JP6209660B2 - Carbon fiber composite material and method for producing the same - Google Patents

Description

  The present invention relates to a carbon fiber composite material in which carbon nanofibers are dispersed and a method for producing the same.

  According to the method for producing a carbon fiber composite material previously proposed by the present inventors, the use of an elastomer improves the dispersibility of the carbon nanofiber, which has been considered difficult so far, and makes the carbon nanofiber uniform in the elastomer. (See, for example, Patent Document 1). According to such a method for producing a carbon fiber composite material, an elastomer and carbon nanofibers are kneaded, and dispersibility of carbon nanofibers having high cohesiveness is improved by shearing force.

  More specifically, when the elastomer and the carbon nanofiber are mixed, the viscous elastomer penetrates into the carbon nanofiber, and a specific part of the elastomer has high activity of the carbon nanofiber due to chemical interaction. In this state, when a strong shearing force is applied to a mixture of an elastomer having high molecular mobility (elasticity) and carbon nanofibers, the carbon nanofibers are deformed as the elastomer is deformed. The fibers also moved, and the aggregated carbon nanofibers were separated and dispersed in the elastomer by the restoring force of the elastomer due to elasticity after shearing. Thus, by improving the dispersibility of the carbon nanofibers in the matrix, expensive carbon nanofibers can be used efficiently as fillers for composite materials.

  In addition, a seal member excellent in tearing fatigue characteristics in which carbon nanofibers are blended with hydrogenated acrylonitrile-butadiene rubber (H-NBR) has been proposed (see, for example, Patent Document 2). It has been found that tear fatigue properties are related to the wear resistance of the rubber composition. There is a need for further improvement in wear resistance of rubber compositions.

JP 2005-97525 A International Publication No. 2011-077756

  An object of the present invention is to provide a carbon fiber composite material in which carbon nanofibers having improved tear fatigue life characteristics are dispersed and a method for producing the same.

(1) The carbon fiber composite material according to the present invention is:
A carbon fiber composite material containing carbon nanofibers for hydrogenated acrylonitrile-butadiene rubber (H-NBR),
The carbon fiber composite material includes zinc methacrylate as a co-crosslinking agent,
The carbon nanofiber includes 20 parts by mass to 45 parts by mass, and the zinc methacrylate includes 4 parts by mass to 20 parts by mass with respect to 100 parts by mass of the hydrogenated acrylonitrile-butadiene rubber (H-NBR).
The carbon nanofiber is a multilayer carbon nanofiber having an average diameter of 9 nm to 20 nm,
120 ° C., Ri der breaking number 950 times in a tensile fatigue test of maximum tensile stress 4N / mm, frequency 1 Hz,
The rupture times of the carbon fiber composite material is characterized in der Rukoto 5 times or more of the rupture times of only different compositions that do not contain the zinc methacrylate of the compounding agent constituting the carbon fiber composite material .

  According to the carbon fiber composite material according to the present invention, by including zinc methacrylate as a co-crosslinking agent, the reinforcing effect of the carbon nanofibers on the hydrogenated acrylonitrile-butadiene rubber is improved, and in particular, the tear fatigue life characteristics are improved. be able to.

(2) A method for producing a carbon fiber composite material according to the present invention includes:
The method for producing the carbon fiber composite material according to (1),
To butadiene rubber (H-NBR), and the carbon nanofibers, the second hydrogenated acrylonitrile - - first hydrogenated acrylonitrile and premix which the zinc dimethacrylate premixed butadiene rubber (H-NBR), A mixing step of mixing
The mixture obtained in the mixing step is passed through an open roll at a roll interval of 0.5 mm or less and 0 ° C. to 50 ° C., and the first hydrogenated acrylonitrile-butadiene rubber (H NBR) and the second hydrogenated acrylonitrile - the carbon nanofibers and disperse the zinc methacrylate butadiene rubber (H-NBR),
In the mixing step, the first hydrogenated acrylonitrile-butadiene rubber (H-NBR) and the second hydrogenated acrylonitrile-butadiene rubber (H-NBR) are combined. NBR) The amount of the premix is determined so that the carbon nanofibers are 20 to 45 parts by mass and the zinc methacrylate is 4 to 20 parts by mass with respect to 100 parts by mass of NBR). To do.

  According to the method for producing a carbon fiber composite material according to the present invention, by including zinc methacrylate as a co-crosslinking agent, the reinforcing effect of the carbon nanofibers on the hydrogenated acrylonitrile-butadiene rubber is improved. It is possible to produce a carbon fiber composite material with improved resistance.

It is a figure which shows typically the manufacturing method of the carbon fiber composite material which concerns on one embodiment. It is a figure which shows typically the manufacturing method of the carbon fiber composite material which concerns on one embodiment. It is a figure which shows typically the manufacturing method of the carbon fiber composite material which concerns on one embodiment.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

(1) A carbon fiber composite material according to an embodiment of the present invention is a carbon fiber composite material containing carbon nanofibers relative to hydrogenated acrylonitrile-butadiene rubber (H-NBR), and the carbon fiber composite material is , Including zinc methacrylate as a co-crosslinking agent, and 20 parts by mass to 45 parts by mass of the carbon nanofibers and 4 parts by mass of the zinc methacrylate with respect to 100 parts by mass of the hydrogenated acrylonitrile-butadiene rubber (H-NBR). The carbon nanofibers are multi-layer carbon nanofibers having an average diameter of 9 nm to 20 nm, and the number of breaks in a tensile fatigue test at 120 ° C., a maximum tensile stress of 4 N / mm, and a frequency of 1 Hz. There Ri der least 950 times, the rupture times of the carbon fiber composite material constituting the carbon fiber composite material Only that does not include the zinc methacrylate of a fixed combination is characterized in der Rukoto 5 times or more of the breaking number of different compositions.

(2) A method for producing a carbon fiber composite material according to an embodiment of the present invention is the method for producing a carbon fiber composite material according to (1) , wherein the first hydrogenated acrylonitrile-butadiene rubber (H-NBR) is used. ) relative to the carbon nanofibers, the second hydrogenated acrylonitrile - has a premix with the zinc dimethacrylate premixed butadiene rubber (H-NBR), a mixing step of mixing, in the mixing step The obtained mixture was passed through an open roll with a roll interval of 0.5 mm or less at 0 ° C. to 50 ° C., and the first hydrogenated acrylonitrile-butadiene rubber (H-NBR) and said second hydrogenated acrylonitrile - dispersing the carbon nanofibers and the zinc methacrylate butadiene rubber (H-NBR) In the mixing step, the hydrogenated acrylonitrile-butadiene rubber (H-NBR) combined with the first hydrogenated acrylonitrile-butadiene rubber (H-NBR) and the second hydrogenated acrylonitrile-butadiene rubber (H-NBR) ( H-NBR) With respect to 100 parts by mass, the blending amount of the premix is determined so that the carbon nanofibers are 20 parts by mass to 45 parts by mass and the zinc methacrylate is 4 parts by mass to 20 parts by mass. Features.

  A. First, the manufacturing method of the carbon fiber composite material concerning this Embodiment is demonstrated.

  1-3 is a figure which shows typically the manufacturing method of the carbon fiber composite material which concerns on one Embodiment.

The step of mixing carbon nanofiber and zinc methacrylate with hydrogenated acrylonitrile-butadiene rubber (H-NBR ) ( hereinafter simply referred to as “elastomer”) is, for example, as shown in FIGS. This can be done using the open roll 2. The first roll 10 and the second roll 20 in the open roll 2 are arranged at a predetermined interval d, for example, 0.5 mm to 1.5 mm, and are rotated forward at rotational speeds V1 and V2 in the directions indicated by the arrows. Or it rotates in reverse.

A-1. First, as shown in FIG. 1, the elastomer 30 wound around the first roll 10 is masticated, and the molecular chain of the elastomer is appropriately cut to generate free radicals. Free radicals of the elastomer generated by mastication are likely to be combined with carbon nanofibers.

A-2. Mixing Next, as shown in FIG. 2, the compounding agent 80 can be put into the bank 34 of the elastomer 30 wound around the first roll 10 and kneaded to obtain a mixture. Here, the compounding agent 80 includes at least carbon nanofibers and zinc methacrylate.

  When the elastomer is hydrogenated acrylonitrile-butadiene rubber (H-NBR), carbon nanofibers and methacrylic acid are applied to the hydrogenated acrylonitrile-butadiene rubber (H-NBR) wound around the first roll 10 as described above. The compounding agent 80 containing zinc can be added and mixed. In this case, for example, it is obtained by mixing zinc methacrylate (polymer alloy) with hydrogenated acrylonitrile-butadiene rubber (H-NBR) before mixing. The premix can be used as zinc methacrylate in the formulation 80. Specifically, first, a pre-mixture prepared by previously mixing zinc methacrylate with a second hydrogenated acrylonitrile-butadiene rubber (H-NBR) is prepared. Next, the first hydrogenated acrylonitrile-butadiene rubber (H-NBR) has a mixing step in which the carbon nanofibers and the premix are added as a compounding agent 80 and mixed. Carbon nanofibers and zinc methacrylate can be mixed with the first hydrogenated acrylonitrile-butadiene rubber (H-NBR) and the second hydrogenated acrylonitrile-butadiene rubber (H-NBR) by the shearing force of the mixing step.

  The step of obtaining the mixture 36 of FIGS. 1 and 2 is not limited to the open roll method, and for example, a closed kneading method or a multi-screw extrusion kneading method can be used.

A-3. Further, as shown in FIG. 3, using an open roll 2 having a roll interval of 0.5 mm or less, a process of obtaining a non-crosslinked carbon fiber composite material 50 by performing thinning at 0 ° C. to 50 ° C. is performed. . In this step, the roll interval d between the first roll 10 and the second roll 20 is set to, for example, 0.5 mm or less, more preferably 0 to 0.5 mm, and the mixture 36 obtained in FIG. Can be put into the open roll 2 and thinning can be performed once to several times. For example, the thinning can be performed about 1 to 10 times. When the surface speed of the first roll 10 is V1 and the surface speed of the second roll 20 is V2, the ratio of the surface speeds (V1 / V2) in thinness is 1.05 to 3.00. And can be 1.05-1.2. By using such a surface velocity ratio, a desired shear force can be obtained.

  The carbon fiber composite material 50 pushed out between the narrow rolls as described above is further greatly deformed as shown in FIG. 3 by the restoring force due to the elasticity of the elastomer, and at that time, the carbon nanofibers move greatly together with the elastomer. The carbon fiber composite material 50 obtained through thinning is rolled with a roll and dispensed into a sheet having a predetermined thickness, for example, 100 μm to 500 μm.

In this thinning process, in order to obtain as high a shearing force as possible, the roll temperature can be set to 0 to 50 ° C., for example, and further set to a relatively low temperature of 5 to 30 ° C. it can. The measured temperature of the elastomer can also be adjusted to 0-50 ° C, and further adjusted to 5-30 ° C. By adjusting to such a temperature range, carbon nanofibers can be dispersed utilizing the elasticity of the elastomer. Due to the shearing force thus obtained, a high shearing force acts on the elastomer, and the aggregated carbon nanofibers are separated from each other so as to be pulled out one by one to the elastomer molecules and dispersed in the elastomer. . In particular, since an elastomer has elasticity, viscosity, and chemical interaction with carbon nanofibers, the carbon nanofibers can be easily defibrated and dispersed. And the carbon fiber composite material 50 excellent in the dispersibility and dispersion stability of carbon nanofiber (it is hard to re-aggregate carbon nanofiber) can be obtained.

  More specifically, when an elastomer and carbon nanofibers are mixed with an open roll, a viscous elastomer penetrates into the carbon nanofibers, and a specific part of the elastomer molecule is chemically interacted with the carbon nanofibers. It binds to the highly active part of the fiber. When the surface of the carbon nanofibers is moderately high by, for example, oxidation treatment, it can be particularly easily bonded to elastomer molecules. Next, when a strong shearing force acts on the elastomer, the carbon nanofibers move as the elastomer molecules move, and the aggregated carbon nanofibers are separated by the restoring force of the elastomer due to the elasticity after shearing. Will be dispersed in the elastomer. In particular, the open roll method is preferable because it can measure and manage not only the roll temperature but also the actual temperature of the mixture.

A-4. In the carbon fiber composite material, the carbon nanofibers are 20 to 45 parts by mass, the zinc methacrylate is 4 to 20 parts by mass with respect to 100 parts by mass of the hydrogenated acrylonitrile-butadiene rubber (H-NBR). , and including. In this case, carbon nanofibers have an average diameter of Ru 20nm following multilayer carbon nanofiber der than 9 nm.

As described in A-2 above, when a premix is used, the mixing step includes the steps of first hydrogenated acrylonitrile-butadiene rubber (H-NBR) and second hydrogenated acrylonitrile-butadiene rubber (H-NBR). ) And 100 parts by mass of hydrogenated acrylonitrile-butadiene rubber (H-NBR) so that the carbon nanofibers are 20 to 45 parts by mass, and the zinc methacrylate is 4 to 20 parts by mass. The amount of the premix can be determined.

  B. The carbon fiber composite material will be described.

B-1. Carbon fiber composite material A carbon fiber composite material is a carbon fiber composite material containing carbon nanofibers relative to hydrogenated acrylonitrile-butadiene rubber (H-NBR ) ( hereinafter simply referred to as “elastomer”). The material is characterized in that it contains zinc methacrylate as a co-crosslinking agent.

  The carbon fiber composite material has a large number of small cell structures formed by carbon nanofibers and the interface phase surrounding the elastomer, and the interface phase is formed into a continuous three-dimensional structure like a three-dimensional network. Has been. The interfacial phase is like a so-called bound rubber formed around the carbon nanofiber including the interface between the elastomer and the carbon nanofiber.

In a carbon fiber composite material with a practical blending ratio of carbon nanofibers (the hardness is not too high), the cell structure is not formed uniformly throughout, but a cell structure aggregate in which a plurality of cell structures are assembled It is formed in a sea-island shape. And the tie structure formed with the carbon nanofiber which connects adjacent cell structure aggregates, and its interface phase is formed. In the tie structure, a plurality of carbon nanofibers that did not form a cell structure in one cell structure aggregate gathered together with carbon nanofibers that did not form a cell structure in the other cell structure aggregate. The cell structure aggregates are connected in a strip shape together with the interfacial phase formed around the carbon nanofibers.

  The cell structure aggregate and the tie structure are considered to greatly influence the physical strength and chemical strength of the carbon fiber composite material. If the amount of carbon nanofibers in the elastomer is small, the cell structure aggregates in the carbon fiber composite material will be sparse, and in particular, the tie structure has a cell structure because the number of carbon nanofibers contained in the tie structure is reduced. The reinforcement effect is small compared to. By further reinforcing the tie structure, the physical and chemical strength of the carbon fiber composite material can be improved.

  Zinc methacrylate is thought to reinforce this tie structure. Therefore, the carbon fiber composite material can improve tear fatigue life characteristics.

B-2. The carbon nanofiber carbon nanofibers having an average diameter of Ri 250nm following multilayer carbon nanofiber der than 0.5 nm, further allows the average diameter is 9nm or 100nm or less, in particular average diameter is 9nm or 20nm or less be able to. When the average diameter of the carbon nanofiber is 0.5 nm or more and 250 nm or less, it can be obtained on the market and can be processed in this embodiment. The average diameter of the carbon nanofiber is the outer diameter of the fiber. The carbon nanofibers can be straight fibers or curved fibers. The average diameter of the carbon nanofibers is obtained by, for example, measuring 200 or more diameters from an image taken with an electron microscope at a magnification of 5,000 (the magnification can be appropriately changed depending on the size of the carbon nanofibers), and calculating the arithmetic average value be able to.

Examples of carbon nanofibers include so-called carbon nanotubes. The carbon nanotube is a multi-wall carbon nanotube (MWNT: multi-wall carbon nanotube) in which one surface of graphite having a carbon hexagonal mesh surface is wound into three or more layers. A carbon material partially having a carbon nanotube structure can also be used. In addition to the name of carbon nanotube, it may be referred to as a name such as graphite fibril nanotube or vapor grown carbon fiber.

Multi-walled carbon nanotubes, an arc discharge method, laser ablation method, is produced to a desired size, such as by vapor deposition. The carbon nanofibers may be improved in adhesion and wettability with the elastomer by performing surface treatment in advance, for example, ion implantation treatment, sputter etching treatment, plasma treatment, etc. before being kneaded with the elastomer. it can.

B-3. Elastomer The elastomer is hydrogenated acrylonitrile-butadiene rubber (H-NBR ) .

Hydrogenated acrylonitrile-butadiene rubber (H-NBR) is sometimes referred to as hydrogenated nitrile rubber, hydrogenated nitrile rubber, hydrogenated acrylonitrile-butadiene rubber, or the like. In the following description, hydrogenated acrylonitrile-butadiene rubber is abbreviated as HNBR. H-NBR can be obtained by hydrogenating double bonds contained in nitrile rubber (NBR). H-NBR has relatively high temperature characteristics and excellent wear resistance. H-NBR can be used in a high-temperature environment of less than 175 ° C, and can be suitably used particularly in an environment up to 150 ° C. H-NBR may have an acrylonitrile content of 30 to 50% by mass and a central value of Mooney viscosity (ML _{1 + 4} 100 ° C.) of 50 to 100.

The carbon fiber composite material has a first spin-spin relaxation time (T2n) of 100 to 3000 μsec in a non-crosslinked body, measured at 150 ° C. by the Hahn echo method using pulsed NMR, and the observation nucleus is ¹ H. In addition, the component fraction (fnn) of the component having the second spin-spin relaxation time can be 0 to 0.2. The carbon fiber composite material has a smaller component fraction (fnn) of the component having the second spin-spin relaxation time (T2nn) than the carbon fiber composite material.

  The crosslinked carbon fiber composite material can have high strength and high rigidity while maintaining flexibility. In addition, the carbon fiber composite material has high heat resistance and can be provided with flexibility and wear resistance. In particular, the carbon fiber composite material can be excellent in tear fatigue life characteristics.

The carbon fiber composite material is composed of 4 to 20 parts by mass of zinc methacrylate with respect to 100 parts by mass of hydrogenated acrylonitrile-butadiene rubber (H-NBR), and has a maximum tensile stress of 4 N / mm and a frequency of 1 Hz. The number of breaks in the tensile fatigue test can be 950 times or more. The number of breaks in a tensile fatigue test of a carbon fiber composite material at 120 ° C., a maximum tensile stress of 4 N / mm, and a frequency of 1 Hz is determined by the addition of methacrylic acid among the ingredients constituting the carbon fiber composite material.
It is more than 5 times the number of breaks of different compositions only with no lead.

  In the method for producing a carbon fiber composite material described here, a compounding agent usually used for processing an elastomer can be added. A well-known thing can be used as a compounding agent. Examples of the compounding agent include a crosslinking agent, a vulcanizing agent, a vulcanization accelerator, a vulcanization retarder, a softening agent, a plasticizer, a curing agent, a reinforcing agent, a filler, an anti-aging agent, a colorant, and an acid acceptor. Can be mentioned. These compounding agents can be added to the elastomer at an appropriate time during the mixing process.

  As described above, the embodiments of the present invention have been described in detail. However, it will be easily understood by those skilled in the art that many modifications can be made without departing from the novel matters and effects of the present invention. Accordingly, all such modifications are intended to be included in the scope of the present invention.

  Examples of the present invention will be described below, but the present invention is not limited thereto.

(1-1) Preparation of Samples of Examples 1 to 4 and Reference Example 1 To an open roll (roll set temperature 20 ° C.), hydrogenated acrylonitrile-butadiene rubber Zetpol 2020 (“H—” in Tables 1 and 2) was used. NZE "." ZETOPL "is a registered trademark.) After mastication, a predetermined amount of multilayer carbon nanofibers having an average diameter of 15 nm shown in Tables 1 and 2 (indicated in Tables 1 and 2 as" MWCNT ") ) And Zeoforte ZSC2295 (shown as “ZSC” in Tables 1 and 2. “ZEOFORTE” is a registered trademark)) were introduced into H-NBR and kneaded, and the mixture was taken out from the roll. Each sample was mixed with peroxide as a crosslinking agent.

Next, this mixture was wound around an open roll (roll temperature 10 to 20 ° C., roll interval 0.3 mm), and thinning was repeated 5 times. At this time, the surface speed ratio of the two rolls was set to 1.1. Furthermore, the carbon fiber composite material obtained by setting the roll gap to 1.1 mm and passing through was put and dispensed. The dispensed sheet was compression molded at 170 ° C. for 12 minutes to obtain a 1 mm thick sheet-like crosslinked carbon fiber composite material sample.

In Tables 1 and 2, “H-NBR” has a bound acrylonitrile content median value of 36.2%, iodine value (median value mg / 100 mg) 28, and a median value of Mooney viscosity (ML _{1 + 4} 100 ° C.) of 78. “ZSC” was a polymer alloy in which 45% by mass of zinc methacrylate was dispersed in H-NBR, and had a Mooney viscosity of 85, a JIS hardness of 95 (shore D: 60), and a base polymer of Zetpol 2020. Since ZSC is an alloy of H-NBR and zinc methacrylate, the blending amount of H-NBR, which is a combination of “H-NBR” and “H-NBR” blended in “ZSC”, is 100 mass. The amount of zinc methacrylate added as parts is indicated in parentheses in the “Zinc methacrylate” column as a reference value.

(1-2) Sample preparation of Comparative Examples 1 to 4 A carbon fiber composite material sample of a crosslinked product of Comparative Examples 1 to 4 was obtained in the same manner as in Examples 1 to 4 and Reference Example 1 except that ZSC was not blended. It was.

(1-3) Basic characteristic test About the carbon fiber composite material sample, rubber hardness (Hs (JIS A)) was measured based on the JIS K6253 test.

  Moreover, about the carbon fiber composite material sample, tensile strength (TS (MPa)), elongation at break (Eb (%)), stress at 25% deformation (σ25 (MPa)), stress at 50% deformation (σ50 ( MPa)) 100% deformation stress (σ100 (MPa)) and fracture energy (fracture E (J)) punched into a JIS No. 6 dumbbell shape using a tensile tester manufactured by Shimadzu Corporation Then, a tensile test was performed based on JIS K6252 at 23 ± 2 ° C. and a tensile speed of 500 mm / min.

  The measurement results are shown in Tables 1 and 2.

(1-4) Tensile test at heat About a carbon fiber composite material sample, tensile strength at 120 ° C. (TS (MPa)), elongation at break (Eb (%)), stress at 25% deformation (σ25 (MPa)) ), 50% deformation stress (σ50 (MPa)) 100% deformation stress (σ100 (MPa)) and fracture energy (fracture E (J)) punched into a JIS No. 6 dumbbell shape Using a tensile tester manufactured by Shimadzu Corporation, a tensile test was performed based on JIS K6252 at a tensile speed of 500 mm / min.

  Moreover, about the carbon fiber composite material sample, as a tear fatigue life (shown as “Tear fatigue (times)” in Tables 3 and 4), the test sample was 10 mm × width 4 mm × thickness 1 mm (the long side is the orientation direction) ) Is cut into a strip-shaped test piece, and a 1 mm depth incision is made with a razor blade in the width direction from the center of the long side of the test piece. Using a TMA / SS6100 testing machine manufactured by SII, Holding near the short side with a chuck, performing a tear fatigue test with repeated tensile loads (0 N / mm to 4 N / mm) under the conditions of a frequency of 1 Hz in an air atmosphere at 120 ° C., until the specimen breaks The number of times was measured.

  The measurement results are shown in Tables 3 and 4.

The samples of Examples 1 to 4 have improved tear fatigue life characteristics at high temperatures as compared with the samples of Comparative Examples 1 to 4 blended with comparable multi-layer carbon nanofibers.

2 Open roll, 10 1st roll, 20 2nd roll, 30 elastomer, 34 bank, 36 mixture, 50 carbon fiber composite material, 80 compounding agent, V1, V2 rotational speed

Claims (2)

A carbon fiber composite material containing carbon nanofibers for hydrogenated acrylonitrile-butadiene rubber (H-NBR),
The carbon fiber composite material includes zinc methacrylate as a co-crosslinking agent,
The carbon nanofiber includes 20 parts by mass to 45 parts by mass, and the zinc methacrylate includes 4 parts by mass to 20 parts by mass with respect to 100 parts by mass of the hydrogenated acrylonitrile-butadiene rubber (H-NBR).
The carbon nanofiber is a multilayer carbon nanofiber having an average diameter of 9 nm to 20 nm,
120 ° C., Ri der breaking number 950 times in a tensile fatigue test of maximum tensile stress 4N / mm, frequency 1 Hz,
The rupture times of the carbon fiber composite material, Ru der 5 times or more of the rupture times of only different compositions that do not contain the zinc methacrylate of the compounding agent constituting the carbon fiber composite material, the carbon fiber composite material . It is a manufacturing method of the carbon fiber composite material according to claim 1,
For the first hydrogenated acrylonitrile-butadiene rubber (H-NBR), a premix of the carbon nanofibers and the second hydrogenated acrylonitrile-butadiene rubber (H-NBR) premixed with the zinc methacrylate, A mixing step of mixing
The mixture obtained in the mixing step is passed through an open roll at a roll interval of 0.5 mm or less and 0 ° C. to 50 ° C., and the first hydrogenated acrylonitrile-butadiene rubber (H -NBR) and the second hydrogenated acrylonitrile-butadiene rubber (H-NBR), the carbon nanofibers and the zinc methacrylate are dispersed,
In the mixing step, the first hydrogenated acrylonitrile-butadiene rubber (H-NBR) and the second hydrogenated acrylonitrile-butadiene rubber (H-NBR) are combined. NBR) Carbon fiber composite that determines the blending amount of the premix so that the carbon nanofibers are 20 to 45 parts by mass and the zinc methacrylate is 4 to 20 parts by mass with respect to 100 parts by mass of NBR) Material manufacturing method.