JP2010106219A - Prepreg, fiber-reinforced resin molded product, and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fiber-reinforced resin molded product and a laminate having excellent flame retardance and mechanical strength in a non-halogen system, and to provide prepreg useful for producing the same. <P>SOLUTION: The prepreg includes: a cycloolefin polymer; cross-linking agent; phosphinic acid salt; and carbon fibers. The fiber-reinforced resin molded product is obtained by curing the prepreg. The laminate is obtained by laminating the prepreg on the prepreg and/or other materials, and then curing the resultant superposed material. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a prepreg, a fiber-reinforced resin molded body, and a laminate. Specifically, the present invention relates to a fiber reinforced resin molded article and a laminate having excellent non-halogen flame retardancy (hereinafter referred to as non-halogen flame retardancy) and mechanical strength, and a prepreg useful for production thereof.

  Fiber reinforced resin consisting of carbon fiber and matrix resin has excellent mechanical properties, so it can be used for sports applications such as golf clubs, tennis rackets, fishing rods, vehicle structures such as automobiles and aircraft, and general industrial applications. Widely used. Among these, in particular, structural materials such as automobiles and airplanes, building materials, and the like are strongly required to have flame retardancy in order to prevent the structural materials from igniting and spreading due to fire. Conventionally used halogenated flame retardants have a high flame retardant effect, but they generate harmful gases such as hydrogen halides and organic halides between ignition and extinguishing. Was demanded.

  For example, in Patent Document 1, a resin film containing 10 to 30 parts by weight of a non-halogen flame retardant is bonded to carbon fiber with respect to 100 parts by weight of an epoxy resin that does not contain a halogen atom, a curing agent, and 100 parts by weight of the epoxy resin. It is described that V-0 is achieved by UL-94, which is an evaluation standard for flame retardancy, and the flame retardancy is excellent.

  Patent Document 2 discloses a method for producing a resin molded body by bulk polymerization of a polymerizable composition containing a cycloolefin monomer having an aromatic ring, a metathesis polymerization catalyst, a chain transfer agent, a crosslinking agent, a flame retardant, and the like. It is disclosed. In this method, halogen flame retardant, antimony flame retardant, metal hydroxide flame retardant, red phosphorus, triphenyl phosphate, tricresyl phosphate, ammonium polyphosphate, guanidine phosphate, phosphazene, etc. It describes that flame retardants such as a flame retardant and a nitrogen flame retardant can be used. Specifically, a combination of red phosphorus, ammonium polyphosphate, and aluminum hydroxide is shown. In addition, this method describes that the polymerizable composition may be polymerized after being impregnated into the fiber reinforcement, and that carbon fiber is used for the fiber reinforcement.

Japanese Patent Laid-Open No. 11-147965 International Publication No. 05/014690 Pamphlet

However, in the prepreg of Patent Document 1, an epoxy resin is mainly used as a matrix resin, and since the resin varnish has a high viscosity, impregnation into carbon fibers becomes difficult, and the fiber obtained by curing the prepreg There is a problem that the mechanical strength or the like of the reinforced resin molded body is lowered under high temperature and high humidity, and the resin molded body described in Patent Document 2 that uses a polymer of cycloolefin monomer as a matrix resin is a fiber reinforcing material. As a result of studies by the present inventor, it is sometimes difficult to impart non-halogen flame retardancy when carbon fiber is used.
An object of the present invention is to provide a fiber reinforced resin molded article and a laminate excellent in non-halogen flame retardancy and mechanical strength. Moreover, the objective of this invention is providing the prepreg useful for manufacture of the said fiber reinforced resin molded object and a laminated body.

  As a result of intensive studies in view of the above problems, the present inventors impregnated a carbon fiber with a polymerizable composition containing a phosphinate as a polymerization catalyst such as a cycloolefin monomer and a ruthenium complex, a crosslinking agent, and a flame retardant, and then polymerized. The fiber reinforced resin molded article or laminate excellent in non-halogen flame retardancy and mechanical strength can be obtained by preparing a prepreg and then laminating and curing the prepreg alone or as desired. I found. In addition, when a specific carbon fiber is used, the impregnation property of the polymerizable composition containing the cycloolefin monomer into the carbon fiber is greatly improved, and the non-halogen flame retardancy of the fiber reinforced resin molded product is accordingly accompanied. And the mechanical strength characteristics can be remarkably improved, and further, by adding a crosslinking aid to the polymerizable composition, the impregnation property of the composition into carbon fibers and the resulting fiber reinforced resin molded product and laminate can be obtained. It was found that the mechanical strength and heat resistance can be improved to a high degree. The present inventor has completed the present invention based on these findings.

That is, the present invention
[1] A prepreg comprising a cycloolefin polymer, a crosslinking agent, a phosphinate, and carbon fiber,
[2] The prepreg according to the above [1], wherein the carbon fiber is an acrylic carbon fiber,
[3] A method for producing a prepreg characterized by polymerizing a polymerizable composition comprising a cycloolefin monomer, a polymerization catalyst, a crosslinking agent, and a phosphinate in the presence of carbon fiber,
[4] The method for producing a prepreg according to the above [3], wherein the polymerization catalyst is a ruthenium complex having a heterocyclic structure,
[5] The method for producing a prepreg according to the above [3] or [4], wherein the polymerizable composition further contains a crosslinking aid,
[6] A fiber-reinforced resin molded article obtained by curing the prepreg according to [1] or [2], [7] the prepreg according to [1] or [2], and the prepreg and / or other material. And a laminate obtained by curing
Is to provide.

  ADVANTAGE OF THE INVENTION According to this invention, the prepreg useful for the fiber reinforced resin molding and laminated body excellent in non-halogen flame retardance and mechanical strength, and those manufacture is provided. Since the fiber-reinforced resin molded body and laminate of the present invention have the above-mentioned properties, they are widely and suitably used as members for vehicles such as automobiles and airplanes, and as various members in fields such as sports, civil engineering, and architecture. can do.

  The prepreg of the present invention comprises a cycloolefin polymer, a crosslinking agent, a phosphinate as a flame retardant, and carbon fiber. The fiber-reinforced resin molded body of the present invention is formed by curing the prepreg, and the laminate of the present invention is formed by laminating the prepreg and the prepreg and / or other materials and then curing.

(Cycloolefin polymer)
The cycloolefin polymer used in the present invention is obtained by polymerizing a cycloolefin monomer having a ring structure formed of carbon atoms and having one polymerizable carbon-carbon double bond in the ring structure. It is a thermoplastic resin. The cycloolefin polymer has a ring structure in the cycloolefin monomer unit, and examples of the ring structure include a saturated cyclic hydrocarbon (cycloalkane) structure and an unsaturated cyclic hydrocarbon (cycloalkene) structure. Since the obtained fiber reinforced resin molded article and laminate are excellent in mechanical strength and heat resistance, the cycloolefin monomer unit is preferably a cycloalkane structure or a cycloalkene structure. The number of carbon atoms constituting the ring structure is not particularly limited, but is usually in the range of 4 to 30, preferably 5 to 20, and more preferably 5 to 15. The ratio of the cycloolefin monomer unit in the cycloolefin polymer may be appropriately selected as desired, but is preferably 50% by weight or more, more preferably 70% by weight or more, and further preferably 90% by weight or more. When the ratio of the cycloolefin monomer unit is within this range, the mechanical strength of the obtained prepreg and the like is improved, which is preferable.

  Specific examples of the cycloolefin polymer 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 monomer, and a hydride thereof. . The molecular weight of the cycloolefin polymer may be appropriately selected as desired, but it is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (eluent: tetrahydrofuran), and usually 1,000 to 1,000. 1,000, preferably 5,000 to 500,000, more preferably 10,000 to 100,000. If the molecular weight of the cycloolefin polymer is within this range, the properties such as the fluidity of the prepreg, the mechanical strength and heat resistance of the fiber-reinforced resin molded product, and the interlayer adhesion of the laminate are highly balanced, which is preferable. .

(Crosslinking agent)
The crosslinking agent used in the present invention is used for the purpose of inducing a crosslinking reaction in a cycloolefin polymer which is a thermoplastic resin. In the present invention, a radical generator is usually preferably used as the crosslinking agent. 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; 3,3,5,7,7-pentamethyl-1,2,4-trioxepane, 3,6,9-triethyl-3 , 6,9-trimethyl-1,4,7-triperoxonane, cyclic peroxides such as 3,6-diethyl-3,6-dimethyl-1,2,4,5-tetroxane; In particular, when a cycloolefin polymer is produced by metathesis polymerization, cyclic peroxides, dialkyl peroxides, and peroxyketals are preferred in that there are few obstacles to the metathesis polymerization reaction.

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

  Examples of the nonpolar radical generator include 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 1,1,2-triphenylethane, 1,1, Examples thereof include 1-triphenyl-2-phenylethane.

When the crosslinking agent used in the present invention is a radical generator, the 1-minute half-life temperature is appropriately selected depending on the conditions of curing (crosslinking of the cycloolefin polymer of the present invention), but is usually 100 to 300 ° C, preferably Is in the range of 150-250 ° C, more preferably 160-230 ° C. Here, the half-life temperature for 1 minute is a temperature at which half of the radical generator decomposes in 1 minute. The 1-minute half-life temperature of the radical generator may be referred to, for example, a catalog or homepage of each radical generator manufacturer (for example, Nippon Oil & Fats Co., Ltd.).
The radical generators can be used alone or in combination of two or more. The amount of the radical generator used for the cycloolefin polymer used in the present invention is usually 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0 to 100 parts by weight of the cycloolefin polymer. The range is from 5 to 5 parts by weight.

(Flame retardants)
In the present invention, a phosphinate is used as a flame retardant. The phosphinic acid salt used in the present invention is not particularly limited as long as it is industrially used. Such phosphinic acid salts are described in, for example, Japanese Patent Application Laid-Open Nos. 2000-219772, 2004-115797, and 2006-328124.

  The phosphinic acid salt is preferably a metal salt of phosphinic acid, among which calcium phosphinic acid salt, zinc phosphinic acid salt, and aluminum phosphinic acid salt are preferably used. Examples of the phosphinic acid salt include monophosphinic acid salts; oligophosphinic acid salts such as diphosphinic acid salts; and phosphinic acid polymer salts; depending on the number of phosphinic acid units. An acid salt is preferably used, and a monophosphinic acid salt is more preferably used.

  Preferable specific examples of the phosphinic acid salt include compounds represented by general formula (1) and general formula (2).

(Wherein R ¹ and R ² each independently represents an alkyl group or an aryl group, R ³ represents an alkylene group, an arylene group, an alkylarylene group, or an arylalkylene group, M represents a metal atom, m and n each represents an integer of 1 to 4, and x represents an integer of 1 to 4.)

Preferable examples of R ¹ and R ² include an alkyl group having 1 to 6 carbon atoms and an aryl group having 3 to 12 carbon atoms. Preferable examples of R ³ include an alkylene group having 1 to 10 carbon atoms; an arylene group, an alkylarylene group, or an arylalkylene group having 6 to 12 carbon atoms; Preferable examples of M include a calcium atom, an aluminum atom and a zinc atom. m is 2 when M is a calcium atom or a zinc atom, and 3 when M is an aluminum atom. Specific examples of the phosphinic acid moiety include dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methandi (methylphosphinic acid), benzene-1,4- (dimethylphosphinic acid), methyl Examples thereof include phenylphosphinic acid and diphenylphosphinic acid.

  Examples of the compound represented by the general formula (1) include aluminum diethylphosphinate, zinc diethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate and the like. Examples of the compound represented by the general formula (2) include aluminum diethyldiphosphinate, zinc diethyldiphosphinate, aluminum dimethyldiphosphinate, zinc dimethyldiphosphinate and the like.

  These phosphinic acid salts can be used alone or in combination of two or more. The blending amount is appropriately selected as desired, but is usually in the range of 1 to 500 parts by weight, preferably 10 to 400 parts by weight, more preferably 20 to 200 parts by weight with respect to 100 parts by weight of the cycloolefin polymer. is there. If the amount of phosphinate is within this range, the resulting fiber reinforced resin molded product and laminate will have non-halogen flame resistance, crack resistance, mechanical strength, heat resistance under high temperature and high humidity, etc. Is highly balanced and suitable.

  In the present invention, if desired, in addition to the phosphinic acid salt, other flame retardants may be added to the prepreg. Other flame retardants include, for example, metal hydroxide flame retardants such as aluminum hydroxide and magnesium hydroxide; metal oxide flame retardants such as magnesium oxide and aluminum oxide; red phosphorus, triphenyl phosphate, tricresyl Phosphoric flame retardants other than phosphinates such as phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate, bisphenol A bis (dicresyl) phosphate; melamine derivatives Flame retardants containing both phosphorus and nitrogen, such as ammonium polyphosphate, melamine phosphate, melamine phosphate, melamine polyphosphate, melam polyphosphate, guanidine phosphate, phosphazenes, etc. ; And the like. These other flame retardants can be used alone or in combination of two or more. The blending amount may be appropriately selected within a range that does not impair the effects of the present invention. However, the content of the phosphinic acid salt in the total flame retardant constituting the prepreg of the present invention is usually 10% by weight or more, preferably It is preferable to be 40% by weight or more.

(Carbon fiber)
As the carbon fiber used in the present invention, a conventionally known material can be used without any particular limitation. There is no limitation in particular in the kind of carbon fiber, For example, various carbon fibers, such as an acrylic type, a pitch type, and a rayon type, can be used. In particular, when the prepreg of the present invention is obtained by bulk polymerization of a cycloolefin monomer by metathesis polymerization to form a cycloolefin polymer by using a polymerizable composition described later, the resulting fiber does not interfere with the metathesis polymerization. Since the properties such as mechanical strength, toughness, and heat resistance of reinforced resin moldings and laminates can be improved to a high degree, the use of acrylic carbon fibers, which are carbon fibers produced using acrylic fibers (polyacrylonitrile fibers) as raw materials, is required. Is preferred. In addition, since acrylic carbon fibers have good affinity with cycloolefin polymers and cycloolefin monomers, the polymer and the monomers have excellent impregnation properties into carbon fibers, resulting in a prepreg with few voids, and curing the prepreg. The fiber reinforced resin molded product and laminate obtained in this manner are favorable in terms of mechanical strength and non-halogen flame retardancy.

  The strength characteristics of the carbon fibers used in the present invention are not particularly limited and may be appropriately selected as desired. 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%. If the strength characteristics of the carbon fiber are within these ranges, the mechanical strength and toughness of the obtained fiber-reinforced resin molded body and laminate are highly balanced, which is preferable.

  The cross-sectional shape of the carbon fiber used in the present invention is not particularly limited, but is preferably substantially circular. When the cross-sectional shape is circular, when the cycloolefin polymer or cycloolefin monomer is impregnated, filament rearrangement is likely to occur, and the cycloolefin polymer or cycloolefin monomer can easily penetrate between the fibers. It is. Furthermore, since the thickness of the fiber bundle can be reduced, there is an advantage that it is easy to obtain a prepreg excellent in drapeability. 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 carbon fiber used in the present invention is appropriately selected as desired without any particular limitation, and both short fiber and long fiber can be used as the carbon fiber, but fiber reinforcement having higher mechanical strength and toughness. When it is desired to obtain a resin molded body or a laminate, it is preferable to use continuous fibers having a fiber length of 1 cm or more, preferably 2 cm or more, more preferably 3 cm or more, and even more preferably 3 cm.

  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, from the viewpoint of obtaining a fiber reinforced resin molded article having higher levels of toughness and impact resistance, the form of carbon fiber is preferably a form of continuous fiber such as woven fabric, unidirectional strand, and roving. As the form of the woven fabric, conventionally known woven fabrics can be used. For example, all of woven structures in which fibers are interlaced such as plain weave, satin weave, twill weave, and triaxial woven fabric can be used. Moreover, as a form of the woven fabric, not only two-dimensional but also a stitched woven fabric or a three-dimensional woven fabric in which fibers are reinforced in the thickness direction of the woven fabric can be used.

The carbon fiber used in the present invention is preferably 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 preferably 1,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 10, The range is from 000 to 30,000.
These carbon fibers can be used alone or in combination of two or more. The blending amount is appropriately selected depending on necessity, but is usually in the range of 10 to 90% by weight, preferably 20 to 85% by weight, more preferably 30 to 80% by weight in the prepreg of the present invention.

(Prepreg)
The prepreg of the present invention contains a cycloolefin polymer, a crosslinking agent, a phosphinate as a flame retardant, and carbon fiber as essential components, and may contain other compounding agents as desired.
Other compounding agents are not particularly limited and are appropriately selected as desired. However, crosslinking aids, fillers, anti-aging agents, elastomer materials, colorants, light stabilizers, pigments, foaming agents, polymer modifiers are selected. An agent etc. can be mentioned.

  In the present invention, by blending a crosslinking aid, it is possible to highly balance the formability of the prepreg and the mechanical strength and heat resistance of the fiber reinforced resin molded article and laminate obtained by curing the prepreg. Is preferred.

  As the crosslinking assistant, a polyfunctional compound having two or more crosslinkable carbon-carbon unsaturated bonds that can participate in the crosslinking reaction induced by the crosslinking agent without involving the polymerization reaction is suitably used. Such a crosslinkable carbon-carbon unsaturated bond is preferably present, for example, as a terminal vinylidene group, particularly as an isopropenyl group or a methacryl group, in the compound constituting the crosslinking aid.

  Specific examples of the crosslinking aid include polyfunctional compounds having two or more isopropenyl groups, such as p-diisopropenylbenzene, m-diisopropenylbenzene, o-diisopropenylbenzene; ethylene dimethacrylate, 1, 3-butylene dimethacrylate, 1,4-butylene dimethacrylate, 1,6-hexanediol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 2, 2'-bis (4-methacryloxydiethoxyphenyl) propane, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, etc. And the like polyfunctional compound having above. Especially, as a crosslinking adjuvant, the polyfunctional compound which has 2 or more of methacryl groups is preferable. Among the polyfunctional compounds having two or more methacryl groups, polyfunctional compounds having three methacryl groups such as trimethylolpropane trimethacrylate and pentaerythritol trimethacrylate are more preferable.

  These crosslinking aids can be used alone or in combination of two or more. The amount of the crosslinking aid is usually 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight, and more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the cycloolefin polymer.

  In the present invention, blending a filler is preferable because the properties such as mechanical strength, heat resistance and chemical resistance of the obtained fiber reinforced resin molded article and laminate can be highly balanced. The filler is not particularly limited as long as it is generally used industrially, and any of inorganic fillers and organic fillers can be used, but inorganic fillers are 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. The blending amount is usually 50 parts by weight or more, preferably 50 to 1,000 parts by weight, more preferably 50 to 750 parts by weight, and further preferably 50 to 500 parts by weight with respect to 100 parts by weight of the cycloolefin polymer. It is a range. If the filler is within this range, the properties such as mechanical strength, heat resistance and chemical resistance of the fiber reinforced resin molded product and laminate are highly balanced, which is preferable.

In the present invention, as an anti-aging agent, 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 is blended. Thus, the heat resistance of the obtained fiber-reinforced resin molded article and laminate can be improved to a high degree without inhibiting the crosslinking reaction, which is preferable. Among these, a phenolic antioxidant and an amine antioxidant are preferable, and a phenolic antioxidant is particularly preferable.
These anti-aging agents can be used alone or in combination of two or more. The blending amount of the antioxidant is appropriately selected as desired, but is usually 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, more preferably 0 to 100 parts by weight of the cycloolefin polymer. .01 to 2 parts by weight.

  In addition, blending the elastomer material is preferable because the toughness of the resulting fiber-reinforced resin molded product and laminate can be improved. 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 compounding quantity is 0.1-100 weight part normally with respect to 100 weight part of cycloolefin polymers, Preferably it is 1-50 weight part, More preferably, it is the range of 3-30 weight part. If the blending amount of the elastomer material is within this range, the toughness of the resulting fiber reinforced resin molded product and laminate can be improved to a high degree, which is preferable.

  As the colorant, a dye or a pigment is used. There are various kinds of dyes, and known ones may be appropriately selected and used. These colorants can be used alone or in combination of two or more. The blending amount is appropriately selected within a range that does not impair the effects of the present invention.

  The thickness of the prepreg of the present invention is appropriately selected as desired, but is usually in the range of 0.001 to 10 mm, preferably 0.005 to 1 mm, more preferably 0.01 to 0.5 mm. When the thickness of the prepreg is within this range, the shapeability at the time of lamination of the prepreg, and the mechanical strength and toughness of the fiber reinforced resin molded body and the laminated body obtained by curing are sufficiently exhibited.

  The amount of the volatile component of the prepreg of the present invention is an amount that volatilizes when heated at 200 ° C. for 1 hour, and is usually 30% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, and most preferably 1%. % By weight or less. If the amount of volatile components in the prepreg, such as unreacted monomers, is excessively large, the prepreg becomes sticky, its operability and storage stability deteriorate, and the cured fiber reinforced resin molded product or laminate There is a possibility that voids are generated, the appearance and mechanical strength are reduced, and there is a problem in the occurrence of bleeding, heat resistance, chemical resistance, and the like.

The method for producing the prepreg of the present invention is not particularly limited. For example, a wet process in which a cycloolefin polymer, a crosslinking agent, and a flame retardant are dissolved in an arbitrary solvent to reduce the viscosity and impregnate the carbon fiber and then remove the solvent. Method: Applying cycloolefin polymer on protective film, aligning carbon fiber on it, impregnating heated and dissolved cycloolefin polymer with a roll or doctor blade, etc. Law). The protective film is not particularly limited, and resins such as polyethylene terephthalate, polypropylene, polyethylene, polycarbonate, polyethylene naphthalate, polyarylate, and nylon; iron, stainless steel, copper, aluminum, nickel, chromium, gold, silver, and the like Examples thereof include metal materials. Although there is no limitation in particular also about the shape, Usually, it uses as metal foil or a resin film. The thickness of these metal foils or resin films is usually 1 to 150 μm, preferably 2 to 100 μm, more preferably 3 to 75 μm from the viewpoint of workability and the like. As a method for producing the prepreg of the present invention, as a cycloolefin monomer, a polymerization catalyst, a crosslinking agent, and a flame retardant, in particular, from the viewpoint of efficiently producing a prepreg having few volatile components and excellent operability and stability. A direct polymerization method in which a polymerizable composition containing a phosphinate is bulk polymerized in the presence of carbon fiber is suitable.
Hereinafter, the production method of the prepreg of the present invention will be described in detail by taking a direct polymerization method as an example.

(Manufacturing method of prepreg)
The polymerizable composition used in the present invention usually contains a cycloolefin monomer, a polymerization catalyst, a crosslinking agent, and a phosphinic acid salt as a flame retardant as essential components, and optionally a polymerization regulator, a chain transfer agent, a polymerization agent. A reaction retarder and other compounding agents are further added. When producing a prepreg using such a polymerizable composition, it is preferable to add other compounding agents to the polymerizable composition in addition to the crosslinking agent and the flame retardant from the viewpoint of improving production efficiency. is there.

  The cycloolefin monomer used in the present invention is a compound having a ring structure formed of carbon atoms and having one polymerizable carbon-carbon double bond in the ring structure. As used herein, “polymerizable carbon-carbon double bond” refers to a chain-polymerizable carbon-carbon double bond. There are various types of polymerization such as ionic polymerization, radical polymerization, and metathesis polymerization. In the present invention, it usually refers to metathesis ring-opening polymerization.

Examples of the ring structure of the cycloolefin monomer include monocycles, polycycles, condensed polycycles, bridged rings, and combination polycycles thereof. Although there is no limitation in particular in carbon number which comprises each ring structure, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is 5-15 pieces.
The cycloolefin monomer may have a hydrocarbon group having 1 to 30 carbon atoms such as an alkyl group, an alkenyl group, an alkylidene group, or an aryl group, or a polar group such as a carboxyl group or an acid anhydride group as a substituent. .

  As the cycloolefin monomer, either a monocyclic cycloolefin monomer or a polycyclic cycloolefin monomer can be used. From the viewpoint of improving the mechanical strength and water resistance of the obtained fiber reinforced resin molded product and laminate, a polycyclic cycloolefin monomer is preferred. As the polycyclic cycloolefin monomer, a norbornene-based monomer is particularly preferable. The “norbornene monomer” refers to a cycloolefin monomer having a norbornene ring structure in the molecule. For example, norbornenes, dicyclopentadiene, tetracyclododecene and the like can be mentioned.

  Cycloolefin monomers are divided into those having no crosslinkable carbon-carbon unsaturated bonds and those having one or more crosslinkable carbon-carbon unsaturated bonds. As used herein, “crosslinkable carbon-carbon unsaturated bond” refers to a carbon-carbon unsaturated bond that does not participate in ring-opening polymerization and can participate in a crosslinking reaction. The crosslinking reaction is a reaction that forms a bridge structure, and there are various forms such as a condensation reaction, an addition reaction, a radical reaction, and a metathesis reaction. In the present invention, usually, a radical crosslinking reaction or a metathesis crosslinking reaction. In particular, it refers to a radical crosslinking reaction. Examples of the crosslinkable carbon-carbon unsaturated bond include carbon-carbon unsaturated bonds other than aromatic carbon-carbon unsaturated bonds, that is, aliphatic carbon-carbon double bonds or triple bonds. Usually refers to an aliphatic carbon-carbon double bond. In the cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds, the position of the unsaturated bond is not particularly limited, and within the ring structure formed of carbon atoms, any other than the ring structure For example, at the end or inside of the side chain.

  Examples of cycloolefin monomers having no crosslinkable carbon-carbon unsaturated bond include cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, and 3-chlorocyclopentene. , Cyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene and other monocyclic cycloolefin monomers; norbornene, 5-methyl-2-norbornene, 5 -Ethyl-2-norbornene, 5-propyl-2-norbornene, 5,6-dimethyl-2-norbornene, 1-methyl-2-norbornene, 7-methyl-2-norbornene, 5,5,6-trimethyl-2 -Norbornene, 5-Fe -2-norbornene, tetracyclododecene, 1,4-methano -1.4.4A. 9a tetrahydrofluorene (MTF), 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano -1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a -Octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5 , 8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5 , 8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano- , 2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a -Octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4 , 5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a , 5,8,8a-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloro-2-norbornene, 5,5-dichloro-2-norbornene, 5-fluoro-2-norbornene, 5,5 6-trifluoro-6-trifluoromethyl-2- Lubornene, 5-chloromethyl-2-norbornene, 5-methoxy-2-norbornene, 5,6-dicarboxyl-2-norbornene anhydrate, 5-dimethylamino-2-norbornene, 5-cyano-2-norbornene, etc. The norbornene-based monomer having no crosslinkable carbon-carbon unsaturated bond is preferable.

Examples of the cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds include 3-vinylcyclohexene, 4-vinylcyclohexene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4- Monocyclic cycloolefin monomers such as cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene; 5-ethylidene-2-norbornene, 5-methylidene -2-norbornene, 5-isopropylidene-2-norbornene, 5-vinyl-2-norbornene, 5-allyl-2-norbornene, 5,6-diethylidene-2-norbornene, dicyclopentadiene, 2,5-norbornadiene, etc. Norbornene-based monomers; Sexual carbon - is a norbornene-based monomer having one or more carbon unsaturated bond.
These cycloolefin monomers can be used alone or in combination of two or more. In addition, any monomer that can be copolymerized with a cycloolefin monomer can be further used as long as the desired effect of the present invention is not inhibited.

As the cycloolefin monomer used in the present invention, the one containing a cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds is used to obtain the mechanical strength of the resulting fiber reinforced resin molded product and laminate. Is improved and suitable.
In the cycloolefin monomer blended in the polymerizable composition of the present invention, a blend of a cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds and a cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bonds The ratio is appropriately selected as desired, but in a weight ratio (cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond / cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bond), usually, It is in the range of 5/95 to 100/0, preferably 10/90 to 90/10, more preferably 15/85 to 70/30. If the blending ratio is within such a range, the obtained fiber-reinforced resin molded body and laminate are suitable because the properties such as mechanical strength, interlayer adhesion, and non-halogen flame retardancy are highly balanced.

  The polymerization catalyst is not particularly limited as long as it can polymerize the cycloolefin monomer, but the polymerizable composition is preferably used directly for bulk polymerization in the production of a prepreg, and is usually metathesis. It is preferable to use a polymerization catalyst.

  Examples of the metathesis polymerization catalyst include a complex formed by bonding a plurality of ions, atoms, polyatomic ions, compounds, etc. with a transition metal atom as a central atom, which is capable of metathesis ring-opening polymerization of the cycloolefin monomer. It is done. As transition metal atoms, atoms of Group 5, Group 6 and Group 8 (according to the long-period periodic table; the same shall apply 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. Examples of the Group 8 atom include Examples thereof include ruthenium and osmium. Among them, group 8 ruthenium and osmium are preferable as the transition metal atom. That is, the metathesis polymerization catalyst used in the present invention is preferably a complex having ruthenium or osmium as a central atom, and more preferably a complex having ruthenium as a central atom. As the complex having ruthenium as a central atom, a ruthenium carbene complex in which a carbene compound is coordinated to ruthenium is preferable. Here, the “carbene compound” is a general term for compounds having a methylene free group, and refers to a compound having an uncharged divalent carbon atom (carbene carbon) as represented by (> C :). Since ruthenium carbene complex is excellent in catalytic activity during polymerization, when the polymerizable composition is subjected to bulk polymerization to obtain a prepreg, the resulting prepreg has little odor derived from unreacted monomers, and has good productivity and good quality. Prepreg is obtained. In addition, it is relatively stable to oxygen and moisture in the air and is not easily deactivated, so that it can be used even in the atmosphere.

  In addition, the use of a ruthenium complex having a heterocyclic structure, for example, a ruthenium complex having a compound having a heterocyclic structure, which will be described later, as a ligand is compatible with acrylic carbon fibers and is obtained by curing. And in a laminated body, each characteristic, such as an external appearance, mechanical strength, heat resistance, and chemical resistance, can be highly balanced, and it is suitable. Examples of atoms other than carbon atoms in the heterocyclic structure include an oxygen atom and a nitrogen atom, and a nitrogen atom is preferable. Moreover, as a heterocyclic structure, an imidazoline ring or an imidazolidine ring structure is preferable. 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-dimesitylimidazolidine-2-ylidene, 1,3-dicyclohexylimidazolidine 2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3-dimesityl-2,3-dihydrobenzii Such as imidazole-2-ylidene and the like.

  Specific examples of a suitable ruthenium carbene complex used as a metathesis polymerization catalyst in the present invention include benzylidene (1,3-dimesityrylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3 -Dimesitylimidazolidin-2-ylidene) (3-methyl-2-buten-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- Hydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4- Triazole-5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityloimidazolidine-2-ylidene ) Ruthenium carbene complexes having a carbene compound having a heterocyclic structure and other neutral electron donors as ligands such as pyridine ruthenium dichloride. Here, the “neutral electron donor” refers to a ligand having a neutral charge when separated from the central metal atom.

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

  If desired, the metathesis polymerization catalyst can be used dissolved or suspended 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 a chain aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, and a hydrocarbon having an alicyclic ring and an aromatic ring.

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

In the present invention, by adding a chain transfer agent to the polymerizable composition, the fluidity and formability of the prepreg, the mechanical strength of the fiber reinforced resin molded product and the laminate, and the adhesion between the materials of the laminate and Each characteristic such as heat resistance can be highly balanced, which is preferable.
As the chain transfer agent, a compound having one aliphatic carbon-carbon double bond that can participate in polymerization, particularly ring-opening polymerization, and can be bonded to the terminal of a polymer obtained by subjecting the polymerizable composition to a polymerization reaction. Is preferred. Examples of the double bond include a terminal vinyl group. The chain transfer agent may have one or more crosslinkable carbon-carbon unsaturated bonds.

Specific examples of such chain transfer agents include 1-hexene, 2-hexene, styrene, vinylcyclohexane, allylamine, glycidyl acrylate, allyl glycidyl ether, ethyl vinyl ether, methyl vinyl ketone, 2- (diethylamino) ethyl acrylate, 4- Chain transfer agents that do not have crosslinkable carbon-carbon unsaturated bonds, such as vinylaniline; divinylbenzene, vinyl methacrylate, allyl methacrylate, styryl methacrylate, allyl acrylate, undecenyl methacrylate, styryl acrylate, ethylene glycol Chain transfer agent having one crosslinkable carbon-carbon unsaturated bond, such as diacrylate; Chain transfer agent having two or more crosslinkable carbon-carbon unsaturated bonds, such as allyltrivinylsilane and allylmethyldivinylsilane And the like. Among these, in the obtained fiber reinforced resin molded article and laminate, those having one or more crosslinkable carbon-carbon unsaturated bonds are preferred from the viewpoint of highly balancing non-halogen flame retardancy and mechanical strength, Those having one crosslinkable carbon-carbon unsaturated bond are more preferred. Among such chain transfer agents, chain transfer agents having one vinyl group and one methacryl group are preferable, and vinyl methacrylate, allyl methacrylate, styryl methacrylate, undecenyl methacrylate, and the like are particularly preferable.
These chain transfer agents can be used alone or in combination of two or more. As a compounding quantity of the chain transfer agent to the polymeric composition of this invention, it is 0.01-10 weight part normally with respect to 100 weight part of cycloolefin monomers, Preferably it is 0.1-5 weight part.

In this invention, the viscosity increase can be suppressed by mix | blending a polymerization reaction retarder with a polymeric composition. Accordingly, a polymerizable composition formed by blending a polymerization reaction retarder is preferable because it becomes easy to uniformly impregnate the polymerizable composition into carbon fibers when preparing a prepreg. 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. These polymerization reaction retarders can be used alone or in combination of two or more. The blending amount is usually 1: 0.01 to 1: 100 parts by weight, preferably 1: 0.1 to 1:10 parts by weight, in a molar ratio of (metal atom in the metathesis polymerization catalyst: polymerization reaction retarder). Parts, more preferably in the range of 1: 0.1 to 1: 5 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 prepared, and other essential components such as a cycloolefin monomer and a crosslinking agent are optionally added. It can be prepared by preparing a liquid (monomer liquid) containing other compounding agents, adding the catalyst liquid to the monomer liquid, and stirring.

  Next, the obtained polymerizable composition is bulk polymerized in the presence of the carbon fiber to obtain the prepreg of the present invention. Here, “bulk polymerization of the polymerizable composition in the presence of carbon fiber” means that bulk polymerization is performed in a state where the carbon fiber and the polymerizable composition are in contact with each other. Specifically, for example, there is a method in which a woven fabric is used as the carbon fiber, the woven fabric is impregnated with a polymerizable composition, and then bulk polymerization is performed. The impregnation of the polymerizable composition into the carbon fiber is preferably performed on the support or in the mold.

  For example, when a protective film is used as a support, the carbon fiber is impregnated with the polymerizable composition. For example, the carbon fiber is placed on the protective film, and a predetermined amount of the polymerizable composition is spray-coated or dip-coated. By applying to a carbon fiber by a known method such as a roll coating method, a curtain coating method, a die coating method, a slit coating method, etc., and if desired, another protective film is stacked thereon and pressed from above with a roller or the like It can be carried out. 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. As the protective film used here, the same film as described above can be used.

  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 conducting polymerization in the mold, a sheet-like or film-like prepreg can be obtained.

  The polymerizable composition used in the present invention has a low viscosity as compared with a polymer varnish obtained by dissolving an epoxy resin or the like in a solvent, which is conventionally used in the production of a prepreg or a laminate, and is suitable for carbon fibers. Since the impregnation is excellent, according to the above method, the carbon fiber can be uniformly impregnated with the cycloolefin polymer obtained by polymerization. The obtained prepreg and the fiber reinforced resin molded product and laminate obtained by curing the prepreg have few voids and excellent mechanical strength.

  In addition, when bulk polymerization is performed, the polymerizable composition does not substantially contain a solvent that does not participate in the reaction, so that a step of removing the solvent after impregnating the carbon fiber is not necessary. It is excellent in productivity, and prepreg is preferable because it does not cause odor or swelling due to the residual solvent. Further, the cycloolefin polymer obtained by polymerization is substantially free of unreacted monomer, and therefore has substantially no odor due to the monomer, and the heat resistance of the resulting fiber reinforced resin molded product and laminate. Will be excellent.

  When the carbon fiber is a short fiber such as chopped, a method of mixing the carbon fiber with the polymerizable composition and then performing bulk polymerization can be used. 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. As a method for bulk polymerization, a method of performing bulk polymerization in a mold in the same manner as described above can be used. 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.

  The polymerizable composition of the present invention usually comprises a metathesis polymerization catalyst. In any of the above methods, the heating temperature for polymerizing the polymerizable composition is usually 50 to 250 ° C., preferably 80. It is -200 degreeC, More preferably, it is the range of 90-150 degreeC, and it is below 1 minute half life temperature of the said crosslinking agent, normally a radical generator, Preferably it is 10 degrees C or less, More preferably, it is 20 degrees C or less. The polymerization time may be appropriately selected, but is usually 10 seconds to 60 minutes, preferably 10 seconds to 20 minutes. Heating the polymerizable composition under such conditions is preferable because a prepreg with less unreacted monomer can be obtained.

  The carbon fiber content of the prepreg of the present invention thus obtained may be appropriately selected as desired, but is usually in the range of 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight. is there.

(Fiber-reinforced resin molded body and laminate)
The fiber-reinforced resin molded body of the present invention can be produced by curing the prepreg if desired and then curing. Moreover, the laminated body of this invention can be manufactured by laminating | stacking the said prepreg, the said prepreg, and / or another material, shaping | molding as needed, and hardening | curing.

  Other materials that may be laminated are appropriately selected as desired, and examples thereof include thermoplastic resin materials and metal materials, and metal materials are particularly preferably used. The thermoplastic resin materials include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, liquid crystal polyester and other polyesters; polyethylene, polypropylene, polybrylene and other polyolefins; polystyrene, polyoxymethylene, polyamide, polycarbonate, polymethylene methacrylate, polyimide, poly Examples include ether imide, polyether ketone, polyether ether ketone, and polysulfone. Examples of the metal material include stainless steel, iron, carbon steel, stainless alloy, aluminum alloy, titanium alloy, magnesium alloy, various other metals, and alloys. Among these, stainless steel, aluminum alloy, and titanium alloy are preferable, and aluminum alloy and titanium alloy are particularly preferable because they are lightweight and have high mechanical strength. The thickness of the metal material is appropriately selected as desired, but is usually in the range of 0.5 to 50 μm, preferably 1 to 30 μm, more preferably 3 to 20 μm, and further preferably 3 to 15 μm.

  In the present invention, when the carbon fiber to be used is a unidirectional material, the prepreg is preferably laminated as a laminate by continuously or intermittently laminating the prepreg layers into 4 or 8 layers. . In that case, it is preferable that the prepregs constituting each layer are laminated with the angles of the carbon fiber directions of each prepreg being shifted from each other. Specifically, when four layers of prepregs are laminated, the angle formed by the direction of the carbon fiber of another prepreg with respect to the direction serving as the reference (one having a smaller absolute value), based on the direction of the carbon fiber of the first prepreg Is preferably laminated so that θ = −45 °, 45 °, 45 °, and −45 ° in this order. Similarly, when 8 layers of prepreg are laminated, it is preferable that the layers are similarly laminated so that θ = 0 °, 90 °, −45 °, 45 °, 45 °, −45 °, 90 °, 0 ° in order. . If each prepreg is laminated in this way, warp does not occur in the obtained fiber-reinforced resin molded product and laminate, and the mechanical strength anisotropy is eliminated, which is preferable.

  The lamination and curing method may be in accordance with a conventional method, for example, using a known press machine 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). Can be hot-pressed. The heating temperature is equal to or higher than the temperature at which a crosslinking reaction is induced by the crosslinking agent. For example, when a radical generator is used as a cross-linking agent, it is usually at least 1 minute half-life temperature, preferably at least 5 ° C. above 1-minute half-life temperature, more preferably at least 10 ° C. above 1-minute half-life temperature. Temperature. Typically, it is in the range of 100 to 300 ° C, preferably 150 to 250 ° C. The heating time is in the range of 0.1 to 180 minutes, preferably 1 to 120 minutes, more preferably 2 to 60 minutes. As a press pressure, it is 0.1-20 MPa normally, Preferably it is 0.1-10 MPa, More preferably, it is 1-5 MPa. Further, the hot pressing may be performed in a vacuum or a reduced pressure atmosphere.

  The fiber-reinforced resin molded body and laminate of the present invention thus obtained are excellent in non-halogen flame retardancy and mechanical strength. For example, OA and AV equipment, structural materials for vehicles such as automobiles and railways, aircraft interior parts, etc. It is widely 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 home appliances; undercovers, scuff plates, pillar trims, props Automobiles such as shafts, drive shafts, wheels, wheel covers, fenders, door mirrors, room mirrors, fascias, 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 suitably used as a vehicle component material for automobiles and aircraft.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples. In addition, the part and% in an Example and a comparative example are a basis of weight unless there is particular notice.

Each characteristic in an Example and a comparative example was measured and evaluated according to the following methods.
(1) Impregnation property to carbon fiber of cycloolefin polymer X-ray analysis of the laminate was performed using an X-ray nondestructive analyzer (manufactured by Matsusada Precision Co., Ltd.) and evaluated according to the following criteria.
Good: Cavity is not recognized Good: Cavity is hardly recognized Bad: Cavity is recognized to a moderate or higher level (2) Non-halogen flame retardancy An indirect flame was applied to a 125 mm x 15 mm x 1 mm laminate for 10 seconds Later, the total calorific value was measured and evaluated according to the following criteria.
Good: Less than 3 KJ / g Possible: 3 KJ or more, less than 6 KJ / g Poor: 6 KJ / g or more (3) Mechanical strength After leaving the laminated plate in a high-temperature and high-humidity tank at 85 ° C. and 85% humidity for 72 hours, the laminated plate According to the test method stipulated in JIS K-7073, the tensile strength of 2 is obtained by measuring the distance between the gauge points at 150 mm and the crosshead speed of 2 mm / min. The rate of change with respect to the tensile strength 1 obtained by measuring in the following manner:
Tensile strength change rate (%) = [(tensile strength 2−tensile strength 1) / tensile strength 1] × 100
And evaluated according to the following criteria.
Good: Change rate after test is less than 10% Poor: Change rate after test is 10% or more

Example 1
In a glass flask, 51 parts of benzylidene (1,3-dimethyl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and 79 parts of triphenylphosphine were dissolved in 952 parts of toluene to form a catalyst. A liquid was prepared.

  A polyethylene bottle is charged with 100 parts of dicyclopentadiene (DCP) as a cycloolefin monomer, 0.74 parts of allyl methacrylate as a chain transfer agent, and di-t-butyl peroxide (186 min, 1 minute half-life temperature 186). ℃) 1.2 parts, acetoalkoxyaluminum diisopropylate (Plenact AL-M, manufactured by Ajinomoto Fine Techno Co., Ltd.) as a dispersant, 1.1 parts as a crosslinking aid, 10 parts trimethylolpropane trimethacrylate as a flame retardant After adding 70 parts of zinc dimethylphosphinate, the catalyst solution was added at a rate of 0.12 mL per 100 g of cycloolefin monomer and stirred to prepare a polymerizable composition.

  Next, 100 parts of this polymerizable composition was cast on a polyethylene naphthalate film (type Q51, thickness 75 μm, manufactured by Teijin DuPont Films), and an acrylic carbon fiber woven pyrofil TR 3110M (manufactured by Mitsubishi Rayon Co.). ) And cast 80 parts of the polymerizable composition thereon. A polyethylene naphthalate film was further covered from above, and the film was pressed from above the film using a roller, and carbon fiber was impregnated with the polymerizable composition. Subsequently, this was heated for 1 minute in the heating furnace heated at 150 degreeC, the polymerizable composition was mass-polymerized, and the prepreg of thickness 0.25mm was obtained.

  This prepreg was cut out to a size of 100 mm square and the polyethylene naphthalate film was peeled off. Then, four sheets were stacked, and 12 μm F 2 copper foil (silane coupling agent-treated electrolytic copper foil, roughness Rz = 1600 nm, Furukawa Circuit Foil Co., Ltd.) was stacked and heat-pressed with a hot press at 3 MPa and 200 ° C. for 15 minutes to produce a laminate (laminate). The laminate was evaluated for impregnation properties, non-halogen flame retardancy, and mechanical strength. The results are shown in Table 1.

(Example 2)
A laminate was obtained in the same manner as in Example 1 except that 50 parts of zinc dimethylphosphinate and 25 parts of aluminum hydroxide were used as the flame retardant, and each characteristic of the laminate was evaluated. The results are shown in Table 1.

(Example 3)
A laminated board was obtained in the same manner as in Example 1 except that the flame retardant was replaced with calcium diphenylphosphinate, and each characteristic of the laminated board was evaluated. The results are shown in Table 1.

(Comparative Example 1)
10 parts of bisphenol A type epoxy resin epicoat 834 (manufactured by Japan Epoxy Resin Co., Ltd.), 40 parts of bisphenol A type epoxy resin epicoat 1002 (manufactured by Japan Epoxy Resin Co., Ltd.), N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane epicoat 604 20 parts (manufactured by Japan Epoxy Resin Co., Ltd.), 30 parts of urethane-modified epoxy resin Adeka Resin EPU-6 (manufactured by ADEKA Co., Ltd.), 5 parts of polyetherimide resin PEI Ultem 1000 (manufactured by Nippon GE Plastics Co., Ltd.), 4,4′-diaminodiphenyl sulfone An epoxy resin composition was prepared by mixing 10 parts of 3- (3,4-dichlorophenyl) -1,1-dimethylurea as a curing accelerator and 3 parts of magnesium hydroxide as a flame retardant.

  A laminated board was obtained in the same manner as in Example 1 except that the polymerizable composition was changed to the epoxy resin composition, and each characteristic of the laminated board was evaluated. The results are shown in Table 1.

(Comparative Example 2)
Lamination was performed in the same manner as in Example 1 except that the flame retardant was replaced with 15 parts of red phosphorus, 50 parts of ammonium polyphosphate, and 50 parts of aluminum hydroxide (average particle size 0.4 μm, bulk specific gravity 1.1 g / mL). A plate was obtained, and the properties of the laminate were evaluated. The results are shown in Table 1.

  From Table 1, it can be seen that the laminates obtained in Examples 1 to 3 are excellent in all the characteristics of impregnation, non-halogen flame retardancy, and mechanical strength. On the other hand, the laminate of Comparative Example 1 obtained by using the matrix resin as an epoxy resin is inferior to any of the properties, and the laminate of Comparative Example 2 that does not use phosphinate as a flame retardant is particularly non-halogen flame retardant. It turns out that the nature is insufficient.

Claims (7)

  A prepreg comprising a cycloolefin polymer, a crosslinking agent, a phosphinate, and carbon fibers.   The prepreg according to claim 1, wherein the carbon fiber is an acrylic carbon fiber.   A method for producing a prepreg comprising polymerizing a polymerizable composition comprising a cycloolefin monomer, a polymerization catalyst, a crosslinking agent, and a phosphinate in the presence of carbon fiber.   The method for producing a prepreg according to claim 3, wherein the polymerization catalyst is a ruthenium complex having a heterocyclic structure.   The method for producing a prepreg according to claim 3 or 4, wherein the polymerizable composition further contains a crosslinking aid.   A fiber reinforced resin molded article obtained by curing the prepreg according to claim 1.   The laminated body formed by laminating | stacking the prepreg of Claim 1 or 2 and the said prepreg and / or another material, and hardening | curing.