JP2011037002A - Metal/fiber-reinforced resin composite and process for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a metal/fiber-reinforced resin composite which comprises a metallic sheet and a fiber-reinforced resin layer, is particularly excellent in adhesiveness between the metallic sheet and the fiber-reinforced resin layer and in energy absorbing property (impact resistance) and is free from problems of peeling, cracking, etc. in a severe thermal shock test. <P>SOLUTION: The metal/fiber-reinforced resin composite is obtained by integrating the fiber-reinforced resin layer containing a cross-linked cycloolefin polymer and a carbon fiber with the metallic sheet. The metal/fiber-reinforced resin composite can be produced by superposing a crosslinkable prepreg including a cycloolefin polymer, a cross-linking agent and the carbon fiber on the metallic sheet and cross-linking the prepreg superposed on the metallic sheet. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a metal / fiber reinforced resin composite comprising a metal plate and a fiber reinforced resin layer and a method for producing the same, and more specifically, a rigid metal plate, and a fiber comprising a cycloolefin polymer, a crosslinking agent and carbon fiber. Metal / consisting of a reinforced resin layer, which has excellent adhesion and impact resistance between the metal plate and the fiber reinforced resin layer, and does not cause peeling and cracking between the metal plate and the fiber reinforced resin layer even after a severe cooling test. The present invention relates to a fiber reinforced resin composite and a method for producing the same.

  A composite material in which a metal and a fiber reinforced resin are laminated and integrated is known as a material that can exhibit both the excellent impact resistance of a metal and the excellent light weight and high mechanical properties of a fiber reinforced resin. In particular, in automobiles and aircraft structures that require lightness, high strength characteristics, and high energy absorption, composite materials in which metals such as steel, aluminum alloys, and titanium alloys and carbon fiber reinforced resins are laminated and integrated are used. Has been used. For example, it is known that a bonnet composed of a metal / fiber reinforced resin composite is lightweight and has high rigidity, and can exhibit high energy absorption characteristics upon impact. Also, for the purpose of reinforcing the body frame, etc., the purpose is to integrate the fiber insert into the metal frame, or to integrate the metal insert to mechanically join the parts made of fiber reinforced resin with bolts etc. Thus, it is known to integrate a fiber reinforced resin and a metal.

  For example, Patent Document 1 proposes a composite material made of an aluminum alloy and a fiber reinforced resin suitable for an automotive horizontal panel such as a bonnet, a roof, and a trunk lid. Patent Document 2 proposes a composite material in which an aluminum alloy suitable for automobile door panels, fenders, rear hatch panels and the like is reinforced with fiber reinforced resin. However, since aluminum alloys and the like used in structures such as automobiles have high rigidity, bending deformation occurs under severe conditions such as high temperature and low temperature repetition, and the adhesive surface with the fiber reinforced resin layer As a result, the shear stress increases and the metal layer and the fiber reinforced resin layer peel off.

  As an improvement of such a problem, for example, Patent Document 3 includes an epoxy resin as a matrix resin, a fiber reinforced resin layer and a metal layer as an epoxy resin, thermoplastic resin particles having an average particle diameter of 3 to 10 μm, and an imidazole silane compound. A metal / fiber reinforced resin composite material bonded by an intermediate layer is disclosed. However, in this method, the peel strength between the metal and the fiber reinforced resin layer is somewhat improved, but the metal and the fiber reinforced resin layer are peeled off or the fiber reinforced resin is subjected to a thermal test or the like to withstand severe temperature conditions. There was a problem that cracks occurred in the resin layer.

JP 2001-191962 A JP 2001-253371 A JP 2006-297927 A

  The present invention relates to a metal / fiber reinforced resin composite material comprising a metal plate and a fiber reinforced resin layer, and in particular, is excellent in adhesion between the metal plate and the fiber reinforced resin layer, energy absorption (impact resistance), and harsh. The object is to obtain a metal / fiber reinforced resin composite that is free from problems such as peeling and cracking in a cold test.

  As a result of intensive studies in view of the above problems, the present inventors have used carbon fibers as the reinforcing fibers of the fiber reinforced resin layer and made the matrix resin a crosslinked product of a cycloolefin polymer, or a cycloolefin polymer, a crosslinking agent, and A crosslinkable prepreg containing carbon fiber is laminated on a rigid metal plate and then cured to provide excellent adhesion and impact resistance, and peeling at the interface between the metal plate and the fiber reinforced resin layer in severe thermal tests It has been found that a metal / fiber reinforced resin composite free from cracks in the fiber reinforced resin layer can be obtained. In addition, by treating the surface of the metal plate with a silane coupling, especially with a silane coupling agent having a reactive group that reacts with the crosslinking agent, the metal / fiber reinforced resin composite has significantly improved resistance to cold tests. I found out. Furthermore, the prepreg can be easily produced by polymerizing a polymerizable composition comprising a cycloolefin monomer, a polymerization catalyst and a crosslinking agent in the presence of carbon fiber, and the obtained prepreg is laminated on a metal plate and cured. It has been found that a metal / fiber reinforced resin composite having excellent properties such as adhesion, impact resistance, and cold test resistance can be obtained. Based on these findings, the present inventors have completed the present invention.

Thus, according to the present invention, the following (1) to (11) are provided.
(1) A metal / fiber reinforced resin composite comprising a cross-linked cycloolefin polymer and a fiber reinforced resin layer containing carbon fibers and a metal plate.
(2) The metal / fiber reinforced resin composite according to (1), wherein the metal plate is made of iron, aluminum, titanium, or an alloy containing them.
(3) The metal / fiber reinforced resin composite according to (1) or (2), wherein the fiber reinforced resin layer contains a filler.
(4) The metal / fiber reinforced resin composite according to any one of (1) to (3), wherein the peel strength between the metal plate and the fiber reinforced resin layer is 10 N · mm / mm or more.
(5) The metal / fiber reinforced resin composite according to any one of (1) to (4), which is a vehicle member.
(6) A method for producing a metal / fiber reinforced resin composite, wherein a crosslinkable prepreg comprising a cycloolefin polymer, a crosslinking agent and carbon fibers is laminated on a metal plate and then crosslinked.
(7) The production method according to (6), wherein the crosslinkable prepreg is obtained by polymerizing a polymerizable composition containing a cycloolefin monomer, a metathesis polymerization catalyst, and a crosslinking agent in the presence of carbon fibers.
(8) The production method according to (6) or (7), wherein the crosslinking agent is a radical generator.
(9) The production method according to (8), wherein the polymerization is performed at a temperature equal to or lower than the 1 minute half-life temperature of the radical generator.
(10) The manufacturing method according to any one of (6) to (9), wherein the surface of the metal plate is treated with a silane coupling agent.
(11) The production method according to (10), wherein the silane coupling agent has a reactive group that reacts with the crosslinking agent.

  ADVANTAGE OF THE INVENTION According to this invention, the metal / fiber reinforced resin composite excellent in the adhesiveness of a metal plate and a fiber reinforced resin layer, energy absorptivity (impact resistance), and a cold test tolerance can be obtained easily. In addition, the metal / fiber reinforced resin composite of the present invention is excellent in adhesion between the metal layer and the fiber reinforced resin layer, impact resistance, resistance to cold test, and the like. It can be suitably used in fields such as civil engineering and construction.

  In the metal / fiber reinforced resin composite of the present invention, the fiber reinforced resin layer and the metal plate are integrated, and in particular, the reinforced fiber of the fiber reinforced resin layer is a carbon fiber, and the matrix resin is a crosslinked product of a cycloolefin polymer. It is characterized by using a thing.

(Cycloolefin polymer)
In the present invention, a crosslinked product of cycloolefin polymer is used as the matrix resin. The crosslinked product of cycloolefin polymer is not particularly limited as long as it is obtained by crosslinking a cycloolefin polymer. As the cycloolefin polymer, a known polymer of cycloolefin monomer can be used without any particular limitation. Specific examples include a ring-opening polymer of a cycloolefin monomer, an addition polymer of a cycloolefin monomer, an addition copolymer of a cycloolefin monomer and a chain olefin, and a hydride thereof.

  A cycloolefin monomer 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. , Tetracycles such as funiltetracyclododecene, pentacycles such as tricyclopentadiene, heptacycles such as tetracyclopentadiene, and alkyl substitutions thereof (methyl, ethyl, propyl, butyl substitutions, etc.), Alkylidene substituted (eg ethylidene substituted), aryl substituted (eg phenyl, tolyl substituted), epoxy group, methacrylic group, hydroxyl group, amino group, carboxyl group, cyano group, halogen group, ether group, ester bond Derivatives with polar groups such as containing groups It is done.

  Examples of the monocyclic cycloolefin include monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclooctene, cyclododecene, 1,5-cyclooctadiene, and derivatives having a substituent. These cycloolefin monomers can be used alone or in combination of two or more.

  The molecular weight of the cycloolefin polymer may be appropriately selected according to the purpose of use, but is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography, usually 1,000 to 1,000,000, Preferably it is the range of 5,000-500,000, More preferably, it is the range of 10,000-100,000.

  The crosslinked product of the cycloolefin polymer used in the present invention is obtained by crosslinking the cycloolefin polymer, and is defined by not dissolving in a solvent. On the other hand, the uncrosslinked cycloolefin polymer is usually dissolved in a solvent. Such a solvent is appropriately selected from solvents such as aromatic hydrocarbons such as benzene and toluene, ethers such as diethyl ether and tetrahydrofuran, and halogenated hydrocarbons such as dichloromethane and chloroform. Any known method such as radical crosslinking or ionic crosslinking can be adopted as the crosslinking method, and it is not limited, but radical crosslinking is preferred.

(Carbon fiber)
In the present invention, carbon fibers are used as the reinforcing fibers. The type of carbon fiber is not particularly limited. For example, carbon fibers produced by various conventionally known methods such as acrylic, pitch-based, rayon-based, etc. can be used. Among them, acrylic carbon fiber (PAN-based) Carbon fiber) is preferable because it can impart high properties such as mechanical strength and impact resistance.

  The strength characteristics of the carbon fibers used in the present invention are not particularly limited and are 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 carbon fiber are within these ranges, characteristics such as adhesion to the metal layer, mechanical strength, and impact resistance are highly balanced, which is preferable.

  The cross-sectional shape of the carbon fiber used in the present invention is not particularly limited and may be appropriately selected according to the purpose of use. For example, it may be flat or circular. For example, when the cross-sectional shape is circular, when the resin is impregnated, the filaments are easily rearranged, the resin can easily penetrate between the fibers, and the thickness of the fiber bundle can be reduced. Since it becomes possible, there are advantages such as easy to obtain a prepreg excellent in drape.

  The length of the carbon fiber 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 carbon fiber used in the present invention is not particularly limited, and can be appropriately selected from woven fabric, nonwoven 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 carbon fiber 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 carbon fibers 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 carbon fiber content in the fiber reinforced resin layer 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 layer)
The fiber reinforced resin layer used in the present invention contains carbon fiber as the reinforcing fiber and a cycloolefin polymer crosslinked product as the matrix resin, and other compounding agents are added to the matrix resin as necessary. May be.

  Other compounding agents are appropriately selected depending on the purpose of use, but include elastomer materials, fillers, anti-aging agents, flame retardants, colorants, light stabilizers, pigments, foaming agents, polymer modifiers, etc. Can be mentioned.

  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 blending amount is usually 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight with respect to 100 parts by weight of the crosslinked product of cycloolefin polymer. It is preferable because the toughness of the metal / fiber reinforced resin composite obtained when the elastomer material is in this range can be improved to a high degree.

  The filler is not particularly limited as long as it is generally used industrially, and either an inorganic filler or an organic filler can be used, but an inorganic filler is preferred. Examples of the inorganic filler include metal particles such as iron, copper, nickel, gold, silver, aluminum, lead, and tungsten; carbon particles such as carbon black, graphite, activated carbon, and carbon balloon; silica, silica balloon, alumina, Inorganic oxide particles such as titanium oxide, iron oxide, zinc oxide, magnesium oxide, tin oxide, beryllium oxide, barium ferrite, strontium ferrite; inorganic carbonate particles such as calcium carbonate, magnesium carbonate, sodium hydrogen carbonate; calcium sulfate, etc. Inorganic sulfate particles; inorganic silicate particles such as talc, clay, mica, kaolin, fly ash, montmorillonite, calcium silicate, glass, glass balloon; titanate particles such as calcium titanate and lead zirconate titanate, Aluminum nitride, silicon carbide particles Whiskers, and the like. Examples of the organic filler include particulate compounds such as wood flour, starch, organic pigments, polystyrene, nylon, polyolefins such as polyethylene and polypropylene, vinyl chloride, and waste plastics. These fillers can be used alone or in combination of two or more, and the blending amount is usually 1 to 1,000 parts by weight, preferably 10 to 100 parts by weight with respect to 100 parts by weight of the cycloolefin polymer. The amount is in the range of 500 parts by weight, more preferably 50 to 350 parts by weight. When the filler is in this range, the metal / fiber reinforced resin composite can be remarkably improved in properties such as mechanical strength, heat resistance, chemical resistance, and cold test resistance.

  Anti-aging agents can be used without particular limitation as long as they are generally used in the resin industry, but phenol-based anti-aging agents, amine-based anti-aging agents, phosphorus-based anti-aging agents and sulfur-based anti-aging agents. By using at least one anti-aging agent selected from the group consisting of inhibitors, it is preferable that the oxidation-deterioration resistance of the resulting fiber-reinforced resin layer can be highly improved without inhibiting the crosslinking reaction. Among these, a phenolic antiaging agent and an amine antiaging agent are preferable, and a phenolic antiaging agent is particularly preferable.

  Examples of phenolic anti-aging agents include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate and 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-t-butyl-m) -Cresol), 3,9-bis (2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10 Tetraoxaspiro [5,5] undecane, tetrakis (methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenylpropionate) methane [ie, pentaerythrimethyl-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenylpropionate)], 6- (4-hydroxy-3-methyl-5-tert-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.

  Examples of the amine-based antiaging agent include 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-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalon Acid-bis- (1,2,2,6,6-pentamethyl-4-piperidyl) and the like.

  Examples of phosphorus antioxidants include 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-tert-butylphenyl) -4,4′-biphenylenediphos Fight, cyclic neopentanetetraylbis (isodecyl phosphite), etc. It is below.

  Sulfur-based antioxidants include, for example, dilauryl 3,3-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3-thiodipropionate, lauryl stearyl 3,3-thiodipropio Nate, pentaerythritol-tetrakis- (β-lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane It is done.

  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 crosslinked product of the cycloolefin polymer. More preferably, it is in the range of 0.01 to 1 part by weight.

  Examples of the flame retardant include phosphorus flame retardants, nitrogen flame retardants, halogen flame retardants, metal hydroxides such as aluminum hydroxide, and antimony compounds such as antimony trioxide. 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 thickness of the fiber reinforced resin layer used in the present invention is appropriately selected according to the purpose of use, but is usually 0.001 to 10 mm, preferably 0.01 to 1 mm, more preferably 0.05 to 0.5 mm. Range. Within this range, the properties of adhesion to the metal layer, mechanical strength, and toughness are highly balanced and suitable.

(Metal plate)
As the material of the metal plate used in the present invention, iron or an alloy thereof such as iron, stainless steel, and carbon steel; aluminum or an alloy thereof; titanium or an alloy thereof; a magnesium alloy; and various other metals and alloys are used. It is done. Among these, iron, aluminum, titanium, or an alloy containing them is preferable, stainless steel, aluminum alloy, and titanium alloy are more preferable, and aluminum alloy and titanium alloy are particularly preferable because they are lightweight and have high strength.

  Although the thickness of the metal plate used for this invention is suitably selected according to the intended purpose, it is 0.01-10 mm normally, Preferably it is 0.05-5 mm, More preferably, it is the range of 0.1-2 mm. . If the thickness of the metal plate is too thin, it is not preferable because the weight that the metal can bear is too small. On the contrary, if the thickness is excessively thick, the shear stress applied to the fiber-reinforced resin bonding surface during bending deformation becomes too high, and there is a concern of shear failure. It is not preferable because it comes out.

  In the metal / fiber reinforced resin composite of the present invention, the fiber reinforced resin layer and the metal plate are integrated, and there is no particular limitation on the manufacturing method. For example, a cycloolefin polymer, a crosslinking agent, and carbon fiber are used. A method of cross-linking the cross-linkable prepreg comprising the above-described specific metal plate is preferable because it can be easily manufactured.

(Crosslinkable prepreg)
The crosslinkable prepreg used in the present invention can contain the above-mentioned cycloolefin polymer, cross-linking agent and the above-mentioned carbon fiber as essential components and other compounding agents as necessary.

  The crosslinking agent used in the present invention is not particularly limited as long as it can crosslink a cycloolefin polymer, but a radical generator is preferable. 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 preferable in that there are few obstacles to the polymerization reaction described later.

  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.

  When the crosslinking agent used in the present invention is a radical generator, the one-minute half-life temperature is appropriately selected depending on the crosslinking conditions, but is usually 100 to 300 ° C, preferably 150 to 250 ° C, more preferably 160. It is in the range of ~ 230 ° C. Here, the half-life temperature for 1 minute is a temperature at which half of the radical generator decomposes in 1 minute. For example, it is 186 ° C. for di-t-butyl peroxide and 194 ° C. for 2,5-dimethyl-2,5-bis (t-butylperoxy) -3-hexyne.

  These crosslinking agents can be used alone or in combination of two or more. The amount of the crosslinking agent used is usually 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 polymer. .

  The method for producing the prepreg used in the present invention is not particularly limited. For example, a wet method in which a cycloolefin polymer and a cross-linking agent are dissolved in a solvent to reduce the viscosity and impregnate the carbon fiber and then remove the solvent. A hot melt that coats a release paper with a cycloolefin polymer containing a crosslinking agent, aligns carbon fibers on the release paper, impregnates the heated and dissolved cycloolefin polymer with a roll or doctor blade, and then cools it. The method (dry method) can be used, and a direct polymerization method in which a polymerizable composition containing a cycloolefin monomer, a polymerization catalyst and a crosslinking agent is polymerized in the presence of carbon fibers is preferable. As the cycloolefin monomer and the crosslinking agent used in the direct polymerization method, the same ones as described above are used.

  The polymerization catalyst used in the present invention is not particularly limited as long as it can polymerize a cycloolefin monomer, but a metathesis polymerization catalyst is usually used. The metathesis polymerization catalyst is capable of metathesis ring-opening polymerization of a cycloolefin monomer, and usually includes a complex formed by bonding a plurality of ions, atoms, polyatomic ions and / or compounds with a transition metal atom as a central atom. . As transition metal atoms, atoms of Group 5, Group 6, and Group 8 (long period periodic table, the same applies hereinafter) are used. Although 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 ruthenium and osmium. Can be mentioned. Among these, a group 8 ruthenium or osmium complex is preferably used as a metathesis polymerization catalyst, and a ruthenium carbene complex is particularly preferable. Since the ruthenium carbene complex is excellent in catalytic activity during bulk polymerization, it is excellent in productivity of a crosslinkable prepreg, and the prepreg obtained has less odor derived from unreacted monomers and is excellent in workability. In addition, it is relatively stable against oxygen and moisture in the air and is not easily deactivated, so that it can be produced even in the atmosphere.

  In the present invention, the use of a ruthenium catalyst having a compound having a heterocyclic structure as a ligand as a polymerization catalyst provides a high balance of properties such as appearance, strength and toughness of the resulting metal / fiber reinforced resin composite material. Is preferred. As a hetero atom which comprises a heterocyclic structure, an oxygen atom, a nitrogen atom, etc. are mentioned, for example, Preferably it is a nitrogen atom. The heterocyclic structure is preferably an imidazoline or imidazolidine structure. Specific examples of the compound having such a heterocyclic structure include 1,3-di (1-adamantyl) imidazolidin-2-ylidene, 1,3- Dimesityloctahydrobenzimidazol-2-ylidene, 1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene, 1,3,4-triphenyl-2,3,4,5-tetrahydro -1H-1,2,4-triazole-5-ylidene, 1,3-dicyclohexylhexahydropyrimidin-2-ylidene, N, N, N ', N'-tetraisopropylformamidinylidene, 1,3-di Mesitylimidazolidine-2-ylidene, 1,3-dicyclohexylimidazolidine-2-ylidene, 1,3-diisopropyl-4- Midazorin-2-ylidene, 1,3-dimesityl-2,3-dihydro-benzimidazol-2-ylidene and the like.

  Examples of preferred ruthenium catalysts include benzylidene (1,3-dimesitylimidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesitylimidazolidin-2-ylidene) (3- Methyl-2-butene-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-octahydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene) (tricyclohexyl) Phosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazol-5-ylidene) ruthenium dichloride, (1 , 3-Diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesitylimidazolidine-2-ylidene) pyridine ruthenium dichloride Examples thereof include a ruthenium complex compound in which a compound having a heterocyclic structure and a neutral electron donating compound are bonded.

  These polymerization catalysts are used alone or in combination of two or more. The polymerization catalyst is used in a molar ratio of (metal atom in catalyst: cycloolefin monomer), usually 1: 2,000 to 1: 2,000,000, preferably 1: 5,000 to 1: 1. The range is from 1,000,000, more preferably from 1: 10,000 to 1: 500,000.

  If necessary, the polymerization catalyst can be used by dissolving or suspending in a small amount of an inert solvent. Such solvents include chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, liquid paraffin and mineral spirits; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane , Decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene, cyclooctane and other alicyclic hydrocarbons; benzene, toluene, xylene and other aromatic hydrocarbons; indene, tetrahydronaphthalene and other alicyclic and aromatic rings A nitrogen-containing hydrocarbon such as nitromethane, nitrobenzene, and acetonitrile; an oxygen-containing hydrocarbon such as diethyl ether and tetrahydrofuran; and the like. Among these, it is preferable to use aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and hydrocarbons having an alicyclic ring and an aromatic ring.

  The polymerizable composition used in the present invention comprises a cycloolefin monomer, a polymerization catalyst and a crosslinking agent as essential components, and if necessary, a polymerization regulator, a chain transfer agent, a polymerization reaction retarding agent, a crosslinking aid, A compounding agent can be added. Examples of other compounding agents include the same elastomer materials, fillers, anti-aging agents, flame retardants, colorants, light stabilizers, pigments, foaming agents, and polymer modifiers as described above.

  The polymerization regulator is blended for the purpose of controlling the polymerization activity or improving the polymerization reaction rate. For example, trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkyl Examples thereof include aluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride, trialkoxyscandium, tetraalkoxytitanium, tetraalkoxytin, and tetraalkoxyzirconium. These polymerization regulators can be used alone or in combination of two or more. The use amount of the polymerization regulator is usually 1: 0.05 to 1: 100, preferably 1: 0.2 to 1:20, in a molar ratio of (metal atom in the polymerization catalyst: polymerization regulator). Preferably it is the range of 1: 0.5-1: 10.

  As the chain transfer agent, chain olefins which may have a substituent can be usually used. Specific examples thereof include aliphatic olefins such as 1-hexene and 2-hexene; olefins having an aromatic group such as styrene, divinylbenzene and stilbene; and alicyclic hydrocarbon groups such as vinylcyclohexane. Olefins; Vinyl ethers such as ethyl vinyl ether; methyl vinyl ketone, 1,5-hexadien-3-one, 2-methyl-1,5-hexadien-3-one, vinyl methacrylate, allyl methacrylate, methacrylate 3- Buten-1-yl, 3-buten-2-yl methacrylate, styryl methacrylate, allyl acrylate, 3-buten-1-yl acrylate, 3-buten-2-yl acrylate, 1-methyl acrylate 3-buten-2-yl, styryl acrylate, ethylene glycol diacrylate Allyl trivinyl silane, allyl methyl divinyl silane, allyl dimethyl vinyl silane, glycidyl acrylate, allyl glycidyl ether, allylamine, 2- (diethylamino) ethanol vinyl ether, 2- (diethylamino) ethyl acrylate, and 4-vinyl aniline.

  These chain transfer agents can be used alone or in combination of two or more, and the addition amount is usually 0.01 to 10% by weight, preferably 0.1 to 10% by weight based on the whole cycloolefin monomer. 5% by weight. When the addition amount of the chain transfer agent is within this range, a prepreg having a high polymerization reaction rate and capable of crosslinking can be obtained efficiently. If the addition amount of the chain transfer agent is too small, crosslinking may proceed simultaneously with the polymerization, and a prepreg capable of crosslinking may not be obtained. Conversely, if the amount added is too large, crosslinking may be difficult.

  It is preferable that the polymerizable composition used in the present invention contains a polymerization reaction retarder because an increase in the viscosity can be suppressed and the reinforcing fiber can be easily impregnated with the polymerizable composition easily. Polymerization retarders include phosphine compounds such as triphenylphosphine, tributylphosphine, trimethylphosphine, triethylphosphine, dicyclohexylphosphine, vinyldiphenylphosphine, allyldiphenylphosphine, triallylphosphine, styryldiphenylphosphine; Lewis bases such as aniline and pyridine Etc. can be used.

  Among these polymerization reaction retarders, a phosphine compound is preferable because of its great effect of suppressing the progress of the polymerization reaction at room temperature or lower, and triphenylphosphine, triethylphosphine, dicyclohexylphosphine, and vinyldiphenylphosphine are more preferable. The amount of the polymerization reaction retarder is usually 1: 0.01 to 1: 100, preferably 1: 0.1 to 1:10, more preferably, in a molar ratio of (ruthenium metal atom: polymerization reaction retarder). It is in the range of 1: 0.1 to 1: 5.

  In the present invention, when a crosslinking aid is blended, it is excellent because it is excellent in impregnation into reinforcing fibers even when a large amount of inorganic filler or the like is blended in the polymerizable composition, and can also improve the adhesion to the metal plate. It is.

  As the crosslinking aid used in the present invention, those generally used can be used without any particular limitation, for example, a bifunctional crosslinking aid having two carbon-carbon unsaturated bonds, carbon-carbon unsaturated. A polyfunctional crosslinking aid having three or more bonds may be mentioned.

  The structure of the crosslinking aid used in the present invention is not particularly limited, but when it is a compound having a highly symmetric structure, the impregnation property of the polymerizable composition containing the cycloolefin monomer into the carbon fiber is enhanced. It is possible to improve it. In particular, when the crosslinking aid is a hydrocarbon and has a highly symmetric structure, the impregnation property of the polymerizable composition into the carbon fiber, and the mechanical strength of the fiber reinforced resin layer obtained by curing, It is suitable for improving toughness and heat resistance.

  Specific examples of such a crosslinking aid include bifunctional crosslinking aids such as p-diisopropenylbenzene, m-diisopropenylbenzene and o-diisopropenylbenzene, 3 such as triisopropenylbenzene and trimethallyl isocyanate. Examples include functional crosslinking aids. Among these, triisopropenylbenzene, p-diisopropenylbenzene, m-diisopropenylbenzene, and o-diisopropenylbenzene are preferable, and m-diisopropenylbenzene is more preferable.

  These crosslinking aids can be used alone or in combination of two or more. The amount of the crosslinking aid is appropriately selected depending on the purpose of use, but is usually 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, more preferably 100 parts by weight of the cycloolefin monomer. 1 to 20 parts by weight, most preferably 5 to 15 parts by weight.

  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 polymerization catalyst is dissolved or dispersed in an appropriate solvent is mixed with a cycloolefin monomer and a crosslinking agent as needed. It can be prepared by adding to a liquid (monomer liquid) and stirring.

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

  For impregnation of the polymerizable composition into the carbon fiber, for example, a predetermined amount of the polymerizable composition is applied to 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, or a slit coating method. Can be applied by applying to a carbon fiber, overlaying a protective film on the carbon fiber as necessary, and pressing from above with a roller or the like. After impregnating the polymerizable composition into the carbon fiber, the polymerizable composition can be bulk polymerized by heating the impregnated product to a predetermined temperature, whereby a sheet-like or film-like prepreg is obtained.

  When impregnation is performed in a mold, carbon fiber is placed in the mold, the polymerizable composition is poured into the mold, and then polymerization is performed. According to this method, a prepreg 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 prepreg. 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 sheet-like or film-like prepreg can be obtained.

  Since the polymerizable composition has a lower viscosity than conventional epoxy resins and is excellent in impregnation with carbon fibers, the carbon fiber material can be uniformly impregnated with a resin obtained by polymerization.

  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. Therefore, a process such as removing the solvent after impregnating the carbon fiber is not necessary, which increases productivity. Excellent, no odor or swelling caused by residual solvent. In particular, since the carbon fiber 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 carbon fiber is short fibers, such as a chop, the method of mixing carbon fiber with polymeric composition and performing bulk polymerization is mentioned. The carbon fiber 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 carbon fibers 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 in the range of 50 to 250 ° C., preferably 100 to 200 ° C., more preferably 120 to 170 ° C., and the crosslinking agent. When a radical generator is used, it is usually at most 1 minute half-life temperature of the radical generator, preferably at most 10 ° C, more preferably at most 20 ° 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 prepreg with little unreacted monomer can be obtained.

  The carbon fiber content of the prepreg used in the present invention thus obtained 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. Range.

  The thickness of the prepreg used in the present invention is appropriately selected according to the purpose of use, but is usually 0.001 to 10 mm, preferably 0.01 to 1 mm, more preferably 0.05 to 0.5 mm. is there. Within this range, it is easy to follow the shape of the metal layer to be laminated, and properties such as mechanical strength and energy absorption are sufficiently exhibited.

  The amount of volatile components of the prepreg used in the present invention is an amount volatilized at 200 ° C. for 1 hour, and is usually 5% by weight or less, preferably 3% by weight or less, more preferably 1% by weight or less. If the amount of volatile components in the prepreg is excessively large, stickiness of the prepreg will occur and the operability will deteriorate, and voids will occur in the fiber reinforced resin layer after crosslinking, resulting in a decrease in mechanical strength, bleed and heat resistance. There is a risk of problems such as degradation. A prepreg having a small amount of volatile components and a small amount of voids can be easily obtained by the direct polymerization method. In the wet method, a large amount of both volatile components and voids may remain. In addition, a large amount of voids may remain even in the hot melt method.

(Metal / fiber reinforced resin composite)
The metal / fiber reinforced resin composite of the present invention can be obtained by laminating the prepreg on the metal plate and then crosslinking the prepreg.

  The metal plate used in the present invention is preferably treated with a silane coupling agent on the surface because the resistance to cold test is further improved. Although what is generally used industrially can be used as a silane coupling agent, The silane coupling agent which has the reactive group which reacts with the said crosslinking agent is used suitably. Although there is no special limitation as a reactive group which reacts with a crosslinking agent, A vinyl group, a methacryloyl group, an acryloyl group, a mercapto group, an amino group etc. are mentioned, A vinyl group is used suitably.

  Examples of such silane coupling agents include allyltrimethoxysilane, 3-butenyltrimethoxysilane, styryltrimethoxysilane, N-β- (N- (vinylbenzyl) aminoethyl) -γ-aminopropyltrimethoxysilane. And its salts, vinyl groups such as allyltrichlorosilane, allylmethyldichlorosilane, styryltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltrichlorosilane Silane coupling agent; β-methacryloxyethyltrimethoxysilane, β-methacryloxyethyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, δ-methacryloxybutyltrimethoxysilane Silane coupling agent having any methacryloyl group; Silane coupling agent having acryloyl group such as γ-acryloxypropyltrimethoxysilane; Mercapto group such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropylmethyldimethoxysilane Silane coupling agent; Silane coupling having an amino group such as γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane Agents; and the like. These silane coupling agents can be used alone or in combination of two or more.

  As a method of crosslinking, a conventional method may be followed, for example, using a known press having a press frame mold for flat plate molding, a press molding machine such as a sheet mold compound (SMC) or a bulk mold compound (BMC). Hot pressing can be performed. The heating temperature is a temperature at which crosslinking of the cross-linking agent occurs, and when a radical generator is used, the temperature is 1 minute half-life temperature of the radical generator, preferably 5 ° C. higher than the 1-minute half-life temperature, More preferably, the temperature is 10 ° C. or more higher than the 1 minute half-life temperature. Usually, it is 100-300 degreeC, Preferably it is the range of 150-250 degreeC. The heating time is in the range of 0.1 to 180 minutes, preferably 1 to 120 minutes, more preferably 2 to 20 minutes. As a press pressure, it is 0.1-20 MPa normally, Preferably it is 1-10 MPa, More preferably, it is 2-5 MPa. Further, the hot pressing may be performed in a vacuum or a reduced pressure atmosphere.

  The peel strength between the metal layer and the fiber reinforced layer of the metal / fiber reinforced resin composite of the present invention thus obtained is appropriately selected according to the purpose of use, but is usually 10 N · mm when used for various structural members. -It is mm or more.

  The metal / fiber reinforced resin composite of the present invention is excellent in mechanical strength, energy absorption, peel strength, and cold test resistance. For example, OA and AV equipment, automobile and railroad vehicle members, aircraft interior parts, etc. 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, laptop 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, room mirrors, feshers, bumpers, bumper beams, bonnets, trunk hoods, aero parts, platforms, cowl louvers, roofs, instrument panels, spirals and various modules Parts; aircraft parts such as landing gear pods, wing reds, spoilers, edges, ladders, and failings; and building materials such as panels. Among these, it is particularly suitable as a member for vehicles such as automobiles and airplanes.

  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) Volatile component amount: A part of the central portion of the prepreg was cut off, and the component amount volatilized at 200 ° C. for 1 hour was measured by gas chromatography. It was expressed as the amount of volatile components in the total weight.

(2) Adhesion: According to ASTM D1781-76, the peel strength between the metal layer and the fiber reinforced resin layer was evaluated by a climbing drum peel method, and judged according to the following criteria.
A: No peeling with a peeling torque of 10 N · mm / mm ×: Peeling with a peeling torque of 10 N · mm / mm

(3) Impact resistance: In accordance with the method described in JP-A-2005-161852, a 45 g golf ball is applied to a test piece (100 mm × 100 mm) of a metal / fiber reinforced resin composite at a speed of 50 m / sec. After impacting 20,000 times, the test piece was cut around the impact location, its cross section was observed and evaluated according to the following criteria.
◎: No cracks are observed ×: Cracks are generated

(4) Resistance to cold test: A sample after performing 200 cycles of a -65 ° C. and 150 ° C. cooling test on a metal / fiber reinforced resin composite test piece (100 mm × 100 mm) was judged according to the following criteria: .
A: Neither peeling nor crack of the metal layer and the fiber reinforced resin layer is observed Δ: Either peeling of the metal layer and the fiber reinforced resin layer or crack is observed ×: Peeling of the metal layer and the fiber reinforced resin layer Both cracks are recognized

Example 1
A catalyst solution was prepared by dissolving 51 parts of benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and 79 parts of triphenylphosphine in 952 parts of toluene. Separately, 100 parts of dicyclopentadiene (DCP), 0.74 parts of allyl methacrylate as a chain transfer agent, 1.2 parts of di-tert-butyl peroxide (half-life temperature of 1 minute at 186 ° C.) as a crosslinking agent, crosslinking aid 20 parts of m-diisopropenylbenzene as an agent, 1.0 part of 3,5-di-tert-butyl-4-hydroxyanisole as a phenolic antioxidant, silica as a filler (manufactured by Admafine, average particle size 0 0.5 μm) 100 parts were mixed to prepare a monomer solution. The above catalyst solution was added thereto at a rate of 0.12 ml per 100 g of cycloolefin monomer and stirred to prepare a polymerizable composition.

Next, 100 parts of the resulting polymerizable composition was cast on a polyethylene naphthalate film (thickness 75 μm), and carbon fibers (continuous fiber plain weave, fiber weight per unit area: 190 g / m) arranged in one direction thereon. m ² , fiber tensile strength 4,900 MPa, fiber tensile elastic modulus: 294 GPa), and then cast 80 parts of the polymerizable composition thereon, and further cover with a polyethylene naphthalate film, and a roller. Used to impregnate the carbon fiber with the polymerizable composition. Subsequently, this was heated for 1 minute in the heating furnace heated at 150 degreeC, the polymerizable composition was block-polymerized, and the prepreg with a thickness of 0.13 mm was obtained. The carbon fiber ratio of the prepreg was 70% by weight, and the volatile component was 0.7%.

  This prepreg was cut into a 100 mm square size and the polyethylene naphthalate film was peeled off. Then, 6 sheets of the prepreg were stacked, and titanium alloy plates (Ti-15V-3Cr-3Al-3Sn, thickness) were formed on both surfaces of the 6-sheet laminate. 0.13 mm: The surface in contact with the prepreg was polished with # 800 sanding paper and then washed with acetone), and then heat-pressed at 3 MPa and 200 ° C. for 15 minutes with a hot press to be metal / fiber A reinforced resin composite was produced. The adhesion, impact resistance, and cold test resistance of this metal / fiber reinforced resin composite were evaluated, and the results are shown in Table 1.

Example 2
Each characteristic was performed in the same manner as in Example 1 except that the titanium alloy plate was washed with acetone and then treated with a silane coupling agent (p-styryltrimethoxysilane; manufactured by Shin-Etsu Chemical Co., Ltd., product name KBM-1403). The results are shown in Table 1.

Example 3
Each characteristic was evaluated in the same manner as in Example 1 except that 20 parts of polybutadiene was added to the polymerizable composition, and the results are shown in Table 1.

Comparative Example 1
Epicoat 1005F (bifunctional bisphenol type resin, epoxy equivalents 950 to 1050) 20 parts, Epicoat 828 (bifunctional bisphenol type resin, epoxy equivalents 176 to 180) 80 parts, dicyandiamide 5 parts as a curing agent, and 1, 1 as a curing accelerator An epoxy resin composition consisting of 4.2 parts of 1 "-4 (methyl-m-phenylene) bis (3,3" dimethylurea) is thinly and evenly applied onto a release paper using a reverse roll coater to form a resin film. Produced. Next, the two resin films are stacked on both sides of the carbon fiber on the carbon fiber (fiber basis weight: 190 g / m ² , fiber tensile strength 4,900 MPa, fiber tensile elastic modulus: 294 GPa) arranged in one direction on the sheet. The epoxy resin composition was impregnated by heating and pressurizing to prepare a unidirectional prepreg. The carbon fiber content of the prepreg was adjusted to 70% by weight.

  Next, after stacking 6 layers of the prepared prepreg in the 0 ° direction, titanium alloy plates (Ti-15V-3Cr-3Al-3Sn, thickness 0.13 mm: surfaces in contact with the prepreg are formed on both surfaces of the 6-layer stack. , Polished with # 800 sanding paper and then washed with acetone) was laminated, and compression molding was performed for 2 hours at a temperature of 150 ° C. and a molding pressure of 981 KPa using a hot press machine. After demolding, each characteristic of the obtained metal / fiber reinforced resin composite was evaluated, and the results are shown in Table 1.

  From the results in Table 1, it can be seen that the metal / fiber reinforced resin composites of the present invention are all excellent in adhesion, impact resistance, and cold test resistance (Examples 1 to 3). On the other hand, it was found that a resin using an epoxy resin as a matrix resin is inferior in impact resistance and cold test resistance although it has high adhesion (Comparative Example 1).

Claims (11)

A metal / fiber reinforced resin composite comprising a cross-linked cycloolefin polymer and a fiber reinforced resin layer containing carbon fibers and a metal plate. The metal / fiber reinforced resin composite according to claim 1, wherein the metal plate is made of iron, aluminum, titanium, or an alloy containing them. The metal / fiber reinforced resin composite according to claim 1 or 2, wherein the fiber reinforced resin layer contains a filler. The metal / fiber reinforced resin composite according to any one of claims 1 to 3, wherein the peel strength between the metal plate and the fiber reinforced resin layer is 10 N · mm / mm or more. The metal / fiber reinforced resin composite according to any one of claims 1 to 4, which is a vehicle member. A method for producing a metal / fiber reinforced resin composite, wherein a crosslinkable prepreg comprising a cycloolefin polymer, a crosslinking agent and carbon fibers is laminated on a metal plate and then crosslinked. The production method according to claim 6, wherein the crosslinkable prepreg is obtained by polymerizing a polymerizable composition containing a cycloolefin monomer, a metathesis polymerization catalyst and a crosslinking agent in the presence of carbon fiber. The production method according to claim 6 or 7, wherein the crosslinking agent is a radical generator. The production method according to claim 8, wherein the polymerization is performed at a temperature equal to or lower than a one-minute half-life temperature of the radical generator. The method according to any one of claims 6 to 9, wherein the surface of the metal plate is treated with a silane coupling agent. The production method according to claim 10, wherein the silane coupling agent has a reactive group that reacts with the crosslinking agent.