JP2017095537A - Prepreg, method for producing prepreg and carbon fiber-reinforced composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a prepreg having excellent appearance quality and mechanical characteristics.SOLUTION: A prepreg is obtained by impregnating a carbon fiber base material with a matrix resin composition comprising component (A): epoxy resin, component (B): epoxy resin curing agent, and component (C): polyvinyl chloride copolymer.SELECTED DRAWING: None

Description

  The present invention relates to a prepreg having excellent mechanical properties and appearance quality, a method for producing the prepreg, and a carbon fiber reinforced composite material, and for applications requiring excellent mechanical properties and appearance quality such as sports equipment and automobiles. In particular, the present invention relates to a prepreg, a prepreg manufacturing method, and a carbon fiber reinforced composite material that can be suitably used.

  A prepreg and carbon fiber reinforced composite material using carbon fiber as a reinforced fiber, utilizing high specific strength and specific modulus, structural materials such as aircraft and automobiles, sports equipment such as tennis rackets, golf shafts and fishing rods, and It is widely used for general industrial products such as bicycles and PC cases. A prepreg and a carbon fiber reinforced composite material using carbon fibers as reinforcing fibers are particularly preferred for sports goods, PC housings, automobiles, and the like because of their unique design characteristics not found in metal materials.

  A prepreg using carbon fibers as reinforcing fibers and a carbon fiber reinforced composite material include a matrix resin composition. From the viewpoint of heat resistance and productivity, the matrix resin composition mainly includes a thermosetting resin. Among them, an epoxy resin composition is preferably used from the viewpoints of adhesiveness with reinforcing fibers and mechanical properties.

  However, generally the cured epoxy resin composition has a yellowish color. In particular, for imparting heat resistance, an epoxy resin such as a trifunctional epoxy resin having three epoxy groups or a tetrafunctional epoxy resin having four epoxy groups is blended, or a polyamine compound or imidazole is used as a curing agent for the epoxy resin composition. When using a compound, the color of the cured epoxy resin tends to be more yellowish. As described above, the prepreg and the carbon fiber reinforced composite material containing the matrix resin composition including the epoxy resin composition which turns yellow upon curing are suitably used in applications requiring appearance quality because the appearance is yellowish. I can't. In particular, when a carbon fiber woven fabric is used as the base material, the cured matrix resin composition is thicker at the crease portion and the concave portion, and thus becomes more yellowish.

  For this reason, in applications where appearance quality is required, a method of blending a pigment or carbon black or the like and coloring it to the same black color as the carbon fiber is usually employed in order to hide the yellowness of the cured epoxy resin composition ( Patent Documents 1 and 2).

JP 2014-162858 A Japanese Patent Laid-Open No. 55-015870

  However, like the techniques disclosed in Patent Document 1 and Patent Document 2, when a pigment or carbon black is blended into the epoxy resin composition, the design of the carbon fiber substrate becomes difficult to see, resulting in poor appearance quality. When the blended pigment or carbon black becomes a foreign substance in the prepreg or carbon fiber reinforced composite material and force is applied to the prepreg or carbon fiber reinforced composite material containing the pigment or carbon black, the prepreg or carbon There arises a problem that the fiber-reinforced composite material is broken and the mechanical properties are deteriorated.

  This invention makes it a subject to provide the prepreg and carbon fiber reinforced composite material which have the outstanding external appearance quality and mechanical characteristic in view of the background which concerns.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a prepreg or the like that satisfies a specific condition, and have reached the present invention.

That is, the prepreg according to the present invention is obtained by impregnating a carbon fiber substrate with a matrix resin composition containing the following component (A), component (B) and component (C).
Component (A): Epoxy resin component (B): Epoxy resin curing agent component (C): Vinyl chloride copolymer.

  Moreover, the manufacturing method of the prepreg which concerns on this invention is a manufacturing method of the prepreg which manufactures the said prepreg, Comprising: The process which dissolves the said component (C) in the said component (A) is included.

Moreover, the carbon fiber reinforced composite material which concerns on this invention contains the matrix resin composition and carbon fiber base material containing the following component (A), a component (B), and a component (C).
Component (A): Epoxy resin component (B): Epoxy resin curing agent component (C): Vinyl chloride copolymer.

  According to the present invention, it is possible to provide a prepreg and a carbon fiber reinforced composite material having excellent appearance quality and mechanical properties.

<Prepreg>
The prepreg according to the present invention is obtained by impregnating a carbon fiber base material with a matrix resin composition containing the following component (A), component (B) and component (C).
Component (A): Epoxy resin component (B): Epoxy resin curing agent component (C): Vinyl chloride copolymer The matrix resin composition contains component (A) and component (C), so that light is emitted. A cured product of the matrix resin composition containing no transmissive black foreign matter is obtained. Therefore, it is possible to provide a prepreg having excellent appearance quality and mechanical properties.

  In the present specification, the “epoxy resin” refers to a compound having one or more epoxy groups in a molecule.

  As the reinforcing fiber in the present invention, carbon fiber is used. Among these, carbon fibers having a strand strength of 3500 MPa or more according to JIS R 7601 are preferable, and carbon fibers having a strand strength of 4500 MPa or more are more preferable. Moreover, a carbon fiber base material is a base material containing carbon fiber, for example, molded objects, such as a sheet | seat formed with carbon fiber. When using carbon fibers formed in a sheet shape, the substrate may be a laminate of a plurality of sheets.

  The fiber diameter of the carbon fiber filament is preferably 3 μm or more, and preferably 12 μm or less.

  The form of the carbon fiber base material in the present invention is a form in which continuous fibers are aligned in one direction, a form in which the continuous fibers are used as a woven fabric, a form in which the tows are aligned in one direction and held with a weft auxiliary yarn, Examples include a multiaxial warp knit in which a plurality of unidirectional carbon fiber sheets are stacked in different directions and fastened with auxiliary yarns, and a non-woven fabric.

  Above all, from the viewpoint of ease of manufacturing a prepreg, a form in which continuous fibers are aligned in one direction, a form in which continuous fibers are used as a woven fabric, a form in which tows are aligned in one direction and held by weft auxiliary yarns, and a plurality A preferred form is a multiaxial warp knit in which carbon fiber sheets in one direction are stacked in different directions and fastened with auxiliary yarns. From the viewpoint of expressing the strength of the obtained fiber-reinforced composite material, a form in which continuous fibers are aligned in one direction is more preferable.

The basis weight of the carbon fiber base material can be freely set according to the purpose of use of the fiber reinforced composite material, but a practically preferable range is 50 g / m ² or more and 2000 g / m ² or less. Since the impregnation of the resin composition to obtain a satisfactory prepreg, more preferably 50 g / ^{m 2} or more 600 g / ^{m 2} or less, further preferably 50 g / ^{m 2} or more 300 g / ^{m 2} or less.

  On the other hand, when obtaining a hollow molded product by filament winding molding, it is preferable to use a carbon fiber tow (carbon fiber bundle) as the carbon fiber substrate.

  The number of carbon fibers constituting the carbon fiber bundle is preferably 1,000 or more, and more preferably 70,000 or less. When the fiber diameter is 3 μm or more, for example, when the filament causes lateral movement on the surface of a roll or a bobbin in various processing processes, it is possible to prevent problems such as cutting or fluffing. About an upper limit, it is about 12 micrometers normally from the difficulty on manufacture of carbon fiber.

<Matrix resin composition>
The matrix resin composition contained in the prepreg according to the present invention and the matrix resin composition used in the method for producing a carbon fiber reinforced composite material according to the present invention described later include the following components (A) to (C).
Component (A): Epoxy resin component (B): Epoxy resin curing agent component (C): Vinyl chloride copolymer.

<Component (A)>
Component (A) may be an epoxy resin.

  As the epoxy resin, it is preferable to mainly use a bifunctional epoxy resin having an aromatic ring in the molecule. By using a bifunctional epoxy resin having an aromatic ring in the molecule, the viscosity of the matrix resin composition can be adjusted to an appropriate range, and the mechanical properties of the cured product are adjusted to an appropriate range. be able to. Here, the component (A) is a bifunctional epoxy resin alone, or when a plurality of types of epoxy resins are included, the amount of the bifunctional epoxy resin is preferably maximized.

  In the present specification, the “bifunctional epoxy resin” means a compound having two epoxy groups in the molecule.

  Examples of the aromatic ring in the bifunctional epoxy resin having an aromatic ring in the molecule include a benzene ring, a naphthalene ring, and a fluorene ring.

  Examples of the bifunctional epoxy resin having an aromatic ring in the molecule include bisphenol A diglycidyl ether type epoxy resin, bisphenol F diglycidyl ether type epoxy resin, bisphenol S diglycidyl ether type epoxy resin, and resorcin diglycidyl ether type. Epoxy resin, hydroquinone diglycidyl ether type epoxy resin, terephthalic acid diglycidyl ester type epoxy resin, bisphenoxyethanol full orange glycidyl ether type epoxy resin, bisphenol full orange glycidyl ether type epoxy resin, biscresol full orange glycidyl ether type epoxy resin, novolak Examples include, but are not limited to, glycidyl ether type epoxy resins and hexahydrophthalic acid glycidyl esters. Not shall. Moreover, only 1 type may be used for an epoxy resin and it may use 2 or more types of epoxy resins together.

  Among bifunctional epoxy resins having an aromatic ring in the molecule, the viscosity of the matrix resin composition can be adjusted to an appropriate range, and the mechanical properties of the cured product can be adjusted to an appropriate range. In view of the capability, a liquid bisphenol A diglycidyl ether type epoxy resin having an epoxy equivalent of 170 g / eq or more and 200 g / eq or less is particularly preferable.

  In addition to the bisphenol A diglycidyl ether type epoxy resin, various epoxy resins can be used for the purpose of improving heat resistance and adjusting the viscosity. For example, a trifunctional or higher functional epoxy resin and an epoxy resin having an aliphatic skeleton can be given.

  Examples of the trifunctional epoxy resin include a triazine skeleton-containing epoxy resin, an aminophenol type epoxy resin, and an aminocresol type epoxy resin. Examples of the tetrafunctional or higher functional epoxy resin include a cresol novolac epoxy resin, a phenol novolac epoxy resin, and an aromatic glycidylamine epoxy resin.

  Examples of the epoxy resin having an aliphatic skeleton include cyclohexanedimethanol diglycidyl ether, butanediol diglycidyl ether, and hexahydrophthalic acid diglycidyl ester.

<Component (B)>
The component (B) may be an epoxy resin curing agent.

  The epoxy resin curing agent may have any structure as long as it can generally cure the epoxy resin. Examples include polyamine curing agents, acid anhydride curing agents, phenol curing agents, mercaptan curing agents, Lewis acid amine complexes, onium salts, and imidazole curing agents. Among these, a polyamine curing agent, an imidazole curing agent, and an acid anhydride curing agent are preferable from the viewpoint of mechanical properties after curing.

  Examples of the polyamine curing agent include dicyandiamide, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine, isophoronediamine, 1,3. -Bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, 1,2-diaminocyclohexane, diaminodiphenylmethane, diaminodiphenylsulfone, polyoxypropylenediamine, polyoxypropylenetriamine, and tertiary amino group compounds as epoxy resins and Examples include so-called amine adduct type curing agents that have been made to have a high molecular weight by reacting with an isocyanate compound or the like. In applications where latency is required, dicyandiamide and diaminodiphenyl sulfone can be preferably used. Dicyandiamide may be used alone, but it is preferable to use a urea compound, an imidazole curing agent and an amine adduct type curing agent in combination as a curing aid in order to accelerate the curing reaction.

  Examples of the imidazole curing agent include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2,4-diamino-6. -[2'-Methylimidazolyl- (1 ')]-ethyl-s-triazine, and so-called amine adduct type curing agents that have been polymerized by reacting imidazole with an epoxy resin, an isocyanate compound, etc. Can be mentioned. One or a plurality of imidazole curing agents may be used as the imidazole curing agent, or a polyamine curing agent or an acid anhydride curing agent may be used in combination.

  Examples of the acid anhydride curing agent include hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methylnadic acid anhydride. In order to accelerate the curing reaction, the acid anhydride curing agent is preferably used in combination with an imidazole curing agent or the like as a curing aid.

  Examples of Lewis acid amine complexes include boron halide amine complexes. Specifically, for example, boron trifluoride / piperidine complex, boron trifluoride / monoethylamine complex, boron trifluoride / triethanolamine complex, etc. And boron trichloride amine complexes such as boron trifluoride amine complex and boron trichloride / octylamine complex. In particular, a boron trichloride amine complex is preferable in that it has excellent solubility in an epoxy resin, excellent pot life when used as a matrix resin composition, and excellent curability.

<Ingredient (C)>
Component (C) may be a vinyl chloride copolymer.

  The vinyl chloride copolymer is preferably a so-called paste vinyl chloride resin in the form of particles. Paste vinyl chloride resin has the property of becoming a paste (vinyl chloride sol) when mixed with a plasticizer or stabilizer. As a method for producing a paste vinyl chloride resin, for example, generally emulsion polymerization, microsuspension polymerization, or seed emulsion polymerization in which particles obtained by the polymerization method are further enlarged as seed particles, and seed microsuspension The method of manufacturing by spray-drying the vinyl chloride resin latex obtained by superposition | polymerization is mentioned.

  Paste vinyl chloride resin has the property of becoming a paste (vinyl chloride sol) when mixed with plasticizers, stabilizers, etc. as described above, but it can also be heated and reduced in viscosity by mixing with epoxy resin and heating. Has the role of a plasticizer and becomes a paste as well. That is, in a matrix resin composition containing particulate paste vinyl chloride resin, paste vinyl chloride resin exists as particles at room temperature (for example, 20 ° C.), but at high temperature, component (A) swells into paste vinyl chloride resin and paste chloride. The vinyl resin is compatible with the component (A). That is, by using the paste vinyl chloride resin as (C), the vinyl chloride copolymer can be present more uniformly without heating and stirring in the process of preparing the matrix resin composition. When the vinyl chloride copolymer is present more uniformly, the cured product of the matrix resin composition becomes more uniform black, and the appearance quality of the prepreg and the carbon fiber reinforced composite material is further improved.

  As the resin viscosity of the component (A) is lower and the reaction between the component (A) and the component (B) is slower at a relatively high temperature, the paste vinyl chloride resin is more compatible with the component (A).

  Conversely, the higher the resin viscosity of component (A) and the more rapid the reaction between component (A) and component (B) at a relatively low temperature, the harder the paste vinyl chloride resin becomes compatible with component (A). When the component (A) having a high resin viscosity is used, or when the reaction between the component (A) and the component (B) is abrupt at a relatively low temperature, heating and stirring are performed in the process of preparing the matrix resin composition. In addition, it is preferable that the paste vinyl chloride resin and the component (A) are previously dissolved. When the paste vinyl chloride resin and the component (A) are sufficiently compatible, the cured product of the matrix resin composition becomes more uniform black, and the appearance quality of the prepreg and the carbon fiber reinforced composite material is further improved.

  The amount of the component (C) in the matrix resin composition is preferably 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the sum of the component (A) and the component (B). preferable. By making the blending amount of the component (C) 1 part by mass or more with respect to 100 parts by mass of the sum of the component (A) and the component (B), the cured product of the matrix resin composition can transmit more light. The appearance quality of the prepreg and the carbon fiber reinforced composite material obtained from the matrix resin composition can be further increased. Moreover, by setting it as 15 mass parts or less, handling of a matrix resin composition can be made easy, and various physical properties can be made excellent in a good balance. In addition, the combination with other components increases the viscosity of the matrix resin composition and lowers the handleability, or makes it difficult to impregnate the carbon fiber substrate when preparing a prepreg from the matrix resin composition. Or the cause of lowering various physical properties of the carbon fiber reinforced composite material obtained from the matrix resin composition can be prevented.

  When kneading component (C) with other components of the matrix resin composition, a known kneading apparatus can be used. Examples of the known kneading apparatus include a raking machine, an attritor, a planetary mixer, a dissolver, a triple roll, a ball mill, and a bead mill. Moreover, these can use 2 or more types together.

  When kneading to obtain a matrix resin composition, in order to uniformly disperse the component (C) in the matrix resin composition, the component (C) is mixed at a relatively high concentration (low dilution rate). It is preferable to knead the mixture into a master batch and add other components later. Further, when the temperature in the system rises due to shearing heat generation or the like due to kneading, it is preferable to perform an operation that does not raise the temperature during kneading, such as kneading while cooling.

  Paste vinyl chloride resins that can be suitably used as component (C) are Kaneka stocks such as PCH-72, PCH-12, PCH-843, PCH-175, PSL-31, PSL-275, and PSL-290R, which are commercially available products. Examples include company-made paste PVC and Ryuron paste made by Tosoh Corporation such as R750, R751, R850, R950, and R650.

<Optional component>
The matrix resin composition contained in the prepreg according to the present invention, and the matrix resin composition contained in the carbon fiber reinforced composite material according to the present invention to be described later are within a range that does not impair the effects of the present invention, if necessary. Various known additives may be included. Additives include thermoplastic elastomers, elastomer particles, core-shell type elastomer particles, diluents, inorganic particles such as silica, carbonaceous components such as carbon nanotubes, flame retardants such as phosphorus compounds, and defoaming agents. Not exclusively.

  In order to improve toughness without reducing the heat resistance of the matrix resin composition, it is preferable to add core-shell type elastomer fine particles. Examples of commercially available core-shell type elastomer fine particles include “Metabrene” (manufactured by Mitsubishi Rayon Co., Ltd.), “Staffyroid” (manufactured by Aika Kogyo Co., Ltd.), and “Paralloid” (manufactured by Dow Chemical Co., Ltd.). Can be mentioned. The core-shell type elastomer fine particles can also be obtained as a masterbatch type epoxy resin dispersed in an epoxy resin in advance. As such a core-shell type elastomer-dispersed epoxy resin, “Kane Ace” (manufactured by Kaneka Corporation) and “Acrylic” Set BP series "(manufactured by Nippon Shokubai Co., Ltd.). In addition to shortening the preparation time of the matrix resin composition, the dispersion state of the rubber particles in the matrix resin composition can be improved, so that it is preferable to use a core-shell type elastomer-dispersed epoxy resin.

<Preparation method of matrix resin composition>
The matrix resin composition contained in the prepreg and the carbon reinforced composite material according to the present invention is prepared by using a planetary mixer and by using a three-one motor equipped with a flask and a stirring blade. As long as it is a known preparation method described in Japanese Patent Publication No. JP-A-2014-74130, etc., any of them can be used. When the component (B) is present relatively uniformly in the matrix resin composition, curing failure does not occur and deterioration of physical properties of the carbon fiber reinforced composite material can be prevented. In particular, when the component (B) is a powder, a known kneading apparatus such as a raking machine, attritor, planetary mixer, dissolver, three-roll, ball mill, and bead mill is used, and the component (B) is contained in the matrix resin composition. It is preferable to treat so that it exists uniformly. In addition, when the component (C) is present relatively uniformly, the cured product of the matrix resin composition becomes more uniform black, so that a known kneading apparatus similar to the component (B) is used and the matrix resin is used. It is preferable to treat so that the component (C) vinyl chloride copolymer is uniformly present in the composition. Furthermore, in order to allow the component (C) to be uniformly present in the matrix resin composition, the component (A) and the component (C) are sufficiently compatible with each other by sufficiently heating and stirring in the process of preparing the matrix resin composition. It is effective. When the component (A) and the component (C) are sufficiently compatible, the viscosity of the matrix resin composition is not increased and the handleability is improved by making the amount of the component (C) to be compatible relatively small. It can be prevented from lowering.

<Hardened product of matrix resin composition that is black capable of transmitting light>
The matrix resin composition contained in the prepreg and the carbon reinforced composite material according to the present invention can be cured by heating, for example, to obtain a cured product of the matrix resin composition that is black capable of transmitting light. Whether the obtained cured product of the matrix resin composition is sufficiently black so that the appearance quality of the prepreg and carbon fiber reinforced composite material containing the matrix resin composition is as good as desired. Measures the transmittance spectrum of the cured product of the matrix resin composition using a spectrophotometer, and calculates the average value T ^B (340-780) of the spectral transmittance at a wavelength of 0.1 nm in the range of 340 nm to 780 nm. It can be determined by calculating. If the average value T ^B (340-780) is between 0.05% and 5.00%, the design of the carbon fiber base material is more easily visible, so the cured product of the obtained matrix resin composition is a prepreg. And it is more preferable because it is black that makes the appearance quality of the carbon fiber reinforced composite material better. Mean value ^T B (340-780) is more preferable because a sufficient black and better quality of appearance if 0.05% to 1.00%. When the average value ^T B (340-780) is 0.05% to 0.50%, particularly preferred for their black to further improve the appearance quality.

<Conditions for measuring blackness of cured product of matrix resin composition>
The method for measuring the transmittance spectrum of the cured product of the matrix resin composition using the above spectrophotometer is as follows.
Apparatus: V-670 (manufactured by JASCO Corporation)
Sample thickness: 1mm
Measurement wavelength range: 340 nm to 780 nm
Measurement speed: 100 nm / min Data acquisition interval: 0.1 nm.

<Method for producing prepreg>
Any prepreg production method may be used as long as it is a known production method such as a solution method using a solution of a matrix resin composition and a hot melt method using a matrix resin composition having a viscosity reduced by heating. In particular, it is preferable to produce a prepreg by a hot melt method because the produced carbon fiber reinforced composite material does not have voids due to a solvent and does not deteriorate mechanical properties.

  In addition, when preparing the matrix resin composition for manufacturing a prepreg, it is preferable to include the process of melt | dissolving a component (C) in a component (A), and it heats and melt | dissolves a component (C) in a component (A) It is more preferable to include the process to do. By dissolving the component (C) in the component (A), the component (A) and the component (C) are compatible, and the component (C) can be uniformly present in the matrix resin composition. As a result, the cured product of the matrix resin composition becomes more uniform black.

<Method for producing carbon fiber reinforced composite material>
The carbon fiber reinforced composite material according to the present invention is obtained by curing the above-described prepreg according to the present invention. Although it does not specifically limit as a method for hardening, For example, it can harden | cure by heating.

  In addition, as a molding method, for example, any molding method such as autoclave molding, vacuum bag molding, press molding, or the like can be used. Among these, the autoclave molding method is preferable because a carbon fiber reinforced composite material (molded product) having excellent mechanical properties can be obtained.

<Method for producing carbon fiber reinforced composite material without prepreg>
The above-mentioned matrix resin composition can also be used in known carbon fiber reinforced composite materials that do not involve prepreg such as the filament winding method and the RTM method, and the same effect as the carbon fiber reinforced composite material that includes prepreg Can be obtained. In the filament winding method and the RTM method, it is necessary to sufficiently reduce the viscosity of the matrix resin composition. When the component (C) in the matrix resin composition is previously compatible with the component (A) during the preparation, It is preferable to reduce the amount of (C) to be used and to select the component (A) having a relatively low viscosity.

<Carbon fiber reinforced composite material>
A carbon fiber reinforced composite material obtained by the above-described method for producing a carbon fiber reinforced composite material for curing a prepreg and a known method for producing a carbon fiber reinforced composite material without using a prepreg is also within the scope of the present invention. That is, the carbon fiber reinforced composite material according to the present invention includes a matrix resin composition containing the following component (A), component (B) and component (C) and a carbon fiber substrate.
Component (A): Epoxy resin component (B): Epoxy resin curing agent component (C): Vinyl chloride copolymer.

[Additional Notes]
As described above, in the prepreg according to the present invention, the amount of the component (C) is 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the sum of the component (A) and the component (B). It is more preferable that

  In the prepreg according to the present invention, the component (B) more preferably contains at least one of a polyamine curing agent, an imidazole curing agent, and an acid anhydride curing agent.

  The carbon fiber reinforced composite material according to the present invention preferably includes the prepreg.

  The raw material of the resin composition used in each example, the preparation method, and the measurement method of each physical property are shown below. The composition of each matrix resin composition and the measurement results of physical properties are summarized in Table 1. In addition, the numerical value of each component of Table 1 represents the mass part number of each component mix | blended with a matrix resin composition. However, the scope of the present invention is not limited to the examples.

<Raw material>
<Component (A)>
・ JER828
“Product Name” jER828
"Components" Bisphenol A epoxy resin (bifunctional epoxy resin; bisphenol A diglycidyl ether type epoxy resin)
(Epoxy equivalent: 189 g / eq)
“Supplier” Mitsubishi Chemical Corporation ET759 Black “Product Name” ET759 Black “Component” Carbon Black 10% Dispersed Bisphenol A Epoxy Resin “Supplier” Dainichi Seika Kogyo Co., Ltd.

<Component (B)>
・ DICY15
"Product Name" jER Cure DICY15
"Component" A mixture of dicyandiamide and silicon dioxide (including 99.0% or more of dicyandiamide)
"Supplier" Mitsubishi Chemical Corporation DCMU99
“Product Name” DCMU-99
“Component” 3- (3,4-Dichlorophenyl) -1,1-dimethylurea “Supplier” Hodogaya Chemical Co., Ltd. 2E4MZ
"Product Name" Curesol 2E4MZ
“Component” 2-ethyl-4-methylimidazole “Supplier” Shikoku Kasei Co., Ltd., XN1045
“Product Name” HARDENER XN1045
"Ingredients" Tetrahydromethylphthalic anhydride (with curing aid)
"Supplier" Nagase ChemteX Corporation / DY9577
"Product name" DY9577
"Components" Boron trichloride amine complex "Supplier" Huntsman Japan Co., Ltd.

<Ingredient (C)>
・ PCH-72
“Product Name” PCH-72 (Paste PVC)
“Components” Vinyl chloride / vinyl acetate copolymer “Supplier” Kaneka R950
“Product Name” Leuron Paste R950 (Paste PVC)
“Components” Vinyl chloride / vinyl acetate copolymer “Supplier” Tosoh Corporation.

[Examples and Comparative Examples]
<Example 1>
(Preparation of matrix resin composition)
A matrix resin composition containing the components shown in Table 1 in the proportions shown in Table 1 was prepared.
A part of jER828 and 5 parts by mass of PCH72 were weighed into a container and premixed, and then mixed with a three-roll mill to obtain a master batch. A master batch, the remaining jER828, and 4 parts by mass of DY9577 are weighed in a glass flask and stirred until it becomes uniform while heating to about 40 ° C. to 50 ° C. using a water bath, and the matrix resin composition is stirred. Obtained.

(Preparation of cured product of matrix resin composition)
The degassed matrix resin composition was sandwiched between two glass plates together with a 1 mm thick Teflon (registered trademark) spacer, and the three edge portions of the glass plate were fixed with clips. The matrix resin composition sandwiched between the glass plates was heated in a dryer at 130 ° C. (temperature increased from room temperature to 2 ° C./min to 130 ° C.) for 2 hours to prepare a cured product of the matrix resin composition.

(Determination of blackness of cured product of matrix resin composition)
Using the spectrophotometer to measure the transmittance spectrum of the cured product of the matrix resin composition using the spectrophotometer, the blackness of the cured product of the matrix resin composition thus prepared is the above-described blackness measurement condition of the cured product of the matrix resin composition. Determination was made by calculating an average value T ^B (340-780) of spectral transmittance at a wavelength of 0.1 nm in a range of 340 nm to 780 nm. The results are shown in Table 1.

<Example 2>
(Preparation of matrix resin composition)
A matrix resin composition containing the components shown in Table 1 in the proportions shown in Table 1 was prepared.
A part of jER828, 5 parts by mass of PCH72, 5.3 parts by mass of DICY15, and 3.3 parts by mass of DCMU99 were weighed and premixed in a container, and then mixed in a three-roll mill. To make a master batch. The master batch and the remaining jER828 were weighed into a glass flask and stirred until it became uniform while heating to about 40 ° C. to 50 ° C. using a water bath to obtain a matrix resin composition.

(Preparation of cured product of matrix resin composition)
The degassed matrix resin composition was heated under the same conditions as in Example 1 to prepare a cured product of the matrix resin composition.

(Determination of blackness of cured product of matrix resin composition)
The blackness of the cured product of the matrix resin composition was determined by calculating an average value T ^B (340-780) under the same conditions as in Example 1. The results are shown in Table 1.

<Example 3>
(Preparation of matrix resin composition)
A matrix resin composition containing the components shown in Table 1 in the proportions shown in Table 1 was prepared.
A part of jER828 and 5 parts by mass of R950 were weighed into a container and premixed, and then mixed with a three-roll mill to obtain a master batch. A master batch, the remaining jER828, and 80 parts by mass of XN1045 are weighed in a glass flask and stirred until it becomes uniform while heating to about 40 ° C. to 50 ° C. using a water bath. Obtained.

(Preparation of cured product of matrix resin composition)
The degassed matrix resin composition was heated under the same conditions as in Example 1 to prepare a cured product of the matrix resin composition.

(Determination of blackness of cured product of matrix resin composition)
The blackness of the cured product of the matrix resin composition was determined by calculating an average value T ^B (340-780) under the same conditions as in Example 1. The results are shown in Table 1.

<Example 4>
(Preparation of matrix resin composition)
A matrix resin composition containing the components shown in Table 1 in the proportions shown in Table 1 was prepared.
A part of jER828 and 5 parts by mass of R950 were weighed into a container and premixed, and then mixed with a three-roll mill to obtain a master batch. A master batch, the remaining jER828, and 10 parts by mass of DY9577 are weighed in a glass flask and stirred until it becomes uniform while warming to about 40 ° C. to 50 ° C. using a water bath to obtain a matrix resin composition. Obtained.

(Preparation of cured product of matrix resin composition)
The degassed matrix resin composition was heated under the same conditions as in Example 1 to prepare a cured product of the matrix resin composition.

(Determination of blackness of cured product of matrix resin composition)
The blackness of the cured product of the matrix resin composition was determined by calculating an average value T ^B (340-780) under the same conditions as in Example 1. The results are shown in Table 1.

<Example 5>
(Preparation of matrix resin composition)
A matrix resin composition containing the components shown in Table 1 in the proportions shown in Table 1 was prepared.
A part of jER828 and 5 parts by mass of R950 were weighed into a container and premixed, and then mixed with a three-roll mill to obtain a master batch. A master batch, the remaining jER828, and 5 parts by mass of 2E4MZ are weighed in a glass flask and stirred using a water bath while heating to about 40 ° C. to 50 ° C. until uniform, and the matrix resin composition is stirred. Obtained.

(Preparation of cured product of matrix resin composition)
The degassed matrix resin composition was heated under the same conditions as in Example 1 to prepare a cured product of the matrix resin composition.

(Determination of blackness of cured product of matrix resin composition)
The blackness of the cured product of the matrix resin composition was determined by calculating an average value T ^B (340-780) under the same conditions as in Example 1. The results are shown in Table 1.

<Comparative Example 1>
(Preparation of matrix resin composition)
A matrix resin composition containing the components shown in Table 1 in the proportions shown in Table 1 was prepared.
A part of jER828, 5.3 parts by mass of DICY15, and 3.3 parts by mass of DCMU99 were weighed into a container and premixed, and then further mixed in a three-roll mill to obtain a master batch. The master batch and the remaining jER828 were weighed into a glass flask and stirred until it became uniform while heating to about 40 ° C. to 50 ° C. using a water bath to obtain a matrix resin composition.

(Preparation of cured product of matrix resin composition)
The degassed matrix resin composition was heated under the same conditions as in Example 1 to prepare a cured product of the matrix resin composition.

(Determination of blackness of cured product of matrix resin composition)
The blackness of the cured product of the matrix resin composition was determined by calculating an average value T ^B (340-780) under the same conditions as in Example 1. The results are shown in Table 1.

<Comparative example 2>
(Preparation of matrix resin composition)
A matrix resin composition containing the components shown in Table 1 in the proportions shown in Table 1 was prepared.
A part of jER828, 5.3 parts by mass of DICY15, and 3.3 parts by mass of DCMU99 were weighed into a container and premixed, and then further mixed in a three-roll mill to obtain a master batch. In a glass flask, weigh the master batch, the remaining jER828, and 4.3 parts by mass of ET759 black, and stir until uniform using a water bath while heating to about 40 ° C to 50 ° C. A composition was obtained.

(Preparation of cured product of matrix resin composition)
The degassed matrix resin composition was heated under the same conditions as in Example 1 to prepare a cured product of the matrix resin composition.

(Determination of blackness of cured product of matrix resin composition)
The blackness of the cured product of the matrix resin composition was determined by calculating an average value T ^B (340-780) under the same conditions as in Example 1. The results are shown in Table 1.

<Comparative Example 3>
(Preparation of matrix resin composition)
A matrix resin composition containing the components shown in Table 1 in the proportions shown in Table 1 was prepared.
A part of jER828, 5.3 parts by mass of DICY15, and 3.3 parts by mass of DCMU99 were weighed into a container and premixed, and then further mixed in a three-roll mill to obtain a master batch. A master batch, the remaining jER828, and 2.2 parts by mass of ET759 black are weighed in a glass flask and stirred until it becomes uniform while heating to about 40 ° C. to 50 ° C. using a water bath. A composition was obtained.

(Preparation of cured product of matrix resin composition)
The degassed matrix resin composition was heated under the same conditions as in Example 1 to prepare a cured product of the matrix resin composition.

(Determination of blackness of cured product of matrix resin composition)
The blackness of the cured product of the matrix resin composition was determined by calculating an average value T ^B (340-780) under the same conditions as in Example 1. The results are shown in Table 1.

The cured products of the matrix resin compositions of Examples 1 to 5 have an average value T ^B (340-780) of 0.05% to 5.00%, so that the tripreg containing the matrix resin composition is included. In addition, it can be considered that the carbon fiber reinforced composite material exhibits a sufficient blackness that does not deteriorate the appearance quality. In Comparative Example 1 does not contain a component (C), the cured product of the matrix resin composition is not blackish indicates color tinged slightly yellowish, the average value T ^{B (340-780)} also a very high value became. Component Comparative Example 2 and 3 containing carbon black containing no (C), Examples 1 to 5 and similarly has blackish an average value ^T B (340-780) are both 0.02% and low In the case of the tripreg and the carbon fiber composite material containing the matrix resin composition, there is a possibility that problems such as the design of the carbon fiber base material being difficult to see may occur.

  The prepreg, the prepreg manufacturing method and the carbon fiber reinforced composite material according to the present invention can be suitably used for applications requiring excellent mechanical properties and appearance quality, such as sports equipment and automobiles.

Claims (6)

A prepreg obtained by impregnating a carbon fiber base material with a matrix resin composition containing the following component (A), component (B) and component (C).
Component (A): Epoxy resin Component (B): Epoxy resin curing agent Component (C): Vinyl chloride copolymer   The prepreg according to claim 1, wherein a blending amount of the component (C) is 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the sum of the component (A) and the component (B).   The prepreg according to claim 1 or 2, wherein the component (B) contains at least one of a polyamine curing agent, an imidazole curing agent, and an acid anhydride curing agent.   The carbon fiber reinforced composite material which is the hardened | cured material of the prepreg of any one of Claims 1-3.   It is a manufacturing method of the prepreg for manufacturing the prepreg of any one of Claims 1-3, Comprising: The manufacturing method of a prepreg including the process of dissolving the said component (C) in the said component (A). The carbon fiber reinforced composite material containing the matrix resin composition containing the following component (A), a component (B), and a component (C), and a carbon fiber base material.
Component (A): Epoxy resin Component (B): Epoxy resin curing agent Component (C): Vinyl chloride copolymer