JP2012067401A - Selecting method for carbon fiber bundle and manufacturing method for prepreg - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of efficiently selecting a carbon fiber bundle useful for manufacturing an excellent prepreg substantially without any crack of fibers, and a method of manufacturing a prepreg using the carbon fiber bundle selected by the above-mentioned selecting method.SOLUTION: A method of selecting a carbon fiber bundle comprises a step (1) of providing a carbon fiber bundle and a step (2) of pulling the carbon fiber bundle in the fiber direction at a tension of 5-20 N to fix it and bringing the carbon fiber bundle into contact with shock-applying means performing reciprocation at a vibration frequency of 10-15 Hz, for 5-10 seconds, or bringing the carbon fiber bundle into contact with vibration means vibrating at a vibration frequency of 10-15 Hz, for 5-10 seconds. In the method, after the step (2), the carbon fiber bundle is employed as reinforcing fibers for prepreg if a crack with a width of 1 mm or more and a length of 50 mm or more is not found between filament yarns of the carbon fiber bundle. And a method of manufacturing a prepreg comprises a step (I) of selecting a carbon fiber bundle according to the above-mentioned selecting method for the carbon fiber bundle, and a step (IIa) of opening the carbon fiber bundle selected in the step (I) to impregnate the opened carbon fibers with a resin composition including a cross-linkable resin to provide a prepreg, or a step (IIb) of opening the carbon fiber bundle selected in the step (I) to impregnate the opened carbon fibers with a polymerizable composition including cycloolefin monomer and a metathesis polymerization catalyst for performing massive polymerization on the polymerizable composition, thereby providing a prepreg.

Description

  The present invention relates to a method for efficiently sorting carbon fiber bundles useful for the production of prepreg, and a method for producing a prepreg using the carbon fiber bundles sorted by this sorting method.

  Carbon fiber is a fiber obtained by carbonizing acrylic fiber or pitch (by-products such as petroleum, coal, coal tar, etc.) at a high temperature. In recent years, carbon fiber bundles of 24,000 or more filaments made of carbon fibers, so-called large tow type carbon fiber bundles, have been put on the market, and business development for prepreg use etc. is being performed using the fiber bundles. . A prepreg is normally used suitably for manufacture of a fiber reinforced composite.

In prepreg manufacturing using large tow type carbon fiber bundles, it is important to ensure required quality and quality, increase production efficiency, and reduce manufacturing costs. For that purpose, it is necessary to make a prepreg having a low thickness and a small thickness unevenness.
However, when a prepreg is manufactured using a large tow type carbon fiber bundle, (a) the number of filaments of the fiber is large and the opening property is inferior, so that the portion where the opening yarn width is narrow has a thickness and is adjacent (B) Further, the thickness unevenness reduces the impregnation property with the resin, and the smoothness deteriorates due to local peeling from the release paper and generation of wrinkles. (C) Furthermore, when using a fiber bundle with inferior spreadability, the processing speed of the prepreg has to be reduced, resulting in a decrease in production efficiency.

On the other hand, for example, Patent Document 1 proposes a method for solving the problem in the case of using large tow for manufacturing a prepreg by using a specific sizing agent attached to the large tow.
However, in this method, it is necessary to attach a specific sizing agent to the large tow, and accordingly, the production efficiency of the prepreg is lowered.

Japanese Patent Laid-Open No. 2003-2898

  The present invention has been made in view of the above-described prior art, and a method for efficiently sorting carbon fiber bundles useful for producing an excellent prepreg substantially free of fiber cracks, and by this sorting method. It aims at providing the manufacturing method of the prepreg which uses the selected carbon fiber bundle.

  The present inventors have found that even when large tow is used, a desired prepreg may be obtained only by opening and impregnating the resin composition. And as a result of earnest research to solve the above problems, the carbon fiber bundle is fixed under a predetermined condition, and the striking means is brought into contact with the carbon fiber bundle under the predetermined condition, or the vibration means is operated under the predetermined condition. Thus, a method for easily and efficiently selecting a carbon fiber bundle useful for producing a desired prepreg, regardless of whether it is a large tow, was found, and the present invention was completed.

Thus, according to the first aspect of the present invention, there is provided the following carbon fiber bundle selection method (i) or (ii).
(I) Step (1) of providing a carbon fiber bundle, and fixing the carbon fiber bundle by pulling the carbon fiber bundle at a tension of 5 to 20 N in the fiber direction and reciprocating the carbon fiber bundle at a frequency of 10 to 15 Hz. In the carbon fiber bundle, the step (2) of bringing the hitting means into contact for 5 to 10 seconds or contacting the vibration means vibrating at a frequency of 10 to 15 Hz for 5 to 10 seconds, after the step (2), A method for selecting a carbon fiber bundle, wherein a crack having a width of 1 mm or more and a length of 50 mm or more is not observed between filament yarns, and the carbon fiber bundle is employed as a prepreg reinforcing fiber.
(Ii) The method for selecting a carbon fiber bundle according to (i), wherein the number of filaments of the carbon fiber bundle is 40,000 or more.

According to a second aspect of the present invention, there is provided a method for producing the following prepregs (iii) and (iv).
(Iii) Step (I) of selecting a carbon fiber bundle according to the method for selecting a carbon fiber bundle described in (i) or (ii) above, and opening the carbon fiber bundle selected in step (I) The manufacturing method of a prepreg which has the process (IIa) which obtains a prepreg by making the carbon fiber impregnated the resin composition containing a crosslinkable resin.
(Iv) Step (I) of selecting a carbon fiber bundle according to the method for selecting a carbon fiber bundle described in (i) or (ii) above, and opening the carbon fiber bundle selected in step (I) The manufacturing method of a prepreg which has the process (IIb) which impregnates the polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst in the carbon fiber, and carries out bulk polymerization of this polymerizable composition.

According to the sorting method of the present invention, it is possible to easily and efficiently sort carbon fiber bundles useful for producing an excellent prepreg substantially free from fiber cracking.
According to the method for producing a prepreg of the present invention, an excellent prepreg can be produced efficiently.

It is a figure which shows one embodiment of the selection method of the carbon fiber bundle of this invention. It is a figure which shows the example of the hitting means used for the selection method of the carbon fiber bundle of this invention. It is a figure which shows an example of the vibration means used for the selection method of the carbon fiber bundle of this invention. It is a perspective view which shows an example of the curved body used for the manufacturing method of the prepreg of this invention. It is the schematic which shows an example of the polymeric composition filling part used for the manufacturing method of the prepreg of this invention. (A) shows the cross section in the horizontal direction of this filling part, (B) shows a mode that this filling part was seen from the front. It is the schematic which shows an example of the manufacturing apparatus used for the manufacturing method of the prepreg of this invention.

  Hereinafter, the present invention will be described in detail by dividing it into 1) a method for selecting a carbon fiber bundle and 2) a method for producing a prepreg.

1) Selection method of carbon fiber bundle The first of the present invention is a step (1) of providing a carbon fiber bundle, and the carbon fiber bundle is pulled and fixed in a fiber direction with a tension of 5 to 20 N. On the other hand, it has a step (2) of bringing a striking means reciprocating at a frequency of 10 to 15 Hz into contact for 5 to 10 seconds or contacting a vibration means vibrating at a frequency of 10 to 15 Hz for 5 to 10 seconds, After the step (2), in the carbon fiber bundle, when no cracks having a width of 1 mm or more and a length of 50 mm or more are observed between the filament yarns, the carbon fiber bundle is employed as a prepreg reinforcing fiber. This is a sorting method.

(I) Step (1)
Step (1) is a step of providing a sorting operation with a carbon fiber bundle for sorting.
The type of carbon fiber used in the present invention is not particularly limited, and various carbon fibers produced by a conventionally known method such as an acrylic type, a pitch type, and a rayon type can be arbitrarily used. Among these, acrylic carbon fibers (PAN-based carbon fibers) are suitable because they can improve properties such as mechanical strength and toughness to a high degree when a fiber-reinforced composite is produced using them.

  The carbon fiber bundle used in the present invention is obtained by bundling single fibers made of carbon fibers with an arbitrary sizing agent. Such a carbon fiber bundle is commercially available. A sizing agent is a kind of paste used to improve the formability of carbon fibers to be treated. The sizing agent is not particularly limited and is appropriately selected depending on the resin. Although appropriately selected from water-soluble urethane, urethane, vinyl ester, epoxy, and polypropylene, urethane and epoxy are usually preferably used. Moreover, the adhesion amount of a sizing agent is 0.1-3 weight part normally with respect to 100 weight part of carbon fibers, Preferably it is 0.2-1 weight part. Since the polymerizable composition containing a cycloolefin monomer has a low viscosity, the carbon fiber bundle is excellent in impregnation property, the carbon fiber bundle is likely to swell, and the bonding force between single fibers is estimated to be loosened. Therefore, the polymerizable composition can be uniformly impregnated into the carbon fiber bundle.

There is no particular limitation on the strength characteristics of the carbon fiber. For example, a prepreg having excellent rigidity can be obtained by appropriately selecting and using carbon fibers having the following strength characteristics according to the purpose. 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%. Further, when the strength characteristics of the carbon fiber are in these ranges, the appearance, mechanical strength, and toughness are highly balanced in the fiber reinforced composite obtained using the carbon fiber, which is preferable.
These carbon fibers can be used alone or in combination of two or more.

  The thickness of the single fiber (filament) made of carbon fiber that constitutes the carbon fiber bundle used in the present invention is not particularly limited as long as it is general. On the other hand, the number of filaments in one carbon fiber bundle is not particularly limited, but is usually 1,000 to 100,000, preferably 6,000 to 80,000, more preferably 12,000 to The range is 60,000. The present invention is particularly suitable for sorting carbon fiber bundles called large tows, particularly large tows having 40,000 or more filaments in carbon fiber bundles.

  Further, as the carbon fiber bundle used in the present invention, carbon fiber bundles obtained by combining a carbon fiber precursor fiber and then applying a flame resistance treatment (JP 2003-2989 A, JP 2007-92218 A). Or a carbon fiber bundle (Japanese Patent Laid-Open No. 2001-214334) obtained by subjecting the carbon fiber precursor fiber to flameproofing to obtain carbonized fiber, and then combining them. In order to efficiently obtain a carbon fiber bundle with fewer cracks, it is preferable to use the former carbon fiber bundle.

(2) Step (2)
In step (2), the carbon fiber bundle provided in step (1) is pulled and fixed in the fiber direction with a tension of 5 to 20 N, and the striking means reciprocates at a frequency of 10 to 15 Hz with respect to the carbon fiber bundle. Is contacted for 5 to 10 seconds, or a vibrating means that vibrates at a frequency of 10 to 15 Hz is contacted for 5 to 10 seconds. When selecting a carbon fiber bundle that can be suitably used as a reinforcing fiber for prepreg, using a predetermined crack between filament yarns of the carbon fiber bundle as an index, whether the fixed carbon fiber bundle is struck under the above conditions Or it is necessary to vibrate. When deviating from the above conditions, the sorting accuracy decreases.

  This step is performed, for example, as shown in FIG. That is, the carbon fiber bundle 1 is fixed to the pair of supports 3 by pulling with a predetermined tension in the fiber direction. Next, the hitting means 2 that reciprocates in the vertical direction (direction indicated by the arrow) at a predetermined frequency is brought into contact with the fixed carbon fiber bundle 1 for a predetermined time. The striking means 2 is driven by a known drive source such as a motor. On the other hand, when using vibration means instead of the striking means 2, the vibration means that vibrates at a predetermined frequency may be brought into contact with the carbon fiber bundle 1 fixed as described above for a predetermined time. The vibration means is also driven in the same manner as the striking means 2.

In the present invention, the striking means is not particularly limited, and means for reciprocating vertically with respect to the fiber direction of the carbon fiber bundle and striking the carbon fiber bundle in contact with the carbon fiber bundle. preferable. On the other hand, the vibration means is not particularly limited, and means for vibrating the carbon fiber bundle in the vertical direction or the lateral direction with respect to the fiber direction of the carbon fiber bundle and bringing the carbon fiber bundle into contact with the carbon fiber bundle. preferable. Examples of the suitable striking means include a rod-shaped object as shown in FIG. 2 (10a), a cylindrical object as shown in (10b), and a plate-like object as shown in (10c) and (10d). . Moreover, as an example of the latter, a convex object as shown to (10e) in FIG. 3 is mentioned. 2 and 3, the width W corresponding to the length of each means is at least the same as the width of the carbon fiber bundle.
As shown in FIG. 1, the carbon fiber bundle is usually fixed to the support body without slack. As the displacement in the vertical direction with respect to the fiber direction of the carbon fiber bundle at the portion where the striking means abuts in the carbon fiber bundle, from the viewpoint of making it easier to determine the presence of a predetermined crack between filament yarns, A range of 10 mm is preferred. When the vibration means is used, the carbon fiber bundle is displaced in the vertical direction or the horizontal direction with respect to the fiber direction of the carbon fiber bundle.

  The step (2) is preferably performed under environmental conditions of a temperature of 18 to 30 ° C. and a humidity of 40 to 90% RH from the viewpoint of making it easier to determine the presence of a predetermined crack between filament yarns.

  After performing the step (2) as shown in FIG. 1, it is determined by any discriminating means whether or not a crack having a width of 1 mm or more and a length of 50 mm or more is recognized between the filament yarns. That is, as a result of the determination, if no cracks having a width of 1 mm or more and a length of 50 mm or more are observed between the filament yarns, it is determined that the carbon fiber bundle is adopted as a reinforcing fiber for prepreg. When a crack having a width of 1 mm or more and a length of 50 mm or more is observed, it is determined that the carbon fiber bundle is not adopted as a prepreg reinforcing fiber.

  The discriminating means is not particularly limited as long as it can discriminate whether or not there is a crack as described above in the carbon fiber bundle. For example, visual observation with the naked eye, visual observation using a magnifying glass, discrimination means using a change in light transmittance, and the like can be given.

  According to the sorting method of the present invention, it is possible to easily and efficiently sort a carbon fiber bundle from which an excellent prepreg substantially free of fiber cracks can be obtained.

2) Manufacturing method of prepreg The manufacturing method of the prepreg of the present invention includes a step (I) of selecting a carbon fiber bundle according to the above-described selection method of the present invention, and opening the carbon fiber bundle selected in the step (I). Carbon fiber obtained by opening the carbon fiber bundle selected in the step (IIa) or the step (I) of obtaining a prepreg by impregnating a fiber composition containing a crosslinkable resin into the fiber A step (IIb) of obtaining a prepreg by impregnating with a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst and bulk polymerizing the polymerizable composition.

(I) Step (I)
In step (I), the carbon fiber bundle is selected according to the above-described method for selecting a carbon fiber bundle of the present invention. The details of the step (I) are as described in the above-described screening method of the present invention.
In the method for producing a prepreg of the present invention, the step (I) and the step (IIa) or the step (IIb) may be performed separately or continuously. When performing separately, the carbon fiber bundle is previously selected in step (I), and then the selected carbon fiber bundle is subjected to step (IIa) or step (IIb) to produce a prepreg. As an aspect in this case, for example, a carbon fiber bundle that has been preliminarily selected as shown in FIG. 1 is used in a prepreg manufacturing apparatus as shown in FIG. 6 to manufacture a prepreg. When performing continuously, the carbon fiber bundle subjected to step (I) may be continuously subjected to step (IIa) or step (IIb) to produce a prepreg. As an aspect in this case, for example, a prepreg can be manufactured by appropriately combining a carbon fiber bundle sorting unit as shown in FIG. 1 and a prepreg manufacturing apparatus as shown in FIG. Can be mentioned. In addition, when performing continuously, when the generation | occurrence | production of a predetermined crack is recognized in the carbon fiber bundle in the selection means, manufacture of the prepreg using this carbon fiber bundle will be stopped. Therefore, the selection means in this case is significant as a quality confirmation of the carbon fiber bundle.

(II) Step (IIa) or Step (IIb)
In the method for producing a prepreg of the present invention, in the step (IIa), the carbon fiber bundle selected in the step (I) is opened, and the opened carbon fiber is impregnated with a resin composition containing a crosslinkable resin. It is the process of obtaining. In step (IIb), the carbon fiber bundle selected in step (I) is opened, and the opened carbon fiber is impregnated with a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst. This is a step of obtaining a prepreg by bulk polymerization of the composition.

  “Opening the carbon fiber bundle selected in step (I)” performed before the steps (IIa) and (IIb) means that the carbon fiber bundle selected in step (I) is loosened and continuously widened. To make it thin. Polymerization containing a resin composition containing a crosslinkable resin or a cycloolefin monomer and a metathesis polymerization catalyst into the carbon fiber bundle by reducing the number of fibers in the thickness direction by opening the carbon fiber bundle. The impregnation of the adhesive composition can be performed more uniformly in a shorter time.

  The method for opening the carbon fiber bundle is not particularly limited. For example, a method of squeezing the fiber with a round bar (Japanese Patent Laid-Open No. 60-9961), a method of spreading each fiber by applying a water stream or a high-pressure air stream. (Japanese Patent Laid-Open No. 52-151362, Japanese Patent Laid-Open No. 57-77342), a method of vibrating each fiber with ultrasonic waves (Japanese Patent Laid-Open No. 1-282362), between two rolls subjected to surface treatment A method of running a fiber bundle at a constant speed in one direction while flowing air at a constant speed (Patent 3063019), a transverse vibrating roll that vibrates in the roll axis direction after striking a continuously running fiber bundle And / or a method of opening using a vertical vibrating roll that vibrates in the vertical direction with respect to the traveling direction of the fiber bundle (Japanese Patent Application Laid-Open No. 2004-225222).

  The crosslinkable resin used in step (IIa) is not particularly limited as long as it is a resin having a crosslinkable functional group or a crosslinkable carbon-carbon unsaturated bond. Examples of the resin include a cycloolefin polymer, an epoxy resin, a phenol resin, a polyimide resin, a triazine resin, a melamine resin, a modified resin obtained by modifying these, and these may be used alone or 2 It can be used in combination of more than one species.

Among these, cycloolefin polymers are preferred because of their good impregnation into carbon fibers. Moreover, as a cycloolefin polymer, it is more preferable to use what is obtained by ring-opening-polymerizing a cycloolefin monomer by a well-known method.
Examples of the crosslinkable functional group include an epoxy group, a hydroxyl group, an isocyanate group, and a sulfonic acid group. The crosslinkable carbon-carbon unsaturated bond will be described later.

  In the present invention, the resin composition to be impregnated into the carbon fiber bundle is added to the crosslinkable resin from the viewpoint of reducing the linear expansion coefficient of the obtained fiber-reinforced composite and improving the elastic modulus and increasing the mechanical strength. It is preferable to contain an inorganic filler.

  The inorganic filler to be used is not particularly limited. For example, hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide; oxides such as silicon oxide (silica), aluminum oxide, magnesium oxide, zinc oxide, titanium oxide; mica, kaolin, fly ash, talc, Silicates such as mica; titanates such as barium titanate, strontium titanate and calcium titanate; carbonates such as sodium carbonate and calcium carbonate; carbides such as silicon carbide and boron carbide; aluminum nitride, boron nitride and nitride Examples thereof include nitrides such as silicon; glass powder; carbon black; metal particles such as aluminum and nickel; These inorganic fillers can be used alone or in combination of two or more. Moreover, what was surface-treated with a well-known silane coupling agent, titanate coupling agent, aluminum coupling agent, etc. can also be used as these inorganic fillers.

  The average particle diameter of the inorganic filler is preferably 0.005 μm or more and less than 100 μm, more preferably 0.01 μm or more and less than 50 μm, still more preferably 0.05 μm or more and less than 25 μm. When the average particle diameter of the inorganic filler is too large, it becomes difficult to enter between the single fibers constituting the carbon fiber bundle, and it is difficult to obtain an effect of improving the mechanical strength. The average particle diameter of the inorganic filler is an average value of the lengths in the longitudinal direction and the short direction when each particle constituting the inorganic filler is viewed three-dimensionally.

  Content of an inorganic filler is 0.5-50 volume% normally in 100 volume% of resin compositions. If the content of the inorganic filler is too small or too large, the dispersibility of the inorganic filler in the carbon fiber is lowered, and it is difficult to obtain the effect of improving the mechanical strength in the obtained fiber-reinforced composite.

If desired, the resin composition may contain a crosslinking agent or a crosslinking aid.
The crosslinking agent is used for the purpose of inducing a crosslinking reaction in the crosslinkable resin. By containing a crosslinking agent, the crosslinkability of the crosslinkable resin can be effectively enhanced.

  Although it does not specifically limit as a crosslinking agent to be used, Usually, a radical generator is used suitably. Examples of the radical generator include organic peroxides, diazo compounds, and nonpolar radical generators, and organic peroxides and nonpolar radical generators are preferable.

  Examples of the organic peroxide include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, and 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, and 2,5-dimethyl-2,5- Dialkyl peroxides such as di (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 and di (isopropyl) Peroxycarbonates such as peroxy) dicarbonate; alkylsilyl peroxides such as t-butyltrimethylsilyl peroxide; 3,3,5,7,7-pentamethyl-1,2,4-trioxepane, 3,6,9-triethyl- Cyclic peroxides such as 3,6,9-trimethyl-1,4,7-triperoxonane and 3,6-diethyl-3,6-dimethyl-1,2,4,5-tetroxane; It is done. Of these, dialkyl peroxides, peroxyketals, and cyclic peroxides are preferred in that there are few obstacles 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, and 1,1,1 -Triphenyl-2-phenylethane and the like.

When a radical generator is used as a crosslinking agent, the 1 minute half-life temperature is appropriately selected depending on the conditions of curing (crosslinking of the prepreg), but is usually 100 to 300 ° C, preferably 150 to 250 ° C, more preferably. It is the range of 160-230 degreeC. Here, the half-life temperature for 1 minute is a temperature at which half of the radical generator decomposes in 1 minute. The 1-minute half-life temperature of the radical generator may be referred to, for example, a catalog or homepage of each radical generator manufacturer (for example, Nippon Oil & Fats Co., Ltd.).
The above radical generators can be used alone or in combination of two or more.

  The blending amount of the radical generator is usually 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the crosslinkable resin. It is a range.

  Examples of the crosslinking assistant include polyfunctional compounds having two or more crosslinkable carbon-carbon unsaturated bonds that can participate in the crosslinking reaction of the crosslinkable resin. The crosslinkable carbon-carbon unsaturated bond contained in the compound constituting the crosslinking aid is preferably present, for example, as a vinylidene group present at the molecular end, and particularly as an isopropenyl group or a methacryl group. It is more preferable that it exists as a methacryl group.

Specific examples of the crosslinking aid include isopropenyl groups such as polyfunctional compounds having two isopropenyl groups such as p-diisopropenylbenzene, m-diisopropenylbenzene, and o-diisopropenylbenzene. 2 or more polyfunctional compounds; ethylene dimethacrylate, 1,3-butylene dimethacrylate, 1,4-butylene dimethacrylate, 1,6-hexanediol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate Polyfunctional compounds having two methacrylic groups such as triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and 2,2′-bis (4-methacryloxydiethoxyphenyl) propane, and trimethylo- And polyfunctional compounds having two or more methacrylic groups, such as polyfunctional compounds having three methacrylic groups, such as rupropane trimethacrylate and pentaerythritol trimethacrylate. Among these, as the crosslinking aid, a polyfunctional compound having two or more methacryl groups is preferable from the viewpoint of improving the heat resistance and crack resistance of the obtained fiber-reinforced composite. Among polyfunctional compounds having two or more methacrylic groups, polyfunctional compounds having three methacrylic groups such as trimethylolpropane trimethacrylate and pentaerythritol trimethacrylate are more preferable.
These crosslinking aids can be used alone or in combination of two or more.

  The amount of the crosslinking aid is usually 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight, and more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the crosslinkable resin.

For example, the resin composition may further contain a compounding agent other than the above, such as an anti-aging agent, a colorant, a light stabilizer, and a foaming agent.
Examples of the anti-aging agent include at least one anti-aging agent selected from the group consisting of a phenol-based anti-aging agent, an amine-based anti-aging agent, a phosphorus-based anti-aging agent and a sulfur-based anti-aging agent. By blending these anti-aging agents, the heat resistance of the fiber-reinforced composite obtained can be highly improved without inhibiting the crosslinking reaction, which is preferable.
As the colorant, a dye or a pigment is used. There are various kinds of dyes, and known ones may be appropriately selected and used. These other compounding agents 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.

  Although it does not specifically limit as a solvent used in order to prepare the said resin composition, For example, Ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; Aromatic hydrocarbons, such as toluene and xylene; Esters, such as ethyl acetate; And ethers such as ethylene glycol monomethyl ether; amides such as N, N-dimethylformamide; alcohols such as methanol and ethanol.

  The method for impregnating the carbon fiber with the resin composition is not particularly limited. For example, the resin composition may be spray coating, dip coating, roll coating, curtain coating, die coating, and slit coating. It can apply by apply | coating to a carbon fiber by a well-known method, stacking a protective film on it as needed, and pressing with a roller etc. from an upper side.

  On the other hand, in the step (IIb), the carbon fiber bundle selected in the step (I) is opened, and the opened carbon fiber is impregnated with a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst, A prepreg is obtained by bulk polymerization of the polymerizable composition.

  The cycloolefin monomer constituting the polymerizable composition is a compound having an alicyclic structure formed of carbon atoms and having one ring-opening polymerizable carbon-carbon double bond in the alicyclic structure. is there.

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

As the cycloolefin monomer, either a monocyclic cycloolefin monomer or a polycyclic cycloolefin monomer can be used. From the viewpoint of improving the heat resistance of the obtained fiber-reinforced composite, a polycyclic cycloolefin monomer is preferable. As the polycyclic cycloolefin monomer, a norbornene-based monomer is particularly preferable.
The “norbornene monomer” refers to a cycloolefin monomer having a norbornene ring structure in the molecule. For example, norbornenes, dicyclopentadiene, tetracyclododecenes and the like can be mentioned.

As the cycloolefin monomer, any of those having no crosslinkable carbon-carbon unsaturated bond and those having one or more crosslinkable carbon-carbon unsaturated bonds can be used.
As used herein, “crosslinkable carbon-carbon unsaturated bond” refers to a carbon-carbon unsaturated bond that does not participate in ring-opening polymerization and can participate in a crosslinking reaction. The crosslinking reaction is a reaction that forms a bridge structure, and there are various forms such as a condensation reaction, an addition reaction, a radical reaction, and a metathesis reaction. However, in the present invention, a radical crosslinking reaction or a metathesis is usually performed. It refers to a crosslinking reaction, particularly a radical crosslinking reaction. Examples of the crosslinkable carbon-carbon unsaturated bond include carbon-carbon unsaturated bonds other than aromatic carbon-carbon unsaturated bonds, that is, aliphatic carbon-carbon double bonds or triple bonds. Usually refers to an aliphatic carbon-carbon double bond. In the cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds, the position of the unsaturated bond is not particularly limited, and in addition to the alicyclic structure formed by carbon atoms, other than the alicyclic structure It may be present at any position of, for example, at the end or inside of the side chain. For example, the aliphatic carbon-carbon double bond may exist as a vinyl group (CH ₂ ═CH—), a vinylidene group (CH ₂ ═C <), or a vinylene group (—CH═CH—). Since it exhibits radical crosslinkability, it preferably exists as a vinyl group and / or vinylidene group, and more preferably as a vinylidene group.

  Examples of cycloolefin monomers having no crosslinkable carbon-carbon unsaturated bond include cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, and 3-chlorocyclopentene. Monocyclic cycloolefin monomers such as cyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, and cycloheptene; norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-propyl-2-norbornene, 5,6-dimethyl-2-norbornene, 1-methyl-2-norbornene, 7-methyl-2-norbornene, 5,5,6-trimethyl- 2-norbornene, 5-fu Nyl-2-norbornene, tetracyclododecene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene (TCD), 2-methyl-1, 4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4 4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2- Hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2, 3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4 5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4 4a, 5,8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2, 3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1, 2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloro-2-norbornene, 5,5-dichloro-2-norbornene, 5-fluoro-2 -Norbornene, 5,5,6-trifluoro-6-trif Fluoromethyl-2-norbornene, 5-chloromethyl-2-norbornene, 5-methoxy-2-norbornene, 5,6-dicarboxyl-2-norbornene anhydrate, 5-dimethylamino-2-norbornene, and 5-cyano Norbornene monomers such as -2-norbornene; and preferred are norbornene monomers having no crosslinkable carbon-carbon unsaturated bond.

Examples of the cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds include 3-vinylcyclohexene, 4-vinylcyclohexene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4- Monocyclic cycloolefin monomers such as cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, and 1,3-cyclooctadiene; 5-ethylidene-2-norbornene, 5- Methylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinyl-2-norbornene, 5-allyl-2-norbornene, 5,6-diethylidene-2-norbornene, dicyclopentadiene, and 2,5- Norbornene monomers such as norbornadiene; Crosslinkable carbon - is a norbornene-based monomer having one or more carbon unsaturated bond.
These cycloolefin monomers can be used alone or in combination of two or more.

The cycloolefin monomer used in the present invention preferably includes a cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds. When such a cycloolefin monomer is used, reliability such as crack resistance is improved in the obtained fiber-reinforced composite, which is preferable.
In the cycloolefin monomer for forming the cycloolefin polymer, the blending ratio of the cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds and the cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bonds is The weight ratio (cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond / cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bond) is usually 5 / 95 to 100/0, preferably 10/90 to 90/10, more preferably 15/85 to 70/30. If the said mixture ratio exists in this range, in the fiber reinforced composite obtained, heat resistance, crack resistance, etc. will improve and it is suitable.

  In addition, as long as expression of the effect of this invention is not inhibited, the polymerizable composition may contain the arbitrary monomers copolymerizable with the cycloolefin monomer mentioned above.

  As the metathesis polymerization catalyst constituting the polymerizable composition, the above-mentioned cycloolefin monomer can be subjected to metathesis ring-opening polymerization, usually a transition metal atom as a central atom, a plurality of ions, atoms, polyatomic ions, compounds, etc. And a complex formed by bonding. As transition metal atoms, atoms of Group 5, Group 6, and Group 8 (according to the 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: Examples include ruthenium and osmium. Of the transition metal atoms, Group 8 ruthenium and osmium are preferred. That is, the metathesis polymerization catalyst used in the present invention is preferably a complex having ruthenium or osmium as a central atom, and more preferably a complex having ruthenium as a central atom. As the complex having ruthenium as a central atom, a ruthenium carbene complex in which a carbene compound is coordinated to ruthenium is preferable.

  Here, the “carbene compound” is a general term for compounds having a methylene free group, and refers to a compound having an uncharged divalent carbon atom (carbene carbon) as represented by (> C :). Since the ruthenium carbene complex is excellent in catalytic activity during bulk polymerization, when the first polymerizable composition is bulk polymerized, there is little odor derived from unreacted monomers, and a high-quality molded product with good productivity can be obtained. Can do. In addition, it is relatively stable to oxygen and moisture in the air and is not easily deactivated, so that it can be used even in the atmosphere.

  Specific examples of the ruthenium carbene complex include complexes represented by the following general formula (1) or (2).

In the general 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 cyclic or chain hydrocarbon group having 1 to 20 carbon atoms. X ¹ and X ² each independently represent an arbitrary anionic ligand. L ¹ and L ² each independently represent a hetero atom-containing carbene compound or a neutral electron donating compound other than the hetero atom-containing carbene compound. R ¹ and R ² may be bonded to each other to form an aliphatic ring or an aromatic ring that may contain a hetero atom. Furthermore, 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.

  A heteroatom means an atom of groups 15 and 16 of the periodic table, and specifically, a nitrogen atom (N), an oxygen atom (O), a phosphorus atom (P), a sulfur atom (S), an arsenic atom (As), selenium atom (Se), and the like. Among these, N, O, P, and S are preferable, and N is particularly preferable from the viewpoint of obtaining a stable carbene compound.

As said ruthenium carbene complex, what has at least one carbene compound which has a heterocyclic structure as a hetero atom containing carbene compound as a ligand is preferable.
As the heterocyclic structure, an imidazoline ring structure or an imidazolidine ring structure is preferable.

  Examples of the carbene compound having a heterocyclic structure include compounds represented by the following general formula (3) or (4).

In the general formula (3) or (4), R ^{3 to} R ⁶ each independently include a hydrogen atom; a halogen atom; or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. Represents a good cyclic or chain hydrocarbon group having 1 to 20 carbon atoms. R ^{3 to} R ⁶ may be bonded to each other in any combination to form a ring.

  Examples of the compound represented by the general formula (3) or (4) include 1,3-dimesitylimidazolidin-2-ylidene, 1,3-di (1-adamantyl) imidazolidin-2-ylidene, 1 , 3-dicyclohexylimidazolidine-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3-di (1-phenyl) Ethyl) -4-imidazoline-2-ylidene, 1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene and the like.

  In addition to the compound represented by the general formula (3) or (4), 1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole-5 -Iridene, 1,3-dicyclohexylhexahydropyrimidin-2-ylidene, N, N, N ', N'-tetraisopropylformamidinylidene, 1,3,4-triphenyl-4,5-dihydro-1H- Hetero atom-containing carbene compounds such as 1,2,4-triazole-5-ylidene and 3- (2,6-diisopropylphenyl) -2,3-dihydrothiazol-2-ylidene can also be used.

In the general formulas (1) and (2), the anionic (anionic) ligands X ¹ and X ² are ligands having a negative charge when separated from the central metal atom. For example, halogen atoms such as fluorine atom (F), chlorine atom (Cl), bromine atom (Br), and iodine atom (I), diketonate group, substituted cyclopentadienyl group, alkoxy group, aryloxy group, and carboxyl Groups and the like. Among these, a halogen atom is preferable and a chlorine atom is more preferable.

  The neutral electron-donating compound may be any ligand as long as it has a neutral charge when it is separated from the central metal. Specific examples thereof include carbonyls, amines, pyridines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, thiocyanates, and the like. Among these, phosphines, ethers and pyridines are preferable, and trialkylphosphine is more preferable.

  Examples of the complex compound represented by the general formula (1) include benzylidene (1,3-dimesityl-4-imidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-4, 5-dibromo-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4-imidazoline-2-ylidene) (3-phenyl-1H-indene-1-ylidene) (tri Cyclohexylphosphine) ruthenium dichloride, (1,3-dimesitylimidazolidine-2-ylidene) (3-methyl-2-buten-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl- Octahydrobenzimidazo -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) (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-Dimesitylimidazolidin-2-ylidene) pyridine ruthenium dichloride, (1,3-Dimesitylimidazolidine-2-ylidene) (2-phenylethylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3- Dimesityl-4-imidazoline-2-ylidene) (2-phenylethylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4,5-dibromo-4-imidazoline-2-ylidene) [(phenylthio) methylene ] (Tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4,5-dibromo-4-imidazoline-2-ylidene) (2-pyrrolidone-1-ylmethylene) (tricyclohexylphosphine) ruthenium dichloride, etc. original A ruthenium complex compound in which each of a child-containing carbene compound and a neutral electron-donating compound other than the compound is bonded;

  A ruthenium compound in which two neutral electron-donating compounds such as benzylidenebis (tricyclohexylphosphine) ruthenium dichloride and (3-methyl-2-buten-1-ylidene) bis (tricyclopentylphosphine) ruthenium dichloride are bonded;

  Two heteroatom-containing carbene compounds such as benzylidenebis (1,3-dicyclohexylimidazolidine-2-ylidene) ruthenium dichloride and benzylidenebis (1,3-diisopropyl-4-imidazoline-2-ylidene) ruthenium dichloride are bonded Ruthenium complex compounds; and the like.

  Examples of the complex compound represented by the general formula (2) include (1,3-dimesityrylimidazolidine-2-ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (t-butylvinylidene) (1 , 3-diisopropyl-4-imidazoline-2-ylidene) (tricyclopentylphosphine) ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) phenylvinylidene ruthenium dichloride, and the like.

  Among these complex compounds, those having one compound represented by the general formula (1) and represented by the general formula (4) as a ligand are most preferable.

  These ruthenium carbene complexes are described in Org. Lett. 1999, Vol. 1, page 953, and Tetrahedron. Lett. 1999, Vol. 40, page 2247, and the like.

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

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

  The polymerizable composition may further contain a polymerization regulator, a polymerization reaction retarding agent, a chain transfer agent, a crosslinking agent, a crosslinking assistant, and / or an antiaging agent.

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

  The polymerization reaction retarder can suppress an increase in the viscosity of the polymerizable composition. Polymerization reaction retarders include phosphine compounds such as triphenylphosphine, tributylphosphine, trimethylphosphine, triethylphosphine, dicyclohexylphosphine, vinyldiphenylphosphine, allyldiphenylphosphine, triallylphosphine, and styryldiphenylphosphine; Lewis such as aniline and pyridine Base; etc. can be used. What is necessary is just to adjust the compounding quantity suitably as needed.

Examples of chain transfer agents include 1-hexene, 2-hexene, styrene, vinylcyclohexane, allylamine, glycidyl acrylate, allyl glycidyl ether, ethyl vinyl ether, methyl vinyl ketone, 2- (diethylamino) ethyl acrylate, and 4-vinylaniline. Chain transfer agents having no crosslinkable carbon-carbon unsaturated bonds; divinylbenzene, vinyl methacrylate, allyl methacrylate, styryl methacrylate, allyl acrylate, undecenyl methacrylate, styryl acrylate, and ethylene glycol diacrylate A chain transfer agent having one crosslinkable carbon-carbon unsaturated bond; a chain transfer agent having two or more crosslinkable carbon-carbon unsaturated bonds, such as allyltrivinylsilane and allylmethyldivinylsilane; Be mentioned Among these, from the viewpoint of improving the heat resistance and crack resistance in a balanced manner in the obtained fiber-reinforced composite, those having one or more crosslinkable carbon-carbon unsaturated bonds are preferable, and the crosslinkable carbon-carbon unsaturated is preferable. Those having one bond are more preferred. Among such chain transfer agents, chain transfer agents having one vinyl group and one methacryl group are preferable, and vinyl methacrylate, allyl methacrylate, styryl methacrylate, and undecenyl methacrylate are particularly preferable.
These chain transfer agents can be used alone or in combination of two or more.

During the polymerization of the polymerizable composition, the chain transfer agent can be bonded to the resulting polymer. However, if the chain transfer agent has a crosslinkable carbon-carbon unsaturated bond, the carbon-carbon unsaturated bond yields Crosslinkability can be imparted to the coalescence.
As a compounding quantity of the chain transfer agent to the polymeric composition used for this invention, it is 0.01-10 weight part normally with respect to 100 weight part of cycloolefin monomers, Preferably it is 0.1-5 weight part. .

  As the cross-linking agent, the cross-linking aid, and the anti-aging agent, the same ones listed as those that can be blended in the resin composition can be used.

  The polymerizable composition may contain other compounding agents such as a colorant, a light stabilizer, and a foaming agent. These specific examples also include the same ones listed as those that can be blended in the resin composition.

  The polymerizable composition used in the present invention can be obtained by mixing the above components. As a mixing method, a conventional method may be followed. For example, a liquid (catalyst liquid) in which a metathesis polymerization catalyst is dissolved or dispersed in an appropriate solvent is prepared, and a cycloolefin monomer is added separately as needed. It can be prepared by preparing a liquid (monomer liquid) containing an agent and the like, adding the catalyst liquid to the monomer liquid, and stirring.

  In the step (IIb), the method for impregnating the polymerizable composition into the carbon fiber is not particularly limited. For example, the polymerizable composition may be spray-coated, dip-coated, roll-coated, curtain-coated, or die-coated. This method can be carried out by applying the carbon fiber to the carbon fiber by a known method such as a method and a slit coating method, overlaying a protective film thereon if desired, and pressing with a roller or the like from above. Thereby, the polymerizable composition can be impregnated in the carbon fiber while opening the carbon fiber bundle.

  Moreover, the heating temperature for polymerizing the polymerizable composition impregnated in the carbon fiber is usually in the range of 30 to 250 ° C., preferably 50 to 200 ° C., more preferably 90 to 150 ° C., and a crosslinking agent. In the case of containing a radical generator, it is usually 1 minute half-life temperature or less of the radical generator, preferably 1 minute half-life temperature of 10 ° C. or less, more preferably 1 minute half-life temperature of 20 ° C. or less. . The polymerization time may be appropriately selected, but is usually 1 second to 20 minutes, preferably 10 seconds to 5 minutes. Heating the polymerizable composition under such conditions is preferable because a prepreg with less unreacted monomer can be obtained.

  In the present invention, the step (IIb) is a line of intersection with a surface intersecting with the traveling direction of the carbon fiber bundle while the carbon fiber bundle traveling continuously is immersed in the polymerizable composition used in the present invention. Is brought into contact with a curved surface that is convex toward the carbon fiber bundle side, and the impregnation of the polymerizable composition into the carbon fiber bundle and the opening of the carbon fiber bundle are performed at a temperature at which bulk polymerization of the polymerizable composition does not occur. The step (a) performed simultaneously under the range, and the step of performing bulk polymerization of the polymerizable composition by heating the opened carbon fiber bundle impregnated with the polymerizable composition and following the step (a). It is preferable to have (b).

  In the above method, the carbon fiber bundle is impregnated into the carbon fiber bundle and the carbon fiber bundle is opened, and the carbon fiber bundle is put into the polymerizable composition under a temperature range in which bulk polymerization of the polymerizable composition does not occur. It is performed at the same time by bringing it into contact with a predetermined curved surface while being immersed in the substrate. When the carbon fiber bundle is immersed in the polymerizable composition to be used, the carbon fiber bundle swells and the bonding force between the single fibers is loosened. As a result, the width between the single fibers can be easily expanded simply by contacting with a predetermined curved surface. It is estimated that it is possible. Such an action is considered to be a characteristic characteristic of the polymerizable composition used in the present invention. Therefore, according to this method, a cycloolefin polymer obtained by bulk polymerization of the polymerizable composition is continuously and efficiently provided with a prepreg having excellent rigidity formed by sufficiently impregnating a carbon fiber bundle that has been appropriately opened. Can be manufactured.

  In the step (a), a carbon fiber bundle that runs continuously is immersed in the polymerizable composition, and an intersection line with a surface that intersects the running direction of the carbon fiber bundle is convex to the carbon fiber bundle side. The carbon fiber bundle is impregnated with the polymerizable composition in contact with a curved surface having a certain curve and the carbon fiber bundle is opened at the same time in a temperature range in which bulk polymerization of the polymerizable composition does not occur. .

  For example, the carbon fiber bundle is continuously run from the feeding means of the carbon fiber bundle toward the winding means of the obtained prepreg. At that time, from the viewpoint of sufficiently opening the carbon fiber bundle without entanglement of the single fiber, it is preferable to moderately tension the carbon fiber bundle to such an extent that the carbon fiber bundle does not sag. The degree of tension is usually preferably such that an average tension of 0.01 to 0.1 g is applied to each single fiber. The tension applied to the traveling carbon fiber bundle can be appropriately performed by, for example, adjusting the traveling speed or using a nip roll or a dancer roll. One carbon fiber bundle may be used, or a plurality of carbon fiber bundles may be used in parallel with each other in one direction and in a sheet shape.

  The immersion of the carbon fiber bundle in the polymerizable composition can be performed, for example, by passing the carbon fiber bundle through the composition. From the viewpoint of sufficiently impregnating the carbon fiber bundle with the polymerizable composition, the running speed is usually 0.5 to 30 m / min, preferably 1 to 10 m / min. In the present invention, while the carbon fiber bundle is soaked in the polymerizable composition as described above, a curved surface in which the intersection line with the surface intersecting the running direction of the carbon fiber bundle is a curve convex toward the carbon fiber bundle side. The carbon fiber bundle is opened simultaneously with the impregnation of the polymerizable composition into the carbon fiber bundle. The impregnation of the polymerizable composition into the carbon fiber bundle and the opening of the carbon fiber bundle may be performed substantially simultaneously, soaking the carbon fiber bundle in the polymerizable composition, and the curved surface of the carbon fiber bundle; Although it is not always necessary to carry out the contact, it is preferable to carry out simultaneously from the viewpoint of obtaining an appropriate opening of the carbon fiber bundle and sufficient impregnation of the polymerizable composition.

  The surface intersecting with the traveling direction of the carbon fiber bundle is usually a surface having an intersection angle of 60 to 120 degrees, and particularly preferably a surface orthogonal to the traveling direction of the carbon fiber bundle. . The intersecting line between the surface and the curved surface is a curve that is convex toward the carbon fiber bundle side, but such a curve is usually a curve that has one maximum point on the carbon fiber bundle side. If the intersecting line with the surface intersecting the running direction of the carbon fiber bundle is a curved surface having such a curve, the gradient is small near the maximum point and increases toward the end. The width between the single fibers to be formed can be uniformly and sufficiently expanded.

  The contact between the carbon fiber bundle and the curved surface is usually performed by bringing the surface of the curved body having such a curved surface into contact with the carbon fiber bundle. As such a curved body, one having a curved surface that is high in the center and symmetrical to the running direction of the carbon fiber bundle is preferable. As an example of such a curved body, there is a kamaboko-shaped curved body 11 shown in FIG. In addition, in FIG. 4, the example of the state which made the carbon fiber bundle 1 contact the surface of the curved body 11 is shown typically. In the present invention, the curved body may be fixed, or may be installed so as to rotate depending on the form. The material of the curved surface of such a curved body is not particularly limited, and examples thereof include arbitrary metals and ceramics. The curved surface may be coated with a synthetic resin such as a fluororesin.

  Step (a) includes, for example, a hollow portion for filling the polymerizable composition between the carbon fiber bundle feeding means and the resulting prepreg winding means, and a surface intersecting the running direction of the carbon fiber bundle. Provided with a polymerizable composition filling portion having a curved surface portion having a curved surface whose convex line is convex toward the carbon fiber bundle side, and a curved body portion projecting into the cavity portion, The carbon fiber bundle that continuously travels can be suitably passed through the polymerizable composition packed in while being in contact with the surface of the curved body portion. FIG. 5 shows an example of such a polymerizable composition filling part. FIG. 5A shows a cross section in the lateral direction at the center of the filling portion, and FIG. 5B shows a state in which the filling portion is viewed from the front. The polymerizable composition filling portion shown in FIG. 5 includes an inlet 13 and an outlet 14 of the carbon fiber bundle 1, a polymerizable composition inlet (not shown), a polymerizable composition filling cavity 15, and the It has the curved-surface body part 12 which protrudes in a cavity part and has the shape shown in FIG. The arrows in FIG. 5 indicate the direction in which the carbon fiber bundle 1 travels.

  Step (a) is performed under a temperature range in which bulk polymerization of the polymerizable composition does not occur. This is because when bulk polymerization of the polymerizable composition occurs, the viscosity of the polymerizable composition increases, and impregnation of the carbon fiber bundle with the composition is inhibited. Such a temperature range may be a temperature range in which bulk polymerization of the polymerizable composition is not substantially started, and a range of −10 to + 20 ° C. is usually preferable from the viewpoint of efficiently performing the step (a). .

  In the step (b), subsequent to the step (a), the polymer composition is impregnated and the opened carbon fiber bundle is heated to perform bulk polymerization of the polymerizable composition.

  In the step (b), the bulk polymerization of the polymerizable composition is further performed by providing a heating furnace after the polymerizable composition filling portion between the carbon fiber bundle feeding means and the prepreg winding means obtained. The heating can be performed by passing the heated carbon fiber bundle impregnated with the polymerizable composition and opening the fiber bundle and heating.

  Since the carbon fiber bundle impregnated and opened by the polymerizable composition is continuously obtained by the step (a), the fiber bundle is heated to a temperature higher than the temperature at which the bulk polymerization of the polymerizable composition is started. Then, bulk polymerization of the polymerizable composition is performed. The polymer obtained by bulk polymerization of the polymerizable composition becomes a matrix resin for the prepreg. From the viewpoint of using the matrix resin as a crosslinkable resin, it is preferable that the heating temperature is such that substantially only bulk polymerization proceeds and no crosslinking reaction occurs. Such heating conditions are as described above.

  Step (a) and step (b) are performed as described above. For the implementation, for example, an apparatus as shown in FIG. 6 is preferably used. In such an apparatus, a delivery machine 21 as a delivery means for the carbon fiber bundle 1, a polymerizable composition filling unit 22, a heating furnace 23, and a take-up machine 24 as a prepreg winding means are arranged in series in this order. ing. The polymerizable composition filling unit 22 includes a mixer 29 in which a monomer liquid tank 25 and a catalyst liquid tank 27 are connected via a tube pump 26 and a tube pump 28, respectively. It is connected to an inlet (not shown). The carbon fiber bundle 1 is sandwiched between the cover film 30 and the support 31 after passing through the polymerizable composition filling portion 22. 6 indicates the direction in which the carbon fiber bundle 1 travels.

  In the embodiment of FIG. 6, the carbon fiber bundle 1 is sandwiched between the cover film 30 and the support 31 after passing through the polymerizable composition filling portion 22, but it is optional to provide a supply means for the cover film and the support. is there. Examples of the cover film include a polyethylene terephthalate film, a polypropylene film, a polyethylene film, a polycarbonate film, a polyethylene naphthalate film, a polyarylate film, a nylon film, and a polytetrafluoroethylene film. Moreover, you may use a release paper as a cover film. Examples of the support include a metal foil made of copper, aluminum, nickel, chromium, gold, silver, and the like in addition to the above film. The surface of the metal foil may be treated with a silane coupling agent, a thiol coupling agent, a titanate coupling agent, and various adhesives. Although the thickness of the said film and metal foil is not specifically limited, Usually, it is 1-150 micrometers.

  In the prepreg manufacturing apparatus shown in FIG. 6, the carbon fiber bundle 1 is sent out by the delivery machine 21 and is run toward the winder 24 in a state where the carbon fiber bundle 1 is moderately tensioned so as not to sag. The carbon fiber bundle 1 sent out by the delivery machine 21 passes through the polymerizable composition filling part 22, and the impregnation of the polymerizable composition into the carbon fiber bundle 1 and the opening of the carbon fiber bundle 1 are performed substantially simultaneously. Is called. In the polymerizable composition, the monomer liquid is sent from the monomer liquid tank 25 to the mixer 29 under liquid feed control by the tube pump 26, and the catalyst liquid is fed from the catalyst liquid tank 27 by the tube pump 28. Under control, it is sent to the mixer 29, prepared by mixing the monomer liquid and the catalyst liquid by the mixer 29, and supplied to the polymerizable composition filling unit 22 from the polymerizable composition inlet. After the preparation of the polymerizable composition, the time until it is supplied to the polymerizable composition filling unit 22 is generally the pot life of the polymerizable composition (from the start of mixing the monomer liquid and the catalyst liquid, The time from the liquid state to the purine state and no longer flowing (also called pot life) is preferably less than 60% of the pot life.

  The carbon fiber bundle 1 (prepreg precursor) that has passed through the polymerizable composition filling portion 22, is impregnated with the polymerizable composition, and has been opened is heated between the cover film 30 and the support 31. Reach furnace 23. Bulk polymerization of the polymerizable composition is performed in the heating furnace 23 to form a prepreg, which is wound up by the winder 24. In addition, after attaching a cover film etc. to a prepreg precursor, before sending to the heating furnace 23, for example, a pair of opposing rolls may be installed, and the thickness of the precursor may be adjusted between the rolls. Good.

  The prepreg obtained as described above has excellent rigidity because a cycloolefin polymer as a matrix resin is sufficiently impregnated in a carbon fiber bundle that has been appropriately opened. Further, since the bulk polymerization of the polymerizable composition is completed, there is no fear that the polymerization reaction further proceeds during storage. Furthermore, it may contain a crosslinking agent such as a radical generator, but unless it is heated to a temperature that causes a crosslinking reaction, it does not cause problems such as changes in surface hardness and is excellent in storage stability.

  The cycloolefin polymer has substantially no cross-linked structure and is soluble in, for example, toluene. The molecular weight of the crosslinkable resin is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (eluent: toluene), and is usually 1,000 to 1,000,000, preferably 5,000 to It is in the range of 500,000, more preferably 10,000 to 100,000. However, the crosslinkable resin may be partially crosslinked.

  The carbon fiber content in the prepreg obtained by the production method of the present invention is appropriately selected according to the purpose, but is usually 10 to 90% by weight, preferably 20 to 85% by weight, more preferably 30 to 80%. It is in the range of wt%. When the carbon fiber content is within this range, the mechanical strength and toughness are highly balanced in the obtained fiber-reinforced composite, which is preferable.

  The thickness of the prepreg obtained by the present invention may be appropriately selected as desired, but is usually in the range of 0.001 to 10 mm, preferably 0.01 to 1 mm, more preferably 0.05 to 0.5 mm. .

  As described above, an excellent prepreg can be efficiently produced using the carbon fiber bundles selected by the selection method of the present invention.

  The prepreg obtained by the present invention is suitably used for producing a fiber-reinforced composite. Such a fiber reinforced composite can be obtained, for example, by forming the prepreg as desired and then crosslinking and curing it. Also, a laminate comprising a fiber-reinforced composite can be obtained by laminating a plurality of the prepregs, or laminating the prepreg and another material, and forming the prepreg as desired, followed by crosslinking and curing. The other material may be appropriately selected as desired, and examples thereof include known thermoplastic resin materials and metal materials.

  Crosslinking and curing can be performed by, for example, hot pressing using a known press having a press frame mold for flat plate molding, a press molding machine such as a sheet mold compound (SMC) or a bulk mold compound (BMC). . The heating temperature is equal to or higher than the temperature at which a crosslinking reaction occurs in the prepreg. When the prepreg contains a radical generator as a crosslinking agent, the radical generator has a half-life temperature of 1 minute or more, preferably 5 ° C or more from the 1-minute half-life temperature. A higher temperature, more preferably a temperature that is 10 ° C. or more higher than the 1 minute half-life temperature. Usually, it is in the range of 100 to 300 ° C, preferably 150 to 250 ° C. The heating time is in the range of 0.1 to 180 minutes, preferably 1 to 120 minutes, more preferably 2 to 20 minutes. As a press pressure, it is 0.1-20 MPa normally, Preferably it is 1-10 MPa, More preferably, it is 2-5 MPa. The hot pressing may be performed in a vacuum or a reduced pressure atmosphere.

  The fiber reinforced composite obtained by using the prepreg of the present invention is lightweight and excellent in appearance, and excellent in mechanical strength and toughness. For example, a housing for OA or AV equipment, a vehicle structural body such as an automobile or a railway It is suitably used for sports applications such as golf shafts and fishing rods, and other general industrial applications as well as materials and aircraft interior parts.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to this. In the following, “parts” and “%” are based on weight unless otherwise specified.

In this example, evaluation was performed according to the following method.
(1) Number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) are converted from the measurement results by gel permeation chromatography using toluene as a developing solvent to the molecular weight of standard polystyrene. And asked.
(2) The polymerization conversion rate was determined by quantifying the residual monomer by gas chromatography of the polymerization reaction product.
(3) The tensile test was performed under the conditions according to ISO 527-5 with the fiber direction set to 0 °.
(4) The degree of fiber cracking in the obtained unidirectional prepreg was expressed as the number of defects by visually counting defects (missing fibers) of 1 square mm or more present per 100 square mm.

Example 1
(Selection of carbon fiber bundles)
The carbon fiber bundles were selected as shown in FIG. As a carbon fiber bundle, a carbon fiber tow having a total length of 500 mm (number of filaments: 60,000; trade name “TRH50 60M”, manufactured by Mitsubishi Rayon Co., Ltd.) was prepared. This is fixed to the support by pulling it in the fiber direction with a tension of 10 N, and the striking means having the shape shown in FIG. 2 (10b), which reciprocates in the vertical direction with respect to the fiber direction at a frequency of 10 to 15 Hz, is applied for 5 seconds. The carbon fiber bundle was beaten. The variation in the vertical direction of the carbon fiber bundle at that time was 8 mm. Since the carbon fiber bundle after impact was not cracked with a width of 1 mm or more and a length of 50 mm or more, it was adopted as a reinforcing fiber for prepreg. Next, a prepreg was produced using the carbon fiber bundle.

(Preparation of prepreg)
In a glass flask, 0.04 part of benzylidene (1,3-dimesityl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and 0.08 part of vinyldiphenylphosphine are added to 0.7 part of tetrahydrofuran. A catalyst solution was prepared by dissolution. In a 200 mL metal container, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene 50 parts, dicyclopentadiene 50 parts, 2,6-bis (1,1-dimethylethyl) -4-methylphenol 0.3 part and mixed uniformly. A monomer liquid was obtained.

  Next, in a polyethylene bottle, 80 parts of the monomer solution, 2.5 parts of allyl methacrylate (Mitsubishi Gas Chemical Co., Ltd.) as a chain transfer agent, and di-t-butyl peroxide (trade name “Kayabutyl D” as a peroxide) "(Registered trademark), manufactured by Kayaku Akzo Co., Ltd.) 3 parts, 8 parts of 2-ethyl-2-hydroxymethyl-1,3-propanediol trimethacrylate and 0.7 parts of the catalyst solution were added with stirring. A polymerizable composition was obtained.

  Next, this polymerizable composition was cast on a polyethylene naphthalate film (trade name “Type Q51”, thickness 75 μm, manufactured by Teijin DuPont Films), and the carbon fiber tow selected above was laid thereon. Further, the polymerizable composition was cast thereon. A polyethylene naphthalate film was further covered from above, and the entire carbon fiber fabric was impregnated with the polymerizable composition while opening the carbon fiber bundle using a roller. Subsequently, this was affixed on the aluminum plate heated at 95 degreeC for 1 minute, the polymerizable composition was bulk-polymerized, and the prepreg was obtained. The number of defects in this prepreg was two. Moreover, when the molecular weight of the matrix resin (cycloolefin polymer) of this prepreg was measured, they were Mw = 32,000 and Mw / Mn = 2.15. The obtained prepreg was dissolved in toluene, the residual monomer was quantified by gas chromatography and the polymerization conversion was calculated to be 99.2%. The carbon fiber content in the prepreg was 75%.

  This prepreg is cut into a 200 mm square size, and four sheets of the prepreg are stacked so that the fiber direction is one direction. Both surfaces of the prepreg are sandwiched between aluminum foils, heated with a hot press at 3 MPa and 200 ° C. for 15 minutes, and 200 mm A laminate of × 200 mm × 1 mm was produced and a tensile test was performed. The results are shown in Table 1.

Example 2
(Selection of carbon fiber bundles)
A carbon fiber tow having a total length of 500 mm (number of filaments: 50,000; trade name “SIGRAFIL C C30”, manufactured by SGL Carbon Co., Ltd.) was hit in the same manner as in Example 1. Since the carbon fiber bundle after impact was not cracked with a width of 1 mm or more and a length of 50 mm or more, it was adopted as a reinforcing fiber for prepreg. Next, a prepreg was produced using the carbon fiber bundle.

(Preparation of prepreg)
A prepreg was prepared in the same manner as in Example 1 except that the carbon fiber tow selected above was used. The number of defects of the obtained prepreg was 3, the molecular weight of the matrix resin was Mw = 31,000, Mw / Mn = 2.08, and the polymerization conversion rate was 98.9%. The carbon fiber content in the prepreg was 75%.

  A laminate was produced in the same manner as in Example 1, and a tensile test was performed. The results are shown in Table 1.

Reference example 1
(Selection of carbon fiber bundles)
A carbon fiber tow having a total length of 500 mm (number of filaments: 50,000; trade name “PANEX 35-50K # 13”, manufactured by Zoltek) was hit in the same manner as in Example 1. Cracks having a width of 1 mm or more and a length of 50 mm or more were observed in the carbon fiber bundle after the impact. Next, for comparison, a prepreg was produced using the carbon fiber bundle.

(Preparation of prepreg)
A prepreg was produced in the same manner as in Example 1 except that the carbon fiber tow was used. The number of defects of the obtained prepreg was 10 or more, the molecular weight of the matrix resin was Mw = 31,000, Mw / Mn = 2.12, and the polymerization conversion rate was 99.4%. The carbon fiber content in the prepreg was 75%.

  A laminate was produced in the same manner as in Example 1, and a tensile test was performed. The results are shown in Table 1.

Reference example 2
(Selection of carbon fiber bundles)
A carbon fiber tow having a total length of 500 mm (number of filaments: 50,000; trade name “PANEX 35-50K # 32”, manufactured by Zoltek) was hit in the same manner as in Example 1. Cracks having a width of 1 mm or more and a length of 50 mm or more were observed in the carbon fiber bundle after the impact. Next, for comparison, a prepreg was produced using the carbon fiber bundle.

(Preparation of prepreg)
A prepreg was produced in the same manner as in Example 1 except that the carbon fiber tow was used. The number of defects of the obtained prepreg was 10 or more, the molecular weight of the matrix resin was Mw = 33,000, Mw / Mn = 2.09, and the polymerization conversion rate was 98.8%. The carbon fiber content in the prepreg was 76%.

  A laminate was produced in the same manner as in Example 1, and a tensile test was performed. The results are shown in Table 1.

  From Table 1, when the unidirectional prepreg was produced using the carbon fiber bundle employed as the prepreg reinforcing fiber according to the carbon fiber bundle sorting method of the present invention (Examples 1 and 2), the number of defects in the obtained prepreg It can be seen that, according to the prepreg, a laminate having high tensile strength can be obtained. On the other hand, when the carbon fiber bundle in which the predetermined crack occurred is used (Reference Examples 1 and 2), it can be seen that the obtained prepreg has a large number of defects, and the prepreg can obtain only a laminate having a low tensile strength.

Example 3
Using the carbon fiber bundle adopted as the prepreg reinforcing fiber in Example 1, the prepreg was continuously produced by the apparatus shown in FIG.
As cycloolefin monomer, 50 parts of dicyclopentadiene and 50 parts of tetracyclododecene, 8 parts of trimethylolpropane trimethacrylate as a crosslinking aid, 2.5 parts of allyl methacrylate as a chain transfer agent, and di-t as a crosslinking agent -3 parts of butyl peroxide was mixed with stirring to prepare a monomer solution.

  Separately, 15 parts of benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride as a metathesis polymerization catalyst was dissolved in 40 parts of toluene to prepare a catalyst solution.

  The monomer solution and the catalyst solution obtained above were placed in the monomer solution tank 25 and the catalyst solution tank 27 of the apparatus shown in FIG. 6, and each tank was cooled to 10 ° C. The monomer liquid and the catalyst liquid are respectively sent from the monomer liquid tank 25 and the catalyst liquid tank 27 through the tube pumps 26 and 28 to the mixer 29 at a flow rate of 15 mL / min and 0.15 mL / min, and are mixed. The composition was fed into the polymerizable composition filling cavity maintained at 10 ° C. in the polymerizable composition filling part 22. Note that a small static mixer was used as the mixer 29.

  On the other hand, the carbon fiber bundle was sent out from the carbon fiber bundle sending machine 21 and was run at a speed of 1 m / min so that an average tension of 0.1 g was applied to each single fiber. When the carbon fiber bundle passes through the polymerizable composition filling portion 7, the carbon fiber bundle is immersed in the polymerizable composition in the polymerizable composition filling cavity 5, and the curved surface of the surface portion 11 ′ of the kamaboko-shaped curved body portion 11 ′. Was subjected to impregnation and opening of the polymerizable composition to form a prepreg precursor. Subsequently, a long continuous polyethylene naphthalate film having a thickness of 25 μm was superposed on both surfaces of the prepreg precursor and continuously sent to a heating furnace 223 maintained at 95 ± 5 ° C. The prepreg precursor was heated in the heating furnace 23 for 3 minutes, and the polymerizable composition was bulk polymerized to form a prepreg. The whole film was wound up by the prepreg winder 9. The thickness of the prepreg was 0.1 mm and the width was 300 mm. The carbon fiber content in the obtained prepreg was 73%, and the cycloolefin polymer was sufficiently impregnated in the fiber bundle. The film thickness accuracy of the prepreg was within ± 5 μm. In addition, breakage of single yarn and fuzzing were not substantially observed. As described above, a prepreg having excellent rigidity could be continuously and efficiently produced.

DESCRIPTION OF SYMBOLS 1 ... Carbon fiber bundle, 2 ... Impacting means, 11 ... Kamaboko-shaped curved surface body, 12 ... Kamaboko-shaped curved body part, 13 ... Introducing port of carbon fiber bundle 1, 14 ... -Outlet port, 15 ... cavity for filling the polymerizable composition, 21 ... delivery device, 22 ... filling portion for the polymerizable composition, 23 ... heating furnace, 24 ... prepreg winder 25 ... Monomer liquid tank, 26, 28 ... Tube pump, 27 ... Catalyst liquid tank, 29 ... Mixer, 30 ... Cover film, 31 ... Support

Claims (4)

  A step (1) of providing a carbon fiber bundle, and a striking means for reciprocating the carbon fiber bundle at a frequency of 10 to 15 Hz by pulling and fixing the carbon fiber bundle at a tension of 5 to 20 N in the fiber direction. A step (2) of contacting a vibrating means that vibrates at a frequency of 10 to 15 Hz for 5 to 10 seconds, or a filament yarn in the carbon fiber bundle after the step (2). A method for selecting a carbon fiber bundle, in which when the crack having a width of 1 mm or more and a length of 50 mm or more is not observed, the carbon fiber bundle is employed as a reinforcing fiber for prepreg.   The method for selecting a carbon fiber bundle according to claim 1, wherein the number of filaments of the carbon fiber bundle is 40,000 or more.   The step (I) of selecting a carbon fiber bundle according to the method for selecting a carbon fiber bundle according to claim 1 or 2, and the carbon fiber bundle selected in step (I) is opened and crosslinkable to the opened carbon fiber. The manufacturing method of a prepreg which has the process (IIa) which obtains a prepreg by impregnating the resin composition containing resin.   The step (I) of selecting a carbon fiber bundle according to the method for selecting a carbon fiber bundle according to claim 1 or 2, and the carbon fiber bundle selected in step (I) is opened, and the opened carbon fiber is subjected to cycloolefin. A method for producing a prepreg having a step (IIb) of obtaining a prepreg by impregnating a polymerizable composition containing a monomer and a metathesis polymerization catalyst and subjecting the polymerizable composition to bulk polymerization.

Images