WO2017138304A1 - 重合性組成物及び複合材料 - Google Patents
重合性組成物及び複合材料 Download PDFInfo
- Publication number
- WO2017138304A1 WO2017138304A1 PCT/JP2017/001242 JP2017001242W WO2017138304A1 WO 2017138304 A1 WO2017138304 A1 WO 2017138304A1 JP 2017001242 W JP2017001242 W JP 2017001242W WO 2017138304 A1 WO2017138304 A1 WO 2017138304A1
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- WIPO (PCT)
- Prior art keywords
- composite material
- polymerizable composition
- fibrous filler
- group
- atom
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- DHWBYAACHDUFAT-UHFFFAOYSA-N tricyclopentylphosphane Chemical compound C1CCCC1P(C1CCCC1)C1CCCC1 DHWBYAACHDUFAT-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
- B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
- B29C70/48—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs and impregnating the reinforcements in the closed mould, e.g. resin transfer moulding [RTM], e.g. by vacuum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
- B29K2033/04—Polymers of esters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Definitions
- the present invention relates to a polymerizable composition and a composite material obtained by curing the polymerizable composition impregnated in a fibrous filler.
- the present invention further relates to a method for producing the composite material.
- Patent Document 1 and Patent Document 2 a cross-linked resin molded article (Patent Document 1 and Patent Document 2) excellent in mechanical strength using carbon fiber as a reinforcing fiber and a composite molded body using glass fiber (Patent Document 3) are known.
- Patent Document 3 a cross-linked resin molded article
- mechanical strength especially bending strength
- these composite molded products including glass fibers generate odors derived from raw material components, especially during thermosetting. There was a problem to do.
- an object of the present invention is to provide a polymerizable composition that does not cause odor after curing, and a composite material including a fibrous filler that has excellent mechanical strength and does not generate odor. Furthermore, the subject of this invention is providing the manufacturing method of this composite material.
- the gist of the present invention is as follows.
- a polymerizable composition comprising a cycloolefin monomer, a metathesis polymerization catalyst, a radical generator, a diisocyanate compound and a polyfunctional (meth) acrylate compound;
- the composite material of the present invention produced using the polymerizable composition of the present invention has an effect of being excellent in mechanical strength and producing no odor. Furthermore, according to the production method of the present invention, it is possible to produce a composite material including a fibrous filler that is excellent in mechanical strength and does not generate odor.
- the composite material of the present invention is a molded product of cycloolefin resin obtained by bulk polymerization of a polymerizable composition containing a cycloolefin monomer in a mold, and is characterized by containing a fibrous filler. .
- the composite material of the present invention can be produced, for example, by the production method of the present invention.
- the production method of the present invention comprises: Placing the fibrous filler in the mold (1), A step (2) of impregnating the fibrous filler with the polymerizable composition of the present invention; A step (3) of obtaining a composite material in which the polymerizable composition impregnated in a fibrous filler is bulk-polymerized to cure the polymerizable composition, and a step (4) of demolding the composite material; It is the method of including.
- the polymerizable composition of the present invention comprises a cycloolefin monomer, a metathesis polymerization catalyst, a radical generator, a diisocyanate compound and a polyfunctional (meth) acrylate compound, and optional components blended as desired according to a known method. It is prepared by mixing appropriately.
- Examples of the optional component include an activator, an activity regulator, an elastomer, and an antioxidant.
- Cycloolefin monomer The 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 monocycles, polycycles, condensed polycycles, bridged rings, and combination polycycles thereof.
- the number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, and more preferably 5 to 15.
- cycloolefin monomers include monocyclic cycloolefin monomers and norbornene monomers, and norbornene monomers are preferred.
- the norbornene-based monomer is a cycloolefin monomer 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. Further, the norbornene-based monomer may have a double bond in addition to the double bond of the norbornene ring.
- Examples of the monocyclic cycloolefin monomer include cyclobutene, cyclopentene, cyclooctene, cyclododecene, cyclopentadiene, 1,5-cyclooctadiene, and the like.
- norbornene-based monomer examples include dicyclopentadiene such as dicyclopentadiene and methyldicyclopentadiene; 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 .
- tetracyclododecenes such as dodeca-9-ene-4,5-dicarboxylic anhydride; 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- Norbornenes such as norbornene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid, 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.
- a cycloolefin monomer having no polar group is preferable because a molded article having low water absorption can be obtained.
- the viscosity of the polymerizable composition can be lowered by using an aromatic condensed ring such as 0 3,8 ] tetradeca-3,5,7,12-tetraene.
- cycloolefin monomers may be used individually by 1 type, and may be used in combination of 2 or more type. By combining, the physical property of the cycloolefin type resin obtained can be adjusted suitably.
- the polymerizable composition of the present invention may contain any monomer copolymerizable with the above-described cycloolefin monomer as long as the expression of the effect of the present invention is not inhibited.
- the metathesis polymerization catalyst used in the present invention is not particularly limited as long as it can perform ring-opening polymerization of a cycloolefin monomer, and a known one can be used.
- the metathesis polymerization catalyst used in the present invention is a complex formed by bonding a plurality of ions, atoms, polyatomic ions and / or compounds with a transition metal atom as a central atom.
- transition metal atoms atoms of Groups 5, 6 and 8 (long-period periodic table, the same applies hereinafter) are used.
- the atoms of each group are not particularly limited, examples of the Group 5 atom include tantalum, examples of the Group 6 atom include molybdenum and tungsten, and examples of the Group 8 atom include: Examples include ruthenium and osmium. Of these transition metal atoms, Group 8 ruthenium and osmium are preferred.
- the metathesis polymerization catalyst used in the present invention is preferably a complex having ruthenium or osmium as a central atom, and more preferably a complex having ruthenium as a central atom.
- a complex having ruthenium as a central atom a ruthenium carbene complex in which a carbene compound is coordinated to ruthenium is preferable.
- the “carbene compound” is a general term for compounds having a methylene free group, and refers to a compound having an uncharged divalent carbon atom (carbene carbon) as represented by (> C :).
- the ruthenium carbene complex is excellent in catalytic activity at the time of bulk ring-opening polymerization, the resulting polymer has little odor derived from unreacted monomers, and a high-quality polymer with good productivity can be obtained. In addition, it is relatively stable to oxygen and moisture in the air and is not easily deactivated, so that it can be used even in the atmosphere. Only one type of metathesis polymerization catalyst may be used, or a plurality of types may be used in combination.
- Examples of the ruthenium carbene complex include those represented by the following general formula (1) or general formula (2).
- R 1 and R 2 each independently include a hydrogen atom; a halogen atom; or 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. Examples of R 1 and R 2 bonded to each other to form a ring include an indenylidene group which may have a substituent, such as a phenylindenylidene group.
- 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 include an alkyl group having 1 to 20 carbon atoms and 2 to 2 carbon atoms.
- alkenyl groups C 2-20 alkynyl groups, C 6-20 aryl groups, C 1-20 alkoxy groups, C 2-20 alkenyloxy groups, C 2-20 alkynyloxy groups Group, aryloxy group having 6 to 20 carbon atoms, alkylthio group having 1 to 8 carbon atoms, carbonyloxy group, alkoxycarbonyl group having 1 to 20 carbon atoms, alkylsulfonyl group having 1 to 20 carbon atoms, 1 to 20 carbon atoms Alkylsulfinyl group, alkyl sulfonic acid group having 1 to 20 carbon atoms, aryl sulfonic acid group having 6 to 20 carbon atoms, phosphonic acid group, aryl phosphinic group having 6 to 20 carbon atoms Phospho groups include an alkyl ammonium group having 1 to 20 carbon atoms, and an aryl ammonium 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.
- 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.
- X 1 and X 2 each independently represent an arbitrary anionic ligand.
- An anionic ligand is a ligand having a negative charge when pulled away from a central metal atom, such as a halogen atom, a diketonate group, a substituted cyclopentadienyl group, an alkoxyl group, an aryloxy group, A carboxyl group etc. can be mentioned.
- L 1 and L 2 represent a hetero atom-containing carbene compound or a neutral electron donating compound other than the hetero atom-containing carbene compound.
- the heteroatom-containing carbene compound and the neutral electron-donating compound other than the heteroatom-containing carbene compound are compounds having a neutral charge when separated from the central metal. From the viewpoint of improving the catalytic activity, a heteroatom-containing carbene compound is preferred.
- a heteroatom means 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. .
- a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom are preferable, and a nitrogen atom is particularly preferable.
- heteroatom-containing carbene compound a compound represented by the following general formula (3) or (4) is preferable, and a compound represented by the following general formula (3) is particularly preferable from the viewpoint of improving catalytic activity.
- R 3 , R 4 , R 5 and R 6 are each independently hydrogen atom; halogen atom; or halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus
- R 5 and R 6 are hydrogen atoms.
- R 3 and R 4 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 particularly preferably a mesityl group.
- neutral electron donating compound examples include oxygen atom, 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 are bonded to each other alone and / or in any combination to form a multidentate chelate
- a fluorinated ligand may be formed.
- the above general formula (1) As the ruthenium carbene complex used in the present invention, among the compounds represented by the above general formula (1) or (2), the above general formula (1) The compound represented is preferable, and among these, the compound represented by the following general formula (5) or general formula (6) is more preferable.
- 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 a halogen atom, an oxygen atom, a nitrogen atom ,
- R 12 is a hydrogen atom; a halogen atom; or a halogen atom, an oxygen atom, a nitrogen atom
- An organic group having 1 to 20 carbon atoms which may contain a sulfur atom, a phosphorus atom or a silicon atom; however, since the effect of the present invention becomes more remarkable, an oxygen atom is preferable as Z.
- R 1 , R 2 , X 1 and L 1 are the same as those in the general formulas (1) and (2), and are bonded individually and / or in any combination to form a polydentate.
- a chelating ligand may be formed, but X 1 and L 1 do not form a multidentate chelating ligand, and R 1 and R 2 are bonded to each other to form a ring. Is more preferable, and an indenylidene group which may have a substituent is more preferable, and a phenylindenylidene group is particularly preferable.
- organic group having 1 to 20 carbon atoms that may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom include those represented by the general formulas (1) and (2). Same as the case.
- 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 having 6 to 20 carbon atoms. These groups may have a substituent and 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, and an aryl group having 6 to 10 carbon atoms.
- the ring is an aromatic ring Any of alicyclic ring and heterocyclic ring may be used, but it is preferable to form an aromatic ring, more preferably an aromatic ring having 6 to 20 carbon atoms, and an aromatic ring having 6 to 10 carbon atoms to be formed. It is particularly preferable to do this.
- R 9 , R 10 and R 11 each independently include a hydrogen atom; a halogen atom; or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom.
- These organic groups each having 1 to 20 carbon atoms 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 include those represented by the general formulas (1) and (2). Same as the case.
- R 9 , R 10 and R 11 are preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and particularly 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, preferably a methylene group.
- R 1 , X 1 , X 2 and L 1 are the same as those in the general formulas (1) and (2), and are bonded to each other alone and / or in any combination to form multidentate chelation. Although a ligand may be formed, it is preferred that X 1 , X 2 and L 1 do not form a multidentate chelating ligand and R 1 is a hydrogen atom.
- R 13 to R 21 are 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 that may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom include those represented by the general formulas (1) and (2). Same as the case.
- 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 they are a hydrogen atom or a halogen atom.
- the amount of the metathesis polymerization catalyst used is preferably 0.005 mmol or more, more preferably 0.01 to 50 mmol, still more preferably 0.015 to 20 with respect to 1 mol of all cycloolefin monomers used in the reaction. Millimolar.
- the radical generator has a function of generating a radical by heating, thereby inducing a crosslinking reaction in the cycloolefin resin.
- the site where the radical generator induces a crosslinking reaction is mainly a carbon-carbon double bond of the cycloolefin resin, but crosslinking may occur even in a saturated bond portion.
- radical generators include organic peroxides, diazo compounds, and nonpolar radical generators.
- organic peroxides include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide; dialkyl such as di-t-butyl peroxide, dicumyl peroxide, and t-butylcumyl peroxide.
- diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide
- 2,5-dimethyl-2,5-di (t-butylperoxy) hexane 2,5-dimethyl-2,5-di (t-butylperoxy) Peroxyketals such as 3-hexyne and 1,3-di (t-butylperoxyisopropyl) benzene
- peroxyesters such as t-butylperoxyacetate and t-butylperoxybenzoate
- Alkylsilyl peroxides such as t- butyl trimethylsilyl peroxide
- Rukarubonato di peroxycarbonate such as (isopropyl peroxy) dicarbonate, and the like.
- dialkyl peroxides are particularly preferable in that there are few obstacles to the metathesis polymerization reaction in bulk polymerization.
- diazo compound examples include 4,4′-bisazidobenzal (4-methyl) cyclohexanone, 4,4′-diazidochalcone, 2,6-bis (4′-azidobenzal) cyclohexanone, and 2,6-bis.
- Nonpolar 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, Examples include 1,1-triphenyl-2-propene, 1,1,1-triphenyl-4-pentene, 1,1,1-triphenyl-2-phenylethane, and the like.
- 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 with respect to 100 parts by mass of the total cycloolefin monomer used. If the amount of radical generator is too small, the crosslinking reaction becomes insufficient and the bending strength of the composite material is lowered. On the other hand, if the amount of radical generator is too large, the crosslinking reaction becomes excessive and the composite material tends to become brittle.
- Diisocyanate compound examples include methylene diphenyl 4,4′-diisocyanate (MDI), toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, and 4-isopropyl-1,3-phenylene.
- MDI methylene diphenyl 4,4′-diisocyanate
- toluene-2,4-diisocyanate 4-methoxy-1,3-phenylene diisocyanate
- 4-isopropyl-1,3-phenylene 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 Of aromatic diisocyanates such as 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, and 4,4'-diisocyanate dibenzyl Aliphatic diisocyanate compounds such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate; 4-cyclohexylene diisocyanate, 4,4′-methylenebis (cyclohexyl) Isocyanates), 1,5-tetrahydronaphthalene
- those compounds having a polyfunctional isocyanate group in which these compounds are isocyanurate bodies, burette bodies, adduct bodies, or polymer bodies, and conventionally known ones can be used without particular limitation.
- dimer of 2,4-toluylene diisocyanate, triphenylmethane triisocyanate, tris- (p-isocyanatephenyl) thiophosphite polyfunctional aromatic isocyanate compound
- polyfunctional aromatic Examples include aliphatic isocyanate compounds, polyfunctional aliphatic isocyanate compounds, fatty acid-modified polyfunctional aliphatic isocyanate compounds, polyfunctional block isocyanate compounds such as blocked polyfunctional aliphatic isocyanate compounds, and polyisocyanate prepolymers.
- aromatic diisocyanate compounds aliphatic diisocyanate compounds, and alicyclic diisocyanate compounds, which are polyfunctional non-blocked isocyanate compounds, are preferably used because of their excellent availability and ease of handling. These compounds can be used alone or in combination of two or more.
- the polyfunctional block type isocyanate compound is a compound in which at least two isocyanate groups in the molecule are reacted with an active hydrogen-containing compound so as to be inactive at room temperature.
- the isocyanate compound generally has a structure in which an isocyanate group is masked by a blocking agent such as alcohols, phenols, ⁇ -caprolactam, oximes, and active methylene compounds.
- a polyfunctional block type isocyanate compound generally has excellent storage stability because it does not react at room temperature, but an isocyanate group is usually regenerated by heating at 140 to 200 ° C. and can exhibit excellent reactivity.
- the active hydrogen reactive group in the molecule is a polyfunctional (meth) acrylate compound used together, preferably a hydroxyl group present in the polyfunctional (meth) acrylate compound, a hydroxyl group on the surface of the fibrous filler described later, cyclohexane It is considered that a chemical bond is formed with the hydroxyl group or the like of the olefin resin, and as a result, the adhesion between the cycloolefin resin and the fibrous filler is improved.
- Diisocyanate compounds may be used alone or in combination of two or more.
- the compounding amount of the diisocyanate compound in the polymerizable composition of the present invention is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and further preferably 2 with respect to 100 parts by mass of the total cycloolefin monomer. ⁇ 10 parts by mass. If it exists in this range, the adhesiveness of a fibrous filler and resin can be made compatible, controlling the intensity
- polyfunctional (meth) acrylate compound a polyfunctional (meth) acrylate compound is used from the viewpoint of improving the adhesiveness of the fibrous filler and improving the mechanical strength of the resulting composite material.
- a polyfunctional (meth) acrylate compound is used from the viewpoint of improving the adhesiveness of the fibrous filler and improving the mechanical strength of the resulting composite material.
- Preferred examples of the polyfunctional (meth) acrylate compound include the following general formula:
- polyfunctional acrylate compound examples include ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and neopentyl glycol dimethacrylate.
- the polyfunctional acrylate compounds may be used alone or in combination of two or more.
- the compounding amount of these compounds is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and further preferably 2 to 10 parts by mass with respect to 100 parts by mass of the total cycloolefin monomer used. is there. If it exists in this range, the function as an adhesive improvement agent or adhesiveness imparting agent of a diisocyanate compound will be synergistically improved, and the adhesiveness between the cycloolefin resin and the fibrous filler will be excellent, which is preferable.
- the polymerizable composition of the present invention may contain optional components such as an activator, an activity regulator, an elastomer, and an antioxidant.
- the activator is a compound that acts as a cocatalyst of the above-described metathesis polymerization catalyst and improves the polymerization activity of the catalyst.
- the activator include alkylaluminum halides such as ethylaluminum dichloride and diethylaluminum chloride; alkoxyalkylaluminum halides obtained by substituting a part of the alkyl groups of these alkylaluminum halides with alkoxy groups; organotin compounds; It is done.
- the amount of the activator used is not particularly limited, but is usually preferably 0.1 to 100 mol, more preferably 1 to 10 mol, relative to 1 mol of the total metathesis polymerization catalyst used in the polymerizable composition.
- the activity regulator is used to prevent polymerization from starting in the course of injection when preparing a polymerizable composition by mixing two or more reaction stock solutions and injecting into a mold to start polymerization. .
- examples of the activity regulator include compounds having an action of reducing the metathesis polymerization catalyst, alcohols, haloalcohols, Esters, ethers, nitriles and the like can be used. Of these, alcohols and haloalcohols are preferable, and haloalcohols are particularly preferable.
- alcohols include n-propanol, n-butanol, n-hexanol, 2-butanol, isobutyl alcohol, isopropyl alcohol, t-butyl alcohol and the like.
- haloalcohols include 1,3-dichloro-2-propanol, 2-chloroethanol, 1-chlorobutanol and the like.
- Lewis base compounds include Lewis base compounds containing phosphorus atoms such as tricyclopentylphosphine, tricyclohexylphosphine, triphenylphosphine, triphenylphosphite, n-butylphosphine; n-butylamine, pyridine, 4-vinylpyridine, acetonitrile, And Lewis base compounds containing nitrogen atoms such as ethylenediamine, N-benzylidenemethylamine, pyrazine, piperidine, imidazole, and the like.
- Norbornene substituted with an alkenyl group such as vinyl norbornene, propenyl norbornene and isopropenyl norbornene is not only a cycloolefin monomer but also an activity regulator. What is necessary is just to adjust the usage-amount of these activity regulators suitably with the compound to be used.
- the elastomer examples include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), and ethylene.
- SBR styrene-butadiene copolymer
- SBS styrene-butadiene-styrene block copolymer
- SIS styrene-isoprene-styrene copolymer
- EPDM ethylene-Propylene-diene terpolymer
- EVA ethylene-vinyl acetate copolymer
- the viscosity can be adjusted by dissolving the elastomer in the polymerizable composition.
- the impact resistance of the obtained composite material can be improved by adding an elastomer
- antioxidants include various antioxidants for plastics and rubbers such as phenols, phosphoruss, and amines.
- the polymerizable composition of the present invention is prepared by appropriately mixing the above components according to a known method, but is prepared by mixing two or more reaction stock solutions immediately before the reaction. Also good.
- the reaction stock solution is not bulk polymerized with only one liquid, but when all the liquids are mixed, each of the above components is divided into two or more liquids so that a polymerizable composition containing each component at a predetermined ratio is obtained.
- Examples of the combination of two or more reaction stock solutions include the following two types (a) and (b) depending on the type of metathesis polymerization catalyst used.
- a polymerizable composition is obtained by using a reaction stock solution (A) containing a cycloolefin monomer and an activator and a reaction stock solution (B) containing a cycloolefin monomer and a metathesis polymerization catalyst and mixing them. Can do.
- a reaction stock solution (solution C) containing a cycloolefin monomer and containing neither a metathesis polymerization catalyst nor an activator may be used in combination.
- reaction stock solution (i) a solution obtained by dissolving or dispersing a metathesis polymerization catalyst in a small amount of an inert solvent is usually used.
- 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; Examples include cyclic ethers such as tetrahydrofuran; diethyl ether, dichloromethane, dimethyl sulfoxide, ethyl acetate, and the like. Aromatic hydrocarbons are preferable, and toluene is particularly preferable.
- the radical generator, diisocyanate compound, polyfunctional (meth) acrylate compound and the optional component may be contained in any of the reaction stock solutions, or may be added in the form of a mixed solution other than the reaction stock solution. .
- the production method of the present invention can be carried out by applying a known resin molding method.
- an appropriate mixing device is selected according to the resin molding method to be applied. It is preferable to use.
- the apparatus include a collision mixing apparatus generally used in a reaction injection molding method, and a low pressure mixer such as a dynamic mixer and a static mixer.
- the reaction stock solution is introduced into these apparatuses, it is immediately mixed to form a polymerizable composition.
- the obtained polymerizable composition is directly injected into a mold.
- the production method of the present invention can be carried out by appropriately applying a known resin molding method depending on the desired shape of the composite material.
- the resin molding method include a reaction injection molding method (RIM method), a resin transfer molding method (RTM method), and an infusion molding method.
- step (1) a fibrous filler is placed in the mold.
- Fibrous filler The fibrous filler used in the present invention is not particularly limited as long as it is used in the field of the present invention. From the viewpoint of availability and usefulness, the fibrous filler is preferably at least one selected from the group consisting of carbon fiber and glass fiber. When carbon fiber and glass fiber are used in combination, the mixing ratio of the two is not limited, but from the viewpoint of the mixing effect, 0.1 to 10 parts by mass of glass fiber is preferable with respect to 1 part by mass of carbon fiber.
- the form of the fibrous filler used in the present invention is not particularly limited, and is appropriately selected from unidirectional materials in which the fibrous filler is aligned in one direction, woven fabric, nonwoven fabric, mat, knit, braided string, roving, chopped, etc. do it. Especially, it is preferable that it is a form of continuous fibers, such as a unidirectional material, a textile fabric, and a roving, and a unidirectional material is more preferable.
- the unidirectional material is suitable because it can highly improve the impregnation property of the polymerizable composition, and since the ratio of fibers is high, the mechanical strength of the resulting composite material can be highly improved.
- As the form of the woven fabric conventionally known woven fabrics can be used.
- woven structures in which fibers such as plain weave, satin weave, twill weave, and triaxial fabric are interlaced can be used.
- woven fabric not only two-dimensional but also a stitched woven fabric or a three-dimensional woven fabric in which fibers are reinforced in the thickness direction of the woven fabric can be used.
- the number of filaments in one fiber bundle yarn is not particularly limited, but is preferably 1,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 10,000 to 30. The range is 1,000.
- the carbon fiber used in the present invention is not particularly limited, and various carbon fibers produced by a conventionally known method such as acrylic, pitch, and rayon can be arbitrarily used.
- PAN-based carbon fiber produced using polyacrylonitrile fiber as a raw material does not inhibit the metathesis ring-opening polymerization reaction, and can improve properties such as mechanical strength and heat resistance in the obtained composite material. Can be used preferably.
- the carbon fiber preferably has a tensile elastic modulus in the range of 200 to 400 GPa, more preferably in the range of 220 to 300 GPa, as determined by a resin-impregnated strand tensile test (JIS R-7601). Moreover, as a carbon fiber, a thing with high tensile elongation is preferable.
- the tensile elongation is preferably 1.7% or more, more preferably 1.85% or more, and particularly preferably 2% or more.
- the tensile elongation of carbon fiber can be measured by the resin impregnated strand tensile test. The higher the tensile elongation of the carbon fiber, the stronger and easy to handle the fiber, and the higher the mechanical strength of the resulting composite material, which is preferable.
- an appropriate amount of an active hydrogen-containing group such as a carboxyl group or a hydroxyl group is present on the surface of the carbon fiber.
- the amount of the active hydrogen-containing group of the carbon fiber can be quantified by the surface oxygen concentration (O / C) measured by X-ray photoelectron spectroscopy.
- the amount of the active hydrogen-containing group of the carbon fiber is preferably 0.02 to 0.2 in O / C.
- the amount of the active hydrogen-containing group of the carbon fiber is O / C, more preferably 0.04 to 0.15, still more preferably 0.06 to 0.1.
- the method for introducing the active hydrogen-containing group into the carbon fiber is not particularly limited, and a commonly used method may be adopted as appropriate. Although there are an ozone method and electrolytic oxidation in an acid solution, the oxidation reaction in the solution is preferably economically excellent. At this time, the amount of the active hydrogen-containing group can be appropriately adjusted depending on the amount of current, temperature, residence time in the acidic bath, acidity, and the like.
- the surface state of the carbon fiber is not particularly limited, and may be smooth or uneven. Since the anchor effect can be expected, it is preferable that the surface is uneven. What is necessary is just to select the degree of this unevenness suitably.
- the introduction of irregularities on the carbon fiber surface can be performed simultaneously with the oxidation reaction in the solution described above, for example.
- the cross-sectional shape of the carbon fiber is not particularly limited, but is preferably substantially circular.
- the cross-sectional shape is circular, when the polymerizable composition is impregnated, rearrangement of the filaments is likely to occur, and the polymerizable composition can easily penetrate between the fibers. Further, it is possible to reduce the thickness of the fiber bundle, and there is an advantage that it is easy to obtain a composite material excellent in drapeability.
- the cross-sectional shape is substantially circular when the ratio of the circumscribed circle radius R to the inscribed circle radius r (R / r) of the cross section is defined as the degree of deformation. 1 or less.
- the length of the carbon fiber may be appropriately selected according to the use, and any of short fibers and long fibers can be used. From the viewpoint of further increasing the mechanical strength of the resulting composite material, the length of the carbon fiber is usually 1 cm or more, preferably 2 cm or more, more preferably 3 cm or more, and in particular, carbon fibers that are continuous fibers are used. preferable.
- the carbon fiber used in the present invention does not need to be pre-adhered with a sizing agent, but has a problem of deterioration in physical properties after molding due to fiber fluffing and adhesion between a cycloolefin polymer as a matrix resin and the carbon fiber. From the viewpoint of further improvement, it is preferable to use carbon fibers formed by previously attaching a sizing agent.
- the sizing agent is not particularly limited, and a known sizing agent can be used.
- the sizing agent include at least one selected from the group consisting of epoxy resins; urethane resins; vinyl ester resins; polyamide resins; nylon resins, polyolefin resins such as polyethylene and polypropylene; polyester resins; it can.
- the sizing agent is preferably at least one selected from the group consisting of an epoxy resin, a urethane resin, a vinyl ester resin, and a polyolefin resin because it is easily available, and more preferably an epoxy resin and / or a vinyl ester resin.
- sizing agents are all products manufactured by Matsumoto Yushi Seiyaku Co., Ltd., such as KP-226, KP-0110, KP-136, KP-300, KP-752, and KP-1005.
- Sizing agent made of resin Sizing agent made of urethane resin such as KP-2816, KP-2817, KP-2807, KP-2820, and KP-2821; Vinyl ester resin such as KP-371 and KP-372 Sizing agent consisting of nylon resin such as KP-1008; Sizing agent consisting of polyethylene resin such as P-138; Sizing agent consisting of polypropylene resin such as TPE-100 and TPE-102; KP-880 and KP Sizing agent made of polyester resin, such as -881.
- the adhesion of the sizing agent to the carbon fiber can be performed by bringing the sizing agent into contact with the carbon fiber.
- the sizing agent is preferably dispersed or dissolved in water or an organic solvent such as acetone and used as a dispersion or solution. From the viewpoint of improving the dispersibility of the sizing agent and improving the liquid stability, it is preferable to appropriately add a surfactant to the dispersion or solution.
- the adhesion amount of the sizing agent to the carbon fiber is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, more preferably 100% by mass of the total amount of the carbon fiber and the sizing agent. 0.5-2% by mass. If the adhesion amount is within this range, moderate convergence of the carbon fiber can be obtained, sufficient abrasion resistance of the carbon fiber can be obtained, and generation of fluff due to mechanical friction can be suppressed. Impregnation improves, and mechanical strength can be improved in the resulting composite material.
- the contact between the carbon fiber and the sizing agent can be appropriately performed by a generally industrially used method such as a roller dipping method or a roller contact method. Since the contact between the carbon fiber and the sizing agent is usually performed using a dispersion or solution of the sizing agent, it is subjected to a drying step after the contact, and water contained in the dispersion or solution of the sizing agent, or What is necessary is just to remove an organic solvent.
- the drying step can be performed by a method using hot air, a hot plate, a roller, various infrared heaters or the like as a heat medium.
- the sizing agent is preferably attached to the carbon fiber after the introduction of the active hydrogen-containing group or the unevenness on the surface of the carbon fiber.
- the glass fiber used in the present invention is not particularly limited, and examples thereof include those having shapes such as continuous fiber, woven fabric and non-woven fabric, and various thicknesses are commercially available.
- the shape and thickness of the glass fiber can be appropriately selected according to the use of the obtained composite material.
- the basis weight of the glass fiber used in the present invention is appropriately selected according to the purpose of use, but is preferably 600 g / m 2 or more, more preferably 600 to 2000 g / m 2 , and even more preferably 640 to 1800 g / m 2. . If the basis weight of the glass fiber is excessively small, a gap is formed between adjacent glass fibers, resulting in insufficient mechanical strength of the composite material. On the other hand, if the basis weight is excessively large, flexibility is obtained. There exists a tendency for it to fall or the location where the adjacent glass fiber overlaps, and to impair the impregnation property of polymeric composition.
- the glass fiber is preferably subjected to a hydrophobic treatment on the surface.
- a hydrophobic treatment on the surface.
- the glass fibers can be uniformly dispersed in the resulting composite material, the rigidity and dimensional stability of the composite material can be made uniform, and the anisotropy can be reduced. be able to.
- the treating agent used for the hydrophobizing treatment include silane coupling agents, titanate coupling agents, aluminum coupling agents, fatty acids, fats and oils, surfactants, waxes, and other polymers. These treatment agents can also function as sizing agents.
- the mold to be used may be appropriately selected according to the resin molding method to be applied in consideration of the desired shape of the composite material.
- the mold used for molding does not necessarily need to be a highly rigid and expensive mold, and is limited to a metal mold. Instead, a resin mold or a simple mold can be used.
- the fibrous filler may be appropriately placed in a selected mold in a manner suitable for carrying out the method according to the resin molding method to be applied [step (1)].
- the inside of the mold may be appropriately replaced with an inert gas such as nitrogen gas, or the inside of the mold may be decompressed.
- step (2) a predetermined polymerizable composition is impregnated into a fibrous filler placed in a mold.
- a split mold structure that is, a mold having a core mold and a cavity mold is usually used.
- the core mold and the cavity mold are produced so as to form a void (cavity) that matches the shape of the desired composite material.
- the fibrous filler is placed in the gap of the mold.
- the impregnation of the polymerizable composition into the fibrous filler is performed by injecting the polymerizable composition into a mold. Since the polymerizable composition of the present invention has a low viscosity and excellent impregnation into a substrate, the fibrous filler can be uniformly impregnated.
- the pressure for injecting the raw material (polymerizable composition) into the mold at the time of molding is about 1/30 to 1/500 of the injection molding for injecting the resin. For this reason, the filling property into the mold is very good, and various shapes can be easily formed. Since the injection pressure into the mold is very small, the internal pressure generated in the mold is also very small, which greatly reduces the strength required for the mold compared to the mold used for injection molding. This makes it easier to design the mold. Therefore, it is easy to design a mold for a large molded product, and it is easy to develop a large-diameter piping member in which it is difficult to deploy the resin-made piping member. Moreover, it has the characteristic that shaping
- the filling pressure (injection pressure) when filling the polymerizable composition into the mold cavity is usually 0.01 to 10 MPa, preferably 0.02 to 5 MPa.
- the mold clamping pressure is usually in the range of 0.01 to 10 MPa.
- RTM resin transfer molding
- a fibrous composition is impregnated with a polymerizable composition by injecting the polymerizable composition into a laminated mold laid with a fibrous filler.
- the RTM method does not require mixing pressure as much as the RIM method when mixing the reaction stock solution. Is possible. Further, since the polymerization rate is generally slower than that of the RIM method, it is often advantageous in terms of impregnation.
- the filling pressure (injection pressure) when filling the polymerizable composition into the mold cavity is usually 0.01 to 10 MPa, preferably 0.02 to 5 MPa.
- the mold clamping pressure is usually in the range of 0.01 to 10 MPa.
- a polymerizable composition is filled into a mold by vacuum pressure (about 0.1 to 100 Pa) and impregnated into a fibrous filler.
- the fibrous filler is placed on the mold, and the fibrous filler is covered with an airtight film and an adhesive sealant in a state where a release sheet and a resin diffusing material are disposed as desired.
- the air in the space is sucked and exhausted to reduce the pressure.
- the polymerizable composition is injected into the airtight space, and the fibrous filler is impregnated with the polymerizable composition.
- This method not only requires half the mold to cover one side with an air-tight film, but it is also a molding method that does not become dirty and has no odor, and can be used for molding high-strength molded products such as large molded products and thick molded products. Is suitable. It is preferable that the release sheet, the resin diffusing material, the airtight film, the sealant, and the polymerizable compounding solution inlet are not easily dissolved in the polymerizable composition during molding as the outermost layer on the side in contact with the compounded solution.
- Examples of the material for the outermost layer on the polymerizable composition side include polyethylene, polypropylene, nylon, polyethylene terephthalate, polyethylene naphthalate, polymethyl (meth) acrylate, silicone resin, and the like, and metal members can also be used.
- a light-resin transfer molding (L-RTM) molding method can also be applied to the production method of the present invention as an improved method.
- L-RTM light-resin transfer molding
- a fibrous filler is placed on the concave mold of the mold composed of irregularities, covered with the convex mold, the outer flange part and the mold Depressurize at the center.
- the inside of the mold is vacuumed (about 0.1 to 100 Pa), the mold is clamped, the polymerizable composition is injected from the outer periphery, and the fibrous filler is impregnated with the composition. Excess polymerizable composition accumulates in the pot in the middle of the mold.
- the polymerizable composition is pushed from the outer periphery, and the injection of the composition is performed by depressurization and pressurization.
- the filling pressure (injection pressure) when filling the polymerizable composition into the cavity of the mold is usually 0.01 to 10 MPa, preferably 0.02 to 5 MPa.
- the mold clamping pressure is usually in the range of 0.01 to 10 MPa.
- impregnation methods for example, a filament winding method or the like in which a fibrous filler is wound in a dry state is prepared, and the fibrous filler is immersed in the polymerizable composition.
- a method of impregnating the composition a method of spraying a polymerizable composition onto the fibrous filler and impregnating the composition, and an individual reaction stock solution in combination with the reaction stock solution with respect to the fibrous filler. These can be sprayed separately, and the reaction stock solution is mixed simultaneously with spraying to impregnate the polymerizable composition.
- the quantitative relationship between the polymerizable composition impregnated in the fibrous filler and the fibrous filler is that the fibrous filler is 0.6 to 4 parts by mass with respect to 1 part by mass of the polymerizable composition.
- the amount is preferably 0.8 to 3 parts by mass, more preferably 1 to 2 parts by mass. If it exists in this range, the bending strength of the composite material obtained will be exhibited suitably, and it is suitable.
- the polymerizable composition may be poured into a mold and impregnated into a fibrous filler and maintained as it is for a predetermined time.
- the maintenance time is usually preferably about 1 to 200 minutes.
- step (3) the polymerizable composition impregnated in the fibrous filler is subjected to bulk polymerization to obtain a composite material in which the polymerizable composition is cured.
- Bulk polymerization is performed by heating a mold into which a polymerizable composition is injected.
- the maximum temperature is preferably 90 ° C. or higher and 300 ° C. or lower.
- the maximum temperature is more preferably 100 to 270 ° C., further preferably 120 to 250 ° C.
- the minimum temperature during bulk polymerization is preferably 40 to 90 ° C, more preferably 50 to 85 ° C.
- the starting temperature of bulk polymerization is usually in the range of 0 to 40 ° C, preferably in the range of 10 to 30 ° C.
- the bulk polymerization is preferably completed in 20 seconds to 60 minutes, more preferably 20 seconds to 40 minutes after the polymerizable composition is injected into a mold or the reaction stock solution is introduced into a predetermined mixing apparatus. Alternatively, it may be maintained for about 60 to 200 minutes. Further, the heating may be performed in one stage or in a plurality of stages including two or more stages.
- the mold temperature is preferably 60 to 110 ° C., more preferably 70 to 100 ° C.
- the heating time is preferably 10 to 120 minutes, more preferably 20 to A mode in which the second stage heating is performed for 100 minutes
- the mold temperature is preferably 111 to 250 ° C., more preferably 120 to 200 ° C.
- the heating time is preferably 10 to 120 minutes, more preferably 20 to 100 minutes.
- the composite material After completion of bulk polymerization, for example, the composite material can be obtained by opening the mold and removing the mold [step (4)].
- demolding means taking out the obtained composite material from the used mold. Since the composite material immediately after production is in a high temperature state, it is preferable to perform demolding after cooling to room temperature.
- the composite material of the present invention is obtained as described above. That is, the composite material of the present invention is obtained by curing a polymerizable composition containing a cycloolefin monomer, a metathesis polymerization catalyst, a radical generator, a diisocyanate compound and a polyfunctional (meth) acrylate compound impregnated in a fibrous filler. is there.
- the strength of the composite material of the present invention can be evaluated as the bending strength of the composite material in a direction substantially perpendicular to the filling direction of the fibrous filler. A specific evaluation method is as described later.
- a composite material having, for example, 60 MPa or more as the bending strength at 23 ° C. is preferable because it can be evaluated as a composite material having sufficient mechanical strength.
- a composite material having a bending strength in the substantially vertical direction of 65 MPa or more is more preferable, and a composite material having 70 MPa or more is more preferable.
- the bending strength in the substantially vertical direction is significantly reduced.
- the composite material of the present invention is produced using the polymerizable composition of the present invention having specific components, the odor generated from the composite material is suppressed. Therefore, according to the present invention, it is possible to greatly improve the working environment of the person engaged in the manufacture of the composite material.
- the presence or absence of the odor of the composite material can be determined, for example, by evaluation by a plurality of panelists described later.
- the amount of the fibrous filler in the composite material of the present invention is preferably 40 to 85% by mass, more preferably 45 to 80% by mass, and still more preferably 50 to 65% by mass. If the amount of the fibrous filler is within such a range, the desired bending strength is sufficiently exhibited by the composite material.
- the amount of the fibrous filler in the composite material of the present invention is It can be calculated from the filling amount of the fibrous filler, the filling amount of the polymerizable composition, or the specific gravity of the composite material.
- Example 1 Infusion molding method A unidirectional carbon fiber (U-200C) manufactured by Nissei Co., Ltd. cut into a 250 mm long and 200 mm wide chrome-plated SS400 flat plate having an inner length of 300 mm and a width of 250 mm subjected to a release treatment. ) (Weight per unit area: 200 g / m 2 ) was laminated in the same direction to obtain a fibrous filler. With the release sheet and the resin diffusing material disposed, the fibrous filler was covered with an airtight film and an airtight sealant to form an airtight space. The inside of the airtight space was reduced to 100 Pa using an oil pump to obtain an integral body.
- the fibrous filler used here is a unidirectional material because unidirectional materials are laminated in the same direction.
- the mold was set to 40 ° C.
- the decompression line and the composition introduction line were closed, and the mold was left for 1 hour.
- the mold was heated to 90 ° C. and allowed to stand for 0.5 hour, and further heated to 200 ° C. and left for 1 hour.
- the composition of the RIM monomer is composed of about 90 parts by mass of dicyclopentadiene and about 10 parts by mass of tricyclopentadiene.
- the amount of the metathesis polymerization catalyst used is 0.055 with respect to 1 mol of all the cycloolefin monomers. Mmol.
- the cured composite material was demolded.
- the odor was determined to be “none”.
- the bending strength in the 0 ° direction of the obtained composite material was measured at 23 ° C. in accordance with JIS K7017. As a result, it was 1440 MPa. Furthermore, the result of measuring the bending strength in the 90 ° direction under the same conditions was 82 MPa. Production conditions and evaluation results are shown in Tables 1 and 2.
- Examples 2 to 5 A composite material was produced in the same manner as in Example 1 except that the production conditions were changed as shown in Table 1. Production conditions and evaluation results are shown in Tables 1 and 2.
- the composite materials of the present invention produced by the method of the examples are all odorless and have a desired bending strength in the 90 ° direction (substantially vertical direction) and have excellent mechanical strength. It turns out that.
- the composite material produced by the method that did not use the diisocyanate compound (Comparative Example 1) had an odor, although the bending strength in the substantially vertical direction exceeded 60 MPa.
- the composite material produced by the method not using TMPT of the polyfunctional acrylate compound had no odor, the bending strength in the substantially vertical direction was much less than 60 MPa. Met.
- the composite material obtained by the production method of the present invention is excellent in mechanical strength, it is generally used in fields where composite materials of fibrous fillers such as glass fibers and carbon fibers are used, such as moving bodies and moving bodies. It can use suitably for the housing
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Abstract
Description
〔1〕シクロオレフィンモノマー、メタセシス重合触媒、ラジカル発生剤、ジイソシアネート化合物及び多官能(メタ)アクリレート化合物を含む重合性組成物;
〔2〕繊維状充填材に含浸した前記〔1〕記載の重合性組成物が硬化した複合材料;
〔3〕型内に繊維状充填材を載置する工程(1)、
前記〔1〕記載の重合性組成物を該繊維状充填材に含浸させる工程(2)、
繊維状充填材に含浸させた該重合性組成物を塊状重合させて、該重合性組成物が硬化した複合材料を得る工程(3)、並びに
該複合材料を脱型する工程(4)、を含む、前記〔2〕に記載の複合材料の製造方法;に関するものである。
型内に繊維状充填材を載置する工程(1)、
本発明の重合性組成物を該繊維状充填材に含浸させる工程(2)、
繊維状充填材に含浸させた該重合性組成物を塊状重合させて、該重合性組成物が硬化した複合材料を得る工程(3)、並びに
該複合材料を脱型する工程(4)、を含む方法である。
本発明の重合性組成物は、シクロオレフィンモノマー、メタセシス重合触媒、ラジカル発生剤、ジイソシアネート化合物及び多官能(メタ)アクリレート化合物、並びに所望により配合される任意成分を、公知の方法に従って、適宜混合することにより調製される。
シクロオレフィンモノマーは、分子内に脂環式構造と炭素-炭素二重結合とを有する化合物である。
テトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-エチリデンテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-フェニルテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、テトラシクロ[6.2.1.13,6.02,7]ドデカ-9-エン-4-カルボン酸、テトラシクロ[6.2.1.13,6.02,7]ドデカ-9-エン-4,5-ジカルボン酸無水物などのテトラシクロドデセン類;
2-ノルボルネン、5-エチリデン-2-ノルボルネン、5-ビニル-2-ノルボルネン、5-フェニル-2-ノルボルネン、アクリル酸5-ノルボルネン-2-イル、メタクリル酸5-ノルボルネン-2-イル、5-ノルボルネン-2-カルボン酸、5-ノルボルネン-2,3-ジカルボン酸、5-ノルボルネン-2,3-ジカルボン酸無水物などのノルボルネン類;
7-オキサ-2-ノルボルネン、5-エチリデン-7-オキサ-2-ノルボルネンなどのオキサノルボルネン類;
テトラシクロ[9.2.1.02,10.03,8]テトラデカ-3,5,7,12-テトラエン(1,4-メタノ-1,4,4a,9a-テトラヒドロ-9H-フルオレンともいう)、ペンタシクロ[6.5.1.13,6.02,7.09,13]ペンタデカ-4,10-ジエン、ペンタシクロ[9.2.1.02,10.03,8]ペンタデカ-5,12-ジエン、トリシクロペンタジエンなどの四環以上の環状オレフィン類;などが挙げられる。
なお、本発明の重合性組成物には、本発明の効果の発現が阻害されない限り、上述したシクロオレフィンモノマーと共重合可能な任意のモノマーが含まれていてもよい。
本発明に用いられるメタセシス重合触媒は、シクロオレフィンモノマーを開環重合できるものであれば特に限定されず、公知のものを使用することができる。
また、R3、R4、R5及びR6は任意の組合せで互いに結合して環を形成していてもよい。
また、ハロゲン原子、酸素原子、窒素原子、硫黄原子、リン原子又は珪素原子を含んでいてもよい炭素数1~20の有機基の具体例としては、上記一般式(1)及び(2)の場合と同様である。
R9、R10及びR11は、水素原子又は炭素数1~20のアルキル基であることが好ましく、水素原子又は炭素数1~3のアルキル基であることが特に好ましい。
R13は、好ましくは炭素数1~20のアルキル基、より好ましくは炭素数1~3のアルキル基であり、R14~R17は、好ましくは水素原子であり、R18~R21は、好ましくは水素原子又はハロゲン原子である。
ラジカル発生剤は、加熱によってラジカルを発生し、それによりシクロオレフィン系樹脂において架橋反応を誘起する作用を有する。ラジカル発生剤が架橋反応を誘起する部位は、主にシクロオレフィン系樹脂の炭素-炭素二重結合であるが、飽和結合部分でも架橋が生ずることがある。
ジイソシアネート化合物としては、例えば、4,4’-ジイソシアン酸メチレンジフェニル(MDI)、トルエン-2,4-ジイソシアネート、4-メトキシ-1,3-フェニレンジイソシアネート、4-イソプロピル-1,3-フェニレンジイソシアネート、4-クロル-1,3-フェニレンジイソシアネート、4-ブトキシ-1,3-フェニレンジイソシアネート、2,4-ジイソシアネートジフェニルエーテル、1,4-フェニレンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート(XDI)、1,5-ナフタレンジイソシアネート、ベンジジンジイソシアネート、o-ニトロベンジジンジイソシアネート、及び4,4’-ジイソシアネートジベンジルなどの芳香族ジイソシアネート化合物;メチレンジイソシアネート、1,4-テトラメチレンジイソシアネート、1,6-ヘキサメチレンジイソシアネート、及び1,10-デカメチレンジイソシアネートなどの脂肪族ジイソシアネート化合物;4-シクロヘキシレンジイソシアネート、4,4’-メチレンビス(シクロヘキシルイソシアネート)、1,5-テトラヒドロナフタレンジイソシアネート、イソホロンジイソシアネート、水添MDI、及び水添XDIなどの脂環式ジイソシアネート化合物;などや、これらのジイソシアネート化合物と低分子量のポリオールやポリアミンを、末端がイソシアネートとなるように反応させて得られるポリウレタンプレポリマー;などが挙げられる。また、これらの化合物をイソシアヌレート体、ビューレット体、アダクト体、又はポリメリック体とした、多官能のイソシアネート基を有するもので、従来使用されている公知のものが、特に限定なく使用できる。そのようなものとしては、例えば、2,4-トルイレンジイソシアネートの二量体、トリフェニルメタントリイソシアネート、トリス-(p-イソシアネートフェニル)チオフォスファイト、多官能芳香族イソシアネート化合物、多官能芳香族脂肪族イソシアネート化合物、多官能脂肪族イソシアネート化合物、脂肪酸変性多官能脂肪族イソシアネート化合物、ブロック化多官能脂肪族イソシアネート化合物などの多官能ブロック型イソシアネート化合物、ポリイソシアネートプレポリマーなどが挙げられる。これらの中でも、入手容易性、及び取り扱い容易性に優れることから、多官能非ブロック型イソシアネート化合物である、芳香族ジイソシアネート化合物、脂肪族ジイソシアネート化合物、及び脂環式ジイソシアネート化合物が好適に用いられる。
これらの化合物は、それぞれ単独で、あるいは2種以上を組み合わせて用いることができる。
さらに本発明においては、繊維状充填材の密着性を高め、得られる複合材料の機械的強度を向上させる観点から、多官能(メタ)アクリレート化合物を用いる。当該化合物をジイソシアネート化合物と共に用いることで、ジイソシアネート化合物の密着性向上剤又は密着性付与剤としての機能が相乗的に高められるものと推定される。
本発明の重合性組成物には、例えば、活性剤、活性調節剤、エラストマー及び酸化防止剤等の任意成分が含まれていても良い。
本発明の重合性組成物は、公知の方法に従って、上記各成分を適宜混合することにより調製されるが、反応直前に2以上の反応原液を混合することにより調製してもよい。当該反応原液は、1液のみでは塊状重合しないが、全ての液を混合すると、各成分を所定の割合で含む重合性組成物となるように、上記した各成分を2以上の液に分けて調製される。かかる2以上の反応原液の組み合わせとしては、用いるメタセシス重合触媒の種類により、下記(a)、(b)の二通りが挙げられる。
本発明の製造方法は、所望する複合材料の形状に応じて、適宜、公知の樹脂成型方法を適用して行うことができる。当該樹脂成型方法としては、例えば、反応射出成型法(RIM法)、レジントランスファー成型法(RTM法)及びインフュージョン成型法が挙げられる。
本発明に使用される繊維状充填材としては、本発明分野で使用されるものであれば特に限定されない。入手性および有用性の観点から、繊維状充填材としては、好ましくは、炭素繊維及びガラス繊維からなる群より選択される1種以上である。炭素繊維とガラス繊維とを併用する場合、両者の混合比率は限定されないが、混合効果の観点から、炭素繊維1質量部に対してガラス繊維0.1~10質量部が好ましい。
織物の形態としては、従来公知のものが利用可能であり、例えば、平織、繻子織、綾織、3軸織物などの繊維が交錯する織り構造の全てが利用できる。また、織物の形態としては、2次元だけでなく、織物の厚み方向に繊維が補強されているステッチ織物や3次元織物等も利用できる。
なお、炭素繊維へのサイジング剤の付着は、前記した、炭素繊維表面への活性水素含有基の導入や凹凸の導入の後に行うのが好ましい。
使用する型は、所望する複合材料の形状を考慮し、適用する樹脂成型方法に従って、適宜選択すればよい。本発明の製造方法では、低粘度の反応原液を用い、比較的低温低圧で成形できるため、成形に用いる型は、必ずしも剛性の高い高価な金型である必要はなく、金属製の型に限らず、樹脂製の型、または単なる型枠を用いることができる。
本法では、特に限定されないが、通常、割型構造、すなわち、コア型とキャビティー型を有する成形型が用いられる。コア型とキャビティー型は、所望する複合材料の形状にあった空隙部(キャビティー)を形成するように作製される。繊維状充填材は、該成形型の空隙部に載置される。重合性組成物の繊維状充填材への含浸は型内に重合性組成物を注入して行われる。本発明の重合性組成物は低粘度であり基材への含浸性に優れるので、繊維状充填材に均一に含浸させることができる。
RTM(レジントランスファーモールディング)法では、繊維状充填材を敷き詰めた合わせ型に重合性組成物を注入することにより、該組成物を繊維状充填材に含浸させる。
RTM法による成形は、RIM法と同様に型内に発生する圧力が小さいことに加え、反応原液を混合する際、RIM法ほど混合圧力を必要としないため、混合設備を比較的簡易化することが可能である。また、一般に重合の速度もRIM法よりも緩やかであることから含浸の面で有利となることが多い。
インフュージョン成形法では、真空圧(0.1~100Pa程度)によって、重合性組成物を型内に充填し、繊維状充填材に含浸させる。具体的には、成形型の上に繊維状充填材を置き、所望により、離型シート及び樹脂拡散材を配置した状態で、繊維状充填材を気密性フィルムと粘着性のシーラントで覆い、気密空間内の空気を吸引排気し、減圧状態にする。この減圧状態で、気密空間内に重合性組成物を注入して、重合性組成物を繊維状充填材に含浸させる。この方法は、片面を気密性フィルムで覆うため金型が半分で済むだけでなく、汚れない、臭気のない成形法で、大型成形品、厚物成形品等、高強度の成形品の成形に適している。離型シート、樹脂拡散材、気密性フィルム、シーラント、重合性配合液導入口は配合液に接する側の最外層として成形中重合性組成物に容易に溶解しないことが好ましい。これら重合性組成物側最外層の材質としてはポリエチレン、ポリプロピレン、ナイロン、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリメチル(メタ)アクリレート、シリコーン樹脂などが挙げられるほか、金属部材も用いることができる。
その他の含浸法として、例えば、フィラメントワインディング法などにより任意の円筒にドライの状態で繊維状充填材を巻き付けたものを用意し、該繊維状充填材を重合性組成物中に浸漬して該組成物を含浸させる方法、該繊維状充填材に対し重合性組成物をスプレーして該組成物を含浸させる方法、該繊維状充填材に対し前記反応原液の組み合わせで個々の反応原液を個別にスプレーし、スプレーと同時に反応原液を混合して重合性組成物を含浸させる方法などを用いることができる。
以上のようにして、本発明の複合材料が得られる。即ち、本発明の複合材料は、繊維状充填材に含浸した、シクロオレフィンモノマー、メタセシス重合触媒、ラジカル発生剤、ジイソシアネート化合物及び多官能(メタ)アクリレート化合物を含む重合性組成物が硬化したものである。本発明の複合材料の強度は、繊維状充填材の充填方向に対する該複合材料の略垂直方向の曲げ強度として評価することができる。具体的な評価方法は後述の通りである。
離型処理された内寸長さ300mm、幅250mmのクロムメッキSS400平板に、長さ250mm、幅200mmに切断した日精株式会社製一方向炭素繊維(U-200C)(目付200g/m2)を5枚同一方向に積層して繊維状充填材とした。離型シート及び樹脂拡散材を配置した状態で、繊維状充填材を気密性フィルムと気密シーラントで覆って気密空間を形成した。オイルポンプを用いて気密空間の内部を100Paまで減圧し、一体物を得た。ここで使用した繊維状充填材は、一方向材を同一方向に積層しているので、一方向材である。
表1に示すように製造条件を変更したこと以外は実施例1と同様の方法で複合材料を製造した。製造条件及び評価結果を表1及び2に示す。
表1に示すように製造条件を変更したこと以外は実施例1と同様の方法で複合材料を製造した。製造条件及び評価結果を表1及び2に示す。
一方、ジイソシアネート化合物を使用しなかった方法(比較例1)で製造された複合材料は、略垂直方向の曲げ強度は60MPaを超えていたものの、臭気が生じていた。さらに、多官能アクリレート化合物のTMPTを使用しなかった方法(比較例2~4)で製造された複合材料は、臭気は無かったものの、略垂直方向の曲げ強度はいずれも60MPaをはるかに下回るものであった。
得られた複合材料の臭気の有無を次のようにして評価した。
本発明分野の研究開発又は製造に数年以上従事する男性5名をパネラーに選んだ。上記の各実施例及び比較例において、200℃昇温1時間放置後、常温まで冷却した複合材料を取り出す際に、目、鼻腔、咽頭いずれかの粘膜に違和感を感じたかどうかについて、各パネラーに尋ねた。1名以上のパネラーが違和感を感じた場合、その複合材料は臭気「有り」と判定し、全てのパネラーが違和感を感じなかった場合、その複合材料は臭気「無し」と判定した。
Claims (7)
- シクロオレフィンモノマー、メタセシス重合触媒、ラジカル発生剤、ジイソシアネート化合物及び多官能(メタ)アクリレート化合物を含む重合性組成物。
- 繊維状充填材に含浸した請求項1又は2記載の重合性組成物が硬化した複合材料。
- 繊維状充填材が一方向材であり、該繊維状充填材の充填方向に対する前記複合材料の略垂直方向の曲げ強度が60MPa以上である、請求項3記載の複合材料。
- 繊維状充填材が炭素繊維及びガラス繊維からなる群より選択される1種以上である、請求項3又は4記載の複合材料。
- 型内に繊維状充填材を載置する工程(1)、
請求項1又は2記載の重合性組成物を該繊維状充填材に含浸させる工程(2)、
繊維状充填材に含浸させた該重合性組成物を塊状重合させて、該重合性組成物が硬化した複合材料を得る工程(3)、並びに
該複合材料を脱型する工程(4)、
を含む、請求項3~5いずれか1項に記載の複合材料の製造方法。 - 塊状重合時の最高温度が90℃以上300℃以下である、請求項6記載の製造方法。
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US16/069,288 US11053366B2 (en) | 2016-02-10 | 2017-01-16 | Polymerizable composition and composite material |
KR1020187024607A KR102685520B1 (ko) | 2016-02-10 | 2017-01-16 | 중합성 조성물 및 복합 재료 |
EP17750029.5A EP3415545B1 (en) | 2016-02-10 | 2017-01-16 | Polymerizable composition and composite material |
CN201780009356.3A CN108602940B (zh) | 2016-02-10 | 2017-01-16 | 聚合性组合物及复合材料 |
JP2017566558A JP6920218B2 (ja) | 2016-02-10 | 2017-01-16 | 重合性組成物及び複合材料 |
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JP2019089910A (ja) * | 2017-11-13 | 2019-06-13 | Rimtec株式会社 | 複合材料の製造方法 |
JP2019143024A (ja) * | 2018-02-20 | 2019-08-29 | 日本ゼオン株式会社 | 反応性組成物および熱可塑性エラストマー |
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KR102685520B1 (ko) | 2024-07-15 |
JP6920218B2 (ja) | 2021-08-18 |
EP3415545B1 (en) | 2021-11-10 |
US20190031846A1 (en) | 2019-01-31 |
EP3415545A4 (en) | 2019-10-09 |
CN108602940A (zh) | 2018-09-28 |
US20210292497A1 (en) | 2021-09-23 |
CN108602940B (zh) | 2020-09-01 |
KR20180104314A (ko) | 2018-09-20 |
EP3415545A1 (en) | 2018-12-19 |
US11053366B2 (en) | 2021-07-06 |
JPWO2017138304A1 (ja) | 2018-12-06 |
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