Molding and method for manufacturing molding

Abstract

To provide a smooth molding.SOLUTION: Provided is a molding which is formed by hardening a polymerizable composition containing cycloolefin monomers and metathesis polymerization catalyst, and includes a surface having the maximum height Pz of a cross-sectional curve, which is measured according to JISB0601:2013, of 50 μm or less. Also provided is a method for manufacturing a molding comprising: a filling step of filling a polymerizable composition containing cycloolefin monomers and metathesis polymerization catalyst into a mold; a primarily hardening step of hardening the polymerizable composition in the mold to obtain a primary-hardened body having Shore A hardness, which is measured according to ASTMD2240, of 5 to 80; a demolding step of exposing a surface of at least a part of the primary-hardened body by removing a part of the mold; and a secondary hardening step of secondarily hardening the primary-hardened body in the state where at least a part of the surface is exposed to obtain a molding having Shore A hardness of 95 or more.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a molded body and a method for manufacturing a molded body, and more particularly to a smooth molded body and a method for manufacturing a molded body that can produce a smooth molded body. [Background technology]

[0002] Cycloolefin polymers obtained by bulk polymerization of a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst are known to have excellent moisture absorption properties, dielectric properties, etc., and are widely used in a wide range of applications, from large molded products such as outer panels of construction machinery, industrial machinery, etc. and septic tanks to electronic devices, optical components, medical containers, etc. in recent years.

[0003] As a method for bulk polymerization of a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst, a method is known in which the polymerizable composition is poured into a mold and polymerized and cured in the mold (for example, Patent Document 1). This method makes it possible to easily produce a cycloolefin polymer. However, this method causes dents and roughness on the surface of the resulting molded product, making it difficult to obtain a smooth molded product. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-271535 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a smooth molded article. [Means for solving the problem]

[0006] The present inventors have conducted studies to achieve the above-mentioned object and have found that the above-mentioned problems can be solved by a production method in which a polymerizable composition is primarily cured in a mold until the hardness falls within a specific range, and then secondary curing is performed in a state in which at least a part of the surface of the primary cured product is exposed, thereby completing the present invention.

[0007] That is, according to the present invention, the following molded article is provided. [1] A molded article obtained by curing a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst, A molded article having a surface in which the maximum height Pz of the cross-sectional curve, measured in accordance with JIS B 0601:2013, is 50 μm or less. [2] The molded article according to [1], wherein the polymerizable composition contains, as the cycloolefin monomer, a cycloolefin monomer having no polar group. [3] The molded article according to [1] or [2], wherein the polymerizable composition contains a dicyclopentadiene as the cycloolefin monomer. [4] The molded article according to any one of [1] to [3], wherein the polymerizable composition further contains at least one selected from a coupling agent, a radical generator, a diisocyanate compound, and a polyfunctional (meth)acrylate compound.

[0008] Furthermore, according to the present invention, there is provided the following method for producing a molded article. [5] a filling step of filling a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst into a mold; a primary curing step of primarily curing the polymerizable composition in the mold to obtain a primary cured product having a Shore A hardness of 5 to 80 as measured in accordance with ASTM D 2240; a demolding step of removing a portion of the mold to expose at least a portion of the surface of the primary cured body; and A method for producing a molded body, comprising a secondary curing step in which the primary cured body is secondary cured with at least a portion of the surface exposed to obtain a molded body having a Shore A hardness of 95 or more. [6] The method for producing a molded article according to [5], wherein the polymerizable composition contains, as the cycloolefin monomer, a cycloolefin monomer having no polar group. [7] The method for producing a molded article according to [5] or [6], wherein the polymerizable composition contains a dicyclopentadiene as the cycloolefin monomer. [8] The method for producing a molded article according to any one of [5] to [7], wherein the polymerizable composition further contains at least one selected from a coupling agent, a radical generator, a diisocyanate compound, and a polyfunctional (meth)acrylate compound. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a smooth molded body and a method for producing a molded body that can produce a smooth molded body. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a diagram illustrating the manner in which a molded body is obtained by a conventional manufacturing method and the manufacturing method of the present invention. [Figure 2] FIG. 2 is a diagram illustrating an example of an embodiment in which a molded body is obtained by the production method of the present invention. [Figure 3] FIG. 3 is a diagram illustrating an example of an embodiment in which a molded body is obtained by the production method of the present invention. [Figure 4] FIG. 4 is a diagram illustrating an example of an embodiment in which a composite is obtained by the production method of the present invention. [Figure 5] FIG. 5 is a diagram illustrating an example of an embodiment in which a composite is obtained by the production method of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0011] <Molded body> The molded article of the present invention is a molded article obtained by curing a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst, and has a surface with a maximum height Pz of a cross-sectional curve of 50 μm or less.

[0012] The maximum height Pz of the cross-sectional curve is an index of surface roughness, and the smaller the value, the smoother the surface. The molded article of the present invention has one or more smooth surfaces whose maximum height Pz of the cross-sectional curve is within the above range.

[0013] The molded article of the present invention may have at least a portion of a surface having a maximum height Pz of a cross-sectional curve within the above range. For example, when the molded article of the present invention is a polyhedron, at least a portion of any face may have a surface having a maximum height Pz of a cross-sectional curve within the above range, or any entire face may have a surface having a maximum height Pz of a cross-sectional curve within the above range.

[0014] Although not particularly limited, the molded article of the present invention preferably has a surface having a maximum cross-sectional curve height Pz of 40 μm or less, more preferably a surface having a maximum cross-sectional curve height Pz of 30 μm or less, even more preferably a surface having a maximum cross-sectional curve height Pz of 20 μm or less, and particularly preferably a surface having a maximum cross-sectional curve height Pz of 10 μm or less. The minimum value of the maximum cross-sectional curve height Pz of the surface is usually 0.1 μm or more.

[0015] Furthermore, the molded article of the present invention is not particularly limited, but preferably has a surface having an arithmetic mean height Pa of the cross-sectional curve of 15 μm or less, more preferably has a surface having an arithmetic mean height Pa of the cross-sectional curve of 10 μm or less, even more preferably has a surface having an arithmetic mean height Pa of the cross-sectional curve of 5 μm or less, and particularly preferably has a surface having an arithmetic mean height Pa of the cross-sectional curve of 3 μm or less. The minimum value of the maximum height Pz of the cross-sectional curve of the surface is usually 0.01 μm or more.

[0016] The area of ​​the surface where the maximum height Pz of the cross-sectional curve is within the above range is not particularly limited, but is usually 1 cm 2 More than 10cm, preferably 2 More preferably, 100 cm 2 That's all.

[0017] In this specification, the maximum profile height Pz and the arithmetic mean profile height Pa are surface roughness values ​​measured in accordance with JIS B 0601:2013.

[0018] The shape of the molded article of the present invention is not particularly limited and can be any shape. In addition, the molded article of the present invention may be a cured product obtained by curing the above-mentioned polymerizable composition alone, or may be a composite of the cured product obtained by curing the polymerizable composition and another member.

[0019] For example, the molded article of the present invention may be a composite formed by laminating a substrate and a cured layer formed by curing the polymerizable composition described above, in which the cured layer in the composite has a surface having a maximum profile height Pz of 50 μm or less.

[0020] The thickness of the molded article of the present invention (when the molded article of the present invention is a composite, the thickness of the cured layer obtained by curing the polymerizable composition) is not particularly limited, but is preferably 0.2 mm or more, more preferably 0.3 mm or more, and even more preferably 0.35 mm or more.

[0021] The polymerizable composition for forming the molded article of the present invention contains a cycloolefin monomer and a metathesis polymerization catalyst.

[0022] [Cycloolefin Monomer] The cycloolefin monomer used in the present invention is a compound having an alicyclic structure and a carbon-carbon double bond in the molecule. The alicyclic structure constituting the cycloolefin monomer may be a monocyclic ring, a polycyclic ring, a fused polycyclic ring, a bridged ring, or a polycyclic ring formed by combining these rings. There is no particular limitation on the number of carbon atoms constituting the alicyclic structure, but it is usually 4 to 30, preferably 5 to 20, and more preferably 5 to 15.

[0023] Examples of cycloolefin monomers include monocyclic cycloolefin monomers and norbornene-based monomers, with norbornene-based monomers being preferred. Norbornene-based monomers are cycloolefin monomers having 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. Furthermore, the norbornene-based monomer may have a double bond in addition to the double bond of the norbornene ring.

[0024] Examples of the monocyclic cycloolefin monomer include cyclobutene, cyclopentene, cyclooctene, cyclododecene, cyclopentadiene, and 1,5-cyclooctadiene.

[0025] Specific examples of norbornene-based monomers include dicyclopentadienes such as dicyclopentadiene, methyldicyclopentadiene, and dicyclopentadiene monoepoxide; 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 .0 2,7 ]dodec-9-ene-4-carboxylic acid, tetracyclo[6.2.1.1 3,6 .0 2,7 ]Tetracyclododecenes such as dodec-9-ene-4,5-dicarboxylic anhydride; norbornenes such as 2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-phenyl-2-norbornene, 5-norbornen-2-yl acrylate, 5-norbornen-2-yl methacrylate, 5-norbornene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid, and 5-norbornene-2,3-dicarboxylic anhydride; oxanorbornenes such as 7-oxa-2-norbornene and 5-ethylidene-7-oxa-2-norbornene; Tetracyclo[9.2.1.0 2,10 .0 3,8 ]tetradeca-3,5,7,12-tetraene (also known as 1,4-methano-1,4,4a,9a-tetrahydro-9H-fluorene), pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13 ]Pentadeca-4,10-diene, pentacyclo[9.2.1.0 2,10 .0 3,8 ] tetracyclic or higher cyclic olefins such as pentadeca-5,12-diene and tricyclopentadiene; and the like.

[0026] Among these cycloolefin monomers, it is preferable to use a cycloolefin monomer having no polar group, since this allows for the production of a molded product with low water absorption. 2,10 .0 3,8 The viscosity of the polymerizable composition can be reduced by using a compound having an aromatic condensed ring such as tetradeca-3,5,7,12-tetraene.

[0027] These cycloolefin monomers may be used alone or in combination of two or more. The polymerizable composition preferably contains a dicyclopentadiene as the cycloolefin monomer. The polymerizable composition may contain any monomer copolymerizable with the cycloolefin monomer, as long as the effects of the present invention are not impaired.

[0028] The content of the cycloolefin monomer in the total polymerizable monomers in the polymerizable composition is not particularly limited, but is preferably 80 to 100 mass%, more preferably 90 to 99.8 mass%, and even more preferably 95 to 99.5 mass%. By setting the total polymerizable monomer content within the above range, the mechanical properties of the obtained molded article can be improved, while the oxidation resistance and heat resistance can be further improved.

[0029] The total content of polymerizable monomers in the polymerizable composition is not particularly limited, but is preferably 10 to 100 mass%, more preferably 15 to 99 mass%, and even more preferably 20 to 98 mass%, relative to 100 mass% of the total polymerizable composition. By setting the total content of polymerizable monomers within the above range, the mechanical properties of the obtained molded article can be improved, while the oxidation resistance and heat resistance can be further improved.

[0030] [(Meth)acrylate Monomers] The polymerizable composition used in the present invention may further contain a (meth)acrylate monomer as a monomer component in addition to the cycloolefin monomer.

[0031] 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, and a monofunctional monomer is more preferred. Furthermore, as the (meth)acrylate monomer, a methacrylate monomer is preferred.

[0032] The (meth)acrylate monomer preferably has a hydrocarbon group having 6 or more carbon atoms, as this provides excellent effects. The hydrocarbon group preferably has 6 to 100 carbon atoms, more preferably 8 to 50 carbon atoms, and even more preferably 10 to 20 carbon atoms.

[0033] Specific examples of monofunctional monomers having 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, and dicyclopentanyl methacrylate.

[0034] Specific examples of bifunctional monomers having 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, and 2,2′-bis(4-methacryloxydiethoxyphenyl)propane.

[0035] Specific examples of polyfunctional monomers having three or more (meth)acryloyl groups include trimethylolpropane trimethacrylate and pentaerythritol trimethacrylate.

[0036] 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 in any ratio.

[0037] In the polymerizable composition, 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 all cycloolefin monomers used. By keeping the content of the (meth)acrylate monomer within the above range, the mechanical properties of the obtained molded article can be improved.

[0038] [Metathesis Polymerization Catalyst] 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 known metathesis polymerization catalysts can be used.

[0039] A metathesis polymerization catalyst is a complex formed by bonding multiple ions, atoms, polyatomic ions, and / or compounds to a transition metal atom as the central atom. The transition metal atoms used are atoms of Groups 5, 6, and 8 (long-form periodic table, the same applies hereinafter). While the atoms of each group are not particularly limited, examples of Group 5 atoms include tantalum, examples of Group 6 atoms include molybdenum and tungsten, and examples of Group 8 atoms include ruthenium and osmium. Among these transition metal atoms, ruthenium and osmium of Group 8 are preferred. That is, as a metathesis polymerization catalyst, complexes with ruthenium or osmium as the central atom are preferred, and complexes with ruthenium as the central atom are more preferred. The use of such a metathesis polymerization catalyst broadens the range of curing conditions under which the molded article of the present invention can be obtained, thereby enabling stable production of the molded article of the present invention.

[0040] As a complex having ruthenium as the central atom, a ruthenium carbene complex in which a carbene compound is coordinated to ruthenium is preferred. Here, "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) represented by (>C:). Ruthenium carbene complexes have excellent catalytic activity during bulk ring-opening polymerization, resulting in polymers with little odor due to unreacted monomers, enabling high-quality polymers to be obtained with good productivity. Furthermore, they are relatively stable against oxygen and moisture in the air and are not easily deactivated, allowing them to be used in the atmosphere. A single metathesis polymerization catalyst may be used, or multiple types may be used in combination.

[0041] Examples of the ruthenium carbene complex include those represented by the following general formula (1) or (2). [ka]

[0042] In the above general formulas (1) and (2), R 1 and R 2are 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, and may be bonded to each other to form a ring. 1 and R 2 Examples of groups bonded to each other to form a ring include an indenylidene group which may have a substituent, such as a phenylindenylidene group.

[0043] 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 include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an alkynyloxy group having 2 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an alkyl group having 2 to 20 carbon atoms, an alkynyloxy group having 2 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an alkyl group having 2 to 20 ...2 to 20 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an alkyl group having 2 to 20 carbon atoms, an alkyl group having 2 to Examples of the organic group include an alkylthio group, 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, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, or silicon atom, may have a substituent. Examples of the substituent 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.

[0044] X 1 and X 2 each independently represents an anionic ligand. The anionic ligand is a ligand that has a negative charge when separated from the central metal atom, and examples thereof include a halogen atom, a diketonate group, a substituted cyclopentadienyl group, an alkoxyl group, an aryloxy group, and a carboxyl group.

[0045] L 1 and L 2 represents a heteroatom-containing carbene compound or a neutral electron donor compound other than a heteroatom-containing carbene compound. Heteroatom-containing carbene compounds and neutral electron donor compounds 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, heteroatom-containing carbene compounds are preferred. The heteroatom refers to an atom of Groups 15 and 16 of the periodic table, and specific examples 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.

[0046] The heteroatom-containing carbene compound is preferably a compound represented by the following general formula (3) or (4), and from the viewpoint of improving catalytic activity, a compound represented by the following general formula (3) is more preferred. [ka]

[0047] In the above general formulas (3) and (4), R 3 , R 4 , R 5 and R 6 each independently represents 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 general formulas (1) and (2). 3 , R 4 , R 5 and R 6 may be bonded to each other in any combination to form a ring.

[0048] In addition, since the effect of the present invention becomes more remarkable, R 5 and R 6 is preferably a hydrogen atom. 3 and R 4 is preferably an aryl group which may have a substituent, more preferably a phenyl group having an alkyl group of 1 to 10 carbon atoms as a substituent, and even more preferably a mesityl group.

[0049] Examples of the neutral electron donor compound include oxygen atoms, water, carbonyls, ethers, nitriles, esters, phosphines, phosphinites, phosphites, sulfoxides, thioethers, amides, imines, aromatic compounds, cyclic diolefins, olefins, isocyanides, and thiocyanates.

[0050] In the above general formulas (1) and (2), R 1 , R 2 , X 1 , X 2 , L 1 and L 2 may be linked together alone and / or in any combination to form a multidentate chelating ligand.

[0051] Furthermore, as the ruthenium carbene complex, among the compounds represented by the above general formula (1) or (2), 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.

[0052] General formula (5) is shown below. [ka]

[0053] In the general formula (5), Z is an oxygen atom, a sulfur atom, a selenium atom, or NR 12 , PR 12 or AsR 12 and R 12represents 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, as this makes the effects of the present invention more pronounced.

[0054] In addition, R 1 , R 2 , X 1 and L 1 are the same as those in the above general formulas (1) and (2), and may be used alone or / and may be bonded to each other in any combination to form a multidentate chelating ligand, but X 1 and L 1 does not form a multidentate chelating ligand, and R 1 and R 2 are preferably bonded to each other to form a ring, more preferably an indenylidene group which may have a substituent, and even more preferably a phenylindenylidene group. Specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, or silicon atom are the same as those in the general formulas (1) and (2) above.

[0055] In the above general formula (5), 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. Examples of the substituent 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. When a ring is formed, the ring may be an aromatic ring, an alicyclic ring, or a heterocyclic ring, but preferably 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.

[0056] In the above general formula (5), R 9 , R 10 and R 11are 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 general formulas (1) and (2) above. R 9 , R 10 and R 11 is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0057] Specific examples of the compound represented by the general formula (5) and methods for producing the same are described in, for example, WO 03 / 062253 (JP 2005-515260 A).

[0058] General formula (6) is shown below. [ka]

[0059] In the above general formula (6), 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 preferably a methylene group.

[0060] In the above general formula (6), [ka] is a single bond or a double bond, preferably a single bond.

[0061] R 1 , X 1 , X 2 and L 1are the same as those in the above general formulas (1) and (2), and may be bonded to each other alone or in any combination to form a multidentate chelating ligand, but X 1 , X 2 and L 1 does not form a multidentate chelating ligand, and R 1 is preferably a hydrogen atom.

[0062] R 13 ~R 21 R 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; these groups may have a substituent and 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 general formulas (1) and (2) above. 13 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and R 14 ~R 17 is preferably a hydrogen atom, and R 18 ~R 21 is preferably a hydrogen atom or a halogen atom.

[0063] Specific examples of the compound represented by the general formula (6) and methods for producing the same are described in WO 11 / 079799 (JP 2013-516392 A).

[0064] As the compound represented by the general formula (1), in addition to the compounds represented by the general formula (5) or (6), the following compound (7) can also be suitably used: In the compound (7), PCy3 represents tricyclohexylphosphine, and Mes represents a mesityl group. [ka]

[0065] 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, relative to 1 mole of the total cycloolefin monomers used in the reaction, because the effects of the present invention become more pronounced.

[0066] The polymerizable composition may contain a coupling agent, a radical generator, a diisocyanate compound, a polyfunctional (meth)acrylate compound, or other optional components, as needed.

[0067] The coupling agent is not particularly limited, but can be exemplified by the silane coupling agent having at least one hydrocarbon group with norbornene structure (norbornene skeleton).Specific examples of such silane coupling agent include bicycloheptenyltrimethoxysilane, bicycloheptenyltriethoxysilane, bicycloheptenylethyltrimethoxysilane, bicycloheptenylethyltriethoxysilane, bicycloheptenylhexyltrimethoxysilane, bicycloheptenylhexyltriethoxysilane, etc., preferably bicycloheptenylethyltrimethoxysilane, bicycloheptenylethyltriethoxysilane, bicycloheptenylhexyltrimethoxysilane, and bicycloheptenylhexyltriethoxysilane, more preferably bicycloheptenylethyltrimethoxysilane and bicycloheptenylethyltriethoxysilane, and even more preferably bicycloheptenylethyltrimethoxysilane.

[0068] The polymerizable composition may also contain a silane coupling agent having a norbornene structure but no hydrocarbon group, 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.

[0069] The amount of the coupling agent in the polymerizable composition is preferably 0.2 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and even more preferably 1 to 3 parts by mass, relative to 100 parts by mass of all cycloolefin monomers used.

[0070] The radical generator generates radicals upon heating, thereby inducing a crosslinking reaction in the cycloolefin resin formed by polymerization of the polymerizable composition. The sites at which the radical generator induces the crosslinking reaction are mainly carbon-carbon double bonds contained in the cycloolefin resin, but crosslinking may also occur in saturated bond moieties.

[0071] Examples of the radical generator include organic peroxides, diazo compounds, and non-polar radical generators. Examples of 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; peroxyketals 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; peroxyesters such as t-butylperoxyacetate and t-butylperoxybenzoate; peroxycarbonates such as t-butylperoxyisopropylcarbonate and di(isopropylperoxy)dicarbonate; and alkylsilyl peroxamides such as t-butyltrimethylsilyl peroxide. Among these, dialkyl peroxides are preferred because they cause less interference with the metathesis polymerization reaction in bulk polymerization.

[0072] Examples of diazo compounds 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.

[0073] Examples of 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, and 1,1,1-triphenyl-2-phenylethane.

[0074] The amount of the radical generator in the polymerizable composition is usually 0.1 to 10 parts by mass, and preferably 0.5 to 5 parts by mass, based on 100 parts by mass of all the cycloolefin monomers used.

[0075] Examples of diisocyanate compounds include 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 dibenzyl ether. Examples of suitable diisocyanate compounds include aromatic diisocyanate compounds such as cyclohexylene 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 to form isocyanate groups at the terminals. Furthermore, conventionally known compounds having polyfunctional isocyanate groups, such as isocyanurates, biuret compounds, adducts, or polymers, 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, and polyisocyanate prepolymers.Among these, polyfunctional unblocked isocyanate compounds, such as aromatic diisocyanate compounds, aliphatic diisocyanate compounds, and alicyclic diisocyanate compounds, are preferably used because of their easy availability and ease of handling. These compounds can be used alone or in combination of two or more.

[0076] A polyfunctional blocked isocyanate compound is one in which at least two isocyanate groups in the molecule are reacted with an active hydrogen-containing compound, rendering 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, ε-caprolactam, oximes, and active methylene compounds. Polyfunctional blocked isocyanate compounds generally do not react at room temperature, resulting in excellent storage stability. However, heating at temperatures typically between 140 and 200°C regenerates the isocyanate groups, enabling the compound to exhibit excellent reactivity.

[0077] 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, based on 100 parts by mass of all cycloolefin monomers.

[0078] It is presumed that the use of a polyfunctional (meth)acrylate compound together with a diisocyanate compound synergistically enhances the function of the diisocyanate compound as an adhesion improver or adhesion imparting agent. Preferred examples of the polyfunctional (meth)acrylate compound include ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and neopentyl glycol dimethacrylate.

[0079] 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, based on 100 parts by mass of all cycloolefin monomers used.

[0080] Other optional components include activators, activity regulators, elastomers, antioxidants, colorants, light stabilizers, and flame retardants.

[0081] 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. Examples of activators that can be used include alkylaluminum halides such as ethylaluminum dichloride and diethylaluminum chloride; alkoxyalkylaluminum halides in which some of the alkyl groups in these alkylaluminum halides are substituted with alkoxy groups; and organotin compounds. The amount of activator used is not particularly limited, but is preferably 0.1 to 100 mol, more preferably 1 to 10 mol, per mol of the total metathesis polymerization catalysts used in the polymerizable composition.

[0082] 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 reaction stock solutions as described below and then injected into a mold to initiate polymerization.

[0083] When a compound of a transition metal of Group 5 or 6 of the periodic table is used as the metathesis polymerization catalyst, examples of the activity modifier include compounds that have the effect of reducing the metathesis polymerization catalyst, such as alcohols, haloalcohols, esters, ethers, nitriles, etc. Among these, alcohols and haloalcohols are preferred, and haloalcohols are more preferred.

[0084] Specific examples of alcohols include n-propanol, n-butanol, n-hexanol, 2-butanol, isobutyl alcohol, isopropyl alcohol, t-butyl alcohol, etc. Specific examples of haloalcohols include 1,3-dichloro-2-propanol, 2-chloroethanol, 1-chlorobutanol, etc.

[0085] Examples of activity regulators, particularly when using ruthenium carbene complexes as metathesis polymerization catalysts, include Lewis base compounds. Examples of 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. Furthermore, norbornenes substituted with alkenyl groups, such as vinylnorbornene, propenylnorbornene, and isopropenylnorbornene, function not only as cycloolefin monomers but also as activity regulators. The amount of these activity regulators used can be adjusted appropriately depending on the compound used.

[0086] Examples of elastomers 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. Dissolving an elastomer in the polymerizable composition allows for adjustment of its viscosity. Adding an elastomer also improves the impact resistance of the resulting composite molded article. The amount of elastomer used is preferably 0.5 to 20 parts by mass, more preferably 2 to 10 parts by mass, per 100 parts by mass of all cycloolefin monomers in the polymerizable composition.

[0087] Antioxidants include various antioxidants for plastics and rubber, such as hindered phenolic compounds such as pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,6-di-t-butyl-p-cresol, and di-t-butyl-4-methylphenol; thiodicarboxylate esters such as dilauryl thiopropionate; and phosphites such as tris(nonylphenyl)phosphite.

[0088] As the colorant, dyes, pigments, etc. are used. There are many types of dyes, and known dyes can be appropriately selected and used. Examples of pigments include carbon black, graphite, yellow lead, iron oxide yellow, titanium dioxide, zinc oxide, trilead tetroxide, red lead, chromium oxide, iron blue, and titanium black.

[0089] Examples of light stabilizers include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, oxanilide-based ultraviolet absorbers, hindered amine-based ultraviolet absorbers, and benzoate-based ultraviolet absorbers.

[0090] Examples of the flame retardant include phosphorus-based flame retardants, nitrogen-based flame retardants, halogen-based flame retardants, and metal hydroxide-based flame retardants such as aluminum hydroxide and magnesium hydroxide.

[0091] The polymerizable composition may further contain a filler. As the filler, various fillers can be used, and although there are no particular limitations, it is preferable to use a particulate inorganic filler.

[0092] The particulate inorganic filler preferably has an aspect ratio of 1 to 2, more preferably 1 to 1.5. The 50% cumulative volume diameter of the particulate inorganic filler is preferably 0.1 to 50 μm, more preferably 1 to 30 μm, and particularly preferably 1 to 10 μm. Here, the aspect ratio refers to the ratio of the average major axis diameter of the filler to the 50% cumulative volume diameter. The average major axis diameter is the number-average major axis diameter calculated as the arithmetic mean value of the major axis diameters of 100 fillers randomly selected from an optical microscope photograph. The 50% cumulative volume diameter is a value determined by measuring the particle size distribution using an X-ray transmission method.

[0093] Specific examples of particulate inorganic fillers include calcium carbonate, calcium hydroxide, calcium silicate, calcium sulfate, aluminum hydroxide, magnesium hydroxide, titanium oxide, zinc oxide, barium titanate, silica, alumina, gadolinia, carbon black, graphite, antimony oxide, red phosphorus, various metal powders, metal alloy powders, clay, various ferrites, hydrotalcite, etc. Among these, magnesium hydroxide, aluminum hydroxide, silica, and alumina are preferred, and aluminum hydroxide and silica are particularly preferred.

[0094] The particulate inorganic filler may have its surface hydrophobized. Using a hydrophobized particulate inorganic filler can prevent aggregation and sedimentation of the particulate inorganic filler in the polymerizable composition and can ensure uniform dispersion of the particulate inorganic filler in the resulting molded article. As a result, the strength of the molded article can be further increased. Examples of treatment agents used for the hydrophobization treatment include silane coupling agents such as vinyl silane, titanate coupling agents, aluminum coupling agents, fatty acids such as stearic acid, oils and fats, surfactants, waxes, etc. The treatment agent used for the hydrophobization treatment may be reacted with the particulate inorganic filler in advance to hydrophobize its surface. Alternatively, the treatment agent used for the hydrophobization treatment may be incorporated into the polymer composition without reacting with the particulate inorganic filler in advance, and the surface of the particulate inorganic filler may be hydrophobized in the polymer composition.

[0095] The polymerizable composition may also contain a fibrous inorganic filler. The fibrous inorganic filler preferably has an aspect ratio of 5 to 100, more preferably 10 to 50. The 50% cumulative volume diameter of the fibrous inorganic filler is preferably 0.1 to 50 μm, more preferably 1 to 30 μm.

[0096] Specific examples of fibrous inorganic fillers include glass fiber, wollastonite, potassium titanate, zonolite, basic magnesium sulfate, aluminum borate, tetrapod-type zinc oxide, gypsum fiber, phosphate fiber, alumina fiber, whisker-like calcium carbonate, and whisker-like boehmite. Among these, wollastonite and whisker-like calcium carbonate are preferred. Furthermore, the fibrous inorganic filler may have its surface hydrophobized, similar to the particulate inorganic filler described above.

[0097] The amount of the inorganic filler in the polymerizable composition is preferably 0 to 1000 parts by mass, more preferably 0 to 500 parts by mass, relative to 100 parts by mass of the total amount of polymerizable monomers.

[0098] [Method of producing polymerizable composition] The polymerizable composition used in the present invention is prepared by appropriately mixing the above-mentioned components according to a known method. The polymerizable composition used in the present invention may also be prepared by mixing two or more reaction stock solutions using a mixer or the like. The reaction stock solution does not undergo bulk polymerization with only one solution, but the above-mentioned components are prepared by dividing them into two or more solutions so that when all the solutions are mixed together, a polymerizable composition containing each component in a predetermined ratio (the total content of each component is 100% by mass) is obtained. The combination of two or more reaction stock solutions can be exemplified by the following two ways (a) and (b), depending on the type of metathesis polymerization catalyst used.

[0099] (a): The metathesis polymerization catalyst may be one that does not have polymerization activity by itself but exhibits polymerization activity when used in combination with an activator. In this case, 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. Furthermore, a reaction stock solution (Liquid C) containing a cycloolefin monomer but not containing a metathesis polymerization catalyst or an activator may also be used in combination.

[0100] (b): When a metathesis polymerization catalyst having polymerization activity by itself is used, 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. In this case, the reaction stock solution (ii) is typically prepared by dissolving or dispersing the metathesis polymerization catalyst in a small amount of an inert solvent. Examples of such solvents 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. Among these, aromatic hydrocarbons are preferred, and toluene is more preferred.

[0101] Optional components such as a coupling agent, a radical generator, a diisocyanate compound, and a polyfunctional (meth)acrylate compound 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.

[0102] Examples of the mixer used for mixing the reaction stock solutions include an impingement mixer that is generally used in reaction injection molding, as well as low-pressure mixers such as a dynamic mixer and a static mixer.

[0103] The molded article of the present invention can be used for, for example, covering materials for power transmission cables (plastic insulated wires, power cables, local and long-distance cables, intra-station cables, broadband cables, high-frequency coaxial cables, high-frequency coaxial (tube) feeders and elliptical waveguides, communication wires and cables, etc.); general circuit boards (rigid printed circuit boards, flexible printed circuit boards, multilayer printed wiring boards, etc.); high-frequency circuit boards (circuit boards for satellite communication devices, etc.); automobile exterior parts (hoods, trunk doors, doors, fenders, grilles, etc.); engine parts such as air intakes and engine covers. Materials; vehicle lighting components such as headlamp housings, rear lamp housings, reflectors, extension reflectors, etc.; automotive interior parts such as instrument panels and seat housings; automotive parts such as automotive motor cases, sensor cases, module component cases, and fuel cell stack separators; bicycle components such as power assist battery components; robot component housings for power assists, industrial robots, and electric wheelchairs; aircraft interior components; ship hull components; televisions, refrigerators, air conditioners, fans, humidifiers, dehumidifiers, washing and drying machines, food The materials can be used for home appliance parts such as dishwashers, microwave ovens, rice cookers, electric jug pots, and dryers; housings for electronic products such as computers, printers, copiers, telephones, fax machines, audio equipment, cameras, game consoles, hard disk drives, mobile phones, and smartphones; electronic components such as connectors, relays, capacitors, sensors, antennas, IC trays, chassis, coil encapsulation, motor cases, and power supply boxes; light source lighting fixtures for backlighting the liquid crystal displays of large liquid crystal display devices; light source lighting fixtures for backlighting the liquid crystal displays of small electronic devices such as mobile phones, smartphones, and tablets; LED reflectors used as light sources for electronic signs such as road traffic signs; optical lens barrels; release films for laminating printed wiring boards; solar cell substrates; packaging and packaging films; LED molding materials; pump casings, impellers, pipe joints, bathtubs, septic tanks, bathroom panels, exterior panels, window sash rails, window insulation, and washbasins; and industrial components such as infusion containers, chemical solution containers, chemical solution piping, gas piping, containers, pallets, and rack columns.

[0104] <Method of manufacturing molded body> The molded article of the present invention can be produced by a production method in which the above-mentioned polymerizable composition is primarily cured in a mold until the Shore A hardness reaches 5 to 80, and then secondary curing is carried out with at least a part of the surface of the primary cured article exposed. The present invention also relates to a production method for such a molded article.

[0105] That is, the production method of the present invention includes a filling step of filling a mold with a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst; a primary curing step of primarily curing the polymerizable composition in the mold to obtain a primary cured product having a Shore A hardness of 5 to 80 as measured in accordance with ASTM D 2240; a demolding step of removing a portion of the mold to expose at least a portion of the surface of the primary cured body; and The method includes a secondary curing step in which the primary cured product is subjected to secondary curing in a state in which at least a portion of the surface is exposed, to obtain a molded product having a Shore A hardness of 95 or more.

[0106] Conventional manufacturing methods do not include a step of exposing the surface of the reaction product of the polymerizable composition during the curing reaction. An embodiment of obtaining a molded product by such a conventional manufacturing method is shown in Figure 1 (1a).

[0107] A polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst shrinks during a curing reaction. In conventional manufacturing methods, the polymerizable composition filled into a mold consisting of an upper mold 11 and a lower mold 12 is subjected to stress that causes it to shrink from the periphery toward the center, while the polymerizable composition in contact with the mold 10 is also subjected to stress that causes it to maintain contact with the mold 10. As a result, the surface of the resulting molded product 21 contains both portions that maintain contact with the mold and portions that shrink away from the mold toward the center. As a result, large dents and small roughness appear on the surface of the molded product 21. Furthermore, because the surface of the polymerizable composition reactant is not exposed, if air bubbles are generated during curing, the bubbles are likely to grow, which can lead to poor appearance due to the bubbles.

[0108] On the other hand, in the production method of the present invention, the polymerizable composition is primarily cured in a mold until the Shore A hardness reaches 5 to 80, and then secondary curing is carried out with at least a part of the surface of the primary cured product exposed. An example of an embodiment in which a molded product is obtained by such a production method is shown in Fig. 1(1b).

[0109] In the secondary curing step of the manufacturing method of the present invention, shrinkage of the cured body occurs in a fixed direction from the exposed surface of the primary cured body to the unexposed surface of the primary cured body. Furthermore, because movement of the surface of the primary cured body during shrinkage is not inhibited, the surface of the primary cured body can move freely. Therefore, the shape of the exposed surface of the primary cured body is maintained, and the shape of the unexposed surface of the primary cured body is also maintained. Furthermore, because the surface of the primary cured body is exposed, even if bubbles are generated during secondary curing, they are less likely to grow, and bubble-induced defects in appearance are less likely to occur. Therefore, the manufacturing method of the present invention allows for high productivity production of molded articles having smooth surfaces with reduced bubble-induced defects in appearance.

[0110] [Filling process] In the filling step, a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst is filled into the mold.

[0111] The polymerizable composition used in the filling step may be any of the polymerizable compositions described above for forming the molded article of the present invention. The polymerizable composition is usually liquid, and the Shore A hardness of the polymerizable composition is either immeasurable (liquid) or less than 5.

[0112] The mold used in the filling step may be one that can be partially removed in the demolding step described below, thereby exposing at least a portion of the surface of the primary cured body.

[0113] The mold is not particularly limited, but for example, a mold formed of a pair of molds, such as a male mold and a female mold, can be used. Furthermore, the mold used does not necessarily have to be a highly rigid and expensive metal mold, and is not limited to a metal mold, but a resin mold or a simple mold frame can be used. When a metal mold is used, the material is not particularly limited, but examples include steel, aluminum, zinc alloy, nickel, copper, chromium, etc., and the metal mold may be manufactured by any method such as casting, forging, thermal spraying, electroforming, etc., or may be plated.

[0114] When a mold having a parting surface is used, a packing may be placed at the parting surface, but from the viewpoint of improving the shape precision of the obtained molded article, it is preferable not to place a packing. The width of the parting surface is usually 10 mm or more, preferably 30 mm or more.

[0115] In the filling step, a release agent may be applied to the inside of the mold in advance, or a release film may be placed inside the mold.

[0116] [Primary curing process] In the primary curing step, the polymerizable composition is primarily cured in a mold to obtain a primarily cured product having a Shore A hardness of 5 to 80. In this specification, the Shore A hardness refers to the surface hardness measured in accordance with ASTM D 2240.

[0117] The Shore A hardness of the primary cured product obtained in the primary curing step is not particularly limited as long as it is 5 to 80, but is preferably 5 to 70, and more preferably 5 to 60. By ensuring that the Shore A hardness of the primary cured product falls within the above range, a molded product can be obtained that has an even smoother surface and in which defects in appearance due to bubbles are further suppressed.

[0118] The curing conditions in the primary curing step are not particularly limited as long as the Shore A hardness of the resulting primary cured product falls within the above range. Specifically, the primary curing temperature may be appropriately selected depending on the type of cycloolefin monomer used, but is preferably 10 to 70°C, more preferably 20 to 50°C. The secondary curing time in the primary curing step is preferably 5 minutes to 3 hours, more preferably 10 minutes to 2 hours.

[0119] Examples of methods for adjusting the curing temperature include adjusting the mold temperature with a heater; adjusting the temperature of a medium such as hot or cold water or oil circulated through piping embedded inside the mold; and the like.

[0120] [Demolding process] In the demolding step, a portion of the mold is removed to expose at least a portion of the surface of the primary cured body.

[0121] In the demolding step, only a part of the mold may be removed, and the remaining mold may be used in the secondary curing step. Alternatively, in the demolding step, all of the mold may be removed.

[0122] When a material other than the polymerizable composition is placed between the polymerizable composition and the mold in the filling step, at least a part of the surface of the primary cured body may be exposed by removing a part of the material together with the mold in the demolding step. Even in this case, when there is a part where the polymerizable composition and the mold are in direct contact, at least a part of the surface of the primary cured body may be exposed by removing a part of the mold at the part where the polymerizable composition and the mold are in direct contact.

[0123] For example, if a release film is placed on at least a portion of the interface between the polymerizable composition and the mold during the filling step, the release film must not remain on the surface of the primary cured body that is exposed during the demolding step. If a release film is present on the surface of the primary cured body and secondary curing is performed while the surface of the primary cured body is not exposed, the release film restricts the movement of the surface of the primary cured body during shrinkage due to secondary curing, making it difficult to achieve uniform movement of the surface. Furthermore, during secondary curing, the release film usually shrinks or expands. This causes the primary cured body to shrink non-uniformly, resulting in increased surface roughness of the resulting molded body. Furthermore, if air bubbles are generated during secondary curing because the surface of the primary cured body is not exposed, the air bubbles are likely to grow, making the product more susceptible to poor appearance due to the air bubbles.

[0124] When all the molds are removed in the demolding step, for example, the primary cured body may be placed on a new substrate 13 and then secondary cured in the secondary curing step. An example of an embodiment in which a molded body is obtained by such a production method is shown in FIG.

[0125] In the demolding step, the primary cured body may be molded using a molding die 14. An example of an embodiment in which a molded body is obtained by such a production method is shown in FIG.

[0126] [Secondary hardening process] In the secondary curing step, the primary cured product is subjected to secondary curing in a state where at least a portion of the surface is exposed, to obtain a molded product having a Shore A hardness of 95 or more.

[0127] In the secondary curing step, the secondary curing is started when the Shore A hardness of the primary cured product is 5 to 80.

[0128] The curing conditions in the secondary curing step are not particularly limited as long as the Shore A hardness of the resulting molded article falls within the above range. Specifically, the secondary curing temperature may be appropriately selected depending on the type of cycloolefin monomer used, but is preferably 30 to 300°C, more preferably 50 to 250°C. The secondary curing time in the secondary curing step is preferably 10 minutes to 5 hours, more preferably 20 minutes to 3 hours.

[0129] Examples of methods for adjusting the curing temperature include adjusting the mold temperature with a heater; adjusting the temperature of a medium such as hot and cold water or oil circulated through piping embedded inside the mold; and the like.

[0130] The Shore A hardness of the resulting molded article is not particularly limited as long as it is 95 or more, but is preferably 97 or more.

[0131] <Method of manufacturing the composite> The manufacturing method of the present invention can be used to manufacture a composite of a cured product obtained by curing a polymerizable composition and another component. By using the manufacturing method of the present invention, coating molding can be performed favorably. The cured product obtained by curing a polymerizable composition in the composite manufactured by the manufacturing method of the present invention has a smooth surface with reduced appearance defects due to bubbles.

[0132] For example, in the filling step, the polymerizable composition 20 and the covering member 15 are supplied into the mold, and the polymerizable composition 20 and the covering member 15 are laminated in the mold. This laminate is then used to perform the primary curing step, the demolding step, and the secondary curing step, thereby performing the covering molding. An example of an embodiment in which a composite 30 is obtained by such a manufacturing method is shown in FIG. 4. In FIG. 4, (4-1) shows the state in the filling step, and (4-2) shows the state after the secondary curing step.

[0133] Alternatively, for example, in the demolding step, the covering member 15 may be covered with a primary cured product, and the resulting product may be used in the secondary curing step. An example of an embodiment in which a composite 30 is obtained by such a production method is shown in FIG. [Example]

[0134] The present invention will be described below based on examples, but the present invention is not limited to these examples. Note that "parts" and "%" are by mass unless otherwise specified.

[0135] <Shore A hardness> Shore A hardness was measured according to ASTM D 2240.

[0136] <Surface roughness of molded body> The surface roughness of the molded body was measured in accordance with JIS B 0601: 2013. Specifically, the maximum height Pz of the cross-sectional curve and the arithmetic mean height Pa of the cross-sectional curve were measured.

[0137] <Average thickness of molded body> 81 measurement points were randomly selected, and the thickness of the molded body at each measurement point was measured using a thickness gauge to determine the average thickness.

[0138] <Appearance of molded product> The appearance of the molded article was visually observed, and if bubbles were present inside the molded article or pores derived from bubbles were present on the surface of the molded article, the appearance was judged to be "poor." On the other hand, if no bubbles or pores were present, the appearance was judged to be "good."

[0139] Example 1 In Example 1, a set of molds (1) consisting of an upper mold and a lower mold was used. When sealed, the mold (1) had a rectangular parallelepiped internal space measuring 200 mm in length, 200 mm in width, and 3.8 mm in height. The width of the parting surface of the mold (1) was 30 mm.

[0140] A reaction stock solution (i) was prepared by mixing 95.3 parts of RIM monomer (manufactured by Zeon Corporation), 2.2 parts of dicyclopentadiene monoepoxide (DCPME), 1.7 parts of bicycloheptenylethyltrimethoxysilane, and 0.8 parts of phenoxyethylene glycol methacrylate. A reaction stock solution (ii) was prepared by mixing 0.4 parts of the compound (7) as a metathesis polymerization catalyst, 57 parts of cyclopentanone as an inert solvent, and 42.6 parts of triphenylphosphine as a reaction retarder. A polymerizable composition was prepared by mixing 100.0 parts of the reaction stock solution (i) and 2.5 parts of the reaction stock solution (ii) at 20°C. The RIM monomer contained 90% by mass of dicyclopentadiene and 10% by mass of tricyclopentadiene as cycloolefin monomers.

[0141] The prepared polymerizable composition was filled into the mold, and the mold (1) was sealed. The temperature of the mold (1) was then adjusted so that the temperature of the polymerizable composition was 35°C, and the primary curing reaction of the polymerizable composition was carried out at 35°C for 35 minutes. At the end of the reaction, the upper mold was removed to expose the upper surface of the primary cured product. The Shore A hardness of the primary cured product at this stage was immediately measured according to the method described above. The results are shown in Table 1.

[0142] Next, with the upper surface of the primary cured product exposed, the temperature of the lower mold of the mold (1) was adjusted so that the temperature of the primary cured product was 175°C, and the secondary curing reaction of the primary cured product was carried out at 175°C for 60 minutes to obtain a molded product. The Shore A hardness, surface roughness, average thickness, and appearance of the obtained molded product were evaluated according to the methods described above. The results are shown in Table 1.

[0143] <Example 2> In Example 2, a mold (2) was used, which was the same as mold (1) except that the height of the internal space was 2.0 mm. A primary cured body and a molded body were obtained in the same manner as in Example 1, except that mold (2) was used instead of mold (1). The primary cured body and the molded body were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0144] Example 3 A primary cured product and a molded product were obtained in the same manner as in Example 1, except that the primary curing conditions were changed from 35°C for 35 minutes to 35°C for 50 minutes. The primary cured product and the molded product were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0145] <Reference example 1> The primary curing was initiated in the same manner as in Example 3. After a set time (20 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, and 50 minutes) had elapsed from the start of the primary curing, the upper mold was removed and the Shore A hardness of the reaction product at each time point was measured according to the method described above. The results are shown in Table 2.

[0146] Example 4 In Example 4, a mold (3) was used which was the same as the mold (1) except that the height of the internal space was 5.0 mm.

[0147] A polymerizable composition was prepared by mixing 20.0 parts of the reaction stock solution (i), 0.5 parts of the reaction stock solution (ii), 67 parts of silica (spherical inorganic filler, trade name "MLR1114", manufactured by Tatsumori Co., Ltd., volume average particle size 10 μm), and 13 parts of a phosphorus / nitrogen-based flame retardant (a mixture of a metal phosphinate and a nitrogen-based compound, trade name "OP-1312", manufactured by Clariant) at a temperature of 20°C.

[0148] The prepared polymerizable composition was filled into the mold, and the mold (3) was sealed. The temperature of the mold (3) was then adjusted so that the temperature of the polymerizable composition was 35°C, and the primary curing reaction of the polymerizable composition was carried out at 35°C for 30 minutes. At the end of the reaction, the upper mold was removed to expose the upper surface of the primary cured product. The Shore A hardness of the primary cured product at this stage was immediately measured according to the method described above. The results are shown in Table 1.

[0149] Next, with the upper surface of the primary cured body exposed, the temperature of the lower mold of the mold (3) was adjusted so that the temperature of the primary cured body was 175°C, and the secondary curing reaction of the primary cured body was carried out at 175°C for 60 minutes to obtain a molded body. The obtained molded body was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0150] <Reference example 2> The primary curing was initiated in the same manner as in Example 4. After a certain period of time (20 minutes, 30 minutes) had elapsed since the start of the primary curing, the upper mold was removed and the Shore A hardness of the reaction product at that time was measured according to the method described above. The results are shown in Table 2.

[0151] <Comparative Example 1> The primary curing reaction of the polymerizable composition was carried out in the same manner as in Example 1. Next, while the mold (1) was kept sealed, the temperature of the lower mold of the mold (1) was adjusted so that the temperature of the primary cured product was 175°C, and a secondary curing reaction of the primary cured product was carried out at 175°C for 60 minutes to obtain a molded product. The obtained molded product was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0152] <Comparative Example 2> In Comparative Example 2, a mold (4) similar to the mold (1) was used, except that the height of the internal space was 5.0 mm. A polymerizable composition was prepared in the same manner as in Example 1. The temperature of the mold (4) was adjusted to 175°C in advance, the polymerizable composition was filled into the mold, and the mold (4) was sealed. Next, while the mold (4) was still sealed, the temperature of the mold (4) was maintained so that the temperature of the polymerizable composition reached 175°C, and a curing reaction of the polymerizable composition was carried out at 175°C for 60 minutes to obtain a molded product. The obtained molded product was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0153] <Comparative Example 3> The polymerizable composition was filled into the mold, the mold (1) was sealed, and the primary curing reaction of the polymerizable composition was carried out in the same manner as in Example 1, except that a PET release film was placed so as to cover the upper surface of the polymerizable composition. Next, with the mold (1) still sealed, the temperature of the lower mold of the mold (1) was adjusted so that the temperature of the primary cured product was 175°C, and a secondary curing reaction of the primary cured product was carried out at 175°C for 60 minutes to obtain a molded product. The obtained molded product was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0154] <Comparative Example 4> In Comparative Example 2, a mold (5) similar to the mold (1) was used, except that the height of the internal space was 5.0 mm. A polymerizable composition was prepared in the same manner as in Example 4. The temperature of the mold (5) was adjusted to 175°C in advance, the polymerizable composition was filled into the mold, and the mold (5) was sealed. Next, while the mold (5) was still sealed, the temperature of the mold (5) was maintained so that the temperature of the polymerizable composition reached 175°C, and a curing reaction of the polymerizable composition was carried out at 175°C for 60 minutes to obtain a molded product. The obtained molded product was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0155] [Table 1]

[0156] [Table 2]

[0157] As is clear from Table 1, a smooth molded article could be obtained by a production method in which a polymerizable composition was primarily cured in a mold until the hardness reached a specific range, and then secondary curing was performed with at least a portion of the surface of the primary cured article exposed. The molded article obtained by this production method had a maximum height Pz of the cross-sectional curve of 50 μm or less.

[0158] On the other hand, when the surface of the polymerizable composition reaction product was not exposed during the curing reaction, a smooth molded product could not be obtained. The maximum height Pz of the cross-sectional curve of the molded product obtained by such a manufacturing method exceeded 50 μm.

Claims

1. A molded article obtained by curing a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst, A molded body having a surface in which the maximum height Pz of the cross-sectional curve measured in accordance with JIS B 0601:2013 is 50 μm or less.

2. The molded article according to claim 1 , wherein the polymerizable composition contains, as the cycloolefin monomer, a cycloolefin monomer having no polar group.

3. The molded article according to claim 1 or 2, wherein the polymerizable composition contains a dicyclopentadiene as the cycloolefin monomer.

4. 3. The molded article according to claim 1, wherein the polymerizable composition further contains at least one selected from the group consisting of a coupling agent, a radical generator, a diisocyanate compound, and a polyfunctional (meth)acrylate compound.

5. a filling step of filling a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst into a mold; a primary curing step of primarily curing the polymerizable composition in the mold to obtain a primary cured product having a Shore A hardness of 5 to 80 as measured in accordance with ASTM D 2240; a demolding step of removing a portion of the mold to expose at least a portion of the surface of the primary cured body; and A method for producing a molded body, comprising a secondary curing step of secondary curing the primary cured body with at least a portion of the surface exposed to obtain a molded body having a Shore A hardness of 95 or more.

6. The method for producing a molded article according to claim 5 , wherein the polymerizable composition contains, as the cycloolefin monomer, a cycloolefin monomer having no polar group.

7. The method for producing a molded article according to claim 5 or 6, wherein the polymerizable composition contains a dicyclopentadiene as the cycloolefin monomer.

8. 7. The method for producing a molded article according to claim 5, wherein the polymerizable composition further contains at least one selected from the group consisting of a coupling agent, a radical generator, a diisocyanate compound, and a polyfunctional (meth)acrylate compound.

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