JP2009203433A - Fiber-reinforced resin and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a fiber-reinforced resin particularly excellent in mechanical strength, toughness and oxidation degradation resistance, with respect to a fiber-reinforced resin formed by polymerizing a polymerizable composition comprising a cycloolefin monomer and a group 10 transition metal compound in the presence of fabric. <P>SOLUTION: A fiber-reinforced resin formed by polymerizing a polymerizable composition comprising a cycloolefin monomer and a group 10 transition metal compound in the presence of fabric is used. The fiber-reinforced resin is obtained by polymerizing a polymerizable composition comprising a cycloolefin monomer and a group 10 transition metal compound in the presence of fabric. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a fiber reinforced resin obtained by polymerizing a cycloolefin monomer in the presence of a fiber material and a method for producing the same. More specifically, a fiber reinforced resin excellent in mechanical strength, toughness, and oxidation degradation resistance obtained by polymerizing a cycloolefin monomer in a fiber material in the presence of a Group 10 metal compound and the fiber reinforced resin can be easily produced. It relates to a manufacturing method.

  Cycloolefin monomers such as dicyclopentadiene have the property that large and complex shapes can be molded by a reaction molding method called RIM. For example, Patent Document 1 discloses a method in which dicyclopentadiene is polymerized and molded simultaneously in a mold using a metathesis polymerization catalyst composed of a Group 6 metal compound such as tungsten hexachloride and a co-catalyst such as alkylaluminum. It is disclosed. It has been reported that the molded body obtained by this method is useful for various applications including bumpers for automobiles because of excellent mechanical strength and toughness. However, the molded body obtained by this method is known to have a limited use due to the problem of oxidative degradation in high-temperature applications because metathesis polymerization introduces unsaturated bonds into the main chain.

  On the other hand, in Patent Document 2, a polymerizable composition composed of norbornene and a palladium-based catalyst which is a Group 10 metal compound is poured into a molding machine at 50 ° C. and reacted for 5 minutes to form a carbon-carbon double bond in the main chain. Disclosed is a method for obtaining a molded body that does not have any. The molded body obtained by this method has the advantage of being excellent in heat resistance in an oxygen atmosphere because it does not form a carbon-carbon double bond in the main chain, but has the disadvantage of poor mechanical strength and toughness.

  In Patent Document 3, an epoxy resin composition comprising an epoxy resin, an amine-based curing agent and a urea-based curing accelerator is thinly and evenly applied onto a release paper to produce a resin film, and then the resin film is A method is disclosed in which a fiber reinforced resin is obtained by laminating from both sides of a carbon fiber, impregnating the resin composition by heating and pressing to form a prepreg, laminating and curing in a molding die. However, the fiber reinforced resin obtained by this method is excellent in mechanical strength and oxidation deterioration resistance, but has a problem of poor toughness.

Japanese Patent Laid-Open No. 58-129013 JP-A-8-325329 JP 2004-99814 A

  The present invention relates to a fiber reinforced resin obtained by polymerizing a polymerizable composition containing a cycloolefin monomer and a Group 10 transition metal compound in the presence of a fiber material, and is particularly excellent in mechanical strength, toughness, and oxidation deterioration resistance. The object is to obtain a fiber reinforced resin.

  As a result of intensive studies in view of the above problems, the present inventors polymerized a polymerizable composition containing a cycloolefin monomer such as norbornene and a Group 10 transition metal compound such as paradium acetylacetonate in the presence of a reinforcing fiber material. Then, the fiber material can be polymerized without causing polymerization inhibition, and the polymerizable composition has excellent compatibility with carbon fibers, excellent mechanical strength and toughness, and excellent resistance to oxidation deterioration. It was found that a resin was obtained. In addition, it has been found that the use of organic fibers or carbon fibers, particularly carbon fibers, as the reinforcing fiber material provides a high balance of mechanical strength, toughness, and resistance to oxidation degradation. Furthermore, adding a crosslinking agent or an elastomer material to the polymerizable composition, or adding any of a phenol-based, amine-based, phosphorus-based, or sulfur-based anti-aging agent will prevent the polymerization of the cycloolefin monomer from being inhibited. It has been found that the strength, toughness and oxidation resistance are further improved. The present inventor has completed the present invention based on these findings.

  Thus, according to the present invention, there is provided a fiber reinforced resin obtained by polymerizing a polymerizable composition containing a cycloolefin monomer and a Group 10 transition metal compound in the presence of a fiber material.

  According to the present invention, there is also provided a method for producing a fiber reinforced resin, wherein a polymerizable composition containing a cycloolefin monomer and a Group 10 transition metal compound is polymerized in the presence of a fiber material.

  ADVANTAGE OF THE INVENTION According to this invention, the fiber reinforced resin containing the cycloolefin resin excellent in mechanical strength, toughness, and oxidation deterioration resistance can be obtained easily. In addition, the fiber reinforced resin of the present invention is excellent in mechanical strength, toughness, and oxidation deterioration resistance characteristics, and therefore, as a material for a wide range of uses such as components for automobiles and aircraft, sports equipment such as golf shafts, and building materials. It can be suitably used.

(Cycloolefin monomer)
The cycloolefin monomer used in the present invention is a compound having a ring structure formed of carbon atoms and having a carbon-carbon double bond in the ring. Examples thereof include norbornene monomers and monocyclic cycloolefins, and norbornene monomers are preferred.

  The norbornene-based monomer is a monomer containing a norbornene ring. The norbornene-based monomer is not particularly limited, and examples thereof include bicyclic compounds such as 2-norbornene and norbornadiene, tricyclic compounds such as dicyclopentadiene and dihydrodicyclopentadiene, tetracyclododecene, and ethylidenetetracyclododecene. , Tetracycles such as phenyltetracyclododecene, pentacycles such as tricyclopentadiene, heptacycles such as tetracyclopentadiene, and alkyl substituents thereof (methyl, ethyl, propyl, butyl substituents, etc.), alkylidene Substituted (eg, ethylidene substituted), aryl substituted (eg, phenyl, tolyl substituted), epoxy group, methacryl group, hydroxyl group, amino group, carboxyl group, cyano group, halogen group, ether group, ester bond contained Derivatives having polar groups such as It is.

  Examples of the monocyclic cycloolefin include monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclooctene, cyclododecene, and 1,5-cyclooctadiene, and derivatives having a substituent.

  These cycloolefin monomers can be used alone or in combination of two or more.

(Group 10 transition metal compounds)
As the Group 10 transition metal compound used in the present invention, a compound containing a Group 10 transition metal element of the periodic table (IUPAC Inorganic Chemical Nomenclature Revised Edition, 1989; long-period type) is exceptional. There is no limitation. Examples of the Group 10 transition metal element include nickel, palladium, platinum and the like, preferably nickel and palladium, and more preferably palladium. Examples of the compound containing a Group 10 transition metal element include nickel inorganic acid salts such as nickel chloride, nickel sulfate and nickel perchlorate; nickel organic acid salts such as nickel acetate and nickel oxalate; nickel acetylacetate Nickel complexes such as nitrates and nickel phthalocyanines; inorganic acid salts of palladium such as palladium chloride, palladium bromide, palladium iodide, palladium sulfate and palladium nitrate; organic acid salts of palladium such as palladium acetate and paradium trifluoroacetate; palladium acetyl Acetonate, bis (allyl) palladium, dichloro (1,5-cyclooctadiene) palladium, dichlorobis (acetonitrile) palladium, dichlorobis (benzonitrile) palladium, carbonyltris (triphenylphosphine) palladium, Chlorobis (triethylphosphine) palladium, diacetbis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, dichloro [1,2-bis (diphenylphosphino) ethane] palladium, bis [1,2-bis (diphenylphosphino) ) Ethane] palladium complexes such as palladium, tetraamine palladium nitrate, tetrakis (acetonitrile) palladium tetrafluoroborate; platinum inorganic salts such as platinum chloride and platinum iodide; platinum complexes such as platinum acetylacetonate Of these, inorganic salts, organic acid salts and complexes of palladium are preferable, and complex compounds of palladium are particularly preferable.

  These Group 10 transition metal compounds can be used alone or in combination of two or more. The amount of the Group 10 transition metal compound is appropriately selected depending on the intended use, but is usually 0.00001 to 1 mol%, preferably 0.0001 to 0.1 mol%, based on the cycloolefin monomer. It is a range.

(Polymerizable composition)
The polymerizable composition used in the present invention contains the cycloolefin monomer and the Group 10 transition metal compound as essential components, and if necessary, a crosslinking agent, an elastomer material, an anti-aging agent, and other additives. Can be added.

  The polymerizable composition used in the present invention is preferable because it contains a cross-linking agent and can improve the mechanical strength and toughness to a higher degree without impairing the oxidation deterioration resistance. The crosslinking agent is not particularly limited as long as it can crosslink the polymer, but a radical generator is usually used. Examples of the radical generator include organic peroxides, diazo compounds, and nonpolar radical generators, with organic peroxides and nonpolar radical generators being preferred.

  Examples of the organic peroxide include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide; dicumyl peroxide, t-butylcumyl peroxide, α, α′-bis (t- Butylperoxy-m-isopropyl) benzene, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, 2,5-dimethyl-2,5-di ( dialkyl peroxides such as t-butylperoxy) hexane; diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; 2,2-di (t-butylperoxy) butane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -2-methyl Peroxyketals such as chlorocyclohexane and 1,1-di (t-butylperoxy) cyclohexane; peroxyesters such as t-butylperoxyacetate and t-butylperoxybenzoate; t-butylperoxyisopropylcarbonate, di (isopropylperoxy) ) Peroxycarbonates such as dicarbonate; alkylsilyl peroxides such as t-butyltrimethylsilyl peroxide; and the like. Of these, dialkyl peroxides and peroxyketals are preferred in that they have little obstacle to the polymerization reaction.

  Examples of the diazo compound include 4,4'-bisazidobenzal (4-methyl) cyclohexanone and 2,6-bis (4'-azidobenzal) cyclohexanone.

  Nonpolar radical generators include 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 1,1,2-triphenylethane, 1,1,1- And triphenyl-2-phenylethane.

  These crosslinking agents can be used alone or in combination of two or more. The amount of the crosslinking agent used is usually in the range of 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the cycloolefin monomer. .

  The polymerizable composition used in the present invention is preferable because the toughness can be remarkably improved by adding an elastomer material.

  Examples of the elastomer material include natural rubber, polyisoprene, polybutadiene, styrene-butadiene copolymer, chloroprene, acrylonitrile-butadiene copolymer, styrene-isoprene-styrene block copolymer, and styrene-butadiene-styrene block copolymer. , Ethylene-propylene copolymer, ethylene-propylene-diene terpolymer, ethylene-vinyl acetate copolymer, and hydrogenated products thereof.

  These elastomer materials can be used alone or in combination of two or more. The amount used is usually in the range of 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight, and more preferably 3 to 30 parts by weight with respect to 100 parts by weight of the cycloolefin monomer.

  The polymerizable composition used in the present invention is at least one selected from the group consisting of a phenol-based anti-aging agent, an amine-based anti-aging agent, a phosphorus-based anti-aging agent and a sulfur-based anti-aging agent as an anti-aging agent. Addition of an anti-aging agent is preferable because the oxidation deterioration resistance of the resulting fiber reinforced resin can be highly improved without inhibiting the polymerization reaction. Among these, a phenolic antiaging agent and an amine antiaging agent are preferable, and a phenolic antiaging agent is particularly preferable.

  A phenolic anti-aging agent is an anti-aging agent having a phenol skeleton in the molecule. The phenolic anti-aging agent is not particularly limited as long as it is a substance usually used in the general resin industry. For example, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5- Methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-amyl-6- (1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate, 3,5- Di-t-butyl-4-hydroxyanisole, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2′-methylene-bis (4-methyl-6-t-) Butylphenol), 4,4'-butylidene-bis (6-tert-butyl-m-cresol), 3,9-bis (2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) Propi Nyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, tetrakis (methylene-3- (3 ′, 5′-di-t-butyl-4 ′) -Hydroxyphenylpropionate) methane [i.e. pentaerythrmethyl-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenylpropionate)], 6- (4-hydroxy-3-methyl- 5-t-butylanilino) -2,4-bisoctylthio-1,3,5-triazine, 2-octylthio-4,6-bis- (3,5-di-t-butyl-4-oxyanilino) -1 , 3,5-triazine and the like.

  An amine anti-aging agent is an anti-aging agent having an amino group in the molecule. The amine-based anti-aging agent is not particularly limited as long as it is a substance usually used in the general resin industry. For example, 1- [2- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionyloxy] ethyl] -4- [3-3,5-di-tbutyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 2- (3,5 Having a piperidine skeleton in the molecule, such as -di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid-bis- (1,2,2,6,6-pentamethyl-4-piperidyl) Etc.

  The phosphorus-based anti-aging agent is an anti-aging agent having a phosphorus atom in the molecule. The phosphorus anti-aging agent is not particularly limited as long as it is usually used in the general resin industry. For example, triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) Phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 9 , 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl phosphite), tetrakis (2 , 4-Di-t-butylphenyl) -4,4′-biphenylene diphosphite, cyclic Tetraylbis (isodecyl phosphite), and the like.

  The sulfur-based anti-aging agent is an anti-aging agent having a sulfur atom in the molecule. Examples of the sulfur aging inhibitor include dilauryl 3,3-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3-thiodipropionate, lauryl stearyl 3,3-thiodiprote. Pionate, pentaerythritol-tetrakis- (β-lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, etc. Can be mentioned.

  These anti-aging agents can be used alone or in combination of two or more. The amount of the anti-aging agent is appropriately selected according to the purpose of use, but is usually 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, based on 100 parts by weight of the cycloolefin monomer. Preferably it is the range of 0.01-1 weight part.

  Examples of other additives include promoters, flame retardants, fillers, colorants, light stabilizers, pigments, foaming agents, and polymer modifiers.

  The promoter is not particularly limited as long as it is a compound that interacts with the Group 10 transition metal compound to generate a polymerization active species for the cycloolefin monomer. Examples of such compounds include alkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, and triisobutylaluminum; aluminumoxy compounds such as methylaluminoxane; dimethylaluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, and methylaluminum dichloride. Lewis containing halogen atoms such as ethylaluminum dichloride, zinc chloride, silicon tetrachloride, tin tetrachloride, aluminum chloride, aluminum bromide, aluminum iodide, boron trichloride, boron trifluoride, phenylboron dichloride, gallium chloride Acid; triethylammonium tetraphenylborate, dimethylanilinium tetraphenylborate, triethylammonium tetra Trimethylsulfonium phenylborate, triethylammonium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) dimethylanilinium, trimethylsulfonium tetraborate (borafluorophenyl) borate, trityl tetra (pentafluorophenyl) borate, ferrocenium tetraphenylborate, tetra And compounds that react with transition metals such as (pentafluorophenyl) borate ferrocenium and tetraphenylborate (tetraphenylporphyrin manganese) to form ionic complexes. These promoters can be used alone or in combination of two or more.

  Examples of the flame retardant include a phosphorus flame retardant, a nitrogen flame retardant, a halogen flame retardant, a metal hydroxide flame retardant such as aluminum hydroxide, and an antimony compound such as antimony trioxide.

  The filler is not particularly limited. For example, calcium carbonate, aluminum hydroxide, magnesium carbonate, sodium hydrogen carbonate, clay, talc, kaika, silica, kaolin, fly ash, montmorillonite, glass balloon, silica balloon, thermal expansion. The vinylidene chloride particles are preferably used. As the colorant, dyes, pigments and the like are used. There are various kinds of dyes, and known ones may be appropriately selected and used.

  These other additives can be used alone or in combination of two or more, and the amount used is appropriately selected within a range not impairing the effects of the present invention.

  The polymerizable composition used in the present invention can be obtained by mixing the above components. As a mixing method, a conventional method may be followed. For example, a liquid (catalyst liquid) in which a Group 10 transition metal compound is dissolved or dispersed in an appropriate solvent is added to the cycloolefin monomer as needed. It can be prepared by adding to the liquid (monomer liquid) and stirring.

(Fiber material)
The type of fiber material used in the present invention is not particularly limited. For example, organic materials such as PET (polyethylene terephthalate) fiber, aramid fiber, ultra-high molecular polyethylene fiber, polyamide (nylon) fiber, and liquid crystal polyester fiber can be used. Examples of fibers include inorganic fibers such as glass fibers, carbon fibers, alumina fibers, tungsten fibers, molybdenum fibers, budene fibers, titanium fibers, steel fibers, boron fibers, silicon carbide fibers, and silica fibers. Among these, organic fiber, glass fiber, or carbon fiber is preferable, and carbon fiber is more preferable. In particular, carbon fiber is suitable because it is excellent in impregnation property of a polymerizable composition containing a cycloolefin monomer, and the mechanical strength, toughness and heat resistance characteristics of the obtained fiber reinforced resin can be highly balanced. The carbon fiber is not particularly limited. For example, carbon fibers produced by various conventionally known methods such as acrylic, pitch, and rayon can be used. Among them, acrylic fiber (polyacrylonitrile fiber) is used as a raw material. Acrylic carbon fibers, which are carbon fibers produced as follows, are preferred because they do not cause polymerization inhibition and can impart high properties such as mechanical strength and toughness.

  The strength characteristic of the fiber material used in the present invention is not particularly limited and is appropriately selected according to the purpose of use. The tensile strength is a strand tensile strength measured according to JIS R7601, and is usually 0.5 to 50 GPa, preferably 1 to 10 GPa, more preferably 2 to 8 GPa. The tensile modulus is a strand tensile modulus measured according to JIS R7601, and is usually in the range of 100 to 1,000 GPa, preferably 200 to 800 GPa, more preferably 300 to 700 GPa. The elongation is a strand tensile elongation measured according to JIS R7601, and is usually 0.1 to 10%, preferably 0.5 to 5%, more preferably 1 to 3%. When the strength characteristics of the fiber are within these ranges, the mechanical strength and toughness are highly balanced, which is preferable.

  The cross-sectional shape of the fiber material used in the present invention is not particularly limited, but is preferably substantially circular. This is because, when 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. Furthermore, since the thickness of the fiber bundle can be reduced, there is an advantage that a prepreg excellent in drape can be easily obtained. Note that 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. Meaning one or less.

  The length of the fiber material used in the present invention is appropriately selected according to the purpose of use without any particular limitation, and both short fibers and long fibers can be used, but higher mechanical strength and toughness are obtained. If desired, the length of the fiber is 1 cm or more, preferably 2 cm or more, more preferably 3 cm or more, and most preferably continuous fiber.

  The form of the fiber material used in the present invention is not particularly limited, and can be appropriately selected from woven fabric, non-woven fabric, mat, knit, braid, unidirectional strand, roving, chopped, and the like. Among these, in order to obtain a fiber reinforced resin having higher levels of toughness and impact resistance, the fibers are preferably in the form of continuous fibers such as woven fabrics, unidirectional strands, and rovings. As the woven form, conventionally known ones can be used. For example, all of woven structures in which fibers such as plain weave, satin weave, twill weave, and triaxial weave are interlaced can be used. Moreover, as a woven fabric form, not only two-dimensional but also a stitch woven fabric and a three-dimensional woven fabric in which fibers are reinforced in the thickness direction of the woven fabric can be used.

  The fiber material used in the present invention is used as a fiber bundle yarn when used in a woven fabric or the like. In this case, the number of filaments in one fiber bundle yarn is not particularly limited, but is 1,000 to 100,000, preferably 2,000 to 20,000, more preferably 5,000 to 15. , 000.

  These fiber materials can be used alone or in combination of two or more, and the amount used is appropriately selected according to the purpose of use, but the fiber material content in the fiber reinforced resin to be obtained is Usually, it is selected to be in the range of 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight.

(Fiber reinforced resin)
The fiber reinforced resin of the present invention is a product in which a polymer obtained by polymerization of the cycloolefin monomer and a fiber material are integrated, and has properties excellent in mechanical strength, toughness, and oxidation deterioration resistance. .

  The amount of the volatile component of the fiber reinforced resin of the present invention is not particularly limited, but is an amount that volatilizes when heated at 200 ° C. for 1 hour, and is usually 5% by weight or less, preferably based on the total weight of the fiber reinforced resin. Is 3% by weight or less, more preferably 1% by weight or less. Such a fiber reinforced resin with a small amount of volatile components is suitable because it has no problems such as foaming and bleeding, and has high mechanical strength, toughness, and resistance to oxidation deterioration.

  The fiber material content in the fiber-reinforced resin of the present invention is appropriately selected according to the purpose of use, but is usually 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight. It is. When in this range, the properties of mechanical strength and toughness are highly balanced, which is preferable.

  The method for producing the fiber reinforced resin of the present invention is not particularly limited, but includes a cycloolefin monomer, a Group 10 transition metal compound, and, if necessary, a crosslinking agent, an elastomer material, a specific anti-aging agent, and other additives. It can obtain easily by superposing | polymerizing the polymeric composition containing this in presence of a fiber material.

  The polymerization method is not particularly limited, but bulk polymerization is preferable. Fiber reinforced resin of various shapes can be obtained by bulk polymerization. Here, “in the presence” means that the polymerization is performed in a state where the fiber material and the polymerizable composition are in contact with each other. Specifically, when the fiber material is a woven fabric, a method in which the fiber material is impregnated with a polymerizable composition and then bulk polymerization is performed. The impregnation of the polymerizable composition into the fiber material is preferably performed on a support or in a mold.

  The impregnation of the polymerizable composition into the fiber material is, for example, a known method such as a spray coating method, a dip coating method, a roll coating method, a curtain coating method, a die coating method, a slit coating method, or the like with a predetermined amount of the polymerizable composition. Can be applied by applying to a fiber material, and if necessary, a protective film is stacked thereon and pressed from above with a roller or the like. After impregnating the polymerizable composition into the fiber material, the polymerizable composition can be bulk polymerized by heating the impregnated product to a predetermined temperature, whereby the fiber-reinforced resin of the present invention in the form of a sheet or film Is obtained.

  When impregnation is performed in a mold, a fiber material is placed in the mold, the polymerizable composition is poured into the mold, and then polymerization is performed. According to this method, a composite material molded body having an arbitrary shape can be obtained. Examples of the shape include a sheet shape, a film shape, a column shape, a columnar shape, and a polygonal column shape. As the mold used here, a conventionally known mold, for example, a mold having a split mold structure, that is, a core mold and a cavity mold, can be used, and a polymerizable composition is injected into these voids (cavities). And bulk polymerization is performed. The core mold and the cavity mold are produced so as to form a gap that matches the shape of the target molded body. Further, the shape, material, size and the like of the mold are not particularly limited. Also, a plate-shaped mold such as a glass plate or a metal plate and a spacer having a predetermined thickness are prepared, and the polymerizable composition is injected into a space formed by sandwiching the spacer between two plate-shaped molds. By performing polymerization in the mold, a fiber reinforced resin in the form of a sheet or film can be obtained.

  The polymerizable composition has a low viscosity as compared with conventional epoxy resins and the like, and is excellent in impregnation with respect to the fiber material. Therefore, the resin obtained by polymerization can be uniformly impregnated into the fiber material.

  In addition, when bulk polymerization is performed, the polymerizable composition has a low content of a solvent or the like that does not participate in the reaction, so that a process such as removing the solvent after impregnating the fiber material is not required, which increases productivity. Excellent, no odor or swelling caused by residual solvent. In particular, since the fiber material does not hinder the polymerization reaction on its surface and does not require preliminary drying or the like, the production method of the present invention is excellent in productivity. Furthermore, the resin obtained by polymerization has a low content of unreacted monomers, a low odor, and excellent heat resistance.

  When the fiber material is a short fiber such as chop, a method in which the fiber material is mixed with the polymerizable composition and then bulk polymerization is used. The fiber material may be added to the monomer liquid and / or the catalyst liquid before mixing the monomer liquid and the catalyst liquid, or may be added after mixing the monomer liquid and the catalyst liquid. Examples of the bulk polymerization method include a method of performing bulk polymerization in a mold in the same manner as described above. Alternatively, short fibers and woven fabrics composed of long fibers may be used in combination, and a polymerizable composition containing short fibers of the fiber material may be impregnated into the woven fabric composed of long fibers in the same manner as described above before polymerization.

  In any of the above methods, the heating temperature for polymerizing the polymerizable composition is usually 50 to 250 ° C., preferably 100 to 200 ° C. The polymerization time may be appropriately selected, but is usually 10 seconds to 20 minutes, preferably within 5 minutes. Heating the polymerization composition to a temperature in this range is preferable because a fiber reinforced resin with little unreacted monomer can be obtained.

  A polymerization reaction is started by heating the polymerizable composition to a predetermined temperature. This polymerization reaction is an exothermic reaction, and once bulk polymerization starts, the temperature of the reaction solution rapidly increases and reaches the peak temperature in a short time (for example, about 10 seconds to 5 minutes). If the maximum temperature during the polymerization reaction is too high, a cross-linking reaction occurs to form a cross-linked body, and there is a possibility that a composite material molded body that can be post-crosslinked cannot be obtained. Therefore, in order to allow only the polymerization reaction to proceed completely and to prevent the crosslinking reaction from proceeding, the peak temperature of the polymerizable composition in the bulk polymerization is not more than the 1 minute half-life temperature of the crosslinking agent, preferably 230 ° C. Hereinafter, it is more preferable to control the temperature below 200 ° C.

  The fiber reinforced resin of the present invention thus obtained is excellent in properties such as mechanical strength, toughness, heat resistance and appearance, and is particularly suitable for structural materials for vehicles such as OA and AV equipment, automobiles and railways, and aircraft interior parts. In addition, it is suitably used for sports applications such as golf shafts and fishing rods and other general industrial applications. Specific applications include, for example, sports applications such as fishing rods, golf club shafts, tennis rackets, and skistocks; displays, FDD carriages, chassis, HDD, MO, motor brush holders, parabolic antennas, notebook computers, mobile phones, Electric / electronic devices such as digital still cameras, PDAs, portable MDs, liquid crystal displays, plasma displays; telephones, facsimiles, VTRs, photocopiers, televisions, irons, hair dryers, rice cookers, microwave ovens, audio equipment, vacuum cleaners, toiletries Supplies, leather discs, compact discs, lighting, refrigerators, air conditioners, typewriters, word processors, office automation equipment and household appliances; undercovers, scuff plates, pillar trims, professionals Automobiles such as rubber shafts, drive shafts, wheels, wheel covers, fenders, door mirrors, rear mirrors, fascias, bumpers, bumper beams, bonnets, trunk hoods, aero parts, platforms, cowl louvers, roofs, instrument panels, spirals and various modules Materials: Landing gear pods, wing reds, spoilers, edges, ladders, building parts such as panels, and construction materials such as panels.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples. In the examples and comparative examples, “part” and “%” are based on weight unless otherwise specified.

Each characteristic in an Example and a comparative example was measured and evaluated according to the following method.
(1) Mechanical strength: According to the test method specified in JIS K-7073, the distance between the gauge points was 150 mm, the tensile strength was measured at a crosshead speed of 2.0 mm / min, and the value of the molded product of Comparative Example 3 was determined. 100 was determined according to the following criteria.
○: 110 or more Δ: 90 or more, less than 110 ×: less than 90

(2) Toughness: The molded product was bent at 90 °, the surface of the bent portion was observed, and judged according to the following criteria.
○: Neither powder falling nor shape deformation is observed Δ: Either powder falling or shape breaking is recognized ×: Both are recognized, or only one of them is severe

(3) Appearance: The molded product was visually observed and judged according to the following criteria.
○: Neither warp nor shape breakage is observed Δ: Either warp or shape breakage is recognized ×: Both warp and shape breakage are recognized, or only one of them is severe

(4) Heat resistance: The molded product is allowed to stand in an oven, and the surface yellowness (YI value) after 150 ° C. × 500 hr is measured using a color difference meter. Evaluated by criteria.
○: 100 or less ×: More than 100

Example 1
A molding machine (inner dimensions 300 mm x 300 mm, 3 mm thick spacer made of polytetrafluoroethylene) was laid down so that the carbon fibers arranged in one direction and cut to 300 x 300 mm were 3 mm thick and then heated to 50 ° C. A 0.001 mol% norbornene solution (catalyst solution) of palladium acetylacetonate and a 0.001 mol% norbornene solution of trityl tetra (pentafluorophenyl) borate are mixed at a ratio of 1: 1 to a glass plate). Then, the reaction was carried out at 50 ° C. for 5 minutes and 200 ° C. for 5 minutes, and after cooling, the molding machine was disassembled to obtain a fiber reinforced resin of 300 mm × 300 mm × 3 mm. The obtained fiber reinforced resin had a volatile component of 0.7% and a carbon fiber ratio of 70% by weight. Further, mechanical strength, toughness, appearance, and oxidation resistance deterioration were evaluated and the results are shown in Table 1.

Example 2
Each characteristic was evaluated in the same manner as in Example 1 except that dicumyl peroxide was added in a ratio of 1.2 parts to 100 parts of norbornene (total amount after mixing) in the catalyst solution. The results are shown in Table 1. The volatile component was 0.6%.

Example 3
Each characteristic was evaluated in the same manner as in Example 2 except that polybutadiene was added in a ratio of 15 parts to 100 parts of the total amount of norbornene (total amount after mixing) in the catalyst solution, and the results are shown in Table 1. Indicated. The amount of volatile components was 0.8%.

Example 4
Example 2 except that 3,5-di-t-butyl-4-hydroxyanisole was added to the catalyst solution so that the ratio was 1.0 part with respect to 100 parts of the total amount of norbornene (total amount after mixing). Each characteristic was evaluated in the same manner as in Example 1, and the results are shown in Table 1. The amount of volatile components was 0.9%.

Comparative Example 1
A 0.05 mol% norbornene solution of tungsten hexachloride and a 0.5 mol% norbornene solution of diethylaluminum chloride were prepared, and a room temperature molding machine (inner dimensions: 300 mm × 300 mm, thickness) while mixing both solutions at a ratio of 1: 1. 3 mm polytetrafluoroethylene spacers were sandwiched between glass plates), and the molding machine was disassembled after 5 minutes to obtain a 300 mm × 300 mm × 3 mm plate-like molded body. Each characteristic was evaluated and the results are shown in Table 1.

Comparative Example 2
A 0.001 mol% norbornene solution of palladium acetylacetonate and a 0.001 mol% norbornene solution of trityl tetra (pentafluorophenyl) borate are prepared, and a 50 ° C. molding machine (internal) is mixed while mixing both solutions at a ratio of 1: 1. 3 mm thick polytetrafluoroethylene spacers sandwiched between glass plates), and after 5 minutes, the molding machine was disassembled to obtain a 300 mm × 300 mm × 3 mm plate-like molded body. . Each characteristic was evaluated and the results are shown in Table 1.

Comparative Example 3
Epicoat 1005F (bifunctional bisphenol type resin, epoxy equivalents 950 to 1050) 20 parts, Epicoat 828 (bifunctional bisphenol type resin, epoxy equivalents 176 to 180), curing agent dicyandiamide 5 parts, curing accelerator 1,1 "- An epoxy resin composition comprising 4.2 parts of 4 (methyl-m-phenylene) bis (3,3 "dimethylurea)) was thinly and evenly applied onto a release paper using a reverse roll coater to prepare a resin film. . Next, the two resin films were overlapped on both sides of the carbon fiber on the carbon fiber arranged in one direction on the sheet, and the epoxy resin composition was impregnated by heating and pressing to prepare a one-way prepreg. Next, using the prepared prepreg, the molded product was laminated so that the thickness of the molded product was 3 mm and placed in a mold, and compression molding was performed for 2 hours at a mold temperature of 150 ° C. and a molding pressure of 981 kPa. After the molding, it was desorbed, and each characteristic was evaluated. The results are shown in Table 1.

  From the results in Table 1, it can be seen that the fiber reinforced resin of the present invention is highly balanced in mechanical strength, toughness, appearance and heat resistance (compared to Examples 1-4 and Comparative Examples 1-3). ) In addition, when a crosslinking agent is added to the polymerizable composition, it can be seen that the mechanical strength, toughness, appearance and heat resistance characteristics of the fiber reinforced resin are highly balanced without impairing the polymerization activity and heat resistance ( Examples 2-4). On the other hand, when a phenolic anti-aging agent is added to the polymerizable composition (Example 4), the fiber reinforced resin is excellent in all of the mechanical strength, toughness, and appearance properties without inhibiting the polymerization activity. However, in particular, in the evaluation of heat resistance, it was found that the yellowness was hardly changed as compared with the examples (Examples 1 to 3) in which the antiaging agent was not blended.

Claims (9)

  A fiber reinforced resin obtained by polymerizing a polymerizable composition containing a cycloolefin monomer and a Group 10 transition metal compound in the presence of a fiber material.   The fiber reinforced resin according to claim 1, wherein the polymerizable composition further comprises a crosslinking agent.   The fiber reinforced resin according to claim 1 or 2, wherein the polymerizable composition further comprises an elastomer material.   The polymerizable composition further comprises at least one anti-aging agent selected from the group consisting of a phenol-based anti-aging agent, an amine-based anti-aging agent, a phosphorus-based anti-aging agent and a sulfur-based anti-aging agent. The fiber reinforced resin in any one of thru | or 3.   The fiber reinforced resin according to any one of claims 1 to 4, wherein the fiber material is made of organic fiber or carbon fiber.   A method for producing a fiber reinforced resin, wherein a polymerizable composition containing a cycloolefin monomer and a Group 10 transition metal compound is polymerized in the presence of a fiber material.   The production method according to claim 6, wherein the polymerizable composition further comprises a crosslinking agent.   8. The production method according to 6 or 7, wherein the polymerizable composition further comprises an elastomer material.   The polymerizable composition further comprises at least one anti-aging agent selected from the group consisting of a phenol-based anti-aging agent, an amine-based anti-aging agent, a phosphorus-based anti-aging agent and a sulfur-based anti-aging agent. The manufacturing method in any one of thru | or 8.