WO2009096580A1

WO2009096580A1 - Method for producing fiber-reinforced plastic

Info

Publication number: WO2009096580A1
Application number: PCT/JP2009/051717
Authority: WO
Inventors: Takashi Kiuchi; Tadao Natsuume
Original assignee: Zeon Corporation
Priority date: 2008-01-31
Filing date: 2009-02-02
Publication date: 2009-08-06
Also published as: JP2011068701A

Abstract

A fiber-reinforced plastic is obtained by impregnating a multiaxially stitched base with a curable composition containing a cycloolefin monomer, a polymerization catalyst and a crosslinking agent, and then curing the curable composition. The multiaxially stitched base is preferably made of carbon fibers, and the polymerization catalyst is preferably composed of a ruthenium catalyst which has a compound containing a heterocyclic structure as a ligand.

Description

Manufacturing method of fiber reinforced plastic

The present invention relates to a method for producing a fiber reinforced plastic, which can easily produce a fiber reinforced plastic excellent in mechanical strength and appearance, suitable for sports applications, vehicle components such as automobiles and aircraft, and other general industrial applications.

Conventionally, fiber reinforced plastics using carbon fibers or glass fibers as reinforcing fibers have been used in various applications because of their excellent specific strength and specific elastic modulus. As a typical method for producing such fiber reinforced plastic, a prepreg obtained by impregnating a matrix resin into a reinforcing fiber base in advance is used, and this prepreg is laminated so that the arrangement direction of the reinforcing fibers is shifted for each layer (pseudo isotropic lamination). And an autoclave molding method for curing the matrix resin. In addition to this, in order to reduce the molding cost of fiber reinforced plastics, there is a resin injection molding method in which a resin-impregnated reinforcing fiber base material is laminated, a matrix resin is injected into the laminated body, and cured.

As a reinforcing fiber base not impregnated with a matrix resin, which is mainly used for resin injection molding, etc., a woven base has been used, but in recent years, sheets with reinforcing fiber yarns arranged in parallel have been cross-laminated. Thus, so-called multi-axis stitch base materials integrated with stitch yarns have been attracting attention (for example, Patent Documents 1 to 3). Such a multi-axis stitch base material has a high productivity of the base material and excellent mechanical properties of the obtained fiber reinforced plastic because there is no labor for weaving the reinforcing fiber yarns compared to a conventional woven base material. In addition, the fiber basis weight per sheet can be increased, and by laminating and integrating in multiple directions in advance, a unit with the desired configuration and characteristics can be obtained, so the labor for laminating is greatly reduced. There is also an advantage that an inexpensive fiber-reinforced plastic can be obtained. However, such a multi-axis stitch base material, on the other hand, has a complicated shape, so that the matrix resin cannot be uniformly impregnated. There was a problem that foaming occurred.

US Patent Application Publication No. 2005/0059309 International Publication No. 01/063033 Pamphlet JP 2007-162151 A

An object of the present invention is to provide a method for producing a fiber-reinforced composite plastic that does not cause voids, deformed shapes, foaming, etc., using a multiaxial stitch base material having excellent mechanical properties.

As a result of intensive studies in view of the above problems, the present inventors have impregnated a curable composition comprising a cycloolefin monomer, a polymerization catalyst, a cross-linking agent, and the like into a multiaxial stitch base material, and then cured the complex composition. It was found that a matrix resin can be uniformly impregnated even on a multi-axis stitch base material having a simple shape, and a fiber-reinforced plastic that does not have a hollow shape or a deformed shape or foaming can be easily produced. Based on these findings, the present inventors have completed the present invention.

Thus, according to the present invention, the step (1) of impregnating a curable composition comprising a cycloolefin monomer, a polymerization catalyst and a crosslinking agent into a multiaxial stitch base, and then the step of curing the curable composition (2) ) Is provided.
The multiaxial stitch base material is preferably made of carbon fiber.
The polymerization catalyst is preferably a ruthenium catalyst having a compound containing a heterocyclic structure as a ligand.

According to the present invention, a fiber-reinforced composite plastic having excellent mechanical strength and appearance can be easily produced using a multiaxial stitch base material having excellent mechanical properties. Further, the fiber reinforced plastic obtained by the production method of the present invention is excellent in mechanical strength and appearance. Therefore, it is suitably used as various members in the fields of vehicles, aircraft, and other vehicle structures, and sports, civil engineering, and architecture. be able to.

The method for producing a fiber reinforced plastic according to the present invention includes a step (1) of impregnating a curable composition comprising a cycloolefin monomer, a polymerization catalyst and a crosslinking agent into a multiaxial stitch base, and then curing the curable composition. Step (2).

(Cycloolefin monomer)
The cycloolefin monomer used in the present invention is a compound having a ring structure formed of carbon atoms and having a carbon-carbon double bond in the ring. Examples thereof include norbornene monomers and monocyclic cycloolefins, and norbornene monomers are preferred. The norbornene-based monomer is a monomer containing a norbornene ring. The norbornene-based monomer is not particularly limited, and examples thereof include bicyclic compounds such as 2-norbornene and norbornadiene, tricyclic compounds such as dicyclopentadiene and dihydrodicyclopentadiene, tetracyclododecene, and ethylidenetetracyclododecene. , Tetracycles such as phenyltetracyclododecene, pentacycles such as tricyclopentadiene, heptacycles such as tetracyclopentadiene, and alkyl substituents thereof (methyl, ethyl, propyl, butyl substituents, etc.), alkylidene Substitutes (eg, ethylidene substitutes), aryl substitutes (eg, phenyl, tolyl substitutes), epoxy groups, methacryl groups, hydroxyl groups, amino groups, carboxyl groups, cyano groups, halogen groups, ether bond-containing groups, esters Derivatives having a polar group such as a bond-containing group Etc., and the like. Examples of the monocyclic cycloolefin include monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclooctene, cyclododecene, 1,5-cyclooctadiene, and derivatives having a substituent. Examples of the substituent of the monocyclic cycloolefin include the same substituents as those of the norbornene monomer. These cycloolefin monomers can be used alone or in combination of two or more.

(Polymerization catalyst)
The polymerization catalyst used in the present invention is not particularly limited as long as it can polymerize a cycloolefin monomer, but a metathesis polymerization catalyst is usually used. The metathesis polymerization catalyst is capable of metathesis ring-opening polymerization of a cycloolefin monomer, and usually includes a complex formed by bonding a plurality of ions, atoms, polyatomic ions and / or compounds with a transition metal atom as a central atom. As transition metal atoms, atoms of Group 5, Group 6, and Group 8 (long-period periodic table, the same applies hereinafter) are used. Although the atoms of each group are not particularly limited, examples of the Group 5 atom include tantalum, examples of the Group 6 atom include molybdenum and tungsten, and examples of the Group 8 atom include ruthenium and osmium. Can be mentioned. Among these, it is preferable to use a group 8 ruthenium or osmium complex as a metathesis polymerization catalyst, and a ruthenium carbene complex is particularly preferable. Since ruthenium carbene complexes have excellent catalytic activity during bulk polymerization, it is possible to efficiently produce fiber-reinforced plastics with less odor originating from unreacted monomers. Further, since it is relatively stable against oxygen and moisture in the air and hardly deactivates, fiber reinforced plastic can be produced even in the atmosphere.

Examples of the ruthenium carbene complex include those represented by the following formula (1) or formula (2).

In the above formulas (1) and (2), R ¹ and R ² may each independently contain a hydrogen atom, a halogen atom, or a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom or silicon atom. It represents a good hydrocarbon group having 1 to 20 carbon atoms.

X ¹ and X ² each independently represents an arbitrary anionic ligand. An anionic ligand is a ligand having a negative charge when pulled away from a central metal atom, such as a halogen atom, a diketonate group, a substituted cyclopentadienyl group, an alkoxyl group, an aryloxy group, A carboxyl group etc. can be mentioned. Among these, a halogen atom is preferable and a chlorine atom is more preferable.

L ¹ and L ² each independently represents a hetero atom-containing carbene compound or a neutral electron donating compound. A hetero atom means an atom of Group 15 and Group 16 of the Periodic Table, and specific examples thereof include N, O, P, S, As, and Se atoms. Among these, from the viewpoint of obtaining a stable carbene compound, N, O, P, S atoms and the like are preferable, and N atoms are particularly preferable.

Examples of the heteroatom-containing carbene compound include compounds represented by the following formula (3) or formula (4).

In the formula, each of R ³ to R ⁶ independently represents a hydrogen atom, a halogen atom, or a carbon atom having 1 to 20 carbon atoms that may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. Represents a hydrogen group. R ³ to R ⁶ may be bonded to each other in any combination to form a ring.

The neutral electron-donating compound may be any ligand as long as it has a neutral charge when separated from the central metal. Specific examples thereof include phosphines, ethers and pyridines, and trialkylphosphine is more preferable.

In the above formulas (1) and (2), R ¹ and R ² may be bonded to each other to form a ring, and further R ¹ , R ² , X ¹ , X ² , L ¹ and L ² May be bonded together in any combination to form a multidentate chelating ligand.

In the present invention, the ruthenium catalyst having a compound having a heterocyclic structure as a ligand as a polymerization catalyst has good compatibility with acrylic carbon fibers, adhesion to the coating film of the fiber reinforced resin substrate, appearance, machine Properties such as strength, heat resistance, and chemical resistance can be highly balanced, which is preferable. 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. Moreover, as a heterocyclic structure, an imidazoline structure and an imidazolidine structure are preferable.
As a ruthenium catalyst having a compound having such a heterocyclic structure as a ligand, ruthenium having a ligand represented by the above formula (1) or (2) and comprising a hetero atom-containing carbene compound as L ¹ or L ² A catalyst can be suitably used. As a hetero atom which comprises a hetero atom containing carbene compound, a nitrogen atom is preferable. Specific examples of such a heteroatom-containing carbene compound include 1,3-di (1-adamantyl) imidazolidin-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1,3-diene (1-phenylethyl) -4-imidazoline-2-ylidene, 1,3-dimesitylimidazolidine-2-ylidene, 1,3-dicyclohexylimidazolidine-2-ylidene, 1,3-diisopropyl-4-imidazoline -2-ylidene, 1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene and the like.

Specific examples of the ruthenium catalyst having a ligand composed of a heteroatom-containing carbene compound include benzylidene (1,3-dimesitymylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3 -Dimesitylimidazolidine-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-dihydride) Benzimidazol-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-dimesitylimidazolidine-2-ylidene) Examples thereof include a ruthenium complex compound in which a hetero atom-containing carbene compound and a neutral electron donating compound are bonded as a ligand, such as pyridine ruthenium dichloride.

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

The polymerization catalyst can be used by dissolving or suspending in a small amount of an inert solvent, if desired. 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, the use of chain aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, and hydrocarbons having an alicyclic ring and an aromatic ring is preferable.

(Crosslinking agent)
The crosslinking agent used in the present invention is not particularly limited as long as it can induce a crosslinking reaction in a curable composition or a polymer obtained by subjecting a curable composition to polymerization. An agent is 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-me Peroxyketals such as tilcyclohexane and 1,1-di (t-butylperoxy) cyclohexane; peroxyesters such as t-butylperoxyacetate and t-butylperoxybenzoate; t-butylperoxyisopropylcarbonate, di (isopropylperoxy) ) Peroxycarbonates such as dicarbonate; alkylsilyl peroxides such as t-butyltrimethylsilyl peroxide; and the like. Of these, dialkyl peroxides and peroxyketals are preferred in that they have little obstacle to the polymerization reaction.

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

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.

These cross-linking 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. .

(Curable composition)
In the curable composition used in the present invention, the cycloolefin monomer, the polymerization catalyst and the crosslinking agent are essential components, and if desired, a chain transfer agent, a polymerization reaction retarding agent, a crosslinking aid, an elastomer material, and an antiaging agent. , Fillers and other additives can be added.

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

These chain transfer agents can be used alone or in combination of two or more, and the addition amount is usually 0.01 to 10 parts by weight, preferably 0. 1 to 5 parts by weight.

It is preferable that the curable composition used in the present invention contains a polymerization reaction retarder, because the increase in viscosity can be suppressed and the multiaxial stitch substrate can be easily impregnated uniformly with the curable composition. 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. When the ruthenium catalyst is used, the amount of the polymerization reaction retarder is usually 1: 0.01 to 1: 100, preferably 1: 0.1 to 1 in a molar ratio of (ruthenium metal atom: polymerization reaction retarder). : 10, more preferably in the range of 1: 0.1 to 1: 5.

The curable composition used in the present invention preferably contains a crosslinking aid. By adding a crosslinking aid to the curable composition, it is possible to highly improve the impregnation of the curable composition into the multiaxial stitch base material and the mechanical strength of the fiber reinforced plastic obtained by curing. It is.

As the crosslinking aid used in the present invention, those generally used can be used without particular limitation. For example, a bifunctional compound having two carbon-carbon unsaturated bonds, a carbon-carbon unsaturated bond can be used. The polyfunctional compound which has 3 or more can be mentioned. The carbon-carbon unsaturated bond means a carbon-carbon double bond or a carbon-carbon triple bond.

The structure of the crosslinking aid used in the present invention is not particularly limited, but there are many curable compositions containing a cycloolefin monomer when the compound has a highly symmetric structure (a compound having a symmetric structure). The impregnation property to the shaft stitch base material is highly improved, which is preferable. In particular, when the crosslinking aid is a hydrocarbon and a compound having a highly symmetrical structure, the impregnation property of the curable composition into the multiaxial stitch base material, and the mechanical strength of the fiber reinforced plastic obtained by curing Can be improved to a high degree.

Specific examples of such crosslinking aids include bifunctional compounds such as p-diisopropenylbenzene, m-diisopropenylbenzene, o-diisopropenylbenzene, and trifunctional such as triisopropenylbenzene and trimethallyl isocyanate. Compound. Of 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 according to 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. When the amount of the crosslinking aid is within this range, the resulting fiber-reinforced plastic is excellent in mechanical strength.

The addition of an elastomer material to the curable composition used in the present invention is preferable because the impact strength can be remarkably improved without lowering the mechanical strength of the resulting fiber-reinforced plastic. Examples of elastomer materials 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, more preferably 3 to 30 parts by weight with respect to 100 parts by weight of the cycloolefin monomer.

The curable 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. By adding an anti-aging agent, the heat resistance of the fiber-reinforced plastic obtained can be improved to a high degree without inhibiting the polymerization reaction and the crosslinking reaction, which is preferable. Among these, a phenolic antiaging agent and an amine antiaging agent are preferable, and a phenolic antiaging agent is particularly preferable.

The phenolic antioxidant is not particularly limited as long as it is a substance usually used in the general resin industry. For example, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5- Methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-amyl-6- (1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate, 3,5- Di-t-butyl-4-hydroxyanisole, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2′-methylene-bis (4-methyl-6-t- Butylphenol), 4,4′-butylidene-bis (6-tert-butyl-m-cresol), 3,9-bis (2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl)) Professional Onyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, tetrakis (methylene-3- (3 ′, 5′-di-t-butyl-4 ′) -Hydroxyphenylpropionate) methane [ie pentaerythrimethyl-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenylpropionate)], 6- (4-hydroxy-3-methyl- 5-t-butylanilino) -2,4-bisoctylthio-1,3,5-triazine, 2-octylthio-4,6-bis- (3,5-di-t-butyl-4-oxyanilino) -1 , 3,5-triazine and the like.

The amine anti-aging agent is not particularly limited as long as it is a substance usually used in the general resin industry. For example, 1- [2- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionyloxy] ethyl] -4- [3-3,5-di-tbutyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 2- (3,5 -Di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid-bis- (1,2,2,6,6-pentamethyl-4-piperidyl) and the like.

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

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

These anti-aging agents can be used alone or in combination of two or more. The amount of the antioxidant used 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, more preferably 100 parts by weight of the cycloolefin monomer. Is in the range of 0.01 to 1 part by weight.

In the present invention, by adding a filler to the curable composition, the mechanical strength and heat resistance of the obtained fiber reinforced plastic can be remarkably improved, which is preferable. The filler is not particularly limited as long as it is generally used industrially, and either an inorganic filler or an organic filler can be used, but an inorganic filler is preferred.

Examples of the inorganic filler include metal particles such as iron, copper, nickel, gold, silver, aluminum, lead, and tungsten; carbon particles such as carbon black, graphite, activated carbon, and carbon balloon; silica, silica balloon, alumina, Inorganic oxide particles such as titanium oxide, iron oxide, zinc oxide, magnesium oxide, tin oxide, beryllium oxide, barium ferrite, strontium ferrite; inorganic carbonate particles such as calcium carbonate, magnesium carbonate, sodium hydrogen carbonate; calcium sulfate, etc. Inorganic sulfate particles; inorganic silicate particles such as talc, clay, mica, kaolin, fly ash, montmorillonite, calcium silicate, glass, glass balloon; titanate particles such as calcium titanate and lead zirconate titanate, Aluminum nitride, silicon carbide grains And whiskers, and the like. Examples of the organic filler include compound particles such as wood powder, starch, organic pigments, polystyrene, nylon, polyolefins such as polyethylene and polypropylene, vinyl chloride, various elastomers, and waste plastics.

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 per 100 parts by weight of the cycloolefin monomer. The amount is in the range of 500 parts by weight, more preferably 50 to 350 parts by weight.

Examples of other additives include flame retardants, colorants, light stabilizers, pigments, foaming agents, polymer modifiers, and the like. Examples of the flame retardant include phosphorus flame retardants, nitrogen flame retardants, halogen flame retardants, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and antimony compounds such as antimony trioxide. As the colorant, dyes, pigments and the like are used. There are various kinds of dyes, and known ones may be appropriately selected and used.

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

The curable 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 solution) in which the polymerization catalyst is dissolved or dispersed in an appropriate solvent is used as a cycloolefin monomer and a crosslinking agent, and other additives as required. It can be prepared by adding to a liquid (monomer liquid) blended and stirring.

(Reinforced fiber)
One feature of the present invention is that the curable composition constitutes a matrix resin layer and a multiaxial stitch base material is used as the reinforcing fiber. Since the curable composition used in the present invention is excellent in fluidity and wettability with reinforcing fibers, it can be uniformly impregnated into a complex-shaped multiaxial stitch base.

As the multi-axis stitch base material used in the present invention, those generally used in industry can be used without any particular limitation. As the multiaxial stitch base material, it is usually possible to use a multi-axis stitch base material formed by laminating a plurality of sheets of reinforcing fiber yarns arranged in one direction and being integrated by stitch yarns. Specifically, in US Patent Application Publication No. 2005/0059309, JP-A 2006-299426, JP-A 2007-160587, JP-A 2007-162151, International Publication No. 01/063033, etc. It can be obtained by the disclosed method.

The constituent fibers of the multiaxial stitch base material used in the present invention are not particularly limited. For example, PET (polyethylene terephthalate) fiber, aramid fiber, ultrahigh molecular polyethylene fiber, polyamide (nylon) fiber, liquid crystal polyester Examples thereof include organic fibers such as fibers; inorganic fibers such as glass fibers, carbon fibers, alumina fibers, tungsten fibers, molybdenum fibers, budene fibers, titanium fibers, steel fibers, boron fibers, silicon carbide fibers, and silica fibers. Among these, organic fiber, glass fiber, and carbon fiber are preferable, and carbon fiber is more preferable. In particular, carbon fiber is excellent in compatibility with a curable composition containing a cycloolefin monomer, and by uniformly impregnating the curable composition, it does not inhibit the polymerization reaction and the crosslinking reaction of the curable composition. The mechanical strength and impact resistance of the obtained fiber reinforced plastic can be improved to a high degree, which is preferable. The type of carbon fiber is not particularly limited. For example, carbon fibers produced by various conventionally known methods such as acrylic, pitch-based, rayon-based, etc. can be used. Among them, acrylic carbon fiber (PAN-based) Carbon fiber) is preferred because it does not cause polymerization inhibition, and properties such as mechanical strength and toughness can be highly enhanced in the fiber-reinforced plastic obtained.

The strength property of the reinforcing fiber is not particularly limited and is appropriately selected according to the purpose of use. The tensile strength is a strand tensile strength measured according to JIS R7601 and is usually in the range of 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 in the range of 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 obtained fiber-reinforced plastic is suitable because the properties of appearance, mechanical strength, and toughness are highly balanced.

The number of filaments when used as a fiber bundle yarn of reinforcing fibers is not particularly limited, but the number of filaments in one fiber bundle yarn is usually 1,000 to 100,000, preferably 2, The range is from 000 to 20,000, more preferably from 5,000 to 15,000.

The stitch yarn is not particularly limited, and polyamide fiber, polyester fiber, polyaramid fiber, polyethylene fiber, polyvinyl alcohol fiber, and the like can be used. Particularly, polyaramid fiber and polyethylene fiber have good adhesion to the curable composition. It is preferable because the elongation is large. The integration of the laminated sheets by stitch yarn is usually performed by so-called stitch bonding in which the stitch yarn is stitched with a needle using a knitting machine, a sewing machine or the like. Examples of the knitting structure of the multi-axis stitch base material include chain knitting, 1 × 1 tricot knitting, and 1 × 1 irregular tricot knitting in which chain knitting and 1 × 1 tricot knitting are combined.

The number of laminated multi-axis stitch base materials used in the present invention is appropriately selected depending on the purpose of use, but is usually in the range of 2 to 100 sheets, preferably 3 to 60 sheets, more preferably 4 to 12 sheets. It is. When the number of laminated multi-axis stitch base materials is within this range, the handleability and the impregnation property of the curable composition are balanced and suitable.

The multi-axis stitch base material used in the present invention is suitable because the mechanical strength is remarkably enhanced when it is substantially isotropic. For example, an isotropic multi-axis stitch base material is usually a pseudo isotropic lamination method in which fiber yarns constituting each sheet are laminated so that the arrangement directions thereof are 0 °, 90 °, and ± 45 ° crossing angles. Can be manufactured.

The reinforcing fiber basis weight of each sheet constituting the multiaxial stitch base material used in the present invention is appropriately selected according to the purpose of use, but is usually 50 to 400 g / m ² , preferably 70 to 300 g / m ^2. More preferably, it is in the range of 100 to 200 g / m ² . If the basis weight of the reinforcing fiber yarn is too small, a gap is formed between adjacent reinforcing fiber yarns, and the mechanical strength of the resulting fiber reinforced plastic tends to be insufficient, and conversely, the basis weight is excessive. If the amount is too large, a portion where adjacent reinforcing fiber yarns overlap each other is formed, so that the thickness becomes thick and the impregnation property of the curable composition tends to be impaired.

The ratio of the multiaxial stitch base material in the fiber reinforced plastic (multiaxial stitch base material + curable composition or matrix resin) may be appropriately selected depending on the intended use, but is usually 10 to 90% by weight, preferably Is in the range of 20 to 80% by weight, more preferably 30 to 70% by weight. When the ratio of the multiaxial stitch base material in the fiber reinforced plastic is within this range, the mechanical strength and impact resistance characteristics are highly balanced, which is preferable.

(Fiber reinforced plastic)
In the present invention, mechanical strength and impact resistance are achieved by carrying out the step (1) of impregnating the curable composition into the multiaxial stitch base, and then the step (2) of curing the curable composition. Highly superior fiber reinforced plastic can be manufactured.

The impregnation of the curable composition into the multiaxial stitch base material is performed by, for example, applying a predetermined amount of the curable composition to a spray coating method, a dip coating method, a roll coating method, a curtain coating method, a die coating method, a slit coating method, or the like. It can apply by apply | coating to a reinforced fiber by a well-known method, if necessary, putting a protective film on it and pressing with a roller etc. from an upper side.

When impregnation is performed in a mold, a multiaxial stitch base material is placed in the mold, and the curable composition is poured into the mold, followed by curing. 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 curable composition is injected into the cavity (cavity). And let it harden. The core mold and the cavity mold are produced so as to form a gap that matches the shape of the multiaxial stitch base material. The material and size 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 curable composition is injected into a space formed by sandwiching the spacer between two plate-shaped molds. Curing can be performed in the mold.

The curable composition has a low viscosity as compared with a conventionally used polymer varnish obtained by dissolving an epoxy resin or the like in a solvent, and is excellent in impregnation with respect to a multiaxial stitch base material. The resulting matrix resin can be uniformly impregnated into the multiaxial stitch base material.

In the present invention, the curing reaction after impregnation with the curable composition comprises 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 simultaneously. You may carry out in order. When the polymerization reaction and the crosslinking reaction are performed simultaneously, the curing temperature is usually in the range of 50 to 300 ° C., preferably 100 to 250 ° C., more preferably 120 to 250 ° C., and the curing time is 0.1 to 180 ° C. It is in the range of minutes, preferably 1 to 120 minutes, more preferably 2 to 20 minutes.

When performing the polymerization reaction and the crosslinking reaction separately, set the conditions 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 a radical generator is used as the crosslinking agent, the polymerization temperature is usually 1 of the radical generator. The half-life temperature is 1 minute or less, preferably 10 ° C. or less, more preferably 20 ° C. or less. The polymerization time may be appropriately selected, but is usually 10 seconds to 20 minutes, preferably within 5 minutes. The polymer obtained here is substantially uncrosslinked and is soluble in, for example, toluene. The molecular weight of the polymer (cycloolefin polymer) is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (eluent: tetrahydrofuran), and is usually 1,000 to 1,000,000, preferably It is in the range of 5,000 to 500,000, more preferably 10,000 to 100,000.

The cross-linking temperature is a temperature at which a cross-linking reaction is induced by the cross-linking agent. When a radical generator is used, it is at least 1 minute half-life temperature, preferably at least 5 ° C. higher than the 1-minute half-life temperature. The temperature is preferably 10 ° C. or more higher than the 1 minute 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.

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

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present 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) Resin impregnation property: X-ray analysis of the 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) Appearance: The laminate was visually observed and judged according to the following criteria.
A: No powder falling, shape collapse, or foaming is observed at all. ○: Most of powder falling, shape collapse, or foaming is not observed. Δ: Any of powder falling, shape collapse, or foaming is observed. All of fall, shape collapse, and foaming are recognized, or only one of them is severe

Production Example 1 (Preparation of Curable Composition A)
A catalyst solution was prepared by dissolving 51 parts of benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and 79 parts of triphenylphosphine in 952 parts of toluene. Separately, 100 parts of dicyclopentadiene (DCP) is added as a cycloolefin monomer, and 1.2 parts of di-t-butyl peroxide (1 minute half-life temperature 186 ° C.) is used as a crosslinking agent. After adding 1 part of 3,5-di-t-butyl-4-hydroxyanisole as an inhibitor and 0.74 part of allyl methacrylate as a chain transfer agent, 0.12 mL of the above catalyst solution is added per 100 g of cycloolefin monomer. Curable composition A was prepared by adding and stirring at a ratio.

Production Example 2 (adjustment of curable composition B)
A curable composition B was prepared in the same manner as in Production Example 1 except that the cycloolefin monomer was replaced with 60 parts of DCP and 40 parts of tetracyclododecene (TCD).

Production Example 3 (adjustment of curable composition C)
A curable composition C was prepared in the same manner as in Production Example 1 except that 40 parts of fused silica was further added as a filler.

Example 1
Reinforced fiber yarns are arranged so as to be -45 ° / 0 ° / + 45 ° / 90 ° / 90 ° / + 45 ° / 0 ° / -45 ° in order from the upper layer with respect to the fiber direction, and stitched together with stitch yarn A multi-axis stitched substrate was prepared. As the reinforcing fiber yarn, a PAN-based carbon fiber having a tensile strength of 4,900 MPa, a tensile elastic modulus of 230 GPa and a filament number of 12,000 was used, and as the stitch yarn, a 56 dtex polyester yarn composed of 24 filaments was used. . The knitting structure was a 1 × 1 irregular tricot knitting with a stitch length of 2.3 mm and a gauge length of 5 mm. Moreover, the fabric weight of each sheet | seat of the reinforced fiber yarn which comprises a multiaxial stitch base material was 150 g / m < ² >.

Next, after the multiaxial stitch base material was placed in the mold, the curable composition A prepared earlier was impregnated, and then cured in an oven at 200 ° C. for 15 minutes to obtain a fiber reinforced plastic. Each characteristic of the fiber reinforced plastic taken out from the mold was evaluated. The results are shown in Table 1.

Example 2
A biaxial stitch base material in which reinforcing fiber yarns are arranged so as to be −45 ° / 0 ° in order from the upper layer with respect to the fiber direction, and stitched together with stitch yarn (nylon yarn consisting of five filaments) was produced. . Similarly, biaxial stitch base materials each having reinforcing fiber yarns arranged so as to be + 45 ° / 90 °, 90 ° / + 45 °, and 0 ° / −45 ° were prepared. As the reinforcing fiber yarn, a PAN-based carbon fiber having a tensile strength of 4,900 MPa, a tensile elastic modulus of 230 GPa and a filament number of 12,000 was used, and as the stitch yarn, a nylon yarn composed of five filaments was used. The knitting structure was a 1 × 1 irregular tricot knitting with a stitch length of 2.3 mm and a gauge length of 5 mm. Moreover, the fabric weight of each sheet | seat of the reinforced fiber yarn which comprises a biaxial stitch base material was 150 g / m < ² >.

Next, these two types of biaxially stitched base materials are reinforced fiber yarns in the order from the upper layer (−45 ° / 0 °) / (+ 45 ° / 90 °) / (90 ° / + 45 °) / (0 ° / The multiaxial stitch base material was produced by laminating to −45 °) and stitching together with stitch yarn. The stitching was performed by 1 × 1 irregular tricot knitting with a stitch length of 5 mm and a gauge length of 5 mm.

Example 3
A fiber reinforced plastic was produced in the same manner as in Example 1 except that the curable composition B was used instead of the curable composition A, and each characteristic was evaluated. The results are shown in Table 1.

Example 4
A fiber reinforced plastic was produced in the same manner as in Example 1 except that the curable composition C was used in place of the curable composition A, and each characteristic was evaluated. The results are shown in Table 1.

Comparative Example 1
An epoxy resin composition comprising 100 parts of Epicoat 828 (manufactured by Yuka Shell Co., Ltd., liquid bisphenol A type epoxy resin), 90 parts of Kayahard MCD (manufactured by Nippon Explosives Co., Ltd., methyl nadic acid anhydride) and 2 parts of benzyldimethylamine Prepared.

A fiber reinforced plastic was obtained in the same manner as in Example 1 except that the curable composition A was changed to the above epoxy resin composition, and each characteristic was evaluated. The results are shown in Table 1.

As is apparent from the results in Table 1, according to the production method of the present invention, fiber reinforcement excellent in resin impregnation and appearance using a multiaxial stitch base material composed of reinforcing fibers such as carbon fibers excellent in mechanical properties. It can be seen that a plastic is obtained (Comparison between Examples 1 to 4 and Comparative Example 1).

Claims

A fiber reinforced plastic comprising a step (1) of impregnating a curable composition comprising a cycloolefin monomer, a polymerization catalyst and a crosslinking agent into a multiaxial stitch base, and then a step (2) of curing the curable composition. Production method.
The manufacturing method according to claim 1, wherein the multi-axis stitch base material is made of carbon fiber.
The production method according to claim 2, wherein the carbon fiber is an acrylic carbon fiber.
The production method according to any one of claims 1 to 3, wherein the polymerization catalyst is a ruthenium catalyst having a compound containing a heterocyclic structure as a ligand.
The method according to any one of claims 1 to 4, wherein the curable composition further comprises a crosslinking aid.