particularly limited, but examples thereof include application using a spin coater, application using a spray coater, and application using a bar coater.
• a method of obtaining a film or sheet by melt-molding the cyclic olefin copolymer (m) according to the present embodiment or the cyclic olefin-based resin composition according to the present embodiment can also be used.
• a laminate By laminating the film or sheet of the present embodiment on a substrate, it can be used for various purposes as a laminate.
• Various known methods can be applied to the method of forming the laminate of the present embodiment.
• a laminate can be produced by laminating a film or sheet produced by the above-described method on a base material and, if necessary, heat-curing the laminate by pressing or the like.
• a laminate can also be produced by laminating an electrical insulating layer containing the above-described crosslinked body on the conductor layer.
• the cyclic olefin copolymer (m) according to the present embodiment or the cyclic olefin resin composition according to the present embodiment may be formed on the surface layer of various multilayer molded articles or multilayer laminated films.
• the resin layer formed from the cyclic olefin copolymer (m) according to the present embodiment or the cyclic olefin resin composition according to the present embodiment preferably has a thickness of 100 ⁇ m or less.
• Various multilayer molded bodies or multilayer laminated films include, for example, an optical lens in which the cyclic olefin copolymer (m) according to the present embodiment or the cyclic olefin resin composition according to the present embodiment is formed on the surface of a resin optical lens.
• the cyclic olefin copolymer (m) according to the present embodiment or the cyclic olefin resin composition according to the present embodiment is formed to impart gas barrier properties to the surface of a multilayer molded article for use or a resin film such as a PET film or a PE film. and multilayer gas barrier films.
• the molded article according to the present embodiment may be, for example, a prepreg.
• the prepreg of the present embodiment is formed by combining the cyclic olefin copolymer (m) of the present embodiment or the cyclic olefin resin composition of the present embodiment with a sheet-like fiber base material.
• the method for producing the prepreg is not particularly limited, and various known methods can be applied. For example, there is a method including a step of impregnating a sheet-like fiber base material with the varnish described above to obtain an impregnated body, and a step of heating the obtained impregnated body to dry the solvent contained in the varnish.
• the impregnation of the sheet-like fiber substrate with the varnish is performed by applying a predetermined amount of varnish to the sheet by a known method such as a spray coating method, a dip coating method, a roll coating method, a curtain coating method, a die coating method, a slit coating method, or the like. It can be carried out by applying to a shaped fiber base material, overlaying a protective film thereon if necessary, and pressing from above with a roller or the like.
• the process of heating the impregnated body and drying the solvent contained in the varnish is not particularly limited. A method such as drying by passing through In this embodiment, after impregnating the sheet-like fiber base material with the varnish, the resulting impregnated body is heated to a predetermined temperature to evaporate the solvent contained in the varnish and obtain a prepreg.
• Inorganic and/or organic fibers can be used as the fibers constituting the sheet-like fiber base material according to the present embodiment, and are not particularly limited.
• Organic fibers such as fiber, polyamide (nylon) fiber, liquid crystal polyester fiber; inorganic fiber such as glass fiber, carbon fiber, alumina fiber, tungsten fiber, molybdenum fiber, titanium fiber, steel fiber, boron fiber, silicon carbide fiber, silica fiber ; etc. can be mentioned.
• organic fibers and glass fibers are preferred, and aramid fibers, liquid crystal polyester fibers and glass fibers are particularly preferred.
• glass fibers include E glass, NE glass, S glass, D glass, H glass, and T glass.
• Impregnation of the varnish into the sheet-like fibrous substrate is carried out, for example, by dipping and coating. Impregnation may be repeated multiple times if desired.
• These sheet-like fiber base materials can be used alone or in combination of two or more, and the amount used is appropriately selected as desired. %, preferably 20 to 80 mass %, more preferably 30 to 70 mass %. Within this range, the dielectric properties and mechanical strength of the obtained laminate are highly balanced, which is preferable.
• the thickness of the prepreg according to the present embodiment is appropriately selected depending on the purpose of use, but is usually 0.001 to 10 mm, preferably 0.005 to 1 mm, more preferably 0.01 to 0.005 mm. 5 mm. If it is in this range, it is preferable because the shapeability during lamination and the mechanical strength and toughness of the laminate obtained by curing can be fully exhibited.
• the cyclic olefin copolymer (m) according to the present embodiment or the cyclic olefin resin composition according to the present embodiment is excellent in dielectric properties, heat resistance, mechanical properties, etc., and thus can be suitably used for circuit boards.
• a method for manufacturing a circuit board a generally known method can be adopted and is not particularly limited.
• the film, sheet or prepreg manufactured by the above method is heated and cured by a lamination press or the like to form an electrical insulating layer.
• a conductor layer is laminated on the obtained electrical insulation layer by a known method to produce a laminate.
• a circuit board can be obtained by subjecting the conductor layers in the laminate to circuit processing or the like.
• Metals such as copper, aluminum, nickel, gold, silver, and stainless steel can be used as metals for the conductor layer.
• a method of forming the conductor layer for example, a method of forming the metal into a foil or the like and heat-sealing it onto the electrical insulating layer, or a method of laminating the metal into a foil or the like onto the electrical insulating layer using an adhesive.
• a method of forming a conductor layer made of the metal on the electrical insulating layer by a method such as sputtering, vapor deposition, or plating can be used.
• the form of the circuit board may be either a single-sided board or a double-sided board.
• Such a circuit board can be used as an electronic device by mounting an electronic component such as a semiconductor element.
• Electronic devices can be manufactured based on publicly known information. Such electronic devices include, for example, servers, routers, supercomputers, mainframes, workstations and other ICT infrastructure devices; GPS antennas, wireless base station antennas, millimeter wave antennas, RFID antennas and other antennas; mobile phones , smartphones, PHS, PDA, tablet terminals; digital equipment such as personal computers, televisions, digital cameras, digital video cameras, POS terminals, wearable terminals, digital media players; electronic control system equipment, in-vehicle communication equipment, cars In-vehicle electronic equipment such as navigation equipment, millimeter-wave radar, and in-vehicle camera modules; semiconductor test equipment, high-frequency measurement equipment;
• a foam can be obtained by cross-linking and foaming the cyclic olefin copolymer (m) according to the present embodiment or the cyclic olefin resin composition according to the present embodiment.
• the foaming agent described above may be added to the cyclic olefin resin composition.
• the crosslinked body (Q) according to the present embodiment is excellent in solvent resistance, heat resistance, mechanical strength, and transparency. Filters, lenses, optical adhesives, optical filters for PDPs, organic EL coating materials, base film substrates for solar cells in the aerospace field, coating materials for solar cells and thermal control systems, semiconductor devices, light-emitting diodes, various memories electronic devices such as hybrid ICs, MCMs, circuit boards, prepregs and laminates used to form insulating layers on circuit boards, overcoat materials or interlayer insulating materials for display parts, etc., substrates for liquid crystal displays and solar cells , medical equipment, automotive parts, release agents, resin modifiers, transparent substrates for displays, lithium-ion battery parts, semiconductor process parts, film capacitors, gas barrier coating materials, wire coating materials, automotive parts, aerospace materials, processing materials for semiconductors, wire coating materials, lithium-ion battery materials, fuel cell materials, capacitor films, flexible display materials, anchor coating materials, transparent adhesives, modifiers, cross-linking aids, medical containers, It can be used for
• it is excellent in stability of dielectric properties over time, and excellent in solvent resistance, heat resistance, transparency, mechanical properties, and the like, so that it can be suitably used for high-frequency applications such as high-frequency circuit boards. Furthermore, since it has excellent gas barrier properties, it can be suitably used as a substrate for a liquid crystal display, a substrate for a solar cell, a film or a sheet.
• composition of the cyclic olefin copolymer (m) used in Synthesis Examples, Examples, and Comparative Examples was measured by the method described below.
• Mn number average molecular weight of the cyclic olefin copolymer (m) used in Synthesis Examples, Examples, and Comparative Examples was measured by GPC measurement and obtained as a standard polystyrene conversion value. GPC measurement was performed under the following conditions. Apparatus: GPC HLC-8321 (manufactured by Tosoh Corporation) Solvent: o-dichlorobenzene Column: TSKgel GMH6-HT ⁇ 2, TSKgel GMH6-HTL ⁇ 2 (both manufactured by Tosoh Corporation) Flow rate: 1.0 ml/min Sample: 1 mg/mL o-dichlorobenzene solution Temperature: 140°C
• Transition metal compound (1) Synthesized by the method described in JP-A-2004-331965.
• Ethylene manufactured by Sumitomo Seika Co., Ltd.
• Modified methylaluminoxane MMAO, manufactured by Tosoh Finechem
• Toluene manufactured by Wako Pure Chemical Industries, Ltd.: Wako special grade
• 5-vinyl-2-norbornene manufactured by Tokyo Chemical Industry Co., Ltd.
• 2-norbornene manufactured by Tokyo Chemical Industry Co., Ltd.
• Acetone manufactured by Wako Pure Chemical Industries, Ltd.: Wako special grade
• Methanol manufactured by Wako Pure Chemical Industries, Ltd.: Wako special grade
• Initiator 1 Permil D (manufactured by NOF Corporation)
• Antioxidant 1 Irganox 1010 (manufactured by BASF)
• Cyclic olefin copolymer (m) [Synthesis Example 1: Cyclic olefin copolymer (m-1)] 372 mL of toluene, 95 mL of 5-vinyl-2-norbornene (hereinafter also referred to as VNB), and 33 mL of a 5 M toluene solution of 2-norbornene (hereinafter also referred to as NB) are placed in a SUS autoclave with an internal volume of 1 L that has been sufficiently purged with nitrogen.
• VNB 5-vinyl-2-norbornene
• NB 2-norbornene
• the polymerization was stopped by adding a small amount of methanol. After completion of the polymerization, ion-exchanged water was added to the resulting polymer solution, and the mixture was stirred for 1 hour, after which the organic layer was filtered with filter paper. This organic layer was poured into acetone to precipitate a polymer, and after stirring, the mixture 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 TD-derived structure in the polymer determined by NMR was 30 mol %
• the composition ratio of the VNB-derived structure was 12 mol %
• the number average molecular weight (Mn) determined by GPC measurement was 11,300.
• composition ratio of the TD-derived structure in the polymer determined by NMR is 14 mol%
• the composition ratio of the NB-derived structure is 17 mol%
• the composition ratio of the VNB-derived structure is 10 mol%
• the number average molecular weight (Mn) determined by GPC measurement is 8. , 400.
• Example 1 Each varnish was produced by the method shown below and evaluated.
• A indicates that the viscosity of the 45% toluene varnish is 100 or more and less than 500 (mPa s), and “A” indicates that it is 500 or more and less than 1000 (mPa s).
• B those with 1000 (mPa ⁇ s) or more, and those with undissolved material were rated as "C”.
• the 20% toluene varnish obtained according to the content in Table 1 was applied on the release-treated PET film in the longitudinal direction at a speed of 10 mm / sec, It was dried at 150° C. for 4 minutes in a blow dryer under a nitrogen stream. Two sheets of the obtained film were stacked, and the pressure was applied to 3.5 MPa by a vacuum press, the temperature was raised from room temperature (25° C.) at a constant rate, and the temperature was maintained at 180° C. for 120 minutes to obtain a laminated film.
• ⁇ Dielectric loss tangent> The dielectric loss tangent at 10 GHz of the film obtained in the above (film formation) was measured by a cylindrical cavity resonator method according to JIS R1641. At this time, a dielectric loss tangent of less than 0.0010 was evaluated as "A”, and a dielectric loss tangent of 0.0010 or more was evaluated as “B”. Moreover, what was impossible to measure was described as "C”. Table 1 shows the results.
• Examples 2 to 4 and Comparative Examples 1 to 4 A 20% toluene varnish, a 45% toluene varnish and a film were prepared and evaluated in the same manner as in Example 1 except that the content of each component was changed to the content shown in Table 1. Table 1 shows the results obtained. At this time, in Comparative Examples 2 and 3, undissolved cyclic olefin copolymer occurred during the production of 45% toluene varnish, and 45% toluene varnish was not obtained. Therefore, for Comparative Examples 2 and 3, it was impossible to measure the varnish viscosity using 45% toluene varnish.
• Comparative Example 3 a varnish-like cyclic olefin copolymer composition (20% toluene varnish) was obtained, but in Comparative Example 2, a varnish-like cyclic olefin copolymer composition (20% toluene varnish) was also not obtained.
• Comparative Example 2 it was not possible to measure the dielectric loss tangent in Comparative Example 2, so the results of Comparative Example 2 in Table 1 are indicated as "not measurable.”
• Examples 1 to 4 it is possible to obtain a crosslinked body having excellent dielectric properties in a high frequency range suitable for circuit boards and the like, and when a varnish containing a large amount of cyclic olefin copolymer is produced also had a low viscosity.
• Comparative Examples 1 to 4 when the varnish was produced in a state containing a large amount of the cyclic olefin copolymer, the cyclic olefin copolymer did not dissolve completely, or even if it dissolved, the viscosity was high. , resulting in poor impregnation.

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