JPWO2017150702A1 - Colloidal solution for producing carbon fiber reinforced plastic, particle adsorbing carbon fiber and method for producing the same, carbon fiber reinforced plastic, and control method - Google Patents

Abstract

Disclosed are a carbon fiber reinforced plastic having improved interfacial adhesion between a carbon fiber and a resin, and a colloid solution for producing a carbon fiber reinforced plastic that can be used in the production thereof.
A colloidal solution for producing carbon fiber reinforced plastic,
(1) containing resin particles, nonionic surfactant, electrolyte and water,
(2) containing resin particles, radical polymerization initiator, and water, or (3) containing solid inorganic particles, electrolyte, and water,
Colloidal solution for producing carbon fiber reinforced plastic.

Description

  The present invention relates to a colloidal solution for producing a carbon fiber reinforced plastic, a particle-adsorbing carbon fiber and a production method thereof, a carbon fiber reinforced plastic, and a control method.

  A material in which a carbon fiber is combined with a thermoplastic resin is expected to be used as a carbon fiber reinforced thermoplastic (CFRTP) in aircraft materials, automobile materials, and the like. However, there is room for improvement in the interfacial adhesion between the thermoplastic resin and the carbon fiber, and it has been very difficult to bond the thermoplastic resin and the carbon fiber. The reason is considered that even if the thermoplastic resin is heated and dissolved, it cannot enter the carbon fiber fabric.

  Various studies have been made as a technique for improving the interfacial adhesion between the thermoplastic resin and the carbon fiber.

  Patent Document 1 discloses a method in which a carbon fiber is electrophoresed in a polyetherimide resin emulsion as a cathode electrode, and a cationized polyetherimide resin is electrodeposited on the carbon fiber and coated. However, the method described in Patent Document 1 requires the use of a liquid polyetherimide resin dissolved in a solvent, and the solvent remains on the carbon fiber as an impurity. For this reason, when the obtained polyetherimide resin-adsorbed carbon fibers are used for the production of carbon fiber reinforced plastic, there is a possibility that the interfacial adhesiveness with the resin of the base material is inferior or the interfacial adhesiveness becomes unstable. It was.

  In Patent Document 2, charged resin particles are adsorbed on a carbonaceous powder, and electrophoresis is performed using a carbon fiber substrate as an electrode in a solution, and the carbonaceous powder is deposited together with the charged resin particles on the carbon fiber substrate. A method for producing a carbon fiber reinforced carbon composite material is disclosed. However, the carbon fiber reinforced carbon composite material is coated with carbon particles because the resin adsorbed on the surface of the carbon powder disappears in the sintering process. For this reason, the said carbon fiber reinforced carbon composite material is inferior to interface adhesiveness with resin, and cannot be used suitably for manufacture of a carbon fiber reinforced thermoplastic.

Special Table 2002-521582 JP-A-5-208868

  Therefore, the main object of the present invention is to provide a carbon fiber reinforced plastic having improved interfacial adhesion between the carbon fiber and the resin and a colloid solution for producing the carbon fiber reinforced plastic that can be used in the production thereof. To do.

  As a result of intensive studies to achieve the above-described object, the present inventors have performed electrophoresis using carbon fibers as a positive electrode or a negative electrode in a colloidal solution containing resin particles or inorganic particles. It has been found that a large amount of resin particles can be adsorbed to the carbon fiber in a short time, thereby improving the interfacial adhesion with the resin. Based on the above findings, the present inventors have further studied and completed the present invention. That is, the present invention relates to the following colloidal solution for producing carbon fiber reinforced plastic, particle adsorbed carbon fiber, method for producing particle adsorbed carbon fiber, carbon fiber reinforced plastic, adsorbed particle amount control method, and interfacial adhesion. Related to sex control method.

Item 1. A colloidal solution for producing carbon fiber reinforced plastic,
(1) containing resin particles, nonionic surfactant, electrolyte and water,
(2) containing resin particles, radical polymerization initiator, and water, or (3) containing solid inorganic particles, electrolyte, and water,
Colloidal solution for producing carbon fiber reinforced plastic.
Item 2. Item 2. The colloid solution for producing carbon fiber reinforced plastic according to Item 1, wherein the resin particles are thermoplastic resin particles.
Item 3. Item 3. The colloid solution for producing a carbon fiber-reinforced plastic according to Item 2, wherein the thermoplastic resin particles are polymer particles of a monomer containing an amide bond-containing monomer.
Item 4. Item 4. The colloid solution for producing a carbon fiber-reinforced plastic according to Item 2 or 3, wherein the thermoplastic resin particles have an average particle size of 0.02 to 0.5 µm.
Item 5. Item 3. The colloid solution for producing a carbon fiber reinforced plastic according to Item 2, wherein the thermoplastic resin particles are polyamide resin particles.
Item 6. Item 6. The colloid solution for producing carbon fiber reinforced plastic according to Item 5, wherein the polyamide-based resin particles are nylon particles.
Item 7. Particle-adsorbed carbon fiber in which thermoplastic resin particles are adsorbed on the surface of carbon fiber.
Item 8. Item 8. The particle-adsorbed carbon fiber according to Item 7, wherein the thermoplastic resin particle is a polymer particle of a monomer containing an amide bond-containing monomer.
Item 9. Item 9. The particle-adsorbed carbon fiber according to Item 7 or 8, wherein the thermoplastic resin particles have an average particle size of 0.02 to 0.5 μm.
Item 10. Item 8. The particle-adsorbed carbon fiber according to Item 7, wherein the thermoplastic resin particle is a polyamide-based resin particle.
Item 11. Item 11. The particle-adsorbed carbon fiber according to Item 10, wherein the polyamide resin particles are nylon particles.
Item 12. A method for producing particle-adsorbed carbon fibers, comprising:
Item 7. A production method comprising a step of performing electrophoresis by applying a voltage using a carbon fiber as a positive electrode or a negative electrode in the colloid solution for producing a carbon fiber-reinforced plastic according to any one of Items 1 to 6.
Item 13. Item 12. A carbon fiber reinforced plastic, wherein the particle-adsorbed carbon fiber according to any one of Items 7 to 11 is contained in a base resin.
Item 14. Item 14. The carbon fiber-reinforced plastic according to Item 13, wherein the resin constituting the resin particles in the particle-adsorbed carbon fiber and the resin of the base material are the same or similar.
Item 15. A method for controlling the amount of particles adsorbed on the surface of a particle-adsorbing carbon fiber,
The carbon fiber is controlled by controlling the magnitude of the voltage applied when the voltage is applied using the carbon fiber as a positive electrode or a negative electrode in the colloid solution for producing a carbon fiber-reinforced plastic according to any one of Items 1 to 6. A control method for controlling the amount of the particles adsorbed on the surface.
Item 16. A method for controlling the interfacial adhesion of a carbon fiber to a resin,
When applying a voltage using the carbon fiber as a positive electrode or a negative electrode in the colloid solution for producing a carbon fiber-reinforced plastic according to any one of Items 1 to 6, the magnitude of the applied voltage is controlled to the carbon fiber. A control method for controlling interfacial adhesion between the carbon fiber and the resin by controlling the amount of the adsorbed particles.

  According to the present invention, (1) containing resin particles, nonionic surfactant, electrolyte and water, (2) containing resin particles, radical polymerization initiator, and water, or (3) inorganic particles, By performing electrophoresis using carbon fiber as a positive electrode or negative electrode in a colloid solution for producing carbon fiber reinforced plastic containing electrolyte and water, a large amount of particles can be adsorbed to carbon fiber in a very short time, Thereby, interface adhesiveness with resin can be improved. Further, when the particle-adsorbing carbon fiber is produced using the colloid solution for producing carbon fiber reinforced plastic of the present invention, the colloid solution for producing carbon fiber reinforced plastic uses resin particles or solid inorganic particles, and the solvent is water. Therefore, no solvent remains on the carbon fiber surface. For this reason, the obtained particle | grain adsorption | suction carbon fiber is excellent in interface adhesiveness with resin used as the base material of a carbon fiber reinforced plastic.

  Here, since the colloid solution for producing a carbon fiber reinforced plastic containing resin particles, a nonionic surfactant, an electrolyte, and water contains an electrolyte, an electric current flows during electrophoresis and effectively ( This is advantageous in that the particles can be adsorbed onto the carbon fibers (in a short time). Further, the colloid solution for producing carbon fiber reinforced plastic containing resin particles, radical polymerization initiator, and water is advantageous in terms of cost because it does not contain a surfactant. Since it does not remain as an impurity, the interfacial adhesion with the carbon fiber is improved. In addition, since the colloid solution for producing carbon fiber reinforced plastic containing solid inorganic particles, electrolyte and water does not contain a surfactant, it is advantageous in terms of cost and when contained in carbon fiber reinforced plastic. Since the inorganic particles remain without melting, an unprecedented high strength carbon fiber reinforced plastic can be obtained.

  In the particle-adsorbed carbon fiber of the present invention, thermoplastic resin particles are adsorbed on the surface of the carbon fiber. For this reason, even when the resin used as the base material of the carbon fiber reinforced plastic is a thermoplastic resin, the interfacial adhesion is excellent. By using the particle-adsorbing carbon fiber having improved interfacial adhesion with the resin in this manner, the carbon fiber and the resin (particularly the thermoplastic resin) can be easily bonded.

  According to the method for producing particle-adsorbed carbon fiber of the present invention, (1) containing resin particles, nonionic surfactant, electrolyte and water, (2) containing resin particles, radical polymerization initiator, and water. Or (3) carbon fiber in a very short time by performing electrophoresis using carbon fiber as a positive electrode or negative electrode in a colloid solution for producing carbon fiber reinforced plastic containing solid inorganic particles, electrolyte and water. A large amount of particles can be adsorbed on the surface. According to this production method, it is possible to uniformly adsorb thermoplastic resin particles, particularly polyamide-based resin particles such as nylon particles, which have been difficult to adsorb to carbon fibers, to the carbon fiber surface. In addition, when producing particle-adsorbing carbon fibers by electrophoresis operation, the amount of particles adsorbed on the carbon fibers can be controlled by changing the applied voltage, whereby the interfacial adhesion can be controlled.

  In the carbon fiber reinforced plastic of the present invention, as described above, particle-adsorbed carbon fibers excellent in interfacial adhesion are contained in a base resin. For this reason, since the particle-adsorbed carbon fiber and the base resin are bonded with high strength, the carbon fiber reinforced plastic has high strength.

After electrophoresis for 30 seconds at 0V, 6.5V, 10V, 20V, or 30V in the colloid solution for producing carbon fiber reinforced plastic of Example 1, or in the colloid solution for producing carbon fiber reinforced plastic of Example 1 It is a SEM image of the carbon fiber surface after immersing a fiber for 24 hours. It is a schematic diagram of the cross section (1) and the cross section (2) in the permeability evaluation sample of Example 1. It is a SEM image of the central part vicinity (circle mark) of a cross section (1). It is a SEM image which goes from a to b of a section (2). 4 is an enlarged view of the SEM image of FIG. It is a graph which shows the relationship between the applied voltage of Example 1, and the amount of particle | grain adsorption, and the SEM image at the time of applied voltage 0V and 30V. It is a graph which shows the relationship between the particle | grain adsorption amount of Example 1, and an interface shear stress. It is a SEM image of the carbon fiber surface after carrying out the electrophoresis for 30 second at 30V in the colloid solution for carbon fiber reinforced plastic manufacture of Example 2. FIG. SEM image (upper left) and enlarged image (lower left) of carbon fiber subjected to electrophoresis at 30 V for 30 seconds in the colloidal solution for producing carbon fiber reinforced plastic of Example 2, and carbon fiber to which nylon powder was adhered SEM image (upper right) is an enlarged image (lower right). It is a graph which shows the result of the fragmentation test of the carbon fiber obtained by the electrophoresis operation of Example 2 (30V for 30 seconds) and the carbon fiber which processed with acetone and removed the sizing agent. 3 is a cross-sectional view of a carbon fiber-resin composite of Example 3. FIG. The photograph on the left is a photograph when the carbon fiber bundle from which the sizing agent has been removed is impregnated with the resin, and the photograph on the right is a photograph when the resin-adsorbed carbon fiber bundle obtained in Example 3 is impregnated with the resin. . The ratio shown below each photograph is the impregnation rate. 3 is a cross-sectional view of a carbon fiber-resin composite of Example 3. FIG. The photograph on the left is a photograph when the carbon fiber bundle from which the sizing agent has been removed is impregnated with the resin, and the photograph on the right is a photograph when the resin-adsorbed carbon fiber bundle obtained in Example 3 is impregnated with the resin. . The ratio shown below each photograph is the ratio (the ratio of the carbon fiber region) occupied by the cross section of the carbon fiber in the cross-sectional view. 6 is an SEM image of Example 4. It is a graph which shows the result of the fragmentation test of the carbon fiber (10V, 20V, 30V) obtained by the electrophoresis operation of Example 4, and the carbon fiber (Fresh) which processed with acetone and removed the sizing agent. 6 is a cross-sectional view of a carbon fiber-resin composite of Example 4. FIG. The photograph on the left is a photograph when the carbon fiber bundle from which the sizing agent has been removed is impregnated with the resin, and the photograph on the right is a photograph when the resin-adsorbed carbon fiber bundle obtained in Example 4 is impregnated with the resin. . The ratio shown above each photograph is the impregnation rate. 6 is a cross-sectional view of a carbon fiber-resin composite of Example 4. FIG. The photograph on the left is a photograph when the carbon fiber bundle from which the sizing agent has been removed is impregnated with the resin, and the photograph on the right is a photograph when the resin-adsorbed carbon fiber bundle obtained in Example 4 is impregnated with the resin. . The ratio shown above each photograph is the ratio (the ratio of the carbon fiber region) occupied by the cross section of the carbon fiber in the cross-sectional view.

1. Colloidal solution for producing carbon fiber reinforced plastic (1-1) Colloidal solution for producing carbon fiber reinforced plastic The colloidal solution for producing carbon fiber reinforced plastic according to the present invention comprises (1) resin particles, nonionic surfactant, electrolyte and water. (2) containing resin particles, a radical polymerization initiator, and water, or (3) containing solid inorganic particles, an electrolyte, and water. By adopting such a configuration, a colloid solution for producing a carbon fiber reinforced plastic can be formed with various particles. In the colloid solution for producing the carbon fiber reinforced plastic of the present invention, the carbon fiber can be positively or negatively charged in water by applying a voltage using the carbon fiber as an electrode (positive electrode or negative electrode). It can be adsorbed on carbon fiber regardless of whether it is positive or negative. For this reason, it is possible to remarkably improve the interfacial adhesion between the carbon fiber and the resin of the base material by performing electrophoresis using the carbon fiber reinforced plastic manufacturing colloid solution and using the carbon fiber as one of the electrodes. In addition, the amount of particles adsorbed on the carbon fiber can be controlled by changing the applied voltage in the electrophoresis operation, whereby the interfacial adhesion between the carbon fiber and the resin can be controlled.

(1) Colloid solution for producing carbon fiber reinforced plastic containing resin particles, nonionic surfactant, electrolyte and water (first embodiment)
The first aspect of the colloidal solution for producing carbon fiber reinforced plastic of the present invention is a colloidal solution containing resin particles, a nonionic surfactant, an electrolyte and water.

  The resin particles are not particularly limited, and various resin particles can be used. When electrophoresis is performed using carbon fiber as an electrode in the carbon fiber reinforced plastic production colloidal solution of the present invention, the particles are adsorbed over almost the entire surface of the carbon fiber, Particles penetrate. In particular, the particle-adsorbed carbon fiber of the present invention can improve the interfacial adhesion with the same or similar resin as the particle. For example, when it is desired to improve the adhesion to an acrylic resin such as polymethyl methacrylate (PMMA), use acrylic resin particles such as polymethyl methacrylate particles, polybutyl acrylate particles, and polyisobutyl acrylate particles as resin particles. In the case where it is desired to improve the adhesiveness with nylon resins (polyamide resins) such as nylon-6 and nylon-12, as polymer particles, monomer polymer particles containing an amide bond-containing monomer, nylon-6, It is preferable to use nylon resin particles such as nylon-12.

  In the case of processing into carbon fiber reinforced plastic using carbon fiber, it has been difficult in the past to bond carbon fiber and thermoplastic resin, but in the colloid solution for producing carbon fiber reinforced plastic of the present invention. By using the resin particles as thermoplastic resin particles, it is possible to improve the interfacial adhesion between the base thermoplastic resin and the carbon fibers. Specific examples of the thermoplastic resin particles include polymer particles of monomers including amide bond-containing monomers, polyamide resin particles, polyphenylene ether particles, polyoxymethylene particles, polybutylene terephthalate particles, polycarbonate particles, polymethyl methacrylate (PMMA). ) Particles, polystyrene particles, polypropylene particles, polyetherimide particles, polyethersulfone particles, and the like. Among these, monomer polymer particles containing amide bond-containing monomers and polyamide resin particles are preferable, and monomer polymer particles containing amide bond-containing monomers are more preferable.

  The polymer particles of the monomer containing an amide bond-containing monomer are not particularly limited as long as they are polymer particles of an amide bond-containing monomer or polymer particles of an amide bond-containing monomer and another monomer.

  The amide bond-containing monomer is not particularly limited as long as it is a monomer that has an amide bond in the molecule and can be polymerized alone or with another monomer to form a polymer. Typically, a monomer having an amide group and an alkenyl group having a double bond at the terminal (for example, a vinyl group, an allyl group, etc.) in the molecule can be given. The molecular weight of the monomer is, for example, 80 to 200, preferably 80 to 150, and more preferably 80 to 100. Specific examples of the amide bond-containing monomer include N-vinylacetamide.

  Other monomers that can form polymer particles of monomers including amide bond-containing monomers are not particularly limited. Examples of the other monomer include styrene monomer, propylene monomer, methyl methacrylate monomer, vinyl acetate monomer, ethylene monomer, aromatic vinyl monomer, and acrylic monomer. When other monomers are used, the molar ratio of the amide bond-containing monomer (amide bond-containing monomer / other monomer) is, for example, 0.2 to 20, preferably 0.5 to 15, more preferably 1 to 8, and further Preferably it is 2-5.

  Polyamide-based resin particles include aliphatic polyamide particles and aromatic polyamide particles. Aliphatic nylon and its copolymer are mentioned as aliphatic polyamide. Specifically, polycapramide (nylon-6), polylauryllactam (nylon-12), polyhexamethylene adipamide (nylon-6,6), caprolactam / laurylactam copolymer (nylon-6 / 12) And nylon particles. Examples of the aromatic polyamide include amorphous aromatic polyamide particles such as crystalline aromatic polyamide particles such as polymetaxylene adipamide, and copolymers of hexamethylenediamine-terephthalic acid-hexamethylenediamine-isophthalic acid. It is done. As the polyamide resin particles, the above nylon particles are particularly preferable. Nylon particles are negatively charged in water.

  These resin particles may be used alone or in combination of two or more. As the resin particles, known or commercially available resin particles can be used, or they may be used after polymerization.

  The nonionic surfactant is not particularly limited as long as the resin particles can be made colloidal, and various types can be used. Specifically, ester type surfactants such as glyceryl laurate, glyceryl monostearate, sorbitan fatty acid ester and sucrose fatty acid ester; ether type surfactants such as polyoxyalkylene alkyl ether and polyoxyalkylene alkyl phenyl ether; Ester ether type surfactants such as polyoxyethylene sorbitan fatty acid ester and sorbitan fatty acid ester polyalkylene glycol; alkanolamide type surfactants such as lauric acid diethanolamide and stearic acid diethanolamide; alkyl glycosides such as decyl glycoside and lauryl glycoside, Examples include higher alcohols such as cetanol and stearyl alcohol. These nonionic surfactants may be used alone or in combination of two or more. As the nonionic surfactant, a known or commercially available nonionic surfactant can be used. When the resin particles are nylon particles, it is preferable to use an ester type surfactant, particularly a sorbitan fatty acid ester such as sorbitan monolaurate.

  The electrolyte is added to facilitate electrophoresis of the colloidal solution for producing carbon fiber reinforced plastic. Examples of the electrolyte include sodium chloride, potassium chloride, and magnesium chloride. By including an electrolyte in the colloidal solution for producing carbon fiber reinforced plastic, the electrophoretic mobility of the colloidal particles is improved when electrophoresis is performed in the colloidal solution, and the amount of colloidal particles adsorbed on the carbon fiber is increased. To increase.

  There is no restriction | limiting in particular as water, Various waters, such as a tap water, industrial water, ion-exchange water, deionized water, a pure water, can be used. In particular, deionized water and pure water are preferred.

  In the first embodiment, a radical polymerization initiator may be further contained. It is preferable to use a cationic polymerization initiator as the radical polymerization initiator. The cationic polymerization initiator (cationic radical polymerization initiator) is not particularly limited, and various types can be used. Specifically, 2,2'-azobis (2-methylpropionamidine) dihydrochloride (V-50), 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (VA-044), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] azo compounds such as disulfate dihydrate (VA-046B). These radical polymerization initiators may be used alone or in combination of two or more. As the radical polymerization initiator, a known or commercially available cationic polymerization initiator can be used.

(2) Colloidal solution for producing carbon fiber reinforced plastic containing resin particles, radical polymerization initiator, and water (second embodiment)
The second aspect of the colloidal solution for producing carbon fiber reinforced plastic of the present invention is a colloidal solution containing resin particles, a radical polymerization initiator, and water.

  As the resin particles, water, and radical polymerization initiator, those similar to those in the first embodiment can be used.

  In the second embodiment, it is preferable to further contain an electrolyte. As the electrolyte, the same electrolyte as in the first embodiment can be used.

(3) Colloidal solution for producing carbon fiber reinforced plastic containing solid inorganic particles, electrolyte and water (third aspect)
The third aspect of the colloidal solution for producing carbon fiber reinforced plastic of the present invention is a colloidal solution containing solid inorganic particles, an electrolyte and water.

  The solid inorganic particles are not particularly limited, and various inorganic particles can be employed. Examples of the inorganic particles include silica particles, alumina particles, iron oxide particles, titanium oxide particles, and carbon particles. When solid inorganic particles are used, even when they are contained in carbon fiber reinforced plastic, they remain without melting, so that a carbon fiber reinforced plastic with unprecedented strength can be obtained.

  These solid inorganic particles may be used alone or in combination of two or more. As the inorganic particles, known or commercially available inorganic particles can be used.

  When preparing a colloidal solution using solid inorganic particles, it is not necessary to add a surfactant. Silica particles are negatively (negatively) charged in water.

  The resin particles or inorganic particles used in the present invention preferably form a colloid solution for producing a carbon fiber reinforced plastic, and from the viewpoint of facilitating adsorption to carbon fibers, the average particle diameter is preferably 0.02 to 5 μm, 0.02-1 micrometer is more preferable and 0.02-0.5 micrometer is still more preferable. The average particle diameter of the resin particles or inorganic particles can be measured by observation with a scanning electron microscope. When resin particles or inorganic particles having the above average particle diameter are commercially available, commercially available products can be used. Alternatively, commercially available resin products or inorganic particles can be finely pulverized using an appropriate pulverizer to obtain a powder having the above average particle diameter.

  The composition of each component in the colloid solution for producing the carbon fiber reinforced plastic of the present invention is not particularly limited. From the viewpoint of facilitating preparation of the colloidal solution for producing carbon fiber reinforced plastic of the present invention and facilitating adsorption of resin particles or inorganic particles on the carbon fiber surface, the water content may be excessive. In the case of the first embodiment of the colloid solution for producing carbon fiber reinforced plastic, the concentration of the resin particles is 0.1 to 2% by weight (particularly 0.1 to 0.5% by weight), and the concentration of the nonionic surfactant is It is preferable to adjust the concentration to 0.5 to 30 mmol / L (particularly 1 to 10 mmol / L) and the electrolyte concentration to 0.5 to 30 mmol / L (particularly 1 to 10 mmol / L). In the case of the second embodiment, the concentration of the resin particles is 0.1 to 2% by weight (particularly 0.1 to 0.5% by weight), and the concentration of the radical polymerization initiator is 2 to 100 mmol / L (particularly 2 to 60 mmol / part). L) is preferably adjusted. In the case of the third embodiment, the concentration of solid inorganic particles is 0.1 to 2% by weight (particularly 0.1 to 0.5% by weight), and the concentration of electrolyte is 0.5 to 30 mmol / L (particularly 1 to It is preferable to adjust so that it may become 10 mmol / L).

  In the colloid solution for producing the carbon fiber reinforced plastic of the present invention, a pH adjuster and an antioxidant are optionally added within a range not impairing the effects of the present invention (for example, 0 to 5% by weight, particularly 0 to 3% by weight). Additives such as an agent, a viscosity modifier, an antifungal agent, an antifoaming agent, a plasticizer, and a stabilizer can be appropriately added. As these additives, known or commercially available products can be used.

(1-2) Method for Producing Colloid Solution for Producing Carbon Fiber Reinforced Plastic As a method for producing a colloid solution for producing carbon fiber reinforced plastic of the present invention, a colloid solution for producing carbon fiber reinforced plastic of resin particles or inorganic particles can be produced. If it is a method, it will not be restrict | limited. For example, if the colloidal solution for producing a carbon fiber reinforced plastic is the first embodiment, the resin particles, the nonionic surfactant, the electrolyte and the monomer that forms the resin particles by mixing the resin and water, or the radical polymerization initiator If the colloidal solution for producing a carbon fiber reinforced plastic is the second aspect by mixing water and forming resin particles, and then adding and mixing a non-ionizable surfactant and electrolyte thereto, If the colloidal solution for producing carbon fiber reinforced plastic is the third aspect by mixing the monomer that forms the resin particles, the radical polymerization initiator, and water, the solid inorganic particles, the electrolyte, and water are mixed. Thus, the colloid solution for producing the carbon fiber reinforced plastic of the present invention can be obtained. Mixing is preferably performed under stirring.

  As the resin particles or inorganic particles, nonionic surfactant, radical polymerization initiator, electrolyte, and water, those described above can be used.

  Mixing is usually preferably performed at room temperature and normal pressure with stirring for several seconds to 30 minutes. Stirring and mixing can be performed, for example, using a magnetic stirrer or the like, or by irradiation with ultrasonic waves or microwaves.

2. Particle adsorption carbon fiber and its manufacturing method (2-1) Particle adsorption carbon fiber In the particle adsorption carbon fiber of the present invention, resin particles or inorganic particles are adsorbed on the surface of the carbon fiber. Particularly preferably, the carbon fiber fabric is impregnated with resin particles or inorganic particles.

  As the resin particles or inorganic particles, those described above can be used. When the base resin used for the carbon fiber reinforced plastic is a thermoplastic resin, the resin particles in the particle-adsorbed carbon fiber of the present invention are also preferably a thermoplastic resin. The thermoplastic resin (thermoplastic resin particles) of the resin particles is the same as defined in “1. Colloidal solution for producing carbon fiber reinforced plastic”. Examples of the base thermoplastic resin include polyamide resins (for example, nylon), polyphenylene ether, polyoxymethylene, polybutylene terephthalate, polycarbonate, methyl methacrylate, styrene, propylene, ether imide, ether sulfone, and the like. Of these, nylon is preferred.

  Examples of the carbon fiber include PAN (polyacrylonitrile) -based carbon fiber and pitch-based carbon fiber. These carbon fibers may be used alone or in combination of two or more.

  Regarding the form of the carbon fiber, any of continuous long fibers, short fibers obtained by cutting the continuous long fibers, milled yarns pulverized into powder, bundles, and the like may be used. These can be variously selected according to the use and required characteristics, such as a sheet shape such as a woven fabric, a knitted fabric, and a non-woven fabric.

  In the case of a carbon fiber bundle, the number of carbon fibers constituting the bundle is not particularly limited, but is preferably 1000 or more, more preferably 1000 to 50000, further preferably 1500 to 40000, and still more preferably 2000 to 30000. . By using the colloid solution for producing the carbon fiber reinforced plastic of the present invention described above, it is more efficient for the carbon fiber in the bundle (core) than the bundle composed of such many carbon fibers. In particular, the resin particles can be adsorbed.

  The size of the carbon fiber is not particularly limited, and the average diameter is preferably about 1,000 to 30,000 nm (particularly about 1,000 to 10,000 nm). The average length of the carbon fiber is not particularly limited and can be appropriately set as necessary.

  From the viewpoint of further improving the interfacial adhesion with the resin, the particle-adsorbed carbon fiber of the present invention preferably has resin particles or inorganic particles adsorbed on almost the entire surface of the carbon fiber, only on the surface of the carbon fiber. More preferably, the resin particles or the inorganic particles penetrate into the carbon fiber fabric. Specifically, it is preferable that resin particles or inorganic particles are adsorbed on 30 to 100%, particularly 60 to 99%, of the area of the carbon fiber surface.

  As described above, a sizing agent may be attached to the surface of the carbon fiber. In this case, the sizing of the carbon fiber surface is performed in order to improve the adsorptivity of the resin particles or inorganic particles on the carbon fiber surface. It is preferable to remove the agent.

  The carbon fiber has a hydroxyl group on its surface and is negatively charged (-). For example, the carbon fiber is positively charged by applying a voltage with the carbon fiber as a positive electrode. The resin particles or inorganic particles can be attracted regardless of whether the resin particles or inorganic particles are charged, and the resin particles or inorganic particles can be adsorbed on the entire surface of the carbon fiber surface. Alternatively, inorganic particles can be permeated.

(2-2) Method for Producing Particle-Adsorbed Carbon Fiber The method for producing the particle-adsorbed carbon fiber of the present invention includes a step of performing electrophoresis using carbon fiber as a positive electrode or a negative electrode in the colloidal solution for producing carbon fiber-reinforced plastic. The manufacturing method provided is mentioned.

  As the carbon fiber, those described above can be used. However, as described above, commercially available carbon fibers often have a sizing agent attached to the surface in order to improve handling properties. In this case, in order to improve the adsorptivity of the resin particles or inorganic particles on the carbon fiber surface, it is preferable to first remove the sizing agent on the carbon fiber surface.

  The method for removing the sizing agent adhering to the carbon fiber surface is not particularly limited, and can be performed by a conventional method. For example, the sizing agent on the carbon fiber surface can be removed by treatment with acetone, 2-butanone (methyl ethyl ketone), tetrahydrofuran, dichloromethane, dichloroethane or the like.

  The method for performing electrophoresis using carbon fiber as a positive electrode or a negative electrode in the colloidal solution for producing carbon fiber reinforced plastic of the present invention is not particularly limited, and can be performed according to a conventional method. When carbon fiber is used as the positive electrode, an electrode of platinum, copper, gold, silver, carbon, or the like can be used as the negative electrode. When carbon fiber is used as a negative electrode, an electrode such as platinum, copper, gold, silver, or carbon can be used as the positive electrode. The temperature of the colloidal solution for producing carbon fiber reinforced plastic is not particularly limited, and is preferably 10 to 30 ° C, and more preferably 10 to 25 ° C, for example. Moreover, the voltage to apply is not specifically limited, For example, 5-50V is preferable and 10-30V is more preferable. The voltage application time is not particularly limited, and for example, 15 seconds to 1 hour is preferable, and 20 seconds to 3 minutes is more preferable.

  Electrophoresis is preferably performed while stirring the electrophoresis solution. Thereby, even if a carbon fiber bundle is used, the resin particles can be more efficiently adsorbed to the carbon fiber inside (core) the bundle. Stirring is usually performed using a stirrer, and the rotation speed in this case is not particularly limited, but is, for example, 50 rpm to 500 rpm, preferably 100 to 300 rpm.

  Particles that have approached the surface of the carbon fiber by the electrophoresis operation have van der Waals forces acting on the carbon fiber, and are firmly adsorbed on the carbon fiber and remain on the carbon fiber. Therefore, by adopting such a method, it is possible to obtain particle-adsorbed carbon fibers in which a larger amount of resin particles or inorganic particles are uniformly adsorbed in an extremely short time compared to the conventional method. Since there is much quantity of the resin particle or inorganic particle adhering to carbon fiber, interface adhesiveness with resin can be improved more.

3. Carbon fiber reinforced plastic In the carbon fiber reinforced plastic of the present invention, the particle-adsorbed carbon fiber of the present invention is contained in a base resin. As described above, since the particle-adsorbed carbon fiber of the present invention can improve the interfacial adhesion with the resin, the carbon fiber-reinforced plastic of the present invention has a strong adhesion between the carbon fiber and the base resin. Yes. For this reason, the strength of the carbon fiber reinforced plastic of the present invention is improved.

  The resin for the base material is not particularly limited, and various resins can be used. In addition, since the particle-adsorbed carbon fiber of the present invention can particularly improve the interfacial adhesion between the resin particles in the particle-adsorbed carbon fiber of the present invention and the same or similar resin, the base resin is the present invention. It is preferable that the resin is the same as or similar to the resin particles in the particle-adsorbed carbon fibers. When a thermoplastic resin is used as the resin particles in the particle-adsorbed carbon fiber of the present invention, the resin used as the base material of the carbon fiber reinforced plastic is also preferably a thermoplastic resin. Examples of the thermoplastic resin include polyamide resins (for example, nylon), polyphenylene ether, polyoxymethylene, polybutylene terephthalate, polycarbonate, polymethyl methacrylate (PMMA), polystyrene, polypropylene, polyetherimide, and polyethersulfone. Can be mentioned.

  In the carbon fiber reinforced plastic of the present invention, the composition of each component is not particularly limited and can be appropriately set as necessary.

  The carbon fiber reinforced plastic of the present invention can be produced according to a conventional method, and can be used in various applications such as automobiles, aircraft, sports-related products, structural materials for producing medical devices, and the like.

4). Control Method When producing particle-adsorbing carbon fibers by electrophoresis operation, the amount of particles adsorbed on the carbon fibers can be controlled by changing the applied voltage. It has been clarified that the interfacial shear strength between the carbon fiber reinforced plastic and the amount of adsorbed particles on the carbon fiber increases as the amount of particles adsorbed on the carbon fiber increases (see the following examples). Therefore, the interfacial adhesion can be controlled by changing the applied voltage in the electrophoresis operation to control the amount of particles adsorbed on the carbon fiber.

  From this, when applying a voltage by using carbon fiber as a positive electrode or a negative electrode in the colloidal solution for producing the carbon fiber reinforced plastic, the present invention adsorbs the carbon fiber by controlling the magnitude of the applied voltage. A method for controlling the amount of particles is provided. Further, the present invention provides the particles adsorbed on the carbon fiber by controlling the magnitude of the applied voltage when the voltage is applied using the carbon fiber as a positive electrode or a negative electrode in the colloidal solution for producing the carbon fiber reinforced plastic. By controlling the amount, a method of controlling the interfacial adhesion between the carbon fiber and the resin is provided.

  Next, examples of the present invention will be described, but the present invention is not limited thereto. In the following examples, various physical properties were evaluated by the following methods.

(1) Observation of carbon fiber surface The form of the carbon fiber was observed with a field emission scanning electron microscope (JSM-7500FA, manufactured by JEOL Ltd.). A sample for SEM observation was prepared as follows. Carbon fibers were coated with an osmium thin film by vapor deposition (Osmium plasma coater OPC60A, manufactured by Philgen Co., Ltd.).

(2) Evaluation of particle adsorption amount The amount of particles adsorbed on the carbon fiber surface was quantitatively measured using a thermogravimetric measuring device (DTG-60AH, manufactured by Shimadzu Corporation). Table 1 shows the experimental conditions. By heating the carbon fibers to which the particles are adsorbed, the particles are melted and only the carbon fibers remain. The reduced weight is the adsorbed particle amount (m ₁ ), the remaining weight is the absolute dry mass (m ₂ ) of the carbon fiber, and the adsorbed amount M [g / m ² ] of the particles per unit surface area of the carbon fiber is as follows: (1).

(3) Fragmentation test The fragmentation test is a test for evaluating the interfacial shear strength of carbon single fiber. Masatoshi Shiotani and Takahisa Akira, "Evaluation of fiber-matrix interfacial shear strength of fiber reinforced composite material", surface, vol33, No22 744-762 (1995). Specifically, the test was performed with a microscope (MS-804, manufactured by Moritex Co., Ltd.) using a tensile tester (10073B, manufactured by Japan Hightech Co., Ltd.). Samples were prepared as follows. A carbon single fiber is sandwiched between two films containing polymethylmethacrylate and hot-pressed at 180 ° C. for 1 minute using a hot press machine (N4003-00, manufactured by NPA System Co., Ltd.) between the two steel plates. The film was quenched by cooling with water at 25 ° C. Thereafter, the film was cut into strips having a gauge length of 25 mm and a width of 4 mm.

Samples were tested to 15% tensile strain at which the fragmentation process saturates, and then the average length of fragmentation carbon fibers (<L>) was measured. The carbon monofilament fragmentation test was performed on 5 samples. The interfacial adhesion (τ _m ) between the carbon fiber and the resin was calculated by the following equation (2).

The critical fiber length (l _c ) can be obtained as follows.

The average diameter (D) of the carbon fiber was measured by diffraction of a He—Ne laser beam from the fiber. The tensile strength (f) of the carbon fiber (length: l _c ) was evaluated by Weibull analysis using the results of the single fiber tensile test. The tensile test was performed using a tensile tester (SDW-1000SS-E-SL, manufactured by Imada Manufacturing Co., Ltd.). The tester was operated at a gauge length of 25 mm and a crosshead speed of 1 mm / min.

Example 1
A colloid solution for producing carbon fiber reinforced plastic was prepared by soap-free emulsion polymerization. The water used for the soap-free emulsion polymerization was purified with a pure water production apparatus (Auto Still WG250, manufactured by Yamato Scientific Co., Ltd.), and then nitrogen gas was blown into water for 20 minutes to remove dissolved oxygen. Methyl methacrylate (MMA, manufactured by Tokyo Chemical Industry Co., Ltd.) was used as a monomer for polymerization. The monomer was selected according to the thermoplastic resin of the film containing polymethyl methacrylate (HBS006, manufactured by Mitsubishi Rayon Co., Ltd.). 2,2′-Azobis (2-methylpropionamidine) dihydrochloride (V-50, manufactured by Sigma-Aldrich) was used as a radical initiator without purification. Resin particles were positively charged by V-50. The chemical structure of V-50 is shown below. In Example 1, carbon fiber (HTS40, manufactured by Toho Tenax Co., Ltd.) was used after treatment with acetone to remove the sizing agent.

  The polymerization reaction was performed in a 100 mL screw tube. Distilled water, an initiator and a monomer were placed in the reactor, and the mixture was heated with stirring to conduct a polymerization reaction for 6 hours. Table 2 shows the experimental conditions.

  The resin particle-adsorbed carbon fiber was produced as follows. About 400 mL of the colloidal solution for producing carbon fiber reinforced plastic prepared above was placed in a plastic container having an internal volume of 500 mL. A platinum electrode was used as the positive electrode and carbon fiber was used as the negative electrode, and the carbon fiber was negatively charged in water by applying a voltage. The voltage was applied for 30 seconds using a DC stabilized power supply (AD-8724D, manufactured by A & D Co., Ltd.), and the applied voltage was changed at 0V, 6.5V, 10V, 20V, or 30V. .

  Each carbon fiber surface was observed by SEM. For comparison, the carbon fiber treated with acetone in the colloidal solution for producing the carbon fiber reinforced plastic prepared above is immersed for 24 hours without applying voltage (0 V), washed with water, and dried at room temperature. The surface of the carbon fiber was similarly observed. A sample for SEM observation was prepared as follows. Carbon fibers were coated with an osmium thin film by vapor deposition (Osmium plasma coater OPC60A, manufactured by Philgen Co., Ltd.). An SEM image of each carbon fiber surface is shown in FIG.

  FIG. 1 shows that the higher the applied voltage, the more resin particles adsorbed on the carbon fiber surface. In addition, by performing electrophoresis at 30 V for 30 seconds, resin particles of the same level as when carbon fibers are immersed in colloid for 24 hours are adsorbed, so that electrophoresis can be performed in a short time of 30 seconds. It can be seen that a large amount of resin particles can be adsorbed.

  Furthermore, the permeability of the particles was observed for the carbon fibers subjected to electrophoresis at 30 V for 30 seconds. First, carbon fibers subjected to electrophoresis at 30 V for 30 seconds were embedded and cured using an epoxy-based strong adhesive (Araldite, manufactured by Nichiban Co., Ltd.). It was cut into a cross section (1) or a cross section (2) shown in FIG. 2 with a cutter and observed with a SEM. FIG. 3 shows an SEM image near the center (circle) of the cross section (1) in FIG. 2, and FIG. 4 shows an SEM image from a to b in the cross section (2). Further, FIG. 5 shows the SEM image of FIG. 4 divided into four parts and enlarged.

  FIG. 3 shows that resin particles are attached to any carbon fiber by electrophoresis. Further, FIG. 5 shows that the resin particles permeate not only toward the end of the carbon fiber but also inside the fiber fabric.

  The applied voltage was set to 0 V, 6.5 V, 10 V, 20 V, or 30 V, and the amount of PMMA particles adsorbed to the carbon fiber when the voltage was applied for 30 seconds was calculated. A graph showing the relationship between the applied voltage and the amount of adsorbed particles is shown in FIG. Further, SEM images at applied voltages of 0 V and 30 V are also shown in FIG.

  From the graph of FIG. 6 and the SEM image, it can be seen that a larger amount of particles are adsorbed on the carbon fiber surface by increasing the applied voltage. The applied voltage and the speed of electrophoresis are proportional, and it is considered that the amount of adsorbed particles increases as the applied voltage increases and a larger amount of particles approach the carbon fiber. Thus, it can be said that the amount of adsorbed particles can be controlled by changing the applied voltage in the electrophoresis operation. In addition, it can be confirmed from the SEM image on the lower side of FIG. 6 that the PMMA particles are adsorbed to the carbon fiber even when the applied voltage is 0 V. This is because the carbon fiber is negatively charged in water. It is considered that the positively charged PMMA particles were adsorbed by electrostatic interaction.

  A fragmentation test was performed on each carbon fiber obtained by applying an applied voltage of 0 V, 6.5 V, 10 V, 20 V, or 30 V and applying the voltage for 30 seconds, respectively, and an interface shear stress was calculated. A graph showing the relationship between the amount of adsorbed particles and the interfacial shear stress is shown in FIG.

  As shown in FIG. 7, along with the increase in the amount of particles adsorbed on the carbon fiber, the interfacial shear strength between the acrylic resin and the carbon fiber is improved, and thus the interfacial shear strength can be controlled by controlling the adsorbed particle amount. Recognize. From this, it is considered that the wettability with the resin is improved and the interfacial adhesion is improved by coating the carbon fiber with the resin component.

Example 2
Nylon 12 true spherical particles (manufactured by Toray Industries, Inc.) 230 mg, water 75 g, nonionic surfactant (Span20, manufactured by Tokyo Chemical Industry Co., Ltd.), and electrolyte (KCl, Kanto Chemical Co., Ltd.) 50 mg), and ultrasonic irradiation was performed for 30 seconds using an ultrasonic cleaner (US-5KS manufactured by SND Co., Ltd.) to disperse nylon particles to obtain a colloid solution for producing carbon fiber reinforced plastic. In addition, the distilled water prepared with the pure water manufacturing apparatus (Auto still WG250, Yamato Scientific Co., Ltd.) was used for water.

  About 400 mL of the colloidal solution for producing carbon fiber reinforced plastic prepared above was placed in a plastic container having an internal volume of 500 mL. The carbon fiber was positively charged in water by applying a voltage using a carbon fiber as the positive electrode and a platinum electrode as the negative electrode. The voltage was applied at 30 V for 30 seconds using a DC stabilized power supply (AD-8724D, manufactured by A & D Co., Ltd.). The surface of the carbon fiber after the electrophoresis treatment was observed in the same manner as in Example 1. The result is shown in FIG.

  FIG. 8 shows that nylon particles are adsorbed on the carbon fiber surface by performing electrophoresis at 30 V for 30 seconds. This is because the negatively charged nylon particles are attracted to and adsorbed to the positively charged carbon fibers.

  For comparison, the nylon powder is put together with carbon fiber in a polyethylene bag with a chuck (Unipack (registered trademark), 120 mm x 85 mm, manufactured by Nihon Co., Ltd.), shaken several times, and the nylon powder is directly applied to the carbon fiber. Was attached. FIG. 9 shows an SEM image (upper left) and an enlarged image (lower left) of a carbon fiber subjected to electrophoresis at 30 V for 30 seconds, and an enlarged image (lower right) of a carbon fiber to which nylon powder is adhered (upper right). Indicates.

  From FIG. 9, it can be seen that the nylon particles attached by the electrophoresis operation are better attached than the powder directly attached.

  A fragmentation test was performed on the carbon fibers obtained by the electrophoresis operation of Example 2 (30 V for 30 seconds) and the carbon fibers treated with acetone to remove the sizing agent for comparison. The result of the fragmentation test is shown in FIG.

  From FIG. 10, it can be seen that by attaching nylon particles to the carbon fiber by electrophoresis operation, the interfacial shear strength was changed from 43.2 MPa to 73.4 MPa, and the interfacial adhesion was improved by about 70%.

Example 3
In a screw tube with an internal volume of 100 mL, 15 g of water, 2,3′-azobis (2-methylpropionamidine) dihydrochloride (V-50, Sigma-Aldrich) 2.03 mM, and N-vinylacetamide monomer (NVA, NVA monomer was polymerized by adding 320 mM (made by Showa Denko KK) and stirring at 70 ° C. and 130 rpm for 6 hours. Thereto, 60 g of water was added to make a total amount of 75 g. Furthermore, 50 mg of KCl and 100 mg of nonionic surfactant (Span20, manufactured by Tokyo Chemical Industry Co., Ltd.) were put therein, and ultrasonic irradiation was performed for 30 seconds using an ultrasonic cleaning machine (US-5KS manufactured by SND Corporation). Thus, a colloid solution for producing carbon fiber reinforced plastic was obtained. In addition, the distilled water prepared with the pure water manufacturing apparatus (Auto still WG250, Yamato Scientific Co., Ltd.) was used for water.

  About 400 mL of the colloidal solution for producing carbon fiber reinforced plastic prepared above was placed in a plastic container having an internal volume of 500 mL. A carbon fiber bundle (manufactured by Toho Tenax Co., Ltd., product number: HTS40, 3k) was used for the positive electrode, a platinum electrode was used for the negative electrode, and a voltage was applied to positively charge the carbon fiber in water. The voltage was applied at 30 V for 30 seconds using a DC stabilized power supply (AD-8724D, manufactured by A & D Co., Ltd.). Moreover, during voltage application, the solution was stirred with a stirrer (200 rpm).

The obtained resin-adsorbed carbon fiber bundle or the untreated carbon fiber bundle was treated with acetone to remove the sizing agent, and the sizing agent-removed carbon fiber bundle was impregnated with nylon resin. Specifically, it was performed according to the following steps 1 to 4.
1. The PA6 film was vacuum dried at 80 ° C. for 24 hours.
2. PA6 film was cut out to 10 mm × 150 mm.
3. The carbon fiber bundle was sandwiched between PA6 films, and the resin was melted by sandwiching at about 0.1 MP for 5 minutes with a hot press machine.
4). Thereafter, a load was applied at 5 MPa for 1 minute.

  The obtained carbon fiber-resin composite was cut perpendicular to the fiber direction of the carbon fiber, and the cross section was observed with SEM. SEM observation images are shown in FIG. 11 (high magnification image) and FIG. 12 (low magnification image).

  As shown in FIG. 11, in the cross section of the carbon fiber-resin composite, in addition to the carbon fiber region and the resin region, there is a gap region that does not correspond to any of these. Based on the area of each region, the resin impregnation rate (= resin region area / resin region area + gap region area) was calculated. The permeation rate is shown in the lower part of FIG. Further, the ratio of the carbon fiber region (= the ratio of the carbon fiber region / the total region) was also calculated. The ratio of the carbon fiber region is shown in the lower part of FIG.

  As shown in FIGS. 11 and 12, by using the resin-adsorbed carbon fiber bundle obtained by attaching poly-N-vinylacetamide to the carbon fiber bundle by electrophoresis, the carbon fibers are densely arranged. It was found that the resin can be impregnated efficiently.

Example 4
A screw tube having an internal volume of 100 mL is charged with 15 g of water, 2.03 mM of azobisisobutyronitrile, 320 mM of styrene monomer (Tokyo Kasei), and 1570 mM of N-vinylacetamide monomer (NVA, Showa Denko), 70 ° C., A polymer of NVA monomer and styrene monomer was prepared by stirring at 130 rpm for 6 hours. Thereto, 60 g of water was added to make a total amount of 75 g. Furthermore, 50 mg of KCl was put therein and irradiated with ultrasonic waves for 30 seconds using an ultrasonic cleaning machine (US-5KS manufactured by SND Corporation) to obtain a colloid solution for producing carbon fiber reinforced plastic. In addition, the distilled water prepared with the pure water manufacturing apparatus (Auto still WG250, Yamato Scientific Co., Ltd.) was used for water.

  About 400 mL of the colloidal solution for producing carbon fiber reinforced plastic prepared above was placed in a plastic container having an internal volume of 500 mL. A carbon fiber bundle [(Toho Tenax Co., Ltd., product number: HTS40, 3k)] (Toho Tenax Co., Ltd., product number: HTS40, 24k)] is used for the positive electrode, and a platinum electrode is used for the negative electrode. Carbon fiber was positively charged in water. The voltage application was performed at 10 V, 20 V, or 30 V for 30 seconds using a DC stabilized power supply (AD-8724D, manufactured by A & D Co., Ltd.). Moreover, during voltage application, the solution was stirred with a stirrer (200 rpm).

  The surface of the single fiber of the sizing agent-removed carbon fiber bundle obtained by treating the obtained resin-adsorbed carbon fiber bundle or the untreated carbon fiber bundle with acetone to remove the sizing agent is the same as in Example 1. And observed. The result is shown in FIG.

  Furthermore, the fragmentation test was done about the single fiber of the obtained resin adsorption carbon fiber bundle and the carbon fiber bundle from which the sizing agent was removed. The result of the fragmentation test is shown in FIG.

  From FIGS. 13 and 14, by attaching poly-N-vinylacetamide to the carbon fiber bundle by electrophoresis, the interfacial shear strength was increased from 42.7 to 88.6, and the interfacial adhesiveness was approximately doubled. I understand.

Subsequently, the obtained resin-adsorbed carbon fiber bundle or the sizing agent-removed carbon fiber bundle was impregnated with a nylon resin. Specifically, it was performed according to the following steps 1 to 4.
1. The PA6 film was vacuum dried at 80 ° C. for 24 hours.
2. PA6 film was cut out to 10 mm × 150 mm.
3. The carbon fiber bundle was sandwiched between PA6 films, and the resin was melted by sandwiching at about 0.1 MP for 5 minutes with a hot press machine.
4). Thereafter, a load was applied at 5 MPa for 1 minute.

  The obtained carbon fiber-resin composite was cut perpendicular to the fiber direction of the carbon fiber, and the cross section was observed with SEM. SEM observation images are shown in FIG. 15 (high magnification image) and FIG. 16 (low magnification image).

  In the same manner as in Example 2, the permeation rate and the ratio of the carbon fiber region were calculated. The impregnation rate is shown in the upper part of each photograph of FIG. 15, and the ratio of the carbon fiber region is shown in the upper part of FIG.

  As shown in FIGS. 15 and 16, by using a resin-adsorbed carbon fiber bundle obtained by attaching poly-N-vinylacetamide to the carbon fiber bundle by electrophoresis, the carbon fibers are densely arranged. It was found that the resin can be impregnated efficiently.

Claims (16)

A colloidal solution for producing carbon fiber reinforced plastic,
(1) containing resin particles, nonionic surfactant, electrolyte and water,
(2) containing resin particles, radical polymerization initiator, and water, or (3) containing solid inorganic particles, electrolyte, and water,
Colloidal solution for producing carbon fiber reinforced plastic.   The colloid solution for producing carbon fiber reinforced plastics according to claim 1, wherein the resin particles are thermoplastic resin particles.   The colloid solution for producing a carbon fiber reinforced plastic according to claim 2, wherein the thermoplastic resin particles are polymer particles of a monomer containing an amide bond-containing monomer.   The colloid solution for producing a carbon fiber reinforced plastic according to claim 2 or 3, wherein the thermoplastic resin particles have an average particle size of 0.02 to 0.5 µm.   The colloid solution for producing carbon fiber reinforced plastics according to claim 2, wherein the thermoplastic resin particles are polyamide resin particles.   The colloid solution for producing carbon fiber reinforced plastics according to claim 5, wherein the polyamide resin particles are nylon particles.   Particle-adsorbed carbon fiber in which thermoplastic resin particles are adsorbed on the surface of carbon fiber.   The particle-adsorbing carbon fiber according to claim 7, wherein the thermoplastic resin particles are polymer particles of a monomer containing an amide bond-containing monomer.   The particle-adsorbed carbon fiber according to claim 7 or 8, wherein an average particle diameter of the thermoplastic resin particles is 0.02 to 0.5 µm.   The particle-adsorbed carbon fiber according to claim 7, wherein the thermoplastic resin particles are polyamide-based resin particles.   The particle-adsorbed carbon fiber according to claim 10, wherein the polyamide-based resin particles are nylon particles. A method for producing particle-adsorbed carbon fibers, comprising:
A production method comprising a step of performing electrophoresis by applying a voltage with a carbon fiber as a positive electrode or a negative electrode in the colloid solution for producing a carbon fiber reinforced plastic according to any one of claims 1 to 6.   The carbon fiber reinforced plastic in which the particle | grain adsorption carbon fiber of any one of Claims 7-11 is contained in resin of a base material.   The carbon fiber reinforced plastic according to claim 13, wherein the resin constituting the resin particles in the particle-adsorbed carbon fibers and the resin of the base material are the same or similar resins. A method for controlling the amount of particles adsorbed on the surface of a particle-adsorbing carbon fiber,
The said carbon is controlled by controlling the magnitude of the applied voltage when applying a voltage with the carbon fiber as a positive electrode or a negative electrode in the colloidal solution for producing a carbon fiber reinforced plastic according to any one of claims 1 to 6. A control method for controlling the amount of the particles adsorbed on the fiber. A method for controlling the interfacial adhesion of a carbon fiber to a resin,
The said carbon fiber by controlling the magnitude | size of the voltage to apply, when applying a voltage by using carbon fiber as a positive electrode or a negative electrode in the colloidal solution for carbon fiber reinforced plastic manufacture of any one of Claims 1-6 A control method of controlling the interfacial adhesion between the carbon fiber and the resin by controlling the amount of the particles adsorbed on the resin.

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