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
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
  • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
• • 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
  • 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
  • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
  • C08K5/134—Phenols containing ester groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
  • C08K5/23—Azo-compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
  • C08L23/083—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic polyenes, i.e. containing two or more carbon-to-carbon double bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L45/00—Compositions 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; Compositions of derivatives of such polymers
• • 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
  • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
  • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D123/04—Homopolymers or copolymers of ethene
  • C09D123/08—Copolymers of ethene
  • C09D123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
  • C09D123/0815—Copolymers of ethene with aliphatic 1-olefins
  • C09D123/0823—Copolymers of ethene with aliphatic cyclic olefins
• • 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
  • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
  • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D123/04—Homopolymers or copolymers of ethene
  • C09D123/08—Copolymers of ethene
  • C09D123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
  • C09D123/083—Copolymers of ethene with aliphatic polyenes, i.e. containing more than one unsaturated bond
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
• • 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
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/04—Homopolymers or copolymers of ethene
  • C08J2323/08—Copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/20—Applications use in electrical or conductive gadgets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • 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

Definitions

• the present invention relates to a cyclic olefin resin composition, a varnish, a crosslinked product, a film, a sheet, a circuit board, an electronic device, and a prepreg.
• Cyclic olefin copolymers have excellent heat resistance, mechanical properties, transparency, dielectric properties, solvent resistance, moldability, dimensional stability, etc., and are therefore used in various fields (for example, patent documents 1 and 2).
• Patent Document 2 describes a cyclic olefin copolymer having a crosslinkable group.
• the crosslinked product obtained by crosslinking this cyclic olefin copolymer has excellent dielectric property stability over time, as well as heat resistance, transparency, and mechanical properties, so it is suitable for high frequency applications such as high frequency circuit boards. It is stated that it can be used for.
• Patent Document 3 describes a crosslinkable resin composition
• a crosslinkable resin composition comprising a cyclic olefin resin, an organic peroxide, a crosslinking aid, and powdered red phosphorus.
• the crosslinked resin molded product obtained by heating and crosslinking this crosslinkable resin composition has dielectric properties in a high frequency band and soldering heat resistance, and has high flame retardancy and high mechanical strength. It is described that it can be suitably used for printed wiring boards, computer parts, and other applications that require dielectric properties, heat resistance, flame retardance, mechanical properties, and the like.
• crosslinked products made of cyclic olefin copolymers having crosslinkable groups have been improved in that they maintain the excellent dielectric properties of cyclic olefin copolymers even after the crosslinking process. There was room for.
• the present invention has been made in view of the above circumstances, and provides a cyclic olefin resin composition that can maintain the excellent dielectric properties of a cyclic olefin copolymer even after a crosslinking step.
• the present inventors have made extensive studies to solve the above problems. As a result, it was discovered that the above problems could be solved by using a specific radical initiator, a hindered phenol compound, and a cyclic olefin copolymer having an iodine value in a specific range, and the present invention was completed. It's arrived.
• cyclic olefin resin compositions varnishes, crosslinked products, films, sheets, circuit boards, electronic devices, and prepregs are provided.
• a cyclic olefin resin composition comprising:
• the above cyclic olefin copolymer (A) is A repeating unit derived from one or more olefins represented by general formula (1), A repeating unit derived from one or more cyclic nonconjugated dienes represented by general formula (2), A repeating unit derived from one or more cyclic olefins represented by general formula (3), including;
• the iodine value of the cyclic olefin copolymer (A) is in the range of 20 g/100 g or more and 120 g/100 g or less, A cyclic olefin resin composition, wherein the cyclic olefin copolymer (A)
• 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
• w is 0 or 1
• R 61 to R 76 and R a1 and R b1 are mutually 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 bonded to each other to form a monocyclic ring. Alternatively, it may form a polycyclic ring.
• u is 0 or 1
• v is 0 or a positive integer
• w is 0 or 1
• R 61 to R 78 and R a1 and R b1 are mutually the same or different.
• R 75 to R 78 may be bonded to each other to form a monocyclic or polycyclic ring.
• the cyclic olefin copolymer (A) is The repeating unit represented by general formula (2) includes a repeating unit derived from 5-vinyl-2-norbornene,
• the repeating unit represented by general formula (3) is a repeating unit derived from bicyclo[2.2.1]-2-heptene or tetracyclo[4.4.0.1 2,5 . 1 7,10 ]-3-Dodecene-derived cyclic olefin resin composition.
• the cyclic olefin resin composition of the present invention can provide a cyclic olefin resin composition that has both heat resistance and dielectric properties.
• a to B indicating a numerical range represents a value greater than or equal to A and less than or equal to B, unless otherwise specified.
• a group such as an alkyl group "has a substituent” means that a hydrogen atom present in the structure is substituted with a substituent, unless otherwise specified.
• the position of the substituents and the number of substituents are not particularly limited.
• the number of carbon atoms of a substituent is not included in the number of carbon atoms of a group having a substituent.
• an ethyl group having a phenyl group as a substituent is considered to be an alkyl group having 2 carbon atoms.
• the solid content in this embodiment refers to components excluding volatile components such as solvents.
• the cyclic olefin resin composition is Cyclic olefin copolymer (A), an azo compound (B) having an azo group in the molecule and containing no heteroatoms other than the nitrogen atoms constituting the azo group; a hindered phenol compound (C);
• a cyclic olefin resin composition comprising:
• the above cyclic olefin copolymer (A) is A repeating unit (X) derived from one or more olefins represented by general formula (1), A repeating unit (Y) derived from one or more cyclic nonconjugated dienes represented by general formula (2), A repeating unit (Z) derived from one or more cyclic olefins represented by general formula (3), including;
• the iodine value of the cyclic olefin copolymer (A) is in the range of 20 g/100 g or more and 120 g/100 g or
• the cyclic olefin resin composition according to this embodiment achieves both heat resistance and dielectric properties is not clear, the following mechanism is presumed. That is, according to the cyclic olefin resin composition according to the present embodiment, a sufficient amount of crosslinked structure can be formed by using a cyclic olefin copolymer having an iodine value within a specific range. Furthermore, by using a specific azo compound that does not produce a polar compound upon decomposition as a radical initiator, deterioration of dielectric properties due to the polar compound can be suppressed.
• the cyclic olefin resin composition according to the present embodiment includes one or more olefin-derived repeating units represented by general formula (1) and one or more cyclic nonconjugated diene represented by general formula (2). and one or more cyclic olefin-derived repeating units represented by general formula (3).
• 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
• w is 0 or 1
• R 61 to R 76 and R a1 and R b1 are mutually the same or different.
• R 104 is an aromatic hydrocarbon group
• 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 bonded to each other to form a monocyclic ring. Alternatively, it may form a polycyclic ring.
• u is 0 or 1
• v is 0 or a positive integer
• w is 0 or 1
• R 61 to R 78 and R a1 and R b1 are mutually the same or different.
• It is an aromatic hydrocarbon group
• R 75 to R 78 may be bonded to each other to form a monocyclic or polycyclic ring.
• the iodine value of the cyclic olefin copolymer (A) of the present embodiment is 20 g/100 g or more, preferably 25 g/100 g or more, more preferably 30 g/100 g or more, and even more preferably 35 g/100 g. or more, and more preferably 40g/100g or more. Thereby, a sufficient amount of crosslinking is formed in the crosslinked body, and heat resistance and mechanical properties can be improved.
• the iodine value of the cyclic olefin copolymer (A) of the present embodiment is 120 g/100 g or less, preferably 115 g or less, more preferably 112 g or less, still more preferably 100 g/100 g or less, More preferably, it is 80g/100g or less. This makes it possible to suppress the production of carbonyl groups and carboxyl groups produced by oxidation of carbon-carbon double bonds, and to suppress the deterioration of dielectric properties caused by the production of these groups.
• the iodine value of the cyclic olefin copolymer (A) of the present embodiment is in the range of 20 g/100 g to 120 g/100 g, preferably in the range of 25 g/100 g to 120 g/100 g, more preferably 30 g /100g or more and 115g/100g or less, more preferably 35g/100g or more and 115g/100g or less, and even more preferably 40g/100g or more and 112g/100g or less. This makes it possible to improve dielectric properties, heat resistance, and mechanical properties.
• the iodine value of the cyclic olefin copolymer (A) can be controlled by selecting copolymerization raw materials, adjusting the charging ratio, etc.
• the number average molecular weight Mn of the cyclic olefin copolymer (A) of this embodiment is 3,000 or more, preferably 3,500 or more, more preferably 4,000 or more, even more preferably 4, It is 500 or more, more preferably 5,000 or more. This makes it possible to improve dielectric properties, heat resistance, and mechanical properties.
• the number average molecular weight Mn of the cyclic olefin copolymer (A) of this embodiment is 30,000 or less, preferably 25,000 or less, more preferably 23,000 or less, even more preferably 20, 000 or less, more preferably 15,000 or less, still more preferably 10,000 or less. This makes it possible to improve moldability such as impregnation into a fiber base material and wiring embedding during circuit board production.
• the number average molecular weight Mn of the cyclic olefin copolymer (A) of this embodiment is in the range of 3,000 to 30,000, preferably in the range of 3,500 to 25,000, more preferably The number is in the range of 4,000 or more and 23,000 or less, more preferably 4,000 or more and 20,000 or less, and even more preferably 4,000 or more and 10,000 or less. This results in good dielectric properties, heat resistance, and mechanical properties, and also good moldability.
• the number average molecular weight Mn of the cyclic olefin copolymer (A) can be controlled by polymerization conditions such as the polymerization catalyst, cocatalyst, amount of H 2 added, and polymerization temperature.
• the Tg of the cyclic olefin copolymer (A) is, for example, 300°C or lower, preferably 250°C or lower, more preferably 200°C or lower, even more preferably 170°C or lower, particularly preferably The temperature is 150°C or less.
• the Tg of the cyclic olefin copolymer (A) is preferably 70°C or higher, more preferably 80°C or higher, and even more preferably 90°C or higher. Thereby, the heat resistance of the cyclic olefin copolymer (A) can be improved.
• the Tg of the cyclic olefin copolymer (A) can be controlled by selecting copolymerization raw materials, adjusting the charging ratio, etc.
• the intrinsic viscosity [ ⁇ ] of the cyclic olefin copolymer (A) measured in decalin at 135°C is preferably more than 0.01 dl/g, more preferably 0.02 dl/g or more, and Preferably it is 0.04 dl/g or more. Thereby, heat resistance and mechanical properties can be further improved.
• the intrinsic viscosity [ ⁇ ] of the cyclic olefin copolymer (A) measured in decalin at 135°C is preferably less than 0.45 dl/g, more preferably 0.40 dl/g or less, and Preferably it is 0.35 dl/g or less. This makes it possible to further improve moldability such as impregnation into a fiber base material and wiring embedding during circuit board production.
• the intrinsic viscosity [ ⁇ ] of the cyclic olefin copolymer (A) can be controlled by polymerization conditions such as the polymerization catalyst, cocatalyst, amount of hydrogenation, and polymerization temperature.
• the content of the cyclic olefin copolymer (A) in the cyclic olefin resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more. , more preferably 25% by mass or more, still more preferably 30% by mass or more, even more preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferably 60% by mass or more. , more preferably 70% by mass or more.
• the content of the cyclic olefin copolymer (A) in the cyclic olefin resin composition is preferably 99% by mass or less, more preferably 98% by mass or less, and preferably 95% by mass or less, The content is more preferably 90% by mass or less, further preferably 80% by mass or less, particularly preferably 75% by mass or less.
• the cyclic olefin resin composition may contain a cyclic olefin copolymer other than the cyclic olefin copolymer (A) (hereinafter referred to as other cyclic olefin copolymer (n)). Note that other cyclic olefin copolymers (n) will be described later.
• the cyclic olefin copolymers (A) are ) is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, still more preferably 25% by mass or more, and even more preferably 30% by mass. % or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferably 60% by mass or more, still more preferably 70% by mass or more.
• the cyclic olefin copolymers (A) are ) is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 80% by mass or less, particularly preferably 75% by mass or less.
• the molar ratio of the repeating unit represented by general formula (1) in the cyclic olefin copolymer (A) is preferably 30 mol% or more, more preferably 35 mol% or more, and even more preferably It is 40 mol% or more.
• the molar ratio of the repeating unit represented by general formula (1) in the cyclic olefin copolymer (A) is preferably 80 mol% or less, more preferably 75 mol% or less, and even more preferably It is 70 mol% or less.
• the molar ratio of the repeating unit represented by general formula (1) in the cyclic olefin copolymer (A) is preferably in the range of 30 mol% or more and 80 mol% or less, more preferably 35 mol% or more. The range is 75 mol% or less, more preferably 40 mol% or more and 70 mol% or less.
• the molar ratio of the repeating unit represented by general formula (2) in the cyclic olefin copolymer (A) is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably It is 10 mol% or more.
• the molar ratio of the repeating unit represented by general formula (2) in the cyclic olefin copolymer (A) is preferably 30 mol% or less, more preferably 25 mol% or less, and even more preferably It is 20 mol% or less.
• the molar ratio of the repeating unit represented by general formula (2) in the cyclic olefin copolymer (A) is preferably in the range of 1 mol% or more and 30 mol% or less, more preferably 5 mol% or more.
• the range is 25 mol% or less, more preferably 10 mol% or more and 20 mol% or less.
• the molar ratio of the repeating unit represented by general formula (3) in the cyclic olefin copolymer (A) is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably It is 10 mol% or more.
• the molar ratio of the repeating unit represented by general formula (3) in the cyclic olefin copolymer (A) is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably It is 30 mol% or less.
• the molar ratio of the repeating unit represented by general formula (3) in the cyclic olefin copolymer (A) is preferably in the range of 1 mol% or more and 40 mol% or less, more preferably 5 mol% or more.
• the range is 35 mol% or less, more preferably 10 mol% or more and 30 mol% or less.
• the monomer that is one of the copolymerization raw materials for the cyclic olefin copolymer (A) is one that undergoes addition copolymerization to form a repeating unit represented by the general formula (1). It is expressed by general formula (1a) corresponding to formula (1).
• R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.
• Examples of the olefin represented by the general formula (1a) 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.
• the olefin represented by the general formula (1a) is preferably ethylene and propylene, and ethylene is preferred. It is particularly preferable that there be.
• biomass-derived monomer biomass-derived ethylene, biomass-derived propylene, etc.
• biomass-derived monomer biomass-derived ethylene, biomass-derived propylene, etc.
• the monomer that is one of the copolymerization raw materials for the cyclic olefin copolymer (A) is one that undergoes addition copolymerization to form a repeating unit represented by the general formula (2). It is a cyclic non-conjugated diene represented by general formula (2a) corresponding to formula (2).
• the cyclic non-conjugated diene may include a structural unit derived from a biomass-derived monomer (cyclic non-conjugated diene).
• u is 0 or 1
• v is 0 or a positive integer, preferably an integer from 0 to 2, more preferably 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, and each of hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, halogenated alkyl group having 1 to 20 carbon atoms, carbon It is a cycloalkyl group having 3 to 15 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 group having 0 to 10 atoms.
• R 75 and R 76 may be bonded to each other to form a monocyclic ring or a polycyclic ring.
• the cyclic non-conjugated diene represented by the general formula (2a) is not particularly limited, but examples thereof include cyclic non-conjugated dienes represented by the following chemical formula.
• 5-vinyl-2-norbornene, 8-vinyl-9-methyltetracyclo[4.4.0.1 2,5 . 1 7,10 ]-3-dodecene is preferred, and 5-vinyl-2-norbornene is particularly preferred.
• the cyclic nonconjugated diene represented by the general formula (2a) can also be specifically represented by the general formula (2b).
• n 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. It is.
• the cyclic olefin copolymer (A) of this embodiment has a characteristic of having a double bond in the side chain portion by containing a repeating unit derived from a cyclic non-conjugated diene represented by general formula (2). .
• a crosslinked structure can be formed by the double bond.
• the monomer that is one of the copolymerization raw materials for the cyclic olefin copolymer (A) is one that undergoes addition copolymerization to form a repeating unit represented by the general formula (3). It is expressed by general formula (3a) corresponding to formula (3).
• u is 0 or 1
• v is 0 or a positive integer, preferably an integer from 0 to 2, more preferably 0 or 1
• w is 0 or 1
• R 61 to R 78 and R a1 and R b1 may be the same or different and each represents 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, or a carbon atom. It is a cycloalkyl group having 3 to 15 atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R 75 to R 78 may be bonded to each other to form a monocyclic or polycyclic ring.
• cyclic olefin represented by general formula (3a) compounds described in International Publication No. 2006/118261 can be used.
• examples of the cyclic olefin represented by the general formula (3a) include bicyclo[2.2.1]-2-heptene (also called norbornene), tetracyclo[4.4.0.1 2,5 . 1 7,10 ]-3-dodecene (also called tetracyclododecene) is preferred, and tetracyclo[4.4.0.1 2,5 . 1 7,10 ]-3-dodecene is more preferred.
• the cyclic olefin represented by the above general formula (3a) may include a structural unit derived from a biomass-derived monomer (cyclic olefin).
• the cyclic olefin copolymer (A) contains a repeating unit derived from 5-vinyl-2-norbornene as a repeating unit represented by the general formula (2), and a repeating unit derived from the general formula (3).
• ) is a repeating unit derived from bicyclo[2.2.1]-2-heptene or tetracyclo[4.4.0.1 2,5 . 1 7,10 ]-3-dodecene-derived repeating unit. This makes it possible to improve dielectric properties, heat resistance, and mechanical properties.
• the cyclic olefin copolymer (A) can be produced, for example, according to the method for producing a cyclic olefin copolymer described in paragraphs 0075 to 0219 of International Publication No. 2012/046443. Details are omitted here.
• the molar ratio of the monomer represented by general formula (1a) is preferably 30 mol% or more, more preferably 35 mol% or more.
• the content is more preferably 40 mol% or more.
• the molar ratio of the monomer represented by general formula (1a) is preferably 80 mol% or less, more preferably 75 mol% or less. The content is more preferably 70 mol% or less.
• the molar ratio of the amount of the monomer represented by the general formula (1a) is preferably in the range of 30 mol% or more and 80 mol% or less, and more preferably is in the range of 35 mol% or more and 75 mol% or less, more preferably 40 mol% or more and 70 mol% or less.
• the molar ratio of the monomer represented by general formula (2a) is preferably 1 mol% or more, more preferably 5 mol% or more.
• the content is more preferably 10 mol% or more.
• the molar ratio of the monomer represented by general formula (2a) is preferably 30 mol% or less, more preferably 25 mol% or less.
• the content is more preferably 20 mol% or less.
• the molar ratio of the charged amount of the monomer represented by general formula (2a) is preferably in the range of 1 mol% or more and 30 mol% or less, and more preferably is in the range of 5 mol% or more and 25 mol% or less, more preferably 10 mol% or more and 20 mol% or less.
• the molar ratio of the monomer represented by general formula (3a) is preferably 1 mol% or more, more preferably 5 mol% or more.
• the content is more preferably 10 mol% or more.
• the molar ratio of the monomer represented by general formula (3a) is preferably 40 mol% or less, more preferably 35 mol% or less.
• the content is more preferably 30 mol% or less.
• the molar ratio of the monomer represented by the general formula (3a) is preferably in the range of 1 mol% or more and 40 mol% or less, and more preferably is in the range of 5 mol% or more and 35 mol% or less, more preferably 10 mol% or more and 30 mol% or less.
• the cyclic olefin resin composition according to the present embodiment includes an azo compound (B) that has an azo group in the molecule and does not contain any heteroatoms other than the nitrogen atoms that constitute the azo group.
• the azo compound (B) is not particularly limited as long as it has an azo group in its molecule and does not contain any heteroatoms other than the nitrogen atoms that constitute the azo group.
• the azo compound (B) generates radicals by heating and functions as a radical initiator.
• the azo compound (B) contains a compound represented by general formula (4).
• R 21 and R 22 each independently represent a hydrogen atom or an alkyl group.
• the alkyl groups represented by R 21 and R 22 do not contain a hetero atom.
• the alkyl group represented by R 21 and R 22 may be a linear alkyl group or a branched alkyl group.
• Specific examples of the alkyl group include linear alkyl groups such as n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, and n-octyl group; s-butyl group, t Examples include branched alkyl groups such as -butyl group and 2,2',4,4'-tetramethylbutyl group.
• Examples of commercially available azo compounds (B) include VR-110 (2,2'-azobis(2,4,4-trimethylpentane), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).
• the number of carbon atoms in the alkyl group represented by R 21 and R 22 is preferably 1 to 8, more preferably 3 to 8, and even more preferably 4 to 8.
• the azo compound (B) contains at least one of the compound represented by formula (5) and the compound represented by formula (6).
• the content of the azo compound (B) is preferably 0.1 parts by mass. part or more, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, still more preferably 1.5 parts by mass or more, still more preferably 2 parts by mass or more. This allows the crosslinking reaction to proceed sufficiently.
• the content of the azo compound (B) is preferably 20 parts by mass or less. It is more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less, still more preferably 7 parts by mass or less, still more preferably 5 parts by mass or less. Thereby, deterioration of dielectric properties can be prevented.
• the content of the azo compound (B) is preferably 0.1 parts by mass.
• the cyclic olefin resin composition according to this embodiment contains a hindered phenol compound (C).
• the hindered phenol compound (C) preferably has a structure represented by general formula (7).
• R 31 represents an alkyl group having 1 to 4 carbon atoms
• R 32 represents hydrogen or an alkyl group having 1 to 4 carbon atoms.
• R 31 and R 32 may or may not have a substituent.
• Examples of the alkyl group having 1 to 4 carbon atoms represented by R 31 include methyl group, ethyl group, propyl group, isopropyl group, isobutyl group, and tertiary butyl group.
• Examples of the hindered phenol compound (C) include pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox1010 manufactured by BASF), octadecyl-3-(3,5- Di-tert-butyl-4-hydroxyphenyl) propionate (Irganox 1076 manufactured by BASF), 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-( Examples include mesitylene-2,4,6-triyl)tri-p-cresol (Irganox 1330 manufactured by BASF).
• both R 31 and R 32 are preferably t-butyl groups. That is, the cyclic olefin resin composition according to the present embodiment preferably includes a compound in which R 31 and R 32 in the general formula (7) are both t-butyl groups. This suppresses oxidative deterioration of the resin during processing and prevents deterioration of dielectric properties.
• the hindered phenol compound (C) is preferably a compound represented by general formula (8). This improves the dispersibility in the resin composition of the present invention and increases the effect of suppressing deterioration of dielectric properties.
• R 33 represents an organic group.
• the organic group represented by R 33 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cyclohexyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cyclohexyl group having 6 to 20 carbon atoms.
• An example is an unsubstituted aryl group.
• Another substituted phenol structure may be linked via the organic group R 33 .
• Examples of the compound represented by the general formula (8) include pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox1010 manufactured by BASF), octadecyl-3-(3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox 1076 manufactured by BASF).
• the content of the hindered phenol compound (C) is preferably 0. 001 parts by mass or more, more preferably 0.005 parts by mass or more, even more preferably 0.01 parts by mass or more, still more preferably 0.02 parts by mass or more, and even more preferably 0.05 parts by mass. It is more than 100%. Thereby, oxidative deterioration of the cyclic olefin resin composition can be suppressed, and deterioration of dielectric properties can be prevented.
• the content of the hindered phenol compound (C) is preferably 1 part by mass. parts by weight or less, more preferably 0.5 parts by weight or less, still more preferably 0.2 parts by weight or less, even more preferably 0.1 parts by weight or less, even more preferably 0.08 parts by weight or less. It is. Thereby, inhibition of the crosslinking reaction of the cyclic olefin resin composition by the hindered phenol compound (C) can be suppressed.
• the content of the hindered phenol compound (C) is preferably 0.
• the range is 0.001 parts by mass or more and 1 part by mass or less, more preferably 0.005 parts by mass or more and 0.5 parts by mass or less, and even more preferably 0.01 parts by mass or more and 0.2 parts by mass or less.
• the content is more preferably 0.02 parts by mass or more and 0.1 parts by mass or less, and even more preferably 0.05 parts by mass or more and 0.08 parts by mass or less.
• the cyclic olefin resin composition according to the present embodiment may contain a cyclic olefin copolymer other than the cyclic olefin copolymer (A), a filler, a flame retardant, a crosslinking aid, etc., as necessary. Good too.
• cyclic olefin copolymers other than the above-mentioned cyclic olefin copolymer (A) are referred to as other cyclic olefin copolymers (n).
• a cyclic olefin copolymer that does not meet the above-mentioned iodine value requirements iodine value is in the range of 20 g/100 g to 120 g/100 g
• the cyclic olefin resin composition according to this embodiment may contain other cyclic olefin copolymers (n).
• Other cyclic olefin copolymers (n) contained in the cyclic olefin resin composition according to the present embodiment are not particularly limited, and known ones can be used.
• the other cyclic olefin copolymer (n) is at least one selected from a copolymer of ethylene or an ⁇ -olefin and a cyclic olefin (n-i), and a ring-opening polymer of a cyclic olefin (n-ii). It is preferable to include. Thereby, the dielectric properties can be made even better.
• the copolymer (ni) does not contain a repeating unit derived from a cyclic non-conjugated diene represented by the above general formula (2).
• the above-mentioned copolymer (n-i) does not contain a repeating unit derived from a cyclic non-conjugated diene represented by the above-mentioned general formula (2).
• the total number of moles of repeating units is 100 mol%, it means that the content of repeating units derived from the cyclic nonconjugated diene represented by the above general formula (2) is 0.05 mol% or less.
• the number average molecular weight Mn of the other cyclic olefin copolymer (n) is preferably 10,000 or more. This makes it possible to further improve dielectric properties, heat resistance, and mechanical properties.
• the number average molecular weight Mn of the other cyclic olefin copolymer (n) is preferably 60,000 or less, more preferably 57,000 or less, even more preferably 55,000 or less. This makes it possible to further improve moldability such as impregnation into a fiber base material and wiring embedding during circuit board production.
• the number average molecular weight Mn of the other cyclic olefin copolymer (n) can be controlled by polymerization conditions such as the polymerization catalyst, cocatalyst, amount of H 2 added, and polymerization temperature.
• the content of the other cyclic olefin copolymer (n) in the cyclic olefin resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more. and more preferably 25% by mass or more.
• the content of the other cyclic olefin copolymer (n) in the cyclic olefin resin composition is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less. and more preferably 75% by mass or less.
• the content of the other cyclic olefin copolymer (n) relative to the total amount of the cyclic olefin copolymer (A) and the other cyclic olefin copolymer (n) is preferably 5% by mass or more. , more preferably 10% by mass or more, still more preferably 20% by mass or more, still more preferably 25% by mass or more.
• the content of the other cyclic olefin copolymer (n) relative to the total amount of the cyclic olefin copolymer (A) and the other cyclic olefin copolymer (n) is preferably 95% by mass or less. , more preferably 90% by mass or less, further preferably 80% by mass or less, still more preferably 75% by mass or less.
• copolymer (ni) of ethylene or ⁇ -olefin and cyclic olefin for example, the polymers described in paragraphs 0030 to 0123 of International Publication No. 2008/047468 can be used.
• polymer that has an alicyclic structure is a polymer that has an alicyclic structure in at least a portion of its repeating structural units (hereinafter also simply referred to as a "polymer that has an alicyclic structure"); Any polymer having a group structure may be used, and specifically, it is preferable to include a polymer having one or more structures represented by the following general formula (13).
• x and y represent a copolymerization ratio, and are real numbers satisfying 0/100 ⁇ y/x ⁇ 95/5.
• x, y are on a molar basis
• n indicates the number of substitutions of the substituent Q and is a real number of 0 ⁇ n ⁇ 2
• R a is selected from the group consisting of hydrocarbon groups having 2 to 20 carbon atoms. 2+n valent group
• R b is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
• R c is a hydrocarbon group having 2 to 10 carbon atoms.
• Q is a tetravalent group selected from the group consisting of hydrogen groups, and Q is COOR d (R d is a hydrogen atom or a monovalent group selected from the group consisting of hydrocarbon groups having 1 to 10 carbon atoms. ), and each of R a , R b , R c and Q may be one type, or may contain two or more types in any proportion.
• p is an integer from 0 to 2.
• a cyclic olefin copolymer represented by the general formula (14) can be exemplified.
• the cyclic olefin copolymer represented by general formula (14) includes, for example, a repeating unit derived from ethylene or a linear or branched ⁇ -olefin having 3 to 30 carbon atoms, and a repeating unit derived from a cyclic olefin. It consists of units.
• R a is a divalent group selected from the group consisting of hydrocarbon groups having 2 to 20 carbon atoms
• R b is a hydrogen atom or a carbonized group having 1 to 10 carbon atoms. It is a monovalent group selected from the group consisting of hydrogen groups, and R a and R b may each be one type or may have two or more types in any ratio, and x and y are It is a real number that indicates the copolymerization ratio (molar basis) and satisfies 5/95 ⁇ y/x ⁇ 95/5, preferably 50/50 ⁇ y/x ⁇ 95/5, more preferably 55/45 ⁇ y /x ⁇ 80/20.
• the copolymer (ni) of ethylene or ⁇ -olefin and cyclic olefin is preferably a copolymer consisting of ethylene and cyclic olefin, and the cyclic olefin is bicyclo[2.2.1]-2-heptene, tetracyclo[ 4.4.0.1 2,5 .
• the copolymer (ni) of ethylene or ⁇ -olefin and cyclic olefin may be a polymer having one or more structures represented by general formula (13) or a polymer having the above general formula (14).
• the expressed cyclic olefin copolymer may be a hydrogenated polymer.
• copolymer (ni) of ethylene or an ⁇ -olefin and a cyclic olefin a copolymer of an ⁇ -olefin having 4 to 12 carbon atoms and a cyclic olefin is also preferable.
• the copolymer of an ⁇ -olefin having 4 to 12 carbon atoms and a cyclic olefin for example, the polymers described in paragraphs 0056 to 0070 of International Publication No. 2015/178145 can be used.
• Examples of the cyclic olefin constituting the copolymer of an ⁇ -olefin having 4 to 12 carbon atoms and a cyclic olefin include norbornene and substituted norbornene, with norbornene being preferred.
• the above cyclic olefins can be used alone or in combination of two or more.
• substituted norbornene is not particularly limited, and examples of the substituent that this substituted norbornene has include a halogen atom and a monovalent or divalent hydrocarbon group.
• substituent that this substituted norbornene has include a halogen atom and a monovalent or divalent hydrocarbon group.
• substituted norbornene include those represented by the following general formula (a).
• R 1 to R 12 may be the same or different, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R 9 and R 10 , R 11 and R 12 may be combined to form a divalent hydrocarbon group, and R 9 or R 10 and R 11 or R 12 may mutually form a ring.
• R 1 to R 12 in general formula (a) may be the same or different, and are selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups.
• R 1 to R 8 include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine, and bromine; an alkyl group having 1 to 20 carbon atoms, and these may be different from each other. , may be partially different, or may be entirely the same.
• R 9 to R 12 include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine, and bromine; an alkyl group having 1 to 20 carbon atoms; a cycloalkyl group such as a cyclohexyl group; a phenyl group, and a tolyl group.
• Substituted or unsubstituted aromatic hydrocarbon groups such as ethylphenyl group, isopropylphenyl group, naphthyl group, anthryl group; examples include benzyl group, phenethyl group, and other aralkyl groups in which an alkyl group is substituted with an aryl group. These may be different from each other, may be partially different, or may be entirely the same.
• R 9 and R 10 or R 11 and R 12 are combined to form a divalent hydrocarbon group
• alkylidene groups such as ethylidene group, propylidene group, isopropylidene group, etc. can be mentioned.
• the ring formed may be monocyclic or polycyclic, or may be a polycyclic ring having a bridge. , a double bond, or a combination of these rings. Further, these rings may have a substituent such as a methyl group.
• substituted norbornene represented by general formula (a) include 5-methyl-bicyclo[2.2.1]hept-2-ene, 5,5-dimethyl-bicyclo[2.2.1]hept- 2-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2.
• dodec-3-ene also simply called tetracyclododecene
• 8-methyltetracyclo[4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene 8-ethyltetracyclo[4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene
• alkyl-substituted norbornene e.g., bicyclo[2.2.1]hept-2-ene substituted with one or more alkyl groups
• alkylidene-substituted norbornene e.g., bicyclo[2.2.1]hept-2-ene substituted with one or more alkylidene groups
• [2.2.1]hept-2-ene is preferred
• 5-ethylidene-bicyclo[2.2.1]hept-2-ene common name: 5-ethylidene-2-norbornene, or simply ethylidenenorbornene
• Examples of the ⁇ -olefin having 4 to 12 carbon atoms constituting the copolymer of ⁇ -olefin having 4 to 12 carbon atoms and a cyclic olefin include ⁇ -olefin having 4 to 12 carbon atoms, and at least one halogen atom. Examples include ⁇ -olefins having 4 to 12 carbon atoms and having one type of substituent, and ⁇ -olefins having 4 to 12 carbon atoms are preferred.
• ⁇ -olefins having 4 to 12 carbon atoms are not particularly limited, but examples include 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, Examples include 3-ethyl-1-hexene, 1-octene, 1-decene, and 1-dodecene. Among these, 1-hexene, 1-octene, and 1-decene are preferred.
• the copolymer of an ⁇ -olefin having 4 to 12 carbon atoms and a cyclic olefin according to the present embodiment has 4 to 12 carbon atoms, when the total number of repeating units contained in the copolymer is 100 mol%.
• the proportion of repeating units derived from ⁇ -olefin is preferably 10 mol% or more and 90 mol% or less, more preferably 15 mol% or more and 80 mol% or less, and still more preferably 20 mol% or more and 70 mol% or less.
• the copolymer of an ⁇ -olefin having 4 to 12 carbon atoms and a cyclic olefin according to the present embodiment is based on cyclic olefin-derived
• the proportion of repeating units is preferably 10 mol% or more and 90 mol% or less, more preferably 20 mol% or more and 85 mol% or less, and still more preferably 30 mol% or more and 80 mol% or less.
• the conditions for the polymerization step to obtain a copolymer of an ⁇ -olefin having 4 to 12 carbon atoms and a cyclic olefin are not particularly limited as long as the desired copolymer can be obtained, and known conditions can be used. , polymerization temperature, polymerization pressure, polymerization time, etc. are adjusted as appropriate.
• a ring-opening polymer (n-ii) of a cyclic olefin can be used as the other cyclic olefin copolymer (n).
• the ring-opening polymer (n-ii) of a cyclic olefin include a ring-opening polymer of a norbornene monomer, and a ring-opening polymer of a norbornene monomer and other monomers capable of ring-opening copolymerization therewith. Examples include ring polymers and hydrides thereof.
• norbornene monomers examples include bicyclo[2.2.1]hept-2-ene (common name: norbornene) and its derivatives (having substituents on the ring), tricyclo[4.3.01, 6.12,5]deca-3,7-diene (common name dicyclopentadiene) and its derivatives, 7,8-benzotricyclo[4.3.0.12,5]dec-3-ene (common name Methanotetrahydrofluorene: also referred to as 1,4-methano-1,4,4a,9a-tetrahydrofluorene) and its derivatives, tetracyclo[4.4.0.1 2,5 .
• substituents on the rings of these derivatives include alkyl groups, alkylene groups, vinyl groups, alkoxycarbonyl groups, and alkylidene groups. Note that the substituent may have one or more substituents. Examples of such derivatives having substituents on the ring include 8-methoxycarbonyl-tetracyclo[4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 2,5 .
• Ring-opening polymers of norbornene-based monomers can be obtained by subjecting the monomer components to known ring-opening polymerization. It can be obtained by polymerization in the presence of a catalyst.
• the ring-opening polymerization catalyst examples include a catalyst consisting of a metal halide such as ruthenium or osmium, a nitrate or an acetylacetone compound, and a reducing agent; a metal halide or acetylacetone compound such as titanium, zirconium, tungsten, or molybdenum; , a catalyst consisting of an organoaluminum compound; etc. can be used.
• Examples of other monomers capable of ring-opening copolymerization with the norbornene monomer include monocyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene.
• Hydrogenated products of ring-opening polymers of norbornene monomers and hydrogenated products of ring-opening polymers of norbornene monomers and other monomers capable of ring-opening copolymerization with them are usually It can be obtained by adding a known hydrogenation catalyst containing a transition metal such as nickel or palladium to a polymerization solution of the polymer to hydrogenate carbon-carbon unsaturated bonds.
• the other cyclic olefin copolymers (n) may be used alone or in combination of two or more.
• the cyclic olefin resin composition according to this embodiment may contain a filler.
• the filler contained in the cyclic olefin resin composition according to the present embodiment is not particularly limited, and any known filler can be used.
• One type of filler may be used alone, or a plurality of types may be used in combination.
• the amount of filler added is appropriately selected depending on the application within a range that does not impair the purpose of the present invention.
• fillers include inorganic fillers and organic fillers.
• examples of the inorganic filler include silica.
• an inorganic filler illustrated in paragraph [0117] of International Publication No. 2017/150218 pamphlet can be used.
• examples of organic fillers include starch and its derivatives.
• organic fillers illustrated in paragraph [0118] of International Publication No. 2017/150218 pamphlet can be used.
• the cyclic olefin resin composition according to this embodiment preferably contains an inorganic filler.
• the cyclic olefin resin composition according to this embodiment may contain a flame retardant.
• the flame retardant contained in the cyclic olefin resin composition according to the present embodiment is not particularly limited, and any known flame retardant can be used.
• One type of flame retardant may be used alone or a combination of multiple types may be used.
• the amount of flame retardant added is appropriately selected depending on the application within a range that does not impair the purpose of the present invention.
• halogen-based flame retardants for example, halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-containing flame retardants, and antimony-based flame retardants can be used.
• Various chlorine-based and bromine-based flame retardants can be used as halogen-based flame retardants. and pentabromodiphenyl ether.
• flame retardants exemplified in Paragraph [0105] of International Publication No. 2017/150218 pamphlet can be used.
• phosphorus-based flame retardants include tris(chloroethyl) phosphate.
• phosphorus-based flame retardants illustrated in paragraph [0106] of International Publication No. 2017/150218 pamphlet can be used.
• the cyclic olefin resin composition according to this embodiment preferably contains a flame retardant.
• the cyclic olefin resin composition according to this embodiment may contain a crosslinking aid.
• the crosslinking aid contained in the cyclic olefin resin composition according to the present embodiment is not particularly limited, and any known one can be used.
• crosslinking aids may be used alone or in combination.
• the amount of the crosslinking aid added is appropriately selected depending on the application within a range that does not impair the purpose of the present invention.
• crosslinking aids include oximes such as p-quinone dioxime and p,p'-dibenzoylquinone dioxime; ethylene dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, cyclohexyl methacrylate, and acrylic acid/ Acrylates or methacrylates such as zinc oxide mixtures, allyl methacrylate; vinyl monomers such as divinylbenzene, vinyltoluene, vinylpyridine; hexamethylene diaryl nadimide, diallyl itaconate, diallyl phthalate, diallyl isophthalate, diallyl monoglycidyl isocyanurate, Allyl compounds such as triallyl cyanurate and triallyl isocyanurate; maleimide compounds such as N,N'-m-phenylene bismaleimide, N,N'-(4,4'-methylene diphenylene) dimaleimide, etc.
• the cyclic olefin resin composition of the present embodiment may optionally contain a heat-resistant stabilizer, a weather-resistant stabilizer, a radiation-resistant agent, a plasticizer, a lubricant, a mold release agent, a nucleating agent, and a friction-abrasive agent. It may contain various additives such as improvers, foaming agents, antistatic agents, colorants, antifogging agents, antiblocking agents, impact agents, surface wetting improvers, hydrochloric acid absorbers, and metal deactivators. .
• the glass transition point (Tg) of the crosslinked product is preferably 80°C or higher, more preferably 90°C or higher, and preferably 100°C or higher. More preferably, the temperature is 110°C or higher. Thereby, heat resistance can be improved.
• the upper limit of the Tg of the crosslinked product is not particularly limited, but may be, for example, 300° C. or less.
• the dielectric loss tangent (Df) of the crosslinked product at 10 GHz is preferably 0.00100 or less, more preferably 0.00095 or less, and 0.00090 or less. It is more preferably 0.00085 or less, even more preferably 0.00080 or less.
• the lower limit of Df of the crosslinked product is not particularly limited, but is, for example, 0.00001 or more.
• the crosslinked body used for measuring the glass transition point and dielectric loss tangent can be obtained, for example, by crosslinking the cyclic olefin copolymer of this embodiment under the following conditions.
• the cyclic olefin resin composition of this embodiment was coated in a molten state on a PET film that had been subjected to a mold release treatment at a speed of 10 mm/sec, and then placed in a blow dryer under a nitrogen stream at 150°C for 4 minutes. By drying, a film-like crosslinked precursor can be obtained.
• Two sheets of the obtained crosslinked precursor are stacked together, pressurized to 3.5 MPa using a vacuum press, heated at a constant rate from room temperature (25°C), and held at 180°C for 120 minutes to obtain a film-like crosslinked product. be able to.
• the cyclic olefin resin composition according to the present embodiment has excellent solvent resistance, heat resistance, mechanical strength, and transparency, so it can be used, for example, in optical fibers, optical waveguides, optical disk substrates, optical filters, lenses, optical adhesives, PDPs, etc. optical filters, coating materials for organic EL, base film substrates for solar cells in the aerospace field, coating materials for solar cells and thermal control systems, electronic devices such as semiconductor elements, light emitting diodes, and various memories, hybrid ICs, and MCMs. , circuit boards, prepregs and laminates used to form insulating layers of circuit boards, overcoat materials or interlayer insulation materials for display parts, substrates for liquid crystal displays and solar cells, medical instruments, automotive parts, separation materials, etc.
• the cyclic olefin resin composition according to the present embodiment has particularly excellent dielectric property stability over time, as well as excellent solvent resistance, heat resistance, transparency, mechanical properties, etc., and therefore is used for high frequency applications such as high frequency circuit boards. It can be suitably used for. Furthermore, since it has excellent gas barrier properties, it can be suitably used as a substrate, film, or sheet for liquid crystal displays and solar cells.
• the varnish according to this embodiment includes the above-described cyclic olefin resin composition and a solvent.
• the solvent for preparing the varnish according to the present embodiment is not particularly limited as long as it does not impair solubility or affinity for the cyclic olefin copolymer (A).
• saturated hydrocarbons such as heptane, hexane, octane, and decane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and decahydronaphthalene; aromatic hydrocarbons such as toluene, benzene, xylene, mesitylene, and pseudocumene; methanol, ethanol, Alcohols such as isopropyl alcohol, butanol, pentanol, hexanol, propanediol, phenol; Ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, acetophenone;
• esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, and butyl formate
• halogenated hydrocarbons such as trichloroethylene, dichloroethylene, and chlorobenzene, and the like
• Preferred examples include heptane, decane, cyclohexane, methylcyclohexane, decahydronaphthalene, toluene, benzene, xylene, mesitylene, and pseudocumene.
• solvents can be used alone or in a mixture of two or more in any ratio.
• the method for producing the varnish may be carried out by any method, but usually includes a step of mixing a cyclic olefin resin composition and a solvent.
• a step of mixing a cyclic olefin resin composition and a solvent There are no restrictions on the order of mixing the components, and the mixing may be carried out in any manner, such as all at once or in parts.
• the device for preparing the varnish There are no restrictions on the device for preparing the varnish, and any device capable of stirring and mixing, batch-type or continuous-type, may be used.
• the temperature at which the varnish is prepared can be arbitrarily selected within the range from room temperature to the boiling point of the solvent.
• the mixture may be further filtered using a mesh, membrane filter, or the like.
• the crosslinked product according to this embodiment is a crosslinked product of the above-mentioned cyclic olefin resin composition.
• the crosslinked product according to this embodiment can be obtained by crosslinking the above cyclic olefin resin composition, the above varnish, prepreg, etc.
• the crosslinking reaction can also be carried out after the molten cyclic olefin resin composition is molded by any method, or after it is impregnated into a base material to form a prepreg.
• a molten cyclic olefin resin composition is formed into a film by any method, and further cooled to obtain a film-like crosslinked precursor, and the resulting crosslinked precursor is heated, etc. to proceed with the crosslinking reaction. can be done.
• a varnish is prepared by dissolving or dispersing the cyclic olefin resin composition in a solvent, the varnish is formed into a film by any method, and further dried to obtain a film-like crosslinked precursor.
• the crosslinking reaction can also be advanced by heating the crosslinked precursor.
• a prepreg can be obtained by impregnating a base material with a molten cyclic olefin resin composition or a varnish prepared from the cyclic olefin resin composition, and crosslinking can be carried out by heating the obtained prepreg. You can also proceed.
• the glass transition point (Tg) of the crosslinked product according to this embodiment is preferably 80°C or higher, more preferably 90°C or higher, even more preferably 100°C or higher, and even more preferably 110°C or higher. It is even more preferable. Thereby, heat resistance can be improved.
• the upper limit of Tg is not particularly limited, but may be, for example, 300° C. or less.
• the dielectric loss tangent (Df) of the crosslinked body according to this embodiment is preferably 0.00100 or less, more preferably 0.00095 or less, even more preferably 0.00090 or less, and 0.00085 or less. It is more preferably at most 0.00080, even more preferably at most 0.00080. Thereby, dielectric properties can be improved.
• the lower limit of Df is not particularly limited, but is, for example, 0.00001 or more.
• the film or sheet according to this embodiment contains the above-mentioned crosslinked product.
• a molten cyclic olefin resin composition or a varnish obtained by dissolving or dispersing the cyclic olefin resin composition in a solvent is applied onto a supporting base material such as a thermoplastic resin film, and then heat-treated, etc.
• a method in which a cyclic olefin resin composition is formed by crosslinking is mentioned.
• the coating method is not particularly limited, but examples include coating using a spin coater, coating using a spray coater, coating using a bar coater, etc.
• the circuit board according to this embodiment includes an electrically insulating layer containing the above-mentioned crosslinked body, and a conductor layer provided on the electrically insulating layer.
• the cyclic olefin resin composition and crosslinked product according to the present embodiment have excellent dielectric properties, heat resistance, mechanical properties, etc., and are therefore suitable for use in circuit boards.
• the method for manufacturing the circuit board according to the present embodiment is not particularly limited and can employ generally known methods. form a layer.
• a conductor layer is laminated on the obtained electrically insulating layer by a known method to produce a laminate.
• a circuit board can be obtained by subjecting the conductor layer in the laminate to circuit processing or the like.
• metals such as copper, aluminum, nickel, gold, silver, and stainless steel can be used.
• Methods for forming the conductor layer include, for example, a method in which the metal is made into a foil or the like and thermally fused onto the electrical insulating layer, a method in which the metal is made into a foil, etc., and bonded onto the electrical insulating layer using an adhesive.
• a method of forming a conductor layer made of the metal on an electrically insulating layer by sputtering, vapor deposition, plating, or the like may be mentioned.
• the circuit board may be either a single-sided board or a double-sided board.
• the electronic device includes the above circuit board. That is, the above circuit board can be used as an electronic device by mounting electronic components such as semiconductor elements.
• Electronic devices can be manufactured based on known information.
• Examples of electronic devices include ICT infrastructure devices such as servers, routers, supercomputers, mainframes, and workstations; antennas such as GPS antennas, wireless base station antennas, millimeter wave antennas, and RFID antennas; Communication equipment such as mobile phones, smartphones, PHS, PDAs, and tablet terminals; Digital equipment such as personal computers, televisions, digital cameras, digital video cameras, POS terminals, wearable terminals, and digital media players; Electronic control system equipment, and in-vehicle communication equipment , car navigation equipment, millimeter wave radar, in-vehicle electronic equipment such as in-vehicle camera modules; semiconductor testing equipment, high-frequency measurement equipment, etc.
• ICT infrastructure devices such as servers, routers, supercomputers, mainframes, and workstations
• antennas such as GPS antennas, wireless base station antennas, millimeter wave antennas, and RFID antennas
• Communication equipment such as mobile phones, smartphones, PHS, PDAs, and tablet terminals
• Digital equipment such as personal computers, televisions, digital cameras,
• the prepreg according to this embodiment includes the above-described cyclic olefin resin composition and a sheet-like fiber base material.
• the method for manufacturing the prepreg according to this embodiment is not particularly limited, and various known methods can be applied.
• a prepreg can be obtained by impregnating a sheet-like fiber base material with a molten cyclic olefin resin composition or a varnish prepared from the cyclic olefin resin composition.
• the sheet-like fiber base material is impregnated with a predetermined amount of varnish by a known method such as spray coating, dip coating, roll coating, curtain coating, die coating, or slit coating. This can be done by applying the protective film to the material, placing a protective film thereon if necessary, and pressing it from above with a roller or the like.
• the varnish When impregnating with varnish, it may include a step of volatilizing the solvent contained in the varnish.
• methods include drying in air or nitrogen using a blow dryer in a batch process, or drying by passing through a heating furnace in a continuous process.
• Inorganic and/or organic fibers can be used as the fibers constituting the sheet-like fiber base material, and examples include, but are not limited to, PET (polyethylene terephthalate) fibers, aramid fibers, ultrahigh molecular polyethylene fibers, and polyamide ( Organic fibers such as 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 silica fibers; etc. be able to. Among these, organic fibers and glass fibers are preferred, and aramid fibers, liquid crystal polyester fibers, and glass fibers are particularly preferred. Examples of glass fiber include E glass, NE glass, S glass, D glass, H glass, and T glass.
• Impregnation into the sheet-like fiber base material is carried out, for example, by dipping and coating. Impregnation may be repeated multiple times if necessary.
• 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, but for example, 10 to 90% by mass of the prepreg or laminate. , preferably from 20 to 80% by weight, more preferably from 30 to 70% by weight. If it is within this range, the dielectric properties and mechanical strength of the obtained laminate will be highly balanced, which is preferable.
• the thickness of the prepreg according to this embodiment is appropriately selected depending on the purpose of use, but is usually 0.001 to 10 mm, preferably 0.005 to 1 mm, and more preferably 0.01 to 0.0 mm. It is 5mm. If it is within this range, properties such as shapeability during lamination and mechanical strength and toughness of the laminate obtained by curing can be sufficiently exhibited, which is preferable.
• the evaluation conditions for the cyclic olefin copolymer are as follows.
• the iodine value of the cyclic olefin copolymer was measured by a titration method according to JIS K 0070 using cyclohexane as a solvent.
• a cyclic olefin copolymer (A1) and a cyclic olefin copolymer (A2), which are cyclic olefin copolymers (A), were obtained by the following procedure.
• the obtained polymer solution was poured into a mixed solvent of acetone/methanol (volume ratio 3/1) containing 0.1 vol% concentrated hydrochloric acid to precipitate the polymer, which was dried under reduced pressure at 80°C for 10 hours to obtain a cyclic olefin-based A copolymer (A1) was obtained.
• the cyclic olefin copolymer (A1) had an iodine value of 42 g/100 g, and a number average molecular weight (Mn) determined by GPC measurement of 7,500.
• the obtained polymer solution was poured into a mixed solvent of acetone/methanol (volume ratio 3/1) containing 0.1 vol% concentrated hydrochloric acid to precipitate the polymer, which was dried under reduced pressure at 80°C for 10 hours to obtain a cyclic olefin-based A copolymer (A2) was obtained.
• the cyclic olefin copolymer (A2) had an iodine value of 110 g/100 g and a number average molecular weight (Mn) of 21,000.
• a cyclic olefin copolymer was obtained by the following procedure. As shown below, the obtained cyclic olefin copolymer has an iodine value of 140 g/100 g, which does not meet the requirements for the cyclic olefin copolymer (A) according to the present embodiment. That is, it corresponds to the above-mentioned "other cyclic olefin copolymer (n)."Hereinafter, the cyclic olefin copolymer obtained in ⁇ Synthesis Example 3> will be referred to as "other cyclic olefin copolymer (n1)". ” is called.
• the polymer was poured into a mixed solvent of acetone/methanol (volume ratio 3/1) to which 1 vol% concentrated hydrochloric acid had been added, and the polymer was precipitated and dried under reduced pressure at 80° C. for 10 hours to obtain a cyclic olefin copolymer.
• the iodine value of the cyclic olefin copolymer was 140 g/100 g, and the number average molecular weight (Mn) was 11,900.
• a varnish was prepared by dissolving the components listed in Table 1 in toluene. Details of each component used to prepare the varnish are as follows.
• ⁇ Radical initiator> ⁇ Azo compound (B1) (2,2'-azobis(2,4,4-trimethylpentane), azo compound represented by the following formula, manufactured by Fujifilm Wako Pure Chemical Industries, product name: VR-110) ⁇ Other azo compounds (1) (2,2'-azobis(N-butyl-2-methylpropionamide), azo compound represented by the following formula, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name: VAm-110 ) ⁇ Peroxide (1) (dicumyl peroxide, manufactured by NOF Corporation, product name: Percumil D)
• a prepreg was obtained by impregnating a fibrous base material (manufactured by Asahi Kasei Corporation, #1035 type, L2 glass) with the obtained varnish and drying at 120°C. At that time, the content (resin content) of the components constituting the resin in the prepreg was adjusted to about 80% by a curing reaction of the resin, initiator, etc. Two sheets of the obtained prepreg were stacked, heated to a temperature of 200°C at a temperature increase rate of 4°C/min, and vacuum pressure molded at 200°C for 120 minutes at a pressure of 3 MPa to obtain a crosslinked body with a thickness of 150 ⁇ m. I got it.

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• 2023
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