JP2009144083A - Method for producing hand lay up molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a hand lay up molded article excellent in the impregnating property of a resin component into reinforcing fibers and also excellent in mechanical strength and tenacity. <P>SOLUTION: This method for producing the hand lay up molded article is characterized by impregnating a molding composition containing a cycloolefin monomer, a ruthenium catalyst having a compound containing a heterocyclic structure as a ligand and a cross-linking agent into acrylic-based carbon fibers and then curing the composition. The molding composition preferably further contains a filler. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a hand lay-up molded product, and more particularly, to a method for producing a hand lay-up molded product having excellent impregnation of resin components into reinforcing fibers and excellent strength and toughness.

  The hand lay-up molding method involves placing reinforcing fibers in a mold having a product shape or a concrete structure that has been repaired or reinforced, applying a thermosetting resin to it, and impregnating the resin with a pressure roll or the like. It is a method of curing. By this method, products having various shapes such as bathtubs, septic tanks, boats, fishing boats, cooling towers, water tanks, pools, ducts and the like can be produced. In the case of repair / reinforcement, the resin can be cured and bonded to the repair / reinforcement surface at the same time.

  In particular, in recent years, concrete structures such as bridges and elevated road piers have been repaired and reinforced by hand lay-up molding. As the method, for example, in Patent Document 1, a unidirectionally arranged reinforcing fiber sheet is impregnated with a resin composition in which an epoxy resin and a curing agent are mixed on-site, and curing of the resin and adhesion to the repair / reinforcement surface are simultaneously performed. A method of performing is disclosed. However, this method has a problem that the stability of the resin composition at room temperature is poor, the cured resin cannot be uniformly impregnated into the reinforcing fiber, and the mechanical strength and toughness of the obtained molded product are not sufficient. .

  In order to solve this problem, for example, Patent Document 2 discloses a hand lay-up molding method in which a carbon fiber to which a curing agent such as an amine compound is attached is impregnated with an epoxy resin and then cured. However, this method has a problem in that the carbon fiber and the epoxy resin are not compatible, so that the impregnation property of the carbon fiber is poor, and the mechanical strength and toughness of the obtained molded product are not sufficient. Further, in recent years, there has been a demand to improve the heat resistance and mechanical strength by adding a filler such as an inorganic filler to the resin composition. There were problems such as further deterioration.

  On the other hand, molding a prepreg obtained by bulk ring-opening polymerization of a cycloolefin monomer using a ruthenium catalyst in the presence of a fiber material by a hand lay-up method has been studied. For example, in Patent Document 3, carbon fibers are impregnated with a polymerizable composition using dicyclopentadiene and ethylidene norbornene as cycloolefin monomers and a ruthenium catalyst having tricyclohexylphosphine as a ligand as a polymerization catalyst. Next, it is disclosed that a semi-cured prepreg cured at a curing temperature of −10 ° C. to 20 ° C. for a period of 1 to 1,000 hours can also be used for hand lay-up molding. However, this method has a problem that the polymerization reaction does not proceed sufficiently in the carbon fiber and the mechanical strength and toughness of the resulting molded product are not sufficient.

  Patent Document 4 discloses a glass fiber as a reinforcing material in a polymerizable composition comprising a cycloolefin monomer and a ruthenium catalyst having 1,3-dimesitylimidazolidine-2-ylideneimidazolidine as a ligand. Further, it is disclosed that a glass cloth, a paper base material, a glass unfolded cloth and the like may be blended, and that a hand lay-up method can be used as a molding method of the polymerizable composition. However, this method is a technique for producing a cross-linked resin copper-clad laminate used as a printed wiring board substrate, and mechanical strength and toughness are not sufficient for application as a structure such as a concrete structure or a bathtub. .

JP-A-3-224901 JP-A-9-11347 JP 2003-171479 A JP 2004-35615 A

  An object of the present invention is to provide a method for producing a hand lay-up molded article that is excellent in impregnation of a resin component into a reinforcing fiber and excellent in mechanical strength and toughness.

  As a result of intensive investigations in view of the above problems, the present inventors have impregnated acrylic carbon fibers with a molding composition containing a cycloolefin monomer, a ruthenium catalyst having a specific structure, and a crosslinking agent, and then curing them. It has been found that a hand lay-up molded product having excellent resin component impregnation into reinforcing fibers and excellent mechanical strength and toughness can be produced. Furthermore, it has been found that the impregnation property of the resin is not impaired even when a large amount of filler is included in the molding composition. The inventors of the present invention have been completed based on these findings.

Thus, according to the present invention, an acrylic carbon fiber is impregnated with a molding composition comprising a cycloolefin monomer, a ruthenium catalyst having a heterocyclic structure-containing compound as a ligand, and a crosslinking agent, and then cured. A method for producing a hand lay-up molded article is provided.
The molding composition preferably further contains a filler.

  ADVANTAGE OF THE INVENTION According to this invention, the hand lay-up molded product excellent in the impregnation property to the reinforced fiber of a resin component and excellent in mechanical strength and toughness can be manufactured easily. Moreover, since the hand lay-up molded product produced by the production method of the present invention is excellent in mechanical strength and toughness, it is suitably used in general industrial fields such as vehicle structures such as automobiles and aircraft, sports applications, civil engineering, and architecture. Can be used.

(Cycloolefin monomer)
The cycloolefin monomer used in the present invention is a compound having a ring structure formed of carbon atoms and having a carbon-carbon double bond in the ring. Examples thereof include norbornene monomers and monocyclic cycloolefins, and norbornene monomers are preferred. The norbornene-based monomer is a monomer containing a norbornene ring. The norbornene-based monomer is not particularly limited, and examples thereof include bicyclic compounds such as 2-norbornene and norbornadiene, tricyclic compounds such as dicyclopentadiene and dihydrodicyclopentadiene, tetracyclododecene, and ethylidenetetracyclododecene. , Tetracycles such as 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, and 1,5-cyclooctadiene, and derivatives having a substituent.

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

(Polymerization catalyst)
In the present invention, a ruthenium catalyst having a compound containing a heterocyclic structure as a ligand (hereinafter, also referred to as “specific ruthenium catalyst”) is used as a metathesis polymerization catalyst for polymerizing a cycloolefin monomer. Such a specific catalyst has a characteristic that does not deteriorate the polymerization activity of the cycloolefin monomer even in the polymerization in the presence of the reinforcing fiber. 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-dimesitylimidazolidin-2-ylidene, 1,3- Dimesitylimidazolidine-2-ylidene, 1,3-dicyclohexylimidazolidine-2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3-dimesityl-2,3-dihydrobenzimidazole 2-Iridene and the like can be mentioned.

  The specific ruthenium catalyst is not particularly limited as long as it has a compound containing a heterocyclic structure as a ligand, but usually a plurality of ions, atoms, polyatomic ions and / or compounds are bonded with a ruthenium atom as a central atom. The complex which becomes is mentioned. Among these, a ruthenium carbene complex is particularly preferable. Ruthenium carbene complex has excellent catalytic activity at the time of bulk polymerization, so it is excellent in the productivity of hand lay-up molded products (hereinafter sometimes simply referred to as “molded products”), and is an unreacted monomer in the resulting molded products. There is little odor derived from it and it 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.

  Examples of preferred specific ruthenium catalysts include benzylidene (1,3-dimesitylimidazolidin-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-dihydrobenzimidazol-2-ylidene) (tricyclohexene) Sylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazol-5-ylidene) ruthenium dichloride, Ligands such as 1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesitylimidazolidine-2-ylidene) pyridine ruthenium dichloride And a ruthenium complex compound in which a compound having a heterocyclic structure and a neutral electron donating compound are bonded.

  These specific ruthenium catalysts are used alone or in combination of two or more. The amount used is usually from 1: 2,000 to 1: 2,000,000, preferably from 1: 5,000 to 1: 1,000, in a molar ratio of (metal atom in catalyst: cycloolefin monomer). 000, more preferably in the range of 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, 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 polymerization catalyst can be used in combination with a polymerization regulator (cocatalyst) for the purpose of controlling the polymerization activity or improving the polymerization reaction rate. Examples of polymerization regulators include aluminum, scandium, tin alkylates, halides, alkoxylates, and aryloxylates. Specific examples of the polymerization regulator include trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride, trialkoxyscandium, tetraalkoxy. Examples thereof include titanium, tetraalkoxytin, and tetraalkoxyzirconium.

  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 metathesis polymerization catalyst: polymerization regulator). More preferably, it is in the range of 1: 0.5 to 1:10.

(Crosslinking agent)
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 usually used. Examples of the radical generator include organic peroxides, diazo compounds, and nonpolar radical generators, with organic peroxides and nonpolar radical generators being preferred.

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

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

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

  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 in the range of 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the cycloolefin monomer. .

(Molding composition)
The molding composition used in the present invention comprises the cycloolefin monomer, the specific ruthenium catalyst, and the crosslinking agent as essential components, and if necessary, a crosslinking aid, a polymerization regulator, a chain transfer agent, and a polymerization reaction retarder. Elastomer materials, anti-aging agents, fillers and other additives can be added.

  In the present invention, it is preferable to blend a crosslinking aid, since a large amount of an inorganic filler or the like is blended in the molding composition because it is excellent in impregnation with acrylic carbon fibers.

  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. However, when it is a compound having a highly symmetric structure, the impregnation property of the molding composition containing the cycloolefin monomer into the acrylic carbon fiber is not limited. Can be improved to a high degree. In particular, when the crosslinking aid is a hydrocarbon and has a highly symmetric structure, the impregnation property of the molding composition into the carbon fiber base material and the mechanical properties of the fiber-reinforced composite material obtained by curing. Since strength, toughness, and heat resistance can be improved to a high degree, it is preferable.

  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.

  As a chain transfer agent, the chain | strand-shaped olefins which may have a substituent can be used, for example. Specific examples thereof include, for example, 1-hexene, divinylbenzene, ethyl vinyl ether, allyl methacrylate, 3-buten-2-yl methacrylate, styryl methacrylate, allyl acrylate, 3-buten-1-yl acrylate, Examples include 3-buten-2-yl acrylate, styryl acrylate, ethylene glycol diacrylate, allyltrivinylsilane, allyldimethylvinylsilane, glycidyl acrylate, allyl glycidyl ether, 2- (diethylamino) ethyl acrylate, and 4-vinylaniline. It is done.

  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 thermoplastic resin having a high polymerization reaction rate and curable can be obtained efficiently. If the addition amount of the chain transfer agent is too small, crosslinking may proceed simultaneously with the polymerization, and post-crosslinking may not be possible. Conversely, even if the amount added is too large, curing may be difficult.

  It is preferable that the molding composition used in the present invention contains a polymerization reaction retarder because the increase in viscosity can be suppressed and the acrylic carbon 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.

  The molding composition used in the present invention is preferable because the toughness can be remarkably improved by adding an elastomer material. Examples of the elastomer material include natural rubber, polyisoprene, polybutadiene, styrene-butadiene copolymer, chloroprene, acrylonitrile-butadiene copolymer, styrene-isoprene-styrene block copolymer, and styrene-butadiene-styrene block copolymer. , Ethylene-propylene copolymer, ethylene-propylene-diene terpolymer, ethylene-vinyl acetate copolymer, and hydrogenated products thereof. These elastomer materials can be used alone or in combination of two or more. The amount used is usually in the range of 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight, and more preferably 3 to 30 parts by weight with respect to 100 parts by weight of the cycloolefin monomer.

  The molding composition used in the present invention is at least one selected from the group consisting of a phenol-based anti-aging agent, an amine-based anti-aging agent, a phosphorus-based anti-aging agent and a sulfur-based anti-aging agent as an anti-aging agent. Addition of an anti-aging agent is preferable because the oxidation deterioration resistance of the resulting fiber reinforced resin can be highly improved without inhibiting the polymerization reaction. Among these, a phenolic antiaging agent and an amine antiaging agent are preferable, and a phenolic antiaging agent is particularly preferable. These anti-aging agents can be used alone or in combination of two or more. The amount of the anti-aging agent is appropriately selected according to the purpose of use, but is usually 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, based on 100 parts by weight of the cycloolefin monomer. Preferably it is the range of 0.01-1 weight part.

  In the present invention, it is preferable to add a filler to the molding composition because the mechanical strength and heat resistance can be remarkably improved. 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. These fillers can be used alone or in combination of two or more, and the amount used 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 monomer. The amount is in the range of 500 parts by weight, more preferably 30 to 350 parts by weight.

  Examples of other additives include flame retardants, colorants, light stabilizers, pigments, foaming agents, and polymer modifiers. Examples of the flame retardant include a phosphorus flame retardant, a nitrogen flame retardant, a halogen flame retardant, a metal hydroxide flame retardant such as aluminum hydroxide, and an antimony compound such as antimony trioxide. 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 molding 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 specific ruthenium catalyst is dissolved or dispersed in an appropriate solvent, and a liquid in which other additives are added to a cycloolefin monomer as required. It can be prepared by adding to (monomer solution) and stirring.

(Reinforced fiber)
As the reinforcing fiber used in the present invention, an acrylic carbon fiber (PAN-based carbon fiber) is used. By using acrylic carbon fiber, the polymerization reaction of the cycloolefin monomer is not hindered, and a molded product with very little unreacted monomer can be obtained. A film can be formed, and properties such as appearance, mechanical strength, toughness, heat resistance, and chemical resistance can be highly balanced, which is preferable.

  Acrylic carbon fiber is a carbon fiber manufactured using acrylic fiber (polyacrylonitrile fiber) as a raw material. The strength characteristics of the acrylic carbon fiber 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 reinforcing fibers are within these ranges, the mechanical strength and the toughness are highly balanced, which is preferable.

  The cross-sectional shape of the acrylic carbon fiber used in the present invention is not particularly limited, and a flat or circular shape can be used. For example, when the cross-sectional shape is circular, when the resin is impregnated, the filaments are easily rearranged, and there is an advantage that the resin can easily penetrate between the fibers. Moreover, since the thickness of the fiber bundle can be reduced when the cross-sectional shape is circular, there is an advantage that it is easy to obtain a prepreg excellent in drape.

  The length of the acrylic 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 can be obtained. If desired, the length of the fiber is 1 mm or longer, preferably 0.5 mm or longer, more preferably 1 cm or longer, and most preferably continuous fiber.

  The form of the acrylic 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 acrylic 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 the number of filaments in one fiber bundle yarn is 1,000 to 100,000, preferably 2,000 to 20. 1,000, more preferably in the range of 5,000 to 15,000.

  These acrylic 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 acrylic carbon fiber contained in the resulting molded product is contained. The amount is usually 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. When the acrylic carbon fiber content is within this range, the mechanical strength and toughness characteristics of the molded product are highly balanced and suitable.

(Hand lay-up molded product)
The hand lay-up molded product of the present invention can be easily obtained by impregnating the molding composition into the acrylic carbon fiber and then curing it.

  As the impregnation method, a conventional method may be followed. For example, a predetermined amount of the molding composition may be 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 the reinforcing fiber, overlaying a protective film on it if necessary, and pressing with a roller or the like from above. When the impregnation is performed in the mold, the reinforcing fiber can be installed in the mold and the molding composition can be poured into the mold. According to this method, an arbitrary shape can be obtained. Examples of the shape include a sheet shape, a film shape, and a plate shape.

  The molding composition used in the present invention has a low viscosity compared to conventional epoxy resins and the like, and is excellent in impregnation with acrylic carbon fibers, so that the cured resin is uniformly dispersed in the reinforcing fiber material. be able to. In addition, the molding composition used in the present invention has a low content of a solvent that does not participate in the reaction, so a step of removing the solvent after impregnating the reinforcing fiber is unnecessary, and the productivity is excellent. Odor, swelling, voids and the like due to the residual solvent do not occur, and the molded product has excellent heat resistance.

  The curing reaction after impregnation with the molding composition is composed of two reactions, a polymerization reaction and a crosslinking reaction, and the polymerization reaction and the crosslinking reaction may be performed simultaneously, or the polymerization reaction and the crosslinking reaction may be performed in this order. Good. When the polymerization reaction and the crosslinking reaction are performed simultaneously, the curing temperature is usually 50 to 300 ° C, preferably 100 to 250 ° C, more preferably 120 to 250 ° C, and the curing time is 0.1 to 180. Minutes, preferably 1 to 120 minutes, more preferably 2 to 20 minutes.

  When the polymerization reaction and the crosslinking reaction are performed separately, the conditions are set separately. The polymerization temperature is usually in the range of 50 to 250 ° C., preferably 100 to 200 ° C., more preferably 120 to 170 ° C. When the crosslinking agent uses a radical generator, it is usually 1 of the radical generator. The fractional half-life temperature or lower, preferably 10 ° C or lower, more preferably 20 ° C or lower. Here, the half-life temperature for 1 minute is a temperature at which half of the radical generator decomposes in 1 minute. The polymerization time may be appropriately selected, but is usually 10 seconds to 20 minutes, preferably within 5 minutes.

  The crosslinking temperature is a temperature at which crosslinking of the crosslinking agent occurs. When a radical generator is used, it is at least 1 minute half-life temperature, preferably at least 5 ° C. higher than 1-minute half-life temperature, more preferably 1 minute. The temperature is at least 10 ° C. higher than the half-life temperature, and is usually in the range of 100 to 300 ° C., preferably 150 to 250 ° C. The crosslinking time is in the range of 0.1 to 180 minutes, preferably 1 to 120 minutes, more preferably 2 to 20 minutes.

  As described above, a hand lay-up molded product having a desired shape and thickness can be produced by appropriately repeating the impregnation of the molding composition into the acrylic carbon fiber and the curing.

  The hand lay-up molded product of the present invention can also be easily obtained by curing a sheet obtained by polymerizing the molding composition by pressurizing and impregnating the reinforcing fiber with a roll or the like. A polymerization sheet of the molding composition can be easily obtained by applying the molding composition to a desired thickness on a support and polymerizing under the above conditions.

  Since the hand layup product of the present invention thus obtained is excellent in mechanical strength and toughness, for example, OA and AV equipment, vehicle structural materials such as automobiles and railways, aircraft interior parts, golf shafts and fishing rods, etc. It is suitably used for sports applications such as 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. Moreover, the manufacturing method of the hand layup molded product of this invention can be used suitably for repair and reinforcement of these products.

  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) Impregnation of resin component: X-ray analysis of a molded product was performed using an X-ray nondestructive analyzer (manufactured by Matsusada Precision Co., Ltd.) and judged according to the following criteria.
(Double-circle): A cavity part is hardly seen (triangle | delta): A cavity is slightly seen.
X: A cavity is seen more than moderate

(2) Mechanical strength: according to the test method specified in JIS K-7073, the distance between the gauge points was 150 mm, the tensile strength of the molded product was measured at a crosshead speed of 2.0 mm / min, and the comparative example 1 was used. The tensile strength of the molded product was set to 100 and judged according to the following criteria.
◎: 150 or more ○: 110 or more, less than 150 Δ: 90 or more, less than 110 ×: less than 90

(3) Toughness: The molded product was bent at 90 °, the surface of the bent portion was observed, and judged according to the following criteria.
◎: Neither powder falling nor shape deformation is recognized at all ○: Neither powder falling nor shape deformation is almost recognized Δ: Either powder falling or shape deformation is recognized x: Both are recognized or either One side alone is terrible

Example 1
In a glass flask, 51 parts of benzylidene (1,3-dimesityl-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. Separately, 100 parts of dicyclopentadiene (DCP) as a cycloolefin monomer is placed in a polyethylene bottle, 0.74 parts of allyl methacrylate as a chain transfer agent, and di-t-butyl peroxide (as a crosslinking agent). 1.2 parts for a 1 minute half-life temperature of 186 ° C., 20 parts of m-diisopropenylbenzene as a crosslinking aid and 1.0 part of 3,5-di-t-butyl-4-hydroxyanisole as a phenolic antioxidant Then, the above catalyst solution was added at a rate of 0.12 ml per 100 g of cycloolefin monomer and stirred to prepare a molding composition.

  Next, a polyester film bonded with a double-sided adhesive tape is fixed to a plywood board, and the molding composition is uniformly applied on the film with a roller. A carbon fiber plain woven fabric (PAN-based carbon fiber, manufactured by Mitsubishi Rayon Co., Ltd.) Pyrofil (registered trademark) was placed, and the same molding composition was uniformly applied thereon with a roller. The ratio of the woven fabric to the molding composition was 6/4 by weight. Subsequently, it was cured at 200 ° C. for 10 minutes, and each characteristic of the obtained molded product was evaluated. The results are shown in Table 1.

Example 2
Except for adding 15 parts of polybutadiene to the molding composition, the same procedure as in Example 1 was performed. Each characteristic of the obtained molded product was evaluated, and the results are shown in Table 1.

Example 3
Except for adding 60 parts of silica (manufactured by Admafine, average particle size of 0.5 μm) to the molding composition, the same procedure as in Example 1 was performed. Each characteristic of the resulting molded product was evaluated, and the results are shown in Table 1. It was shown to.

Comparative Example 1
Carbon fiber plain woven fabric (PAN-based carbon fiber, manufactured by Mitsubishi Rayon Co., Ltd., Pyrofil: registered trademark) is dipped in a 6.0% aqueous solution of metaxylylenediamine, dried with a hot air dryer, and then metaxylylenediamine on the fiber surface. Was attached. The amount of adhesion was 10 parts with respect to 100 parts of fibers.

  Next, a polyester film bonded with a double-sided tape is fixed to a plywood board, and 100 parts of Epicoat 828 (epoxy resin made by Japan Epoxy Resin Co., Ltd.) and 3 parts of silica (manufactured by Admafine, average particle size 0.5 μm) The above-prepared carbon fiber plain woven fabric was placed thereon, and the same epoxy resin was further uniformly applied thereon with a roller. Each characteristic of the obtained molded product was evaluated, and the results are shown in Table 1.

Comparative Example 2
Epoxy resin composition to which 100 parts of Epicoat 828 (manufactured by Japan Epoxy Resin, liquid bisphenol A type epoxy resin), 90 parts of Kayahard MCD (manufactured by Nippon Kayaku Co., Ltd., methylnadic acid anhydride), and 2 parts of benzyldimethylamine are added. Was prepared.

  Except for changing the molding composition to the above epoxy resin composition, the same procedure as in Example 1 was carried out. Each characteristic of the obtained molded product was evaluated, and the results are shown in Table 1.

  From the results in Table 1, it can be seen that the hand lay-up molded product obtained by the production method of the present invention is excellent in all the characteristics of impregnation, strength and toughness (Examples 1 to 3). On the other hand, it can be seen that those using an epoxy resin as the matrix resin are not satisfactory in either characteristic (Comparative Examples 1 and 2).

Claims (2)

A hand layup characterized in that an acrylic carbon fiber is impregnated with a molding composition comprising a cycloolefin monomer, a ruthenium catalyst having a compound containing a heterocyclic structure as a ligand, and a crosslinking agent, and then cured. Manufacturing method of molded products. The manufacturing method according to claim 1, wherein the molding composition further contains a filler.