JP2009143158A - Pultrusion molding method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pultrusion molding method for producing a molding which is excellent in properties to impregnate reinforcing fibers with a cycloolefin resin component, mechanical strength, and heat resistance. <P>SOLUTION: By the pultrusion molding method, after continuous carbon fibers produced from acrylic carbon fibers are impregnated with a curable composition containing a cycloolefin monomer, a polymerization catalyst of a ruthenium compound having a heterocyclic structure-containing ligand, a crosslinking agent, a polymerization reaction retarding agent, and a crosslinking auxiliary, the composition is cured. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a pultrusion molding method of cycloolefin resin, and more particularly to a pultrusion molding method that gives a molded product excellent in impregnation of resin components into reinforcing fibers and excellent in mechanical strength and heat resistance.

  As a means to improve the strength of polyolefins such as polypropylene, it is known to mix reinforcing fibers such as glass fibers, and generally fiber reinforcement by mixing and extruding short fibers such as chopped strands. Manufactured polyolefin resins are being manufactured. This method has an advantage that a fiber-reinforced polyolefin resin having high mechanical strength can be obtained very easily. However, in recent years, a higher degree of mechanical strength tends to be required for the resin, and the conventional fiber reinforced polyolefin resin cannot cope with the problem that the fiber breakage cannot be avoided during the kneading in the extruder.

  On the other hand, a pultrusion molding method has attracted attention as a method for improving such problems and producing a resin composition reinforced with continuous fibers without causing fiber breakage. This method basically involves impregnating a thermoplastic resin while drawing continuous reinforcing fibers. For example, in Patent Document 1, a continuous emulsion fiber or an emulsion or solution of a thermoplastic resin is passed through a tank. Thereafter, the solvent is removed by heating and the resin is melted and impregnated into the fiber. Patent Document 2 describes a method of impregnating a continuous fiber with a molten resin while pulling through a crosshead die. A method of impregnating with a melt using polystyrene having a small molecular weight, Patent Document 4 discloses a method of impregnating a thermoplastic resin having a very low viscosity while drawing continuous fibers, Patent Document 5 discloses an unsaturated carboxylic acid, etc. A method of impregnating with a modified polyolefin, Patent Document 6 includes a method of impregnating a polyolefin resin composition containing a heavy metal deactivator, Patent Document 7 The method of impregnating the polyolefin resin composition combining a polyethylene naphthalate fiber, Patent Document 8, a method of impregnating the polyolefin resin composition combining wholly aromatic polyester. However, in these methods, it is difficult to uniformly disperse the polyolefin resin into the continuous fibers, and the obtained molded product has problems of poor mechanical properties and heat resistance.

  On the other hand, a method of impregnating a continuous fiber with a thermosetting resin has been studied. For example, as a method of producing a pipe by a pultrusion molding method, Patent Document 9 discloses a reinforcing material such as glass, carbon, ceramic, boron, a cycloolefin monomer such as dicyclopentadiene, and benzylidenebis (tricyclohexylphosphine) ruthenium dichloride. A method of impregnating a reactive mixture comprising a metathesis ring-opening polymerization catalyst such as triphenylphosphine and a flame retardant and then introducing the mixture into a heated die and simultaneously shaping and curing, or a reinforcing material And a method in which a reactive mixture is introduced and cured. However, although these methods can improve the heat resistance of the molded product to some extent, the impregnation property of the thermosetting resin into the continuous fiber is not sufficient, and the mechanical strength and heat resistance of the molded product obtained by curing are not sufficient. Was not enough.

U.S. Pat. No. 2,877,501 U.S. Pat. No. 4,439,387 US Patent No. 3022210 Japanese Patent Laid-Open No. 57-181852 Japanese Patent Laid-Open No. 3-121146 JP 2004-211051 A JP 2006-8995 A JP 2006-291171 A U.S. Patent No. 6410110

  An object of the present invention is to provide a pultrusion molding method that provides a molded article that is excellent in impregnation of a cycloolefin resin component into reinforcing fibers and that is excellent in mechanical strength and heat resistance.

  As a result of intensive studies in view of the above problems, the present inventors have found that a cycloolefin monomer, a polymerization catalyst having metathesis activity, a crosslinking agent such as dicumyl peroxide, a bifunctional crosslinking aid, and a trifunctional crosslinking aid. When continuous carbon fiber is impregnated with a curable composition blended with a crosslinking aid of the above, it is excellent in impregnation into continuous carbon fiber, and further, the mechanical strength and heat resistance of a molded product obtained by continuous curing are improved. I found it excellent. Moreover, by using acrylic continuous carbon fiber as continuous carbon fiber, the impregnation property of the curable composition containing a cycloolefin monomer into continuous carbon fiber is extremely excellent, and the mechanical strength and heat resistance of the obtained molded product are excellent. I found that it was highly balanced. Further, by adding a polymerization reaction retarder to the curable composition, and by using a polymerization catalyst having a specific structure as a polymerization catalyst, impregnation of continuous carbon fiber with a curable composition containing a cycloolefin monomer. And the mechanical strength and heat resistance of the molded product were found to be further improved. Based on these findings, the present inventors have completed the present invention.

Thus, according to the present invention, there is provided a pultrusion molding method in which a continuous carbon fiber is impregnated with a curable composition comprising a cycloolefin monomer, a polymerization catalyst, a crosslinking agent and a crosslinking aid and then cured.
The continuous carbon fiber is preferably an acrylic carbon fiber.
The curable composition preferably contains a polymerization reaction retarder.
The pre-polymerization catalyst is preferably a ruthenium compound having a heterocyclic structure-containing ligand.

  According to the present invention, a pultrusion molded product having excellent mechanical strength and heat resistance can be easily produced. In addition, the pultrusion molded product in which the cycloolefin resin produced in the present invention is uniformly dispersed is particularly excellent in mechanical strength and heat resistance, so that it is a member for vehicles such as automobiles and airplanes, sports applications, and civil engineering. It can be suitably used in general industrial fields such as construction.

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

  In the present invention, it is preferable to use a ruthenium catalyst having a heterocyclic structure-containing ligand because properties such as appearance, strength, and toughness of the obtained molded article are highly balanced. 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- Examples include dicyclohexylimidazolidine-2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene, and the like.

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

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

  If necessary, the polymerization catalyst can be used by dissolving or suspending in a small amount of an inert solvent. Such solvents include chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, liquid paraffin, 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.

(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; alkylsilyl peroxides such as t-butyltrimethylsilyl peroxide; and the like. Of these, dialkyl peroxides and peroxyketals are preferred in that they have little obstacle to the polymerization reaction.

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

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

  When the crosslinking agent is a radical generator, the one-minute half-life temperature is appropriately selected depending on the curing conditions, but is usually 100 to 300 ° C, preferably 150 to 250 ° C, more preferably 160 to 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. .

(Crosslinking aid)
The curable composition used in the present invention contains a crosslinking aid as an essential component. By adding a crosslinking aid to the curable composition, the impregnation of the curable composition into continuous carbon fibers and the mechanical strength and heat resistance characteristics of the molded product obtained by curing are highly improved. This is preferable.

  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 the compound has a highly symmetric structure, the curable composition containing a cycloolefin monomer can be impregnated into continuous carbon fibers. Highly improved and suitable. In particular, when the crosslinking aid is a hydrocarbon and has a highly symmetrical structure, the impregnation property of the curable composition into continuous carbon fibers, and the mechanical strength and toughness of the molded product obtained by curing. It is suitable for improving the properties and heat resistance.

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

  These crosslinking aids can be used alone or in combination of two or more. The amount of the crosslinking aid is appropriately selected depending on the purpose of use, but is usually 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, more preferably 100 parts by weight of the cycloolefin monomer. 1 to 20 parts by weight, most preferably 5 to 15 parts by weight. When the crosslinking aid is excessively small, the impregnation property of the curable composition into the continuous carbon fiber is inferior, and conversely, when it is excessively large, the properties such as mechanical strength, toughness and heat resistance of the molded product are present. May decrease.

(Curable composition)
The curable composition used in the present invention contains the above-mentioned cycloolefin monomer, polymerization catalyst, crosslinking agent and crosslinking aid as essential components, and a polymerization reaction retarder, chain transfer agent, anti-aging agent, elastomer as necessary. Materials, fillers and other additives can be added.

  When the curable composition used in the present invention contains a polymerization reaction retarder, it is preferable because the continuous carbon fiber can be more easily impregnated. Examples of the polymerization reaction retarder include phosphine compounds such as triphenylphosphine, tributylphosphine, trimethylphosphine, triethylphosphine, dicyclohexylphosphine, vinyldiphenylphosphine, allyldiphenylphosphine, triallylphosphine, styryldiphenylphosphine; aniline, pyridine, etc. Lewis base; 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 amount of the polymerization reaction retarder used is a molar ratio of [metal atom of polymerization catalyst (for example, ruthenium metal): polymerization reaction retarder], usually 1: 0.01 to 1: 100, preferably 1: 0.1 to 0.1. The range is 1:10, more preferably 1: 0.1 to 1: 5.

  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, allyl dimethyl vinyl silane, glycidyl acrylate, allyl glycidyl ether, and 2- (diethylamino) ethyl acrylate.

  These chain transfer agents can be used alone or in combination of two or more, and the blending amount thereof 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 blending amount of the chain transfer agent is within this range, it is preferable because the properties of the mechanical strength and toughness of the obtained molded product can be highly balanced.

  The curable composition used in the present invention can be remarkably improved in toughness 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 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 mechanical strength and heat resistance of the resulting molded product can be improved to a high degree without inhibiting the polymerization 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. 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 0.01-3 weight part.

  In the present invention, it is preferable to add a filler to the curable composition because the 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 50 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 phosphorus flame retardants, nitrogen flame retardants, halogen flame retardants, metal hydroxides such as aluminum hydroxide, and antimony compounds such as antimony trioxide. As the colorant, dyes, pigments and the like are used. There are various kinds of dyes, and known ones may be appropriately selected and used. These other additives can be used alone or in combination of two or more, and the amount used is appropriately selected within a range not impairing the effects of the present invention.

  The curable composition used for this invention can be obtained by mixing the said component. As a mixing method, a conventional method may be used. For example, a liquid (monomer) in which a polymerization catalyst is dissolved or dispersed in an appropriate solvent (catalyst liquid) and other additives are added to a cycloolefin monomer as necessary. It can be prepared by adding to the liquid and stirring.

(Continuous carbon fiber)
The type of continuous carbon fiber used in the present invention is not particularly limited, and for example, carbon fibers produced by various conventionally known methods such as acrylic, pitch-based, rayon-based, etc. can be used. Acrylic carbon fiber (PAN-based carbon fiber) is excellent in impregnation of curable composition containing cycloolefin monomer, does not cause polymerization inhibition, and the mechanical strength and heat resistance of the resulting molded product are highly enhanced. Is preferred. Here, the acrylic carbon fiber is a carbon fiber manufactured using acrylic fiber (polyacrylonitrile fiber) as a raw material.

  The strength characteristics of the continuous 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 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 0.1 to 10%, preferably 0.5 to 5%, more preferably 1 to 3%. When the strength characteristics of the continuous carbon fiber are within these ranges, the mechanical strength and the toughness are highly balanced and suitable.

  These continuous carbon fibers can be used alone or in combination of two or more, and the amount used is appropriately selected according to the purpose of use, but the carbon fiber content in the obtained molded product is Usually, it is selected to be in the range of 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight. When the continuous carbon fiber content is in this range, the mechanical strength and toughness characteristics are highly balanced, which is preferable.

(Protrusion molding)
In the pultrusion molding method, the curable composition is basically impregnated while drawing continuous carbon fibers, and then shaped as necessary, cured, and continuously molded.

  As a method for impregnating the continuous carbon fiber with the curable composition, a conventional method may be used. For example, a method of impregnating a continuous carbon fiber through an impregnation bath containing the curable composition, a curable composition A method of continuously spraying the carbon fiber, a method of allowing the curable composition to flow into the crosshead die while impregnating the carbon fiber through the crosshead die, and the like can be performed. The curable composition used in the present invention has a lower viscosity than epoxy resins and polyolefin resins used as conventional matrix resins, and is particularly compatible with reinforcing fibers such as carbon fibers. Since it is excellent, the reinforcing fiber (bundle) can be uniformly impregnated.

  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 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.

  Since the molded product obtained by the pultrusion molding method of the present invention is particularly excellent in mechanical strength and heat resistance, for example, tubular bodies such as pipes, tubes, tanks, rotors, fly-hole rotors, and composite tubular bodies such as axles. It is suitably used for sports vessels such as golf shafts and fishing rods, and other general industrial applications, including pressure vessels, OA and AV equipment, vehicle structural materials such as automobiles and railways, and aircraft interior parts.

  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 the curable composition: The impregnation property of the curable composition was observed on the properties after the impregnation and judged according to the following criteria.
A: Uniformly impregnated and no generation of bubbles B: Uniform impregnation but slight generation of bubbles X: Not impregnated uniformly

(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) Heat resistance: The molded product was left still in an oven at 220 ° C., taken out after 50 hours, the appearance was observed, and judged according to the following criteria.
◎: No change in shape or discoloration Δ: No change in shape is observed, but discoloration ×: Change in shape

Example 1
A catalyst solution was prepared by dissolving 51 parts of benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and 79 parts of triphenylphosphine in 952 parts of toluene. Separately, 100 parts of dicyclopentadiene (DCP) is added as a cycloolefin monomer to a polyethylene bottle, 20 parts of m-diisopropenylbenzene as a crosslinking aid, and 3,5 as a phenolic antioxidant. -1.0 part of di-t-butyl-4-hydroxyanisole, 0.74 part of allyl methacrylate as a chain transfer agent, 1.2 part of di-t-butyl peroxide (186 min at 1 minute half-life temperature) as a crosslinking agent After the addition, the catalyst solution was added at a rate of 0.12 ml per 100 g of cycloolefin monomer and stirred to prepare a curable composition (matrix resin) and transferred to a resin bath.

  Next, after pulling a pitch-based carbon fiber bundle from the creel with a tension of 400 g / st, the resin bath was impregnated with the curable composition for 10 seconds, and the carbon was put in a mold whose temperature was controlled at 150 ° C. The fiber bundle was allowed to stay for 70 seconds to form FRP. Then, the FRP (continuous fiber reinforced composite material) molded product having a width of 50 mm and a molding thickness of 1.5 mm was processed by curing at a temperature of 200 ° C. for 300 seconds and winding with a winder. Each characteristic of the obtained molded product was evaluated and shown in Table 1.

Example 2
A molded product was obtained in the same manner as in Example 1 except that acrylic carbon continuous fiber was used as the carbon fiber (carbon fiber content 50%). Each characteristic was evaluated, and the results are shown in Table 1.

Comparative Example 1
Except using a curable composition comprising 100 parts of dicyclopentadiene, 0.083 parts of benzylidenebis (tricyclohexylphosphine) ruthenium dichloride and 0.0938 parts of triphenisphosphine, a molded product (containing carbon fiber) was used. The amount was 52%), and each characteristic was evaluated. The results are shown in Table 1.

  From the results of Table 1, it can be seen that the molding method of the present invention is such that the resin component is uniformly impregnated into the continuous carbon fiber, and the obtained molded product is excellent in mechanical strength and heat resistance (Examples 1 and 2). ). In addition, when an acrylic continuous carbon fiber is used as the continuous carbon fiber, the impregnation property of the curable composition containing the cycloolefin monomer is extremely excellent, and the mechanical strength and heat resistance of the resulting molded product are highly balanced. (Example 2).

Claims (4)

A pultrusion molding method in which a continuous carbon fiber is impregnated with a curable composition comprising a cycloolefin monomer, a polymerization catalyst, a crosslinking agent and a crosslinking aid, and then cured. The molding method according to claim 1, wherein the continuous carbon fiber is an acrylic carbon fiber. The molding method according to claim 1 or 2, wherein the curable composition contains a polymerization reaction retarder. The molding method according to claim 1, wherein the polymerization catalyst is a ruthenium compound having a heterocyclic structure-containing ligand.