Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
  • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
  • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
  • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
• • 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
  • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
  • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
  • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
  • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
  • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
  • C08G2261/3324—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from norbornene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
  • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
  • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
  • C08G2261/3325—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other polycyclic systems
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/40—Polymerisation processes
  • C08G2261/41—Organometallic coupling reactions
  • C08G2261/418—Ring opening metathesis polymerisation [ROMP]

Definitions

• the present invention relates to a polymerizable composition and a molded article.
• Cycloolefin resins have excellent heat resistance, low water absorption, low dielectric constant, and other properties, and in recent years have been used in a wide range of fields, including optical components, electronic devices, medical equipment, and automotive parts.
• Patent Document 1 discloses a polymerizable composition that contains a cycloolefin monomer ( ⁇ ) represented by a specific general formula (I) and/or a cycloolefin monomer ( ⁇ ) represented by a specific general formula (II), a silane coupling agent having at least one hydrocarbon group with a norbornene structure, and a metathesis polymerization catalyst.
• the object of the present invention is to provide a polymerizable composition that can give a molded article with excellent flame retardancy.
• the inventors conducted research to achieve the above object, and discovered that the above problems could be solved by combining a specific flame retardant and an inorganic filler with a polymerizable composition mainly composed of a cycloolefin monomer, thus completing the present invention.
• a polymerizable composition comprising a cycloolefin monomer, a metathesis polymerization catalyst, at least one flame retardant selected from the group consisting of a phosphorus-based flame retardant, a phosphorus/nitrogen-based flame retardant, and a nitrogen-based flame retardant, and an inorganic filler.
• the inorganic filler is a scaly particle or a spherical particle.
• the flame retardant is a phosphorus-based flame retardant and a nitrogen-based flame retardant.
• the present invention provides a polymerizable composition that can give molded articles with excellent flame retardancy.
• the polymerizable composition of the present invention contains a cycloolefin monomer, a metathesis polymerization catalyst, at least one flame retardant selected from a phosphorus-based flame retardant, a phosphorus/nitrogen-based flame retardant, and a nitrogen-based flame retardant, and an inorganic filler.
• the polymerizable composition of the present invention by containing the above-mentioned components in combination, can give a molded article with excellent flame retardancy.
• This excellent flame retardancy is an effect that can only be obtained when the above-mentioned specific flame retardant and inorganic filler are combined and blended into a polymerizable composition mainly composed of a cycloolefin monomer, and is an effect that cannot be obtained when one or both of these are not blended.
• a cycloolefin monomer is a compound having an alicyclic structure and a carbon-carbon double bond in the molecule.
• Examples of the alicyclic structure constituting the cycloolefin monomer include a monocyclic ring, a polycyclic ring, a condensed polycyclic ring, a bridged ring, and a polycyclic ring formed by combining these rings.
• Cycloolefin monomers include monocyclic cycloolefin monomers and norbornene-based monomers, with norbornene-based monomers being preferred.
• Norbornene-based monomers are cycloolefin monomers that have a norbornene ring structure in the molecule. These may be substituted with a hydrocarbon group such as an alkyl group, an alkenyl group, an alkylidene group, or an aryl group, or a polar group.
• Norbornene-based monomers may also have a double bond in addition to the double bond of the norbornene ring.
• Examples of monocyclic cycloolefin monomers include cyclobutene, cyclopentene, cyclooctene, cyclododecene, cyclopentadiene, and 1,5-cyclooctadiene.
• norbornene-based monomers include dicyclopentadienes such as dicyclopentadiene, methyldicyclopentadiene, and dicyclopentadiene monoepoxide; Tetracyclododecenes such as tetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-ethylidenetetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-phenyltetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, tetracyclo[6.2.1.1 3,6 .
• cycloolefin monomers it is preferable to use a cycloolefin monomer having no polar group, since it is possible to obtain a molded product having low water absorption.
• a cycloolefin monomer having an aromatic condensed ring such as tetracyclo[9.2.1.0 2,10 . 0 3,8 ]tetradeca-3,5,7,12-tetraene, can reduce the viscosity of the polymerizable composition.
• cycloolefin monomers may be used alone or in combination of two or more.
• the polymerizable composition used in the present invention preferably contains dicyclopentadienes as the cycloolefin monomer.
• the polymerizable composition of the present invention may contain any monomer that is copolymerizable with the cycloolefin monomer, as long as the effect of the present invention is not inhibited.
• the content of the cycloolefin monomer in the polymerizable composition of the present invention is not particularly limited, but is preferably 8 to 60 mass%, more preferably 10 to 50 mass%, and even more preferably 15 to 30 mass%. By setting the content within the above range, the obtained molded article can have excellent strength and even more excellent flame retardancy.
• the polymerizable composition of the present invention may further contain a (meth)acrylate monomer as a monomer component in addition to the cycloolefin monomer.
• the (meth)acrylate monomer may be a polyfunctional monomer having three or more (meth)acryloyl groups, but a monofunctional monomer having one (meth)acryloyl group or a bifunctional monomer having two (meth)acryloyl groups is preferred, with a monofunctional monomer being more preferred. Furthermore, a methacrylate monomer is preferred as the (meth)acrylate monomer.
• (Meth)acrylate monomers preferably have a hydrocarbon group with 6 or more carbon atoms, as this provides excellent effects.
• the number of carbon atoms in the hydrocarbon group is preferably 6 to 100, more preferably 8 to 50, and even more preferably 10 to 20.
• monofunctional monomers with one (meth)acryloyl group include benzyl methacrylate, hexyl methacrylate, phenyl methacrylate, phenoxyethyl methacrylate, octenyl methacrylate, tolyl methacrylate, cyclohexyl methacrylate, adamantyl methacrylate, lauryl methacrylate, stearyl methacrylate, tetrahydrofurfuryl methacrylate, methoxydiethylene glycol methacrylate, phenoxyethylene glycol methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, etc.
• bifunctional monomers with two (meth)acryloyl groups include ethylene dimethacrylate, 1,3-butylene dimethacrylate, 1,4-butylene dimethacrylate, 1,6-hexanediol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, bisphenol dimethacrylate, tricyclodecane dimethanol dimethacrylate, 1,3-adamantyl dimethanol dimethacrylate, 1,4-adamantyl dimethanol dimethacrylate, 2,2'-bis(4-methacryloxydiethoxyphenyl)propane, etc.
• polyfunctional monomers having three or more (meth)acryloyl groups include trimethylolpropane trimethacrylate and pentaerythritol trimethacrylate.
• a monofunctional monomer having one (meth)acryloyl group, a bifunctional monomer having two (meth)acryloyl groups, and a polyfunctional monomer having three or more (meth)acryloyl groups may be used in any combination and in any ratio.
• the content of the (meth)acrylate monomer is not particularly limited, but is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 8 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total cycloolefin monomers used.
• the obtained molded article can be made to have excellent strength and even more excellent flame retardancy.
• the metathesis polymerization catalyst used in the present invention is not particularly limited as long as it can ring-opening polymerize a cycloolefin monomer, and any known metathesis polymerization catalyst can be used.
• the metathesis polymerization catalyst used in the present invention is a complex in which a plurality of ions, atoms, polyatomic ions and/or compounds are bonded to a transition metal atom as the central atom.
• a transition metal atom atoms of Groups 5, 6 and 8 (long-form periodic table, the same applies below) are used.
• the atoms of each group are not particularly limited, but an example of an atom of Group 5 is tantalum, an example of an atom of Group 6 is molybdenum or tungsten, and an example of an atom of Group 8 is ruthenium or osmium. Among these transition metal atoms, ruthenium and osmium of Group 8 are preferred.
• a complex with ruthenium or osmium as the central atom is preferred, and a complex with ruthenium as the central atom is more preferred.
• a complex with ruthenium as the central atom a ruthenium carbene complex in which a carbene compound is coordinated to ruthenium is preferred.
• carbene compound is a general term for compounds having a methylene free radical, and refers to a compound having an uncharged divalent carbon atom (carbene carbon) as represented by (>C:).
• Ruthenium carbene complexes have excellent catalytic activity during bulk ring-opening polymerization, so the resulting polymer has little odor due to unreacted monomers, and high-quality polymers can be obtained with good productivity. In addition, they are relatively stable against oxygen and moisture in the air and are not easily deactivated, so they can be used in the atmosphere.
• the metathesis polymerization catalyst may be used alone or in combination of multiple types.
• Examples of the ruthenium carbene complex include those represented by the following general formula (1) or (2).
• R 1 and R 2 are each independently a hydrogen atom, a halogen atom, or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom, and these groups may have a substituent or may be bonded to each other to form a ring.
• An example of R 1 and R 2 bonded to each other to form a ring is an indenylidene group which may have a substituent, such as a phenylindenylidene group.
• organic groups having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom
• alkyl groups having 1 to 20 carbon atoms alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, alkenyloxy groups having 2 to 20 carbon atoms, alkynyloxy groups having 2 to 20 carbon atoms, aryloxy groups having 6 to 20 carbon atoms, and alkyl groups having 1 to 20 carbon atoms.
• alkylthio group having 1 to 8 carbon atoms examples include a carbonyloxy group, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, an alkylsulfinyl group having 1 to 20 carbon atoms, an alkylsulfonic acid group having 1 to 20 carbon atoms, an arylsulfonic acid group having 6 to 20 carbon atoms, a phosphonic acid group, an arylphosphonic acid group having 6 to 20 carbon atoms, an alkylammonium group having 1 to 20 carbon atoms, and an arylammonium group having 6 to 20 carbon atoms.
• These organic groups having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom, may have a substituent.
• substituents include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms.
• X1 and X2 each independently represent any anionic ligand.
• the anionic ligand is a ligand that has a negative charge when separated from the central metal atom, and examples of the anionic ligand include a halogen atom, a diketonate group, a substituted cyclopentadienyl group, an alkoxyl group, an aryloxy group, and a carboxyl group.
• L 1 and L 2 represent a heteroatom-containing carbene compound or a neutral electron donor compound other than a heteroatom-containing carbene compound.
• a heteroatom-containing carbene compound and a neutral electron donor compound other than a heteroatom-containing carbene compound are compounds that have a neutral charge when separated from a central metal. From the viewpoint of improving catalytic activity, a heteroatom-containing carbene compound is preferred.
• the heteroatom means an atom of Groups 15 and 16 of the periodic table, and specific examples thereof include a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, an arsenic atom, and a selenium atom. Among these, from the viewpoint of obtaining a stable carbene compound, a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom are preferred, and a nitrogen atom is more preferred.
• heteroatom-containing carbene compound a compound represented by the following general formula (3) or (4) is preferable, and from the viewpoint of improving catalytic activity, a compound represented by the following general formula (3) is more preferable.
• R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom, a halogen atom, or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom.
• Specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom are the same as those in the above general formulas (1) and (2).
• R 3 , R 4 , R 5 and R 6 may be bonded to each other in any combination to form a ring.
• R5 and R6 are hydrogen atoms.
• R3 and R4 are preferably an aryl group which may have a substituent, more preferably a phenyl group having an alkyl group having 1 to 10 carbon atoms as a substituent, and further preferably a mesityl group.
• neutral electron donor compound examples include oxygen atoms, water, carbonyls, ethers, nitriles, esters, phosphines, phosphinites, phosphites, sulfoxides, thioethers, amides, imines, aromatics, cyclic diolefins, olefins, isocyanides, and thiocyanates.
• R 1 , R 2 , X 1 , X 2 , L 1 and L 2 may each be alone and/or bonded to each other in any combination to form a multidentate chelating ligand.
• the compound represented by the above general formula (1) is preferred because it makes the effects of the present invention more pronounced, and among these, the compound represented by the following general formula (5) or general formula (6) is more preferred.
• Z is an oxygen atom, a sulfur atom, a selenium atom, NR 12 , PR 12 or AsR 12 , and R 12 is a hydrogen atom; a halogen atom; or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom; however, an oxygen atom is preferred as Z because the effects of the present invention become more pronounced.
• R 1 , R 2 , X 1 and L 1 are the same as those in the above general formulae (1) and (2), and may form a multidentate chelating ligand either alone or in any combination by bonding with each other, but it is preferable that X 1 and L 1 do not form a multidentate chelating ligand and that R 1 and R 2 bond with each other to form a ring, more preferably an indenylidene group which may have a substituent, and even more preferably a phenylindenylidene group.
• organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom are the same as those in the above general formulae (1) and (2).
• R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a heteroaryl group having 6 to 20 carbon atoms, and these groups may have a substituent or may be bonded to each other to form a ring.
• substituents examples include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and when a ring is formed, the ring may be any of an aromatic ring, an alicyclic ring, and a heterocyclic ring, but it is preferable to form an aromatic ring, more preferably an aromatic ring having 6 to 20 carbon atoms, and even more preferably an aromatic ring having 6 to 10 carbon atoms.
• R 9 , R 10 and R 11 are each independently a hydrogen atom; a halogen atom; or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom; and these groups may have a substituent or may be bonded to each other to form a ring.
• Specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom are the same as those in the above general formulas (1) and (2).
• R 9 , R 10 and R 11 are preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
• m is 0 or 1.
• m is preferably 1, in which case Q is an oxygen atom, a nitrogen atom, a sulfur atom, a methylene group, an ethylene group, or a carbonyl group, and is preferably a methylene group.
• R 1 , X 1 , X 2 and L 1 are the same as those in the above general formulae (1) and (2), and may form a polydentate chelating ligand either alone or in any combination with each other, but it is preferred that X 1 , X 2 and L 1 do not form a polydentate chelating ligand and that R 1 is a hydrogen atom.
• R 13 to R 21 are hydrogen atoms, halogen atoms, or organic groups having 1 to 20 carbon atoms which may contain halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, or silicon atoms; these groups may have a substituent and may be bonded to each other to form a ring.
• organic groups having 1 to 20 carbon atoms which may contain halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, or silicon atoms are the same as those in the above general formulas (1) and (2).
• R 13 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, R 14 to R 17 are preferably hydrogen atoms, and R 18 to R 21 are preferably hydrogen atoms or halogen atoms.
• the content of the metathesis polymerization catalyst is preferably 0.005 mmol or more, more preferably 0.01 to 50 mmol, and even more preferably 0.015 to 20 mmol, per mole of the total cycloolefin monomers used in the reaction.
• the polymerizable composition of the present invention contains at least one flame retardant selected from phosphorus-based flame retardants, phosphorus/nitrogen-based flame retardants, and nitrogen-based flame retardants.
• the flame retardant used in the present invention may be any of solid, liquid, and combinations thereof.
• the flame retardant used in the present invention is preferably a non-halogen flame retardant that does not generate halogen-containing harmful substances when incinerated.
• the polymerizable composition of the present invention preferably does not contain a halogen flame retardant that generates halogen-containing harmful substances when incinerated.
• Phosphorus-based flame retardants are flame retardants that have phosphorus atoms but no nitrogen atoms.
• Examples of phosphorus-based flame retardants include organic phosphorus-based flame retardants and inorganic phosphorus-based flame retardants.
• Examples of organic phosphorus-based flame retardants include phosphoric acid esters such as triphenyl phosphate; organic phosphonic acid compounds such as phosphonic acid esters such as diphenyl methanephosphonate and diethyl phenylphosphonate; organic phosphinic acid compounds such as methyl phosphinate; phosphine oxides such as triphenylphosphine oxide and tricresylphosphine oxide; and the like.
• inorganic phosphorus-based flame retardants include red phosphorus; orthophosphoric acid; phosphorous acid; hypophosphorous acid; polyphosphoric acid such as metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid; polyphosphorous acid such as metaphosphorous acid and pyrophosphorous acid; non-condensed (phosphite) salts; condensed (phosphite) salts; and the like.
• phosphine oxides are preferred from the viewpoint that the effect of the present invention is more pronounced.
• Nitrogen/phosphorus flame retardants are flame retardants having phosphorus and nitrogen atoms.
• nitrogen/phosphorus flame retardants include melamine phosphate compounds such as melamine polyphosphate, melamine orthophosphate, and melamine pyrophosphate; piperazine phosphate compounds such as piperazine orthophosphate, piperazine pyrophosphate, and piperazine polyphosphate; phosphonitrile compounds such as phosphonitrilic acid phenyl ester and (poly)phenoxyphosphazene; phosphate ester amide; phosphate amide; ammonium phosphate such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and the like.
• melamine polyphosphate, melamine polyphosphate, and phosphonitrilic acid phenyl ester are preferred from the viewpoint of making the effects of the present invention more pronounced.
• Nitrogen-based flame retardants are flame retardants that have nitrogen atoms but no phosphorus atoms.
• nitrogen-based flame retardants include guanidine compounds, melamine compounds, and triazine compounds.
• melamine compounds are preferred, and melamine cyanurate is more preferred, from the viewpoint that the effects of the present invention are more pronounced.
• the content of at least one flame retardant selected from phosphorus-based flame retardants, phosphorus/nitrogen-based flame retardants, and nitrogen-based flame retardants in the polymerizable composition of the present invention is not particularly limited, but is preferably 8 to 35 mass%, more preferably 10 to 30 mass%, and even more preferably 10 to 20 mass%.
• the content of the flame retardant is preferably 20 to 100 mass parts, more preferably 30 to 90 mass parts, and even more preferably 40 to 80 mass parts, relative to 100 mass parts of the total cycloolefin monomers used.
• the polymerizable composition of the present invention may contain only one flame retardant selected from phosphorus-based flame retardants, phosphorus/nitrogen-based flame retardants, and nitrogen-based flame retardants, or may contain two or more flame retardants selected from these.
• the polymerizable composition of the present invention may contain a phosphorus-based flame retardant and a nitrogen-based flame retardant.
• the ratio of the content of the phosphorus-based flame retardant to the content of the nitrogen-based flame retardant in the polymerizable composition of the present invention is not particularly limited, but is preferably 99:1 to 10:90, more preferably 95:5 to 40:60, and even more preferably 90:10 to 70:30, in terms of mass ratio expressed as [content of phosphorus-based flame retardant: content of nitrogen-based flame retardant].
• the polymerizable composition of the present invention contains an inorganic filler.
• the inorganic filler is preferably a scaly particle or a spherical particle. That is, the polymerizable composition of the present invention preferably contains a scaly inorganic filler or a spherical inorganic filler.
• the scaly particles preferably have a ratio L/t of the average diameter (D50) L to the thickness t, where t is the thickness and L is the average diameter (D50) measured by a laser diffraction particle size measurement method, of 5 or more, and more preferably 10 or more.
• the thickness t of the scaly inorganic filler is preferably 0.5 to 10 ⁇ m, more preferably 0.8 to 5 ⁇ m, and even more preferably 1 to 3 ⁇ m
• the average diameter (D50) L is preferably 10 to 300 ⁇ m, more preferably 15 to 200 ⁇ m, and even more preferably 20 to 100 ⁇ m.
• the spherical particles preferably have a ratio Dmax/Dmin (aspect ratio) of 1 to 2, and more preferably 1 to 1.5, where Dmax is the longest diameter and Dmin is the shortest diameter.
• the spherical inorganic filler preferably has a volume average particle size of 0.1 to 60 ⁇ m, and more preferably 1 to 40 ⁇ m.
• Inorganic filler components include inorganic oxides such as silica, alumina, titanium oxide, zinc oxide, and antimony oxide; aluminum hydrates such as alumina monohydrate, magnesium hydrate, calcium hydrate, nickel hydrate, iron hydrate, copper hydrate, zinc borate hydrate, and zinc stannate hydrate; metal nitrides such as silicon nitride and boron nitride; carbonates such as calcium carbonate, magnesium carbonate, and barium carbonate; calcium hydroxide; aluminum hydroxide; magnesium hydroxide; calcium silicate; calcium sulfate; barium titanate; red phosphorus; various metal powders; clay; various ferrites; hydrotalcite; glass; carbon-based materials such as carbon black, graphite, and fullerene; and the like.
• the inorganic fillers may be used alone or in combination of two or more.
• At least one selected from inorganic oxides, metal hydrates, metal nitrides and glass is preferred, as it does not inhibit the ring-opening polymerization reaction and can further improve the flame retardancy of the resulting molded body, at least one selected from silica, alumina monohydrate and glass is more preferred, and at least one selected from silica and glass is even more preferred.
• the inorganic filler is preferably at least one selected from spherical inorganic oxide particles, scaly metal hydrate particles, scaly metal nitride particles, and scaly glass particles (glass flakes), more preferably at least one selected from spherical silica particles, scaly alumina monohydrate particles, and scaly glass particles, and even more preferably at least one selected from spherical silica particles and scaly glass particles.
• the inorganic filler may have its surface hydrophobized.
• a hydrophobized inorganic filler By using a hydrophobized inorganic filler, aggregation and sedimentation of the inorganic filler in the polymerizable composition can be suppressed, and the inorganic filler can be uniformly dispersed in the resulting molded product.
• treatment agents used for the hydrophobization include silane coupling agents such as vinyltrimethoxysilane, titanate coupling agents, aluminate coupling agents, fatty acids such as stearic acid, oils and fats, surfactants, waxes, etc.
• the inorganic filler can also be hydrophobized by simultaneously mixing the treatment agent with the inorganic filler when preparing the polymerizable composition.
• the content of the inorganic filler in the polymerizable composition of the present invention is not particularly limited, but is preferably 15 to 85% by mass, more preferably 50 to 80% by mass, and even more preferably 60 to 70% by mass. By setting the content within the above range, the obtained molded article can have excellent strength and even more excellent flame retardancy.
• the content of the scaly particles in the polymerizable composition of the present invention is not particularly limited, but is preferably 10 to 150 parts by mass, more preferably 20 to 100 parts by mass, and even more preferably 30 to 60 parts by mass, per 100 parts by mass of the total cycloolefin monomers used.
• a scaly inorganic filler is used as the inorganic filler, even if the content of the scaly particles is relatively small, the obtained molded article can have excellent strength, even better flame retardancy, and excellent gas barrier properties.
• the content of the spherical inorganic filler in the polymerizable composition of the present invention is not particularly limited, but is preferably 50 to 1000 parts by mass, more preferably 120 to 700 parts by mass, and even more preferably 200 to 500 parts by mass, per 100 parts by mass of the total cycloolefin monomers used.
• scaly particles are used as the inorganic filler, even if the content of the scaly particles is relatively small, the obtained molded product can have excellent strength, even better flame retardancy, and excellent gas barrier properties.
• the ratio of the content (total content) of at least one flame retardant selected from phosphorus-based flame retardants, phosphorus/nitrogen-based flame retardants, and nitrogen-based flame retardants to the content of inorganic filler in the polymerizable composition of the present invention is not particularly limited, but is preferably 90:10 to 2:98, more preferably 75:25 to 3:97, even more preferably 60:40 to 5:95, and particularly preferably 30:70 to 10:90, in mass ratio expressed as [flame retardant content: inorganic filler content].
• the polymerizable composition may contain a coupling agent, a radical generator, a diisocyanate compound, a polyfunctional (meth)acrylate compound, or other optional components as necessary.
• Coupling agents include, but are not limited to, silane coupling agents having at least one hydrocarbon group having a norbornene structure (norbornene skeleton).
• silane coupling agents include bicycloheptenyl trimethoxysilane, bicycloheptenyl triethoxysilane, bicycloheptenyl ethyl trimethoxysilane, bicycloheptenyl ethyl triethoxysilane, bicycloheptenyl hexyl trimethoxysilane, bicycloheptenyl hexyl triethoxysilane, etc., but are preferably bicycloheptenyl ethyl trimethoxysilane, bicycloheptenyl ethyl triethoxysilane, bicycloheptenyl hexyl trimethoxysilane, and bicycloheptenyl hexyl trieth
• the polymerizable composition may also contain a silane coupling agent that does not have a hydrocarbon group having a norbornene structure, or a coupling agent other than a silane coupling agent, such as a thiol coupling agent, an aluminate coupling agent, a titanate coupling agent, or a fatty acid ester.
• a silane coupling agent that does not have a hydrocarbon group having a norbornene structure
• a coupling agent other than a silane coupling agent such as a thiol coupling agent, an aluminate coupling agent, a titanate coupling agent, or a fatty acid ester.
• the content of the coupling agent in the polymerizable composition of the present invention is not particularly limited, but is preferably 0.1 to 5 mass%, more preferably 0.5 to 1 mass%.
• the content of the coupling agent in the polymerizable composition of the present invention is preferably 0.2 to 10 mass parts, more preferably 0.5 to 5 mass parts, and even more preferably 1 to 3 mass parts, based on 100 mass parts of all cycloolefin monomers used.
• the radical generator generates radicals when heated, which have the effect of inducing a crosslinking reaction in the cycloolefin resin formed by polymerization of the polymerizable composition.
• the sites where the radical generator induces the crosslinking reaction are mainly the carbon-carbon double bonds contained in the cycloolefin resin, but crosslinking can also occur in saturated bond portions.
• Radical generators include, for example, organic peroxides, diazo compounds and non-polar radical generators.
• organic peroxides include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, and cumene hydroperoxide; dialkyl peroxides such as di-t-butyl peroxide, dicumyl peroxide, and t-butylcumyl peroxide; diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; peroxy ketals such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne, and 1,3-di(t-butylperoxyisopropyl)benzene; peroxy esters such as t-butylperoxyacetate and t-butylperoxybenzoate
• diazo compounds examples include 4,4'-bisazidobenzal(4-methyl)cyclohexanone, 4,4'-diazidochalcone, 2,6-bis(4'-azidobenzal)cyclohexanone, 2,6-bis(4'-azidobenzal)-4-methylcyclohexanone, 4,4'-diazidodiphenylsulfone, 4,4'-diazidodiphenylmethane, and 2,2'-diazidostilbene.
• Non-polar radical generators include 2,3-dimethyl-2,3-diphenylbutane, 2,3-diphenylbutane, 1,4-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 1,1,2,2-tetraphenylethane, 2,2,3,3-tetraphenylbutane, 3,3,4,4-tetraphenylhexane, 1,1,2-triphenylpropane, 1,1,2-triphenylethane, triphenylmethane, 1,1,1-triphenylethane, 1,1,1-triphenylpropane, 1,1,1-triphenylbutane, 1,1,1-triphenylpentane, 1,1,1-triphenyl-2-propene, 1,1,1-triphenyl-4-pentene, 1,1,1-triphenyl-2-phenylethane, etc.
• the amount of the radical generator in the polymerizable composition is usually 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, per 100 parts by mass of the total cycloolefin monomers used.
• Diisocyanate compounds include, for example, 4,4'-methylenediphenyl diisocyanate (MDI), toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanate diphenyl ether, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, and 4,4'-diisocyanate dibenzidine.
• MDI 4,4'-methylenediphenyl diisocyanate
• toluene-2,4-diisocyanate 4-me
• diisocyanate examples include aromatic diisocyanate compounds such as benzyl; aliphatic diisocyanate compounds such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate; alicyclic diisocyanate compounds such as 4-cyclohexylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, hydrogenated MDI, and hydrogenated XDI, and polyurethane prepolymers obtained by reacting these diisocyanate compounds with low molecular weight polyols or polyamines so that the terminals are isocyanate.
• aromatic diisocyanate compounds such as benzyl
• aliphatic diisocyanate compounds such as methylene diisocyanate, 1,4-te
• known compounds having a polyfunctional isocyanate group which are obtained by converting these compounds into isocyanurate, biuret, adduct, or polymeric compounds, and which have been conventionally used, can be used without particular limitation.
• examples of such compounds include a dimer of 2,4-toluylene diisocyanate, triphenylmethane triisocyanate, tris-(p-isocyanatophenyl)thiophosphite, polyfunctional aromatic isocyanate compounds, polyfunctional aromatic aliphatic isocyanate compounds, polyfunctional aliphatic isocyanate compounds, fatty acid modified polyfunctional aliphatic isocyanate compounds, polyfunctional blocked isocyanate compounds such as blocked polyfunctional aliphatic isocyanate compounds, polyisocyanate prepolymers, etc.
• aromatic diisocyanate compounds aliphatic diisocyanate compounds, and alicyclic diisocyanate compounds, which are polyfunctional unblocked isocyanate compounds, are preferably used because of their ease of availability and ease of handling. These compounds can be used alone or in combination of two or more.
• a multifunctional blocked isocyanate compound is one in which at least two isocyanate groups in the molecule are reacted with an active hydrogen-containing compound to render the compound inactive at room temperature.
• the isocyanate compound generally has a structure in which the isocyanate groups are masked with a blocking agent such as alcohols, phenols, ⁇ -caprolactam, oximes, and active methylene compounds.
• Multifunctional blocked isocyanate compounds generally do not react at room temperature, and therefore have excellent storage stability, but are usually heated to 140 to 200°C, where the isocyanate groups are regenerated, allowing them to exhibit excellent reactivity.
• the diisocyanate compounds may be used alone or in combination of two or more.
• the amount of the diisocyanate compound in the polymerizable composition is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 2 to 10 parts by mass, per 100 parts by mass of the total cycloolefin monomers.
• polyfunctional (meth)acrylate compounds include ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and neopentyl glycol dimethacrylate.
• the polyfunctional (meth)acrylate compounds may be used alone or in combination of two or more.
• the amount of the polyfunctional (meth)acrylate compound in the polymerizable composition is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 2 to 10 parts by mass, per 100 parts by mass of the total cycloolefin monomers used.
• ingredients include activators, activity regulators, elastomers, antioxidants, UV absorbers, light stabilizers, etc.
• the activator is a compound that acts as a cocatalyst for the metathesis polymerization catalyst described above and improves the polymerization activity of the catalyst.
• activators that can be used include alkylaluminum halides such as ethylaluminum dichloride and diethylaluminum chloride; alkoxyalkylaluminum halides in which part of the alkyl groups of these alkylaluminum halides are replaced with alkoxy groups; and organotin compounds.
• the amount of activator used is preferably 0.1 to 100 moles, and more preferably 1 to 10 moles, per mole of the total metathesis polymerization catalyst used in the polymerizable composition.
• the activity regulator is used to prevent polymerization from starting during the injection process when a polymerizable composition is prepared by mixing two or more reactant solutions as described below and then injected into a mold to initiate polymerization.
• examples of the activity regulator include compounds that have the effect of reducing the metathesis polymerization catalyst, and alcohols, haloalcohols, esters, ethers, nitriles, etc. can be used. Among these, alcohols and haloalcohols are preferred, and haloalcohols are more preferred.
• alcohols include n-propanol, n-butanol, n-hexanol, 2-butanol, isobutyl alcohol, isopropyl alcohol, and t-butyl alcohol.
• haloalcohols include 1,3-dichloro-2-propanol, 2-chloroethanol, and 1-chlorobutanol.
• Lewis base compounds can be used as activity regulators.
• Lewis base compounds include phosphorus-containing Lewis base compounds such as tricyclopentylphosphine, tricyclohexylphosphine, triphenylphosphine, triphenylphosphite, and n-butylphosphine; and nitrogen-containing Lewis base compounds such as n-butylamine, pyridine, 4-vinylpyridine, acetonitrile, ethylenediamine, N-benzylidenemethylamine, pyrazine, piperidine, and imidazole.
• Norbornenes substituted with alkenyl groups such as vinylnorbornene, propenylnorbornene, and isopropenylnorbornene, function as the cycloolefin monomer and also as activity regulators.
• the amount of these activity regulators used can be adjusted appropriately depending on the compound used.
• elastomers examples include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), ethylene-propylene-diene terpolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), and hydrogenated versions of these.
• SBR styrene-butadiene copolymer
• SBS styrene-butadiene-styrene copolymer
• SIS ethylene-propylene-diene terpolymer
• EVA ethylene-vinyl acetate copolymer
• hydrogenated versions of these By dissolving an elastomer in the polymerizable composition, the viscosity can be adjusted. In addition, the impact resistance of
• Antioxidants include various types of antioxidants for plastics and rubber, such as phenol-based, phosphorus-based, and amine-based antioxidants.
• the polymerizable composition of the present invention is prepared by appropriately mixing the above-mentioned components according to a known method.
• the polymerizable composition of the present invention may be prepared by mixing two or more reaction stock solutions using a mixing device or the like.
• the reaction stock solution does not undergo bulk polymerization with only one liquid, but the above-mentioned components are prepared by dividing them into two or more liquids so that when all the liquids are mixed together, a polymerizable composition containing each component in a predetermined ratio (total of the contents of each component is 100% by mass) is obtained.
• the following two types (a) and (b) can be mentioned, depending on the type of metathesis polymerization catalyst used.
• the metathesis polymerization catalyst may be one that does not have polymerization reaction activity by itself, but exhibits polymerization reaction activity when used in combination with an activator.
• a reaction stock solution (liquid A) containing a cycloolefin monomer and an activator and a reaction stock solution (liquid B) containing a cycloolefin monomer and a metathesis polymerization catalyst are used and mixed to obtain a polymerizable composition.
• a reaction stock solution (liquid C) containing a cycloolefin monomer and neither a metathesis polymerization catalyst nor an activator may be used in combination.
• a polymerizable composition can be obtained by mixing a reaction stock solution (i) containing a cycloolefin monomer with a reaction stock solution (ii) containing a metathesis polymerization catalyst.
• the reaction stock solution (ii) is usually a solution in which the metathesis polymerization catalyst is dissolved or dispersed in a small amount of an inert solvent.
• solvents examples include aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and trimethylbenzene; ketones such as methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and 4-hydroxy-4-methyl-2-pentanone; cyclic ethers such as tetrahydrofuran; diethyl ether, dichloromethane, dimethyl sulfoxide, and ethyl acetate. Of these, aromatic hydrocarbons are preferred, and toluene is more preferred.
• Optional components such as coupling agents, radical generators, diisocyanate compounds, and polyfunctional (meth)acrylate compounds may be contained in any of the reaction stock solutions, or may be added in the form of a mixed liquid other than the reaction stock solutions.
• the mixing device used to mix the above reactant liquids may be, for example, an impingement mixer commonly used in reaction injection molding, or a low-pressure mixer such as a dynamic mixer or static mixer.
• the molded article of the present invention can be obtained by curing the polymerizable composition of the present invention.
• the molded article of the present invention can be obtained by completely curing or partially curing the polymerizable composition of the present invention.
• the method for curing the polymerizable composition is not particularly limited and may be selected depending on the composition of the monomer contained in the polymerizable composition and the type of metathesis polymerization catalyst, and examples of the method include a method in which the polymerizable composition is left at room temperature or a method in which the polymerizable composition is heated to a predetermined temperature.
• the polymerizable composition of the present invention and the molded article of the present invention have excellent flame retardancy and also have properties such as heat resistance, low water absorption, and low dielectric constant, and are therefore suitable for use as various components requiring these properties, and are particularly suitable for use as sealing materials for protecting parts in electrical and electronic applications.
• ⁇ Flame retardancy test (2)> Three flat test pieces, each 150 mm long and 150 mm wide, were cut out from the molded body. Using the obtained test pieces, a combustion test was performed based on the UL94-5V (flat) combustion test standard. Specifically, the flat test piece was held horizontally and exposed to a 125 mm flame from below for 5 seconds 5 times, and the test results were determined based on the above test standard from the combustion behavior. In the above test standard, if a test result represented by "5VA” was obtained, it was recorded as "5VA” in Table 1, and if a test result represented by "5VA” was not obtained, it was recorded as "X” in Table 1. If a test result represented by "5VA” was obtained, it can be determined that the molded body has extremely excellent flame retardancy.
• Example 1 A monomer solution consisting of 95.3 parts of RIM monomer (manufactured by Zeon Corporation) set at 20 ° C., 2.2 parts of dicyclopentadiene monoepoxide (DCPME), 1.7 parts of bicycloheptenylethyltrimethoxysilane, and 0.8 parts of phenoxyethylene glycol methacrylate, 0.04 parts of the compound (7) as a metathesis polymerization catalyst, 50 parts of a phosphorus-based flame retardant (phosphine oxide, trade name "PQ60", manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and 330 parts of a spherical inorganic filler (spherical silica, trade name "MLR1114", manufactured by Tatsumori Co., Ltd., volume average particle size 10 ⁇ m) was prepared.
• RIM monomer manufactured by Zeon Corporation
• DCPME dicyclopentadiene monoepoxide
• PQ60 phosphorus
• the composition of the RIM monomer was about 90% by mass of dicyclopentadiene and about 10% by mass of tricyclopentadiene, and the amount of the metathesis polymerization catalyst used was 0.055 mmol per mole of all of these cycloolefin monomers.
• a mold made of aluminum 5052 with release treatment and inner dimensions of 300 mm in length, 250 mm in width, and 4 mm in depth was prepared, and covered with an aluminum 5052 flat plate.
• the mold was then set to 25°C, and an amount of the polymerizable composition was introduced such that the thickness of the resulting molded body was 1.0 mm.
• the mold was left for 1 hour, and then the temperature was raised to 120°C and left for 1 hour.
• the mold was then cooled to room temperature and demolded to obtain a molded body.
• the obtained molded body was used to carry out the flame retardancy test (1) and the flame retardancy test (2) according to the method described above. The results are shown in Table 1.
• Example 2 A polymerizable composition was prepared in the same manner as in Example 1, except that 40 parts of a scaly inorganic filler (glass flake, product name "GF001", manufactured by Glassflake, average diameter (D50) 27 to 32 ⁇ m, standard thickness 1.0 to 1.3 ⁇ m measured with a laser diffraction particle size measuring device (Malvern Mastersizer 2000)) was used instead of the spherical inorganic filler.
• a scaly inorganic filler glass flake, product name "GF001", manufactured by Glassflake, average diameter (D50) 27 to 32 ⁇ m, standard thickness 1.0 to 1.3 ⁇ m measured with a laser diffraction particle size measuring device (Malvern Mastersizer 2000)
• a molded article was obtained using the obtained polymerizable composition in the same manner as in Example 1, and a test was performed in the same manner as in Example 1. The results are shown in Table 1.
• Example 3 A polymerizable composition was prepared in the same manner as in Example 1, except that 60 parts of a nitrogen-based flame retardant (melamine cyanurate) was used instead of the phosphorus-based flame retardant. A molded article was obtained from the obtained polymerizable composition in the same manner as in Example 1, and a test was performed in the same manner as in Example 1. The results are shown in Table 1.
• a nitrogen-based flame retardant melamine cyanurate
• Example 4 A polymerizable composition was prepared in the same manner as in Example 1, except that 40 parts of a scaly inorganic filler was used instead of the spherical inorganic filler, and 60 parts of a nitrogen-based flame retardant (melamine cyanurate) was used instead of the phosphorus-based flame retardant.
• a molded product was obtained from the obtained polymerizable composition in the same manner as in Example 1, and a test was performed in the same manner as in Example 1. The results are shown in Table 1.
• Example 5 A polymerizable composition was prepared in the same manner as in Example 1, except that a nitrogen-based flame retardant was used together with the phosphorus-based flame retardant, and the amount of the phosphorus-based flame retardant was 50 parts and the amount of the nitrogen-based flame retardant was 17 parts.
• a molded product was obtained from the obtained polymerizable composition in the same manner as in Example 1, and a test was performed in the same manner as in Example 1. The results are shown in Table 1.
• Example 6 A polymerizable composition was prepared in the same manner as in Example 1, except that 40 parts of a scaly inorganic filler was used instead of the spherical inorganic filler, and a nitrogen-based flame retardant was used together with the phosphorus-based flame retardant, with the amount of the phosphorus-based flame retardant being 50 parts and the amount of the nitrogen-based flame retardant being 17 parts.
• a molded body was obtained using the obtained polymerizable composition in the same manner as in Example 1, and a test was performed in the same manner as in Example 1. The results are shown in Table 1.
• Example 1 A polymerizable composition was prepared in the same manner as in Example 1, except that the spherical inorganic filler and the phosphorus-based flame retardant were not used. A molded article was obtained from the obtained polymerizable composition in the same manner as in Example 1, and a test was performed in the same manner as in Example 1. The results are shown in Table 1.
• Example 2 A polymerizable composition was prepared in the same manner as in Example 1, except that no spherical inorganic filler was used. A molded article was obtained using the obtained polymerizable composition in the same manner as in Example 1, and a test was performed in the same manner as in Example 1. The results are shown in Table 1.
• Example 3 A polymerizable composition was prepared in the same manner as in Example 1, except that 60 parts of a nitrogen-based flame retardant (melamine cyanurate) was used instead of the phosphorus-based flame retardant, and no spherical inorganic filler was used. A molded product was obtained from the obtained polymerizable composition in the same manner as in Example 1, and a test was performed in the same manner as in Example 1. The results are shown in Table 1.
• a nitrogen-based flame retardant melamine cyanurate
• Example 4 Except for not using a phosphorus-based flame retardant, a polymerizable composition was prepared in the same manner as in Example 1. Using the obtained polymerizable composition, a molded article was obtained in the same manner as in Example 1, and a test was performed in the same manner as in Example 1. The results are shown in Table 1.
• Example 5 A polymerizable composition was prepared in the same manner as in Example 1, except that 40 parts of a scaly inorganic filler was used instead of the spherical inorganic filler, and no phosphorus-based flame retardant was used. A molded product was obtained from the obtained polymerizable composition in the same manner as in Example 1, and a test was performed in the same manner as in Example 1. The results are shown in Table 1.
• the polymerizable compositions containing a cycloolefin monomer, a metathesis polymerization catalyst, at least one flame retardant selected from a phosphorus-based flame retardant, a phosphorus/nitrogen-based flame retardant, and a nitrogen-based flame retardant, and an inorganic filler were capable of giving molded articles having excellent flame retardancy (Examples 1 to 6).
• a scaly inorganic filler was used as the inorganic filler, a molded article having extremely excellent flame retardancy could be obtained (Examples 2, 4, and 6).
• polymerizable compositions not containing either or both of the above-mentioned flame retardant and inorganic filler could not give molded articles having excellent flame retardancy (Comparative Examples 1 to 5).

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