JP2018111905A - Carbon material and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a carbon material having a specific surface shape by control of a strength of an interface between a carbon material and a resin and fracture toughness of the interface.SOLUTION: There are provided a carbon material of which a surface is covered with oval swelling having both a length and a width in a range of 10-120 nm, where the oval swelling includes oval swelling having a length of longer than 70 nm, and 200-300 pieces of the oval swelling are present per 1 μmof the surface of the carbon material; and a method for producing a carbon material which includes a step of heating an organic polymer substance in a non-oxidation atmosphere containing a gaseous substance (A) made of at least one of acetylene and an acetylene derivative to higher than 400°C, further heating the organic polymer substance to 1,000°C or higher, and subjecting the organic polymer substance to a carbonization treatment.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a carbon material and a manufacturing method thereof.

Carbon materials, such as carbon fiber, have excellent mechanical strength, so they are extremely useful as industrial materials such as automotive parts, aerospace materials, sports and leisure materials, pressure vessels, etc. . In the future, it is expected to be used in a wider range of fields.
In general, carbon fiber is prepared by heating a precursor fiber bundled with precursor filaments such as polyacrylonitrile in a flameproof furnace filled with an oxidizing atmosphere and then flameproofing the resulting fiber. It is obtained by heating in a carbonization furnace filled with an inert atmosphere and performing carbonization treatment (for example, Patent Document 1).
In general, carbon fibers are used as a carbon fiber reinforced composite material having an epoxy resin or the like as a matrix, and the strength and toughness of the carbon fiber reinforced composite material are affected by the strength of the interface between the carbon fiber and the matrix and the fracture toughness of the interface. In order to control the strength of the interface between the carbon fiber and the matrix and the fracture toughness of the interface, the carbon fiber surface is generally chemically modified (surface treatment).

JP 2009-256831 A

  The strength of the interface between the carbon material and the resin and the fracture toughness of the interface are controlled not only by chemical modification of the carbon material surface but also by controlling the nanoscale shape of the carbon material surface. In this manufacturing method, the nanoscale shape of the carbon fiber surface cannot be controlled.

  The present invention has been made in view of the above circumstances, and by providing a carbon material having a specific surface shape and controlling the carbonization process of the carbon material, the carbon material having the specific surface shape is provided. The object is to provide a method of manufacturing.

The present invention has the following aspects.
[1] A carbon material whose surface is covered with an elliptical bulge whose length and width are both in the range of 10 to 120 nm, and the elliptical bulge having a length greater than 70 nm in the elliptical bulge. Contains carbon material.
[2] The carbon material according to [1], wherein there are 200 or more and 300 or less elliptical bulges per square μm of the surface of the carbon material.
[3] A method for producing the carbon material according to [1] or [2], wherein the organic material is high in a non-oxidizing atmosphere containing a gaseous substance (A) composed of at least one of acetylene and an acetylene derivative. A method for producing a carbon material, comprising a step of carbonizing by heating a molecular substance to over 400 ° C.
[4] The method for producing a carbon material according to [3], wherein the organic polymer substance includes a vinyl polymer.
[5] The method for producing a carbon material according to [4], wherein the vinyl polymer includes at least one of an acrylonitrile polymer and a derivative of an acrylonitrile polymer.
[6] The method for producing a carbon material according to [4], wherein the vinyl polymer includes at least one of an olefin polymer and a derivative of the olefin polymer.
[7] The method for producing a carbon material according to [6], wherein the olefin polymer includes at least one of polyethylene and polypropylene.
[8] The method for producing a carbon material according to [3], including a step of oxidizing the organic polymer substance precursor to obtain the organic polymer substance before the carbonizing process.
[9] The method for producing a carbon material according to [8], wherein the oxidation treatment is a step of oxidizing the organic polymer precursor to 200 to 350 ° C. in an oxidizing atmosphere.
[10] The method for producing a carbon material according to [8] or [9], wherein the organic polymer substance precursor includes a vinyl polymer.
[11] The method for producing a carbon material according to [10], wherein the vinyl polymer includes at least one of an acrylonitrile polymer and a derivative of an acrylonitrile polymer.
[12] The method for producing a carbon material according to [10], wherein the vinyl polymer includes at least one of an olefin polymer and a derivative of the olefin polymer.
[13] The method for producing a carbon material according to [12], wherein the olefin polymer includes at least one of polyethylene and polypropylene.
[14] The volume concentration of the gaseous substance (A) is 2% by volume or more with respect to the total volume of the gas forming the non-oxidizing atmosphere, and any one of [3] to [13] Carbon material manufacturing method.
[15] The method for producing a carbon material according to any one of [3] to [14], wherein the non-oxidizing atmosphere includes nitrogen gas.
[16] Any one of [3] to [15], including a step of further heating to 1000 ° C. or higher in a nitrogen atmosphere after heating the organic polymer substance to over 400 ° C. in the non-oxidizing atmosphere. The manufacturing method of the carbon material as described in one.
[17] The method for producing a carbon material according to any one of [3] to [16], wherein the organic polymer substance is fibrous.
[18] The method for producing a carbon material according to any one of [3] to [17], wherein in the carbonizing treatment, tension is applied to the organic polymer substance.

  ADVANTAGE OF THE INVENTION According to this invention, the carbon material which requires a specific surface shape, and its manufacturing method can be provided.

2 is a grayscale image showing the surface shape of the carbon fiber of Example 1. FIG. 3 is a 3D perspective view showing the surface shape of the carbon fiber of Example 1. FIG. 3 is a gray scale image showing the surface shape of the carbon fiber of Example 2. FIG. 3 is a 3D perspective view showing a surface shape of a carbon fiber of Example 2. FIG. 2 is a gray scale image showing a surface shape of a carbon fiber of Comparative Example 1. FIG. It is a 3D perspective view which shows the surface shape of the carbon fiber of the comparative example 1.

"Carbon materials"
The carbon material of the present invention is coated with an elliptical bulge (hereinafter referred to as an “elliptical nanoscale bulge”) whose surface has a length and width both in the range of 10 nm to 120 nm. The elliptical nanoscale bulge covering the surface of the carbon material includes an elliptical nanoscale bulge having a length of more than 70 nm.
The oval shape referred to in the present invention is not limited to a geometrical ellipse, but is surrounded by a closed curve that does not intersect with itself, approximated to a circle, an ellipse, an egg shape, a kidney shape, a heart shape, a comma shape, or the like. An area that is convex outward in the majority of the circumference (the length of the curve), is circumscribed at least two points in the area surrounded by the curve, and is surrounded by a straight line that does not intersect the curve This means the shape of the region where the total area of the regions (recesses) is smaller than the area of the region surrounded by the curve.
The elliptical nanoscale bulge covering the surface of the carbon material of the present invention is observed with a scanning probe microscope. Strictly speaking, the closed curve that forms the periphery of the elliptical nanoscale bulge is a solid, but the shape of the projected image of the shape image obtained by the scanning probe microscope (SPM) onto the SPM scanning plane (XY plane) It expresses with.
According to the present invention, the length of the elliptical nanoscale bulge is a region surrounded by a projected image of the closed curved line forming the periphery of the elliptical nanoscale bulge on the scanning plane of the SPM (enclosed by the closed curved line). The maximum ferret diameter of the flat area).
The width of the elliptical nanoscale bulge means the minor axis of the ellipse having the same area and length (maximum ferret diameter) as those of the “planar region surrounded by the closed curve”.
The length of the elliptical nanoscale bulge covering the surface of the carbon material of the present invention is preferably 105 nm or less.
The number of elliptical nanoscale bulges covering the surface of the carbon material of the present invention is preferably 50 or more and 400 or less, and more preferably 200 or more and 300 or less, per square μm of the surface of the carbon material. It is more preferable.
The elliptical nanoscale bulge covering the surface of the carbon material of the present invention preferably includes an elliptical nanoscale bulge having a height of 10 nm or more, and preferably 20 nm or less.
The height of the bulge of the elliptical nanoscale referred to in the present invention is the height (Z value) of the SPM image at each position of both ends of the maximum ferret diameter, which is the length of the bulge of the elliptical nanoscale. It means the difference between the average value (midpoint) and the height (Z value) of the SPM image at the apex of the elliptical nanoscale bulge.
The center line average roughness of the surface of the carbon material due to the elliptical nanoscale swelling covering the surface of the carbon material of the present invention is preferably 2 nm or more.
The carbon material of the present invention can be obtained by a production method described later.
For example, when the carbon material is carbon fiber, it is combined with a matrix resin, molded as a composite material, and used for various applications.
The matrix resin is not particularly limited. For example, a thermosetting resin such as an epoxy resin or a phenol resin, a radical polymerization resin such as an acrylic resin, a vinyl ester resin, or an unsaturated polyester resin, a thermoplastic acrylic resin, a polyamide resin, or a polyimide resin. And thermoplastic resins such as polycarbonate resin, polypropylene resin, and polyethylene resin. Moreover, the modified body of these resin can also be used. Moreover, you may use a commercial item as matrix resin.
The application of the composite material using the carbon fiber made of the carbon material of the present invention is not particularly limited, and includes a wide range of uses such as automotive materials, aerospace materials, sports / leisure materials, and industrial materials such as pressure vessels. Can be used for
Applications other than the carbon fiber of the carbon material of the present invention include transparent conductive films, electronic parts such as transistors and capacitors, filler agents such as reinforcing fillers and conductive fillers, etc. The carbon materials of the present invention are widely used. Can be used for

"Production method of carbon materials"
Hereinafter, an embodiment of a method for producing the carbon material of the present invention will be described.
The method for producing a carbon material according to the present embodiment is a method for obtaining a carbon material by heat-treating an organic polymer substance, and includes a carbonization step described below. Moreover, the method for producing the carbon material of the present invention may include an oxidation step described below before the carbonization step.
<Organic polymer materials>
Organic polymer materials include vinyl polymers made from vinyl monomers, organic cellulose such as lignin extracted from wood, cellulose or regenerated cellulose such as rayon, pitches made from petroleum, coal, etc. Examples include molecular substances. These may be used alone or in combination of two or more. Among these, an organic polymer substance of a vinyl polymer is preferable because it is excellent in productivity and mechanical characteristics on an industrial scale.
Examples of vinyl polymers include polymers containing at least one of acrylonitrile polymers and acrylonitrile polymer derivatives (hereinafter also referred to as “polymer A”), olefin polymers, and derivatives of olefin polymers. Examples thereof include a polymer containing at least one (hereinafter also referred to as “polymer B”).

  The acrylonitrile polymer may be a homopolymer of acrylonitrile or a copolymer of acrylonitrile and a vinyl monomer copolymerizable with acrylonitrile. The ratio of the acrylonitrile unit is preferably 70% by mass or more and the ratio of the vinyl monomer unit is preferably 30% by mass or less with respect to the total (100% by mass) of all the units constituting the acrylonitrile polymer. More preferably, the proportion of acrylonitrile units is 90 to 98% by mass, and the proportion of vinyl monomer units is 2 to 10% by mass.

  The vinyl monomer is not particularly limited as long as it can be copolymerized with acrylonitrile. For example, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate Acrylic esters such as hydroxypropyl acrylate; methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, uraryl methacrylate, 2-hydroxyethyl methacrylate , Methacrylates such as hydroxypropyl methacrylate, diethylaminoethyl methacrylate; acrylic acid, methacrylic acid, itaconic acid, acrylamide, N-methylolacrylamide, dia Unsaturated monomers such as tonacrylamide, styrene, vinyl toluene, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl bromide, vinylidene bromide, vinyl fluoride, vinylidene fluoride, butadiene; p-sulfophenylmethallyl ether, methallyl Examples include sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and alkali metal salts thereof. These may be used alone or in combination of two or more.

  The acrylonitrile-based polymer can be obtained by a known polymerization method such as solution polymerization, suspension polymerization or emulsion polymerization. It is desirable to remove impurities such as unreacted monomers from the acrylonitrile-based polymer obtained by polymerization.

Examples of the acrylonitrile-based polymer derivative include the above-described acrylonitrile homopolymer derivatives, acrylonitrile and vinyl monomer copolymer derivatives, and the like.
Examples of the acrylonitrile homopolymer derivative include sulfur-modified polyacrylonitrile.
Examples of the derivative of the copolymer of acrylonitrile and the vinyl monomer include hydrogenated nitrile rubber.

The polymer A may be composed of at least one of an acrylonitrile-based polymer and an acrylonitrile-based polymer derivative, or contains a component other than these (hereinafter also referred to as “other component A”). Also good.
Examples of the other component A contained in the polymer A include a silicone-based oil agent, a phosphate ester, and phosphoric acid.
The ratio of at least one of the acrylonitrile-based polymer and the acrylonitrile-based polymer derivative is preferably 70 to 100% by mass, and the ratio of the other component A is preferably 0 to 30% by mass with respect to the total mass of the polymer A.

Examples of the olefin polymer include ethylene homopolymer (polyethylene), propylene homopolymer (polypropylene), ethylene and propylene copolymer, ethylene, propylene and copolymer of monomers copolymerizable with these, or Examples thereof include a mixture of these polymers. Among these, polyethylene, polypropylene, a mixture of polyethylene and polypropylene are preferable in terms of production cost.
Examples of the monomer copolymerizable with ethylene and propylene include vinyl acetate, methyl methacrylate, and methyl acrylate. These may be used alone or in combination of two or more.

  The olefin polymer can be obtained by a known polymerization method such as gas phase polymerization, solution polymerization or suspension polymerization. It is desirable to remove impurities such as by-products from the olefin polymer obtained by polymerization.

Examples of the olefin polymer derivative include polyethylene derivatives, polypropylene derivatives, and copolymers of ethylene and vinyl acetate.
Examples of the polyethylene derivative include maleic anhydride-modified polyethylene, chlorosulfonated polyethylene, and chlorinated polyethylene.
Examples of the polypropylene derivative include maleic anhydride-modified polypropylene, chlorosulfonated polypropylene, and chlorinated polypropylene.

The polymer B may be composed of at least one of an olefin polymer and an olefin polymer derivative, or contains a component other than these (hereinafter also referred to as “other component B”). Also good.
Examples of the other component B contained in the polymer B include various elastomers and various inorganic fillers.
The ratio of at least one of the olefin polymer and the olefin polymer derivative is preferably 70 to 100% by mass, and the ratio of the other component B is preferably 0 to 30% by mass with respect to the total mass of the polymer B.

The organic polymer substance may contain components other than the above-described polymer (hereinafter also referred to as “optional component”).
Examples of the optional component include other carbon materials such as carbon black, carbon nanotube, and fullerene, and glass materials such as colloidal silica and glass fiber.
The ratio of the optional component is preferably 0 to 30% by mass with respect to the total mass of the organic polymer substance.

The organic polymer substance has a mass average molecular weight of preferably 5,000 to 800,000, and more preferably 10,000 to 400,000. If the mass average molecular weight is within the above range, the fluidity when heated is in an appropriate region, and thus the moldability tends to be easy.
In addition, in this specification, "mass average molecular weight" is the value which converted the molecular weight measured using gel permeation chromatography (GPC) into polystyrene.

In addition, as the organic polymer substance, various polymers can be used as organic polymer substance precursors, and organic polymer substances obtained by oxidizing the organic polymer substance precursor can be used.
Examples of the organic polymer precursor include a vinyl polymer using vinyl monomers as a raw material exemplified in the description of the organic polymer material, lignin extracted from wood, cellulose, or regenerated cellulose such as rayon. , Pitches made from petroleum, coal and the like. These may be used alone or in combination of two or more. Among these, an organic polymer substance precursor of a vinyl polymer is preferable because it is excellent in productivity and mechanical characteristics on an industrial scale.
Examples of the vinyl polymer include a polymer (polymer A) including at least one of the acrylonitrile polymer and the acrylonitrile polymer derivative exemplified above, an olefin polymer, and at least one of the olefin polymer derivatives. And a polymer (polymer B).

The shape of the organic polymer substance and the shape of the organic polymer substance precursor are not particularly limited, and examples thereof include a fiber form, a powder form, and a film form.
When a fibrous organic polymer material is used, a fibrous carbon material can be obtained. Hereinafter, the fibrous carbon material is also referred to as “carbon fiber”, and the fibrous organic polymer substance is also referred to as “fiber made of an organic polymer substance” or “precursor fiber”. The fibrous organic polymer precursor is also referred to as “precursor fiber”.

The precursor fiber is obtained by spinning a spinning stock solution containing an organic polymer material precursor or an organic polymer material (hereinafter collectively referred to as “organic polymer material (precursor)”). . Precursor fibers can be produced by an appropriate spinning method according to the type of organic polymer substance (precursor).
When the organic polymer substance (precursor) is a pitch made from petroleum, coal, or the like, precursor fibers can be obtained by melt spinning.
When the organic polymer substance (precursor) is regenerated cellulose such as rayon, the precursor fiber can be obtained by a method of spinning viscose rayon into dilute sulfuric acid from a spinning nozzle.
When the organic polymer substance (precursor) is soluble in a solvent, the precursor polymer can be obtained by spinning the organic polymer substance (precursor) once dissolved in the solvent. .

The solvent used in the spinning dope is not particularly limited. For example, when the organic polymer substance (precursor) contains the polymer A, organic solvents such as dimethylacetamide, dimethylsulfoxide, dimethylformamide; zinc chloride, thiocyanate Examples thereof include an aqueous solution of an inorganic compound such as sodium acid. An organic solvent is preferable in that the metal is less likely to be mixed into the produced fiber and the process is simplified.
When the organic polymer substance (precursor) contains the polymer B, examples of the solvent include normal hexane, benzene, xylene, toluene, chloroform, and the like.
When the organic polymer substance (precursor) is lignin, examples of the solvent include acetone, chloroform, and 2-butanone.

  The concentration of the organic polymer substance (precursor) in the spinning dope depends on the degree of polymerization in the spinning process, but is preferably 17% by mass or more and 19% by mass or more with respect to the total mass of the spinning dope. More preferred. As an upper limit, 30 mass% or less is preferable, and 25 mass% or less is more preferable.

The method for spinning the spinning dope is not particularly limited, and wet spinning, dry wet spinning, dry spinning, and the like can be applied.
The coagulated yarn obtained by the wet spinning method, the dry wet spinning method, the dry spinning method, etc. is subjected to a conventionally known water washing, bath drawing, oil application, drying densification, drawing, etc. A precursor fiber having fineness is used.

Examples of the oil agent include conventionally known silicone-based oil agents and oil agents composed of organic compounds not containing silicon. In addition to these, it is possible to prevent adhesion between single fibers in the oxidation step and carbonization step described later. If present, it can be suitably used as an oil.
It is preferable that the precursor fiber provided with the oil agent is dried and densified by heating. It is efficient to carry out the drying treatment by bringing it into contact with a roll heated to 50 to 200 ° C.
Moreover, it is preferable that the dried precursor fiber is continuously stretched. The stretching method is not particularly limited, and a dry heat stretching method, a hot plate stretching method, a steam stretching method, and the like can be applied.

  The number of single fibers of the precursor fiber is preferably 200 to 300,000, more preferably 1,000 to 200,000, and even more preferably 12,000 to 100,000. When the number of single fibers is within the above range, the precursor fibers can be easily handled in the oxidation step and the carbonization step, and the carbon fibers obtained can be handled easily when formed into a composite material.

When the organic polymer substance (precursor) is in a powder form, a powdery carbon material can be obtained.
When the organic polymer substance (precursor) is in a pellet form, a pellet-like carbon material can be obtained. The pellet-shaped organic polymer substance (precursor) can be obtained by, for example, manufacturing a polymer containing an organic polymer substance (precursor) and then forming the polymer into a pellet using a granulator or the like. can get.
When the organic polymer substance (precursor) is in the form of a film, a film-like carbon material can be obtained. The film-like organic polymer substance (precursor) is prepared, for example, by dissolving a powder of an organic polymer substance (precursor) in a solvent to prepare a cast solution, and applying the cast solution on a substrate. It can be obtained by a method of removing the solvent by drying, a method of extruding the cast solution with a T-die or the like and coagulating it in a coagulating liquid, and subsequently removing the solvent by washing and drying.
As the solvent, the solvents exemplified above in the description of the spinning dope can be used.

<Oxidation process>
The oxidation step is a step of obtaining an organic polymer material by oxidizing an organic polymer material precursor.
In the oxidation step, it is preferable to oxidize the organic polymer precursor by heating to 200 to 350 ° C. in an oxidizing atmosphere.
Here, the “oxidizing atmosphere” is an air atmosphere or an atmosphere containing a known oxidizing substance such as oxygen or nitrogen dioxide. Among these, the air atmosphere is preferable as the oxidizing atmosphere from the economical aspect.

“Oxidation treatment” means “flame-proofing treatment” when the organic polymer substance precursor contains an acrylonitrile polymer, and the organic polymer substance precursor is made from petroleum, coal or the like as a raw material. When the pitch is the same, it means “infusibilization”.
Hereinafter, a precursor fiber obtained by subjecting a precursor fiber made of an organic polymer substance precursor containing an acrylonitrile polymer to flame resistance is also referred to as “flame resistance fiber”. Precursor fibers obtained by infusibilizing precursor fibers composed of organic polymer substance precursors are also referred to as “infusible fibers”.

  The temperature of the oxidation treatment in the oxidizing atmosphere is preferably 200 to 350 ° C. If the temperature of the oxidation treatment is 200 ° C. or higher, it is possible to suppress the oxidation reaction rate from slowing down, so that the oxidation treatment can be performed in a short time. On the other hand, if the temperature of the oxidation treatment is 350 ° C. or less, the organic polymer substance can be prevented from being thermally decomposed.

  When the precursor fiber contains an acrylonitrile-based polymer, the time required for the oxidation treatment of the precursor fiber is preferably 10 minutes or more, more preferably 15 minutes or more, and more preferably 20 minutes or more from the viewpoint of improving the productivity and performance of the carbon fiber. Is more preferable. If the time required for the oxidation treatment is 10 minutes or more, the oxidation reaction proceeds sufficiently, and spots are hardly generated. Further, fluff and bundle breakage are less likely to occur in the carbonization step performed after the oxidation step, and the productivity can be favorably maintained. The upper limit of the time required for the oxidation treatment is preferably 80 minutes, and more preferably 60 minutes. If the time required for the oxidation treatment is 80 minutes or less, carbon fibers having sufficient strength can be easily obtained.

The method for the oxidation treatment is not particularly limited, and a method using a conventionally known hot air circulating furnace (for example, a flameproofing furnace) or a method of contacting the heated solid surface can be employed.
In the method using a hot air circulating furnace, the precursor fiber that has entered the hot air circulating furnace is usually taken out of the hot air circulating furnace and then folded by a folding roll disposed outside the hot air circulating furnace. The method of passing repeatedly is taken.
In the method of contacting the heated solid surface, a method of intermittently bringing the precursor fiber into contact with the heated solid surface is employed.

When the precursor fiber contains an acrylonitrile-based polymer, in the oxidation step, it is preferable to heat until the density (ρ) of the fiber after the oxidation treatment becomes 1.25 to 1.45 g / cm ³ , more preferably 1 .28 to 1.40 g / cm ³ . If the density (ρ) of the fiber after the oxidation treatment is within the above range, the remaining amount of carbon fiber in the carbonization step described later is increased, which is advantageous in terms of economy.
The fiber density (ρ) is a value measured by the density gradient tube method.

<Carbonization process>
The carbonization step is a step of carbonizing by heating the organic polymer substance to over 400 ° C. in a non-oxidizing atmosphere containing a gaseous substance (A) made of at least one of acetylene and an acetylene derivative.
In addition, from the viewpoint of further improving the heat resistance and mechanical properties of the obtained carbon material, the carbonization step is performed in a nitrogen atmosphere after the organic polymer substance is heated to over 400 ° C. in the non-oxidizing atmosphere. A step of further heating to 1000 ° C. or higher may be included.
In addition, when performing the oxidation process mentioned above before the carbonization process, the organic polymer substance precursor (for example, a flame-resistant fiber, an infusible fiber, etc.) after an oxidation process is carbonized.
Hereinafter, the step of heating the organic polymer substance to over 400 ° C. in a non-oxidizing atmosphere is also referred to as “first carbonization step”, and after this first carbonization step, 1000 ° C. or higher in a nitrogen atmosphere. The step of heating to 2 is also referred to as “second carbonization step”.

(First carbonization process)
The first carbonization step is performed in a non-oxidizing atmosphere containing the gaseous substance (A).
The gaseous substance (A) consists of at least one of acetylene and an acetylene derivative.
The acetylene derivative is not particularly limited as long as it is a substance that contains a triple bond between carbon atoms in the molecule and is a gas at the temperature at which the carbonization step is performed, but ethyl acetylene, tert-butyl acetylene, etc. Can be mentioned.
The gaseous substance (A) may be a single gas of acetylene, a single gas of acetylene derivatives, or a mixed gas of acetylene and acetylene derivatives. In the case of a mixed gas of acetylene and an acetylene derivative, the proportion of acetylene is preferably 50 to 99 mol%, and the proportion of acetylene derivative is 1 to 50 with respect to the total (100 mol%) of all molecules constituting the mixed gas. Mole% is preferred.
From the economical viewpoint, the gaseous substance (A) is preferably acetylene gas.

Here, the “non-oxidizing atmosphere” is an atmosphere that does not substantially contain a known oxidizing substance such as oxygen and nitrogen dioxide. “Substantially” means that the volume concentration of the oxidizing substance is 1.0% by volume or less with respect to the total volume of the gas forming the non-oxidizing atmosphere.
Examples of components other than the gaseous substance (A) contained in the non-oxidizing atmosphere include non-oxidizing gases such as nitrogen, argon, and helium (hereinafter also referred to as “non-oxidizing gases”). Among these, nitrogen is preferable from the viewpoint of economy. The proportion of nitrogen in the component (100 mol%) other than the gaseous substance (A) contained in the non-oxidizing atmosphere is preferably 99 mol% or more.

The volume concentration of the gaseous substance (A) is preferably 1% by volume or more, more preferably 2% by volume or more, and further preferably 5% by volume or more with respect to the total volume of the gas forming the non-oxidizing atmosphere. If the organic polymer substance is carbonized in a non-oxidizing atmosphere in which the volume concentration of the gaseous substance (A) is 1% by volume or more, the carbonization yield is further improved. In particular, when the volume concentration of the gaseous substance (A) is 2% by volume or more, the carbonization yield is further improved. From the viewpoint of production cost, the volume concentration of the gaseous substance (A) is preferably 30% by volume or less, more preferably 20% by volume or less, and more preferably 15% by volume with respect to the total volume of the gas forming the non-oxidizing atmosphere. More preferred are:
Considering the balance between the improvement in carbonization yield and the production cost, the volume concentration of the gaseous substance (A) is preferably 2 to 30% by volume with respect to the total volume of the gas forming the non-oxidizing atmosphere. -20 volume% is more preferable, and 2-15 volume% is further more preferable.

The volume concentration of the non-oxidizing gas is preferably 99% by volume or less, more preferably 98% by volume or less, and still more preferably 95% by volume or less with respect to the total volume of the gas forming the non-oxidizing atmosphere. The volume concentration of the non-oxidizing gas is preferably 70% by volume or more, more preferably 80% by volume or more, and still more preferably 85% by volume or more with respect to the total volume of the gas forming the non-oxidizing atmosphere.
Considering the balance between improvement in carbonization yield and production cost, the volume concentration of the non-oxidizing gas is preferably 70 to 98% by volume, and preferably 80 to 98% with respect to the total volume of the gas forming the non-oxidizing atmosphere. Volume% is more preferable, and 85 to 98 volume% is more preferable.

The temperature of the carbonization treatment in the first carbonization step is over 400 ° C, and preferably 450 ° C or higher. If the temperature of carbonization processing exceeds 400 degreeC, a carbonization yield will improve. As for the temperature of the carbonization process in a 1st carbonization process, 1000 degrees C or less is preferable. If the carbonization temperature is 1000 ° C. or lower, the carbonization yield can be maintained satisfactorily.
In particular, when the second carbonization step is not performed after the first carbonization step, the temperature of the carbonization treatment in the first carbonization step is 1000 ° C. or less in that the carbonization yield can be maintained satisfactorily. Preferably, 800 degrees C or less is more preferable.
When the second carbonization step is performed after the first carbonization step, and the temperature of the carbonization treatment in the second carbonization step is 1000 ° C. or higher and lower than 1200 ° C., the carbonization yield is good The temperature of the carbonization treatment in the first carbonization step is preferably 850 ° C. or less, and more preferably 800 ° C. or less.
Moreover, when the temperature of the carbonization process in a 2nd carbonization process is 1200 degreeC or more and less than 1400 degreeC, the temperature of the carbonization process in a 1st carbonization process is 850 at the point which can maintain a carbonization yield favorably. ° C or lower is preferable, and 800 ° C or lower is more preferable.
Moreover, when the temperature of the carbonization process in a 2nd carbonization process is 1400 degreeC or more and 2000 degrees C or less, the temperature of the carbonization process in a 1st carbonization process is 850 at the point which can maintain a carbonization yield favorably. ° C or lower is preferable, and 580 ° C or lower is more preferable.

The carbonization treatment time in the first carbonization step is preferably 0.5 minutes or more, more preferably 1 minute or more, further preferably 5 minutes or more, particularly preferably 10 minutes or more, and most preferably 15 minutes or more. If the time of the carbonization process in a 1st carbonization process is 0.5 minute or more, since the carbonization yield becomes high, it is preferable. The carbonization yield tends to be further improved as the time of the carbonization treatment in the first carbonization process becomes longer. However, even if it is too long, the improvement of the carbonization yield reaches its peak. From the viewpoint of productivity, the time for the carbonization treatment in the first carbonization step is preferably 300 minutes or less, more preferably 240 minutes or less, and even more preferably 180 minutes or less.
Considering the balance between improvement in carbonization yield and productivity, the time for carbonization treatment in the first carbonization step is preferably 0.5 to 300 minutes, more preferably 1 to 240 minutes, and more preferably 5 to 180 minutes. Is more preferable, 10 to 180 minutes is particularly preferable, and 15 to 180 minutes is most preferable.

As a carbonization treatment method in the first carbonization step, for example, in a state in which a mixed gas of a gaseous substance (A) and a non-oxidizing gas is introduced into a carbonization furnace set to be higher than 400 ° C. By passing a molecular material (an organic polymer material obtained by oxidizing an organic polymer material precursor when the oxidation process described above is performed before the carbonization process), an organic polymer material is passed. Is heated and carbonized.
As long as the temperature of the carbonization treatment exceeds 400 ° C., the temperature may be constant or the temperature may be raised. When raising the temperature, for example, multiple heating zones are installed in the carbonization furnace, and the temperature of each heating zone is set so that the temperature increases from the upstream heating zone toward the downstream heating zone. This can be realized by sequentially passing from the heating zone on the side toward the heating zone on the downstream side.
In the first carbonization step, it is preferable that the organic polymer material (for example, flame-resistant fiber, infusible fiber, etc.) after the oxidation treatment is carbonized under tension. By controlling the strength (or elongation rate) of the tension, the size, height, and number per unit surface area of the surface of the obtained carbon material can be appropriately controlled.

(Second carbonization process)
The temperature of the carbonization treatment in the second carbonization step is 1000 ° C. or higher, and preferably 1200 ° C. or higher. If the temperature of the carbonization treatment is 1000 ° C. or higher, the effect of improving heat resistance and mechanical properties can be sufficiently obtained.
In consideration of the balance between the carbonization yield and the heat resistance and mechanical properties, the temperature of the carbonization treatment in the second carbonization step is preferably 2000 ° C. or less, and more preferably 1600 ° C. or less.

  The time for the carbonization treatment in the second carbonization step is preferably 0.5 to 30 minutes, and more preferably 1 to 20 minutes. If the time of the carbonization treatment in the second carbonization step is 0.5 minutes or more, it is preferable for improving the mechanical properties of the obtained carbon material, and if it is 30 minutes or less, the resulting carbon material machine. It is preferable because the characteristics are improved and the productivity is increased.

As a carbonization treatment method in the second carbonization step, for example, an organic polymer material after the first carbonization step is performed in a carbonization furnace filled with nitrogen gas and set at 1000 ° C. or higher. By passing through, the organic polymer substance is heated and carbonized.
The temperature of the carbonization treatment may be constant as long as it is 1000 ° C. or higher, and the temperature may be raised. When raising the temperature, for example, multiple heating zones are installed in the carbonization furnace, and the temperature of each heating zone is set so that the temperature increases from the upstream heating zone toward the downstream heating zone. This can be realized by sequentially passing from the heating zone on the side toward the heating zone on the downstream side.

<Other processes>
The carbon material obtained by the carbonization step can be used as it is as the carbon material, but if necessary, the carbon material graphitized by a known method may be used as the carbon material. For example, a graphitized carbon material can be obtained by heating the carbon material in an inert atmosphere at a maximum temperature exceeding 2000 ° C. and 3000 ° C. or less.

In addition, when the carbon material is carbon fiber, sizing treatment can also be performed in order to impart convergence to the carbon fiber.
The sizing agent used for the sizing treatment is not particularly limited as long as desired characteristics can be obtained, and examples thereof include a sizing agent mainly composed of an epoxy resin, a polyether resin, an epoxy-modified polyurethane resin, and a polyester resin. A known method can be used as the sizing method.

<Effect>
According to the method for producing a carbon material of the present invention described above, the organic polymer substance is heated to over 400 ° C. in a non-oxidizing atmosphere containing a gaseous substance (A) composed of at least one of acetylene and an acetylene derivative. A carbon material having a specific nanoscale surface shape can be obtained by heating and carbonizing.

  In the above-described oxidation step, precursor fibers composed of organic polymer material precursors (that is, fibrous organic polymer material precursors) are oxidized, but in a shape other than fibrous or An oxidation treatment may be performed before the organic polymer substance precursor that has been melted or dissolved is carbonized.

One aspect of the present invention is a step of carbonizing an organic polymer substance by heating to over 400 ° C. in a non-oxidizing atmosphere containing a gaseous substance (A) composed of at least one of acetylene and an acetylene derivative. A method for producing a carbon material including a (first carbonization step), wherein the volume concentration of the gaseous substance (A) is 2 to 30% by volume with respect to the total volume of the gas forming the non-oxidizing atmosphere. is there.
In another aspect of the present invention, the volume concentration of the gaseous substance (A) is 2 to 30% by volume with respect to the total volume of the gas forming the non-oxidizing atmosphere, and in the first carbonization step, It is a manufacturing method of the carbon material whose time of carbonization processing is 0.5 to 300 minutes.
In another aspect of the present invention, the volume concentration of the gaseous substance (A) is 2 to 30% by volume with respect to the total volume of the gas forming the non-oxidizing atmosphere, and in the first carbonization step, This is a method for producing a carbon material in which the carbonization time is 10 to 180 minutes.
In another aspect of the present invention, the volume concentration of the gaseous substance (A) is 2 to 30% by volume with respect to the total volume of the gas forming the non-oxidizing atmosphere, and in the first carbonization step, This is a method for producing a carbon material in which the carbonization time is 15 to 180 minutes.
In another aspect of the present invention, the volume concentration of the gaseous substance (A) is 2 to 20% by volume with respect to the total volume of the gas forming the non-oxidizing atmosphere, and in the first carbonization step, It is a manufacturing method of the carbon material whose time of carbonization processing is 0.5 to 300 minutes.
In another aspect of the present invention, the volume concentration of the gaseous substance (A) is 2 to 20% by volume with respect to the total volume of the gas forming the non-oxidizing atmosphere, and in the first carbonization step, This is a method for producing a carbon material in which the carbonization time is 10 to 180 minutes.
In another aspect of the present invention, the volume concentration of the gaseous substance (A) is 2 to 20% by volume with respect to the total volume of the gas forming the non-oxidizing atmosphere, and in the first carbonization step, This is a method for producing a carbon material in which the carbonization time is 15 to 180 minutes.
In another aspect of the present invention, the volume concentration of the gaseous substance (A) is 2 to 15% by volume with respect to the total volume of the gas forming the non-oxidizing atmosphere, and in the first carbonization step, It is a manufacturing method of the carbon material whose time of carbonization processing is 0.5 to 300 minutes.
In another aspect of the present invention, the volume concentration of the gaseous substance (A) is 2 to 15% by volume with respect to the total volume of the gas forming the non-oxidizing atmosphere, and in the first carbonization step, This is a method for producing a carbon material in which the carbonization time is 10 to 180 minutes.
In another aspect of the present invention, the volume concentration of the gaseous substance (A) is 2 to 15% by volume with respect to the total volume of the gas forming the non-oxidizing atmosphere, and in the first carbonization step, This is a method for producing a carbon material in which the carbonization time is 15 to 180 minutes.

One aspect of the present invention is that carbon is obtained by heating an organic polymer substance to more than 400 ° C. and 1000 ° C. or less in a non-oxidizing atmosphere containing a gaseous substance (A) composed of at least one of acetylene and an acetylene derivative. It is a manufacturing method of a carbon material including the process (first carbonization process) of carrying out a chemical conversion process, and does not include the process of heating an organic type polymeric substance to 1000 degreeC or more in nitrogen atmosphere after the said process.
Another aspect of the present invention is that carbon is obtained by heating an organic polymer substance to more than 400 ° C. and 1000 ° C. or less in a non-oxidizing atmosphere containing a gaseous substance (A) composed of at least one of acetylene and an acetylene derivative. Gas for forming the non-oxidizing atmosphere without the step of heating the organic polymer substance to 1000 ° C. or higher in a nitrogen atmosphere after the step. The volume concentration of the gaseous substance (A) is 2 to 30% by volume with respect to the total volume of the carbon material, and the carbonization treatment time in the first carbonization step is 0.5 to 300 minutes. It is a manufacturing method.
Another aspect of the present invention is that carbon is obtained by heating an organic polymer substance to more than 400 ° C. and 1000 ° C. or less in a non-oxidizing atmosphere containing a gaseous substance (A) composed of at least one of acetylene and an acetylene derivative. Gas for forming the non-oxidizing atmosphere without the step of heating the organic polymer substance to 1000 ° C. or higher in a nitrogen atmosphere after the step. The volume concentration of the gaseous substance (A) is 2 to 20% by volume with respect to the total volume of the carbon material, and the carbonization process in the first carbonization step takes 10 to 180 minutes. It is.
Another aspect of the present invention is that carbon is obtained by heating an organic polymer substance to more than 400 ° C. and 1000 ° C. or less in a non-oxidizing atmosphere containing a gaseous substance (A) composed of at least one of acetylene and an acetylene derivative. Gas for forming the non-oxidizing atmosphere without the step of heating the organic polymer substance to 1000 ° C. or higher in a nitrogen atmosphere after the step. The volume concentration of the gaseous substance (A) is 2 to 15% by volume with respect to the total volume of the carbon material, and the carbonization treatment time in the first carbonization step is 15 to 180 minutes. It is.

One aspect of the present invention is that carbon is obtained by heating an organic polymer substance to more than 400 ° C. and not more than 850 ° C. in a non-oxidizing atmosphere containing a gaseous substance (A) composed of at least one of acetylene and an acetylene derivative. It is a manufacturing method of a carbon material including the process (1st carbonization process) of performing a chemical conversion process, and the process of heating an organic type polymeric substance to 1000-2000 degreeC in nitrogen atmosphere after the said process.
Another aspect of the present invention is that carbon is obtained by heating an organic polymer substance to more than 400 ° C. and 850 ° C. or less in a non-oxidizing atmosphere containing a gaseous substance (A) composed of at least one of acetylene and an acetylene derivative. Gas for forming the non-oxidizing atmosphere, including a step of performing a chemical treatment (first carbonization step), and a step of heating the organic polymer substance to 1000 to 2000 ° C. in a nitrogen atmosphere after the step. The volume concentration of the gaseous substance (A) is 2 to 30% by volume with respect to the total volume of the carbon material, and the carbonization treatment time in the first carbonization step is 0.5 to 300 minutes. It is a manufacturing method.
Another aspect of the present invention is that carbon is obtained by heating an organic polymer substance to more than 400 ° C. and 850 ° C. or less in a non-oxidizing atmosphere containing a gaseous substance (A) composed of at least one of acetylene and an acetylene derivative. Gas for forming the non-oxidizing atmosphere, including a step of performing a chemical treatment (first carbonization step), and a step of heating the organic polymer substance to 1000 to 2000 ° C. in a nitrogen atmosphere after the step. The volume concentration of the gaseous substance (A) is 2 to 20% by volume with respect to the total volume of the carbon material, and the carbonization process in the first carbonization step takes 10 to 180 minutes. It is.
Another aspect of the present invention is that carbon is obtained by heating an organic polymer substance to more than 400 ° C. and 850 ° C. or less in a non-oxidizing atmosphere containing a gaseous substance (A) composed of at least one of acetylene and an acetylene derivative. Gas for forming the non-oxidizing atmosphere, including a step of performing a chemical treatment (first carbonization step), and a step of heating the organic polymer substance to 1000 to 2000 ° C. in a nitrogen atmosphere after the step. The volume concentration of the gaseous substance (A) is 2 to 15% by volume with respect to the total volume of the carbon material, and the carbonization treatment time in the first carbonization step is 15 to 180 minutes. It is.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

<SPM observation of surface shape of carbon material>
The surface of the obtained carbon material (carbon fiber) was evaluated using an atomic force microscope (product name: Dimension V) manufactured by Bruker as a scanning probe microscope. As the cantilever, RTEPS-300 manufactured by Bruker was used, and scanning was performed in a tapping mode under the conditions of a scanning range of 600 nm × 600 nm, an aspect ratio of 1.0, and a scanning speed of 1.0 Hz to obtain a shape image of 512 × 512 pixels. Arbitrarily 10 single fibers were selected, and one shape image was obtained for each.
When the obtained shape image is displayed as a grayscale image, the darker the shade of gray, the higher the surface shape at that position (closer to the probe) (FIGS. 1, 3, and 5).
When the carbon material is carbon fiber, the obtained shape image has a wrinkle structure having a length of 600 nm or more extending in the fiber axis direction of the carbon fiber and the carbon of the present invention, which is generated in the process of shaping (spinning) the precursor fiber. Since an elliptical nanoscale bulge characteristic of the material is observed, surface irregularities along the fiber axis direction of the carbon fiber in the vicinity of the ridges of the ridges of the ridge structure are extracted from the shape image, and the centerline average roughness The thickness (Ra) was calculated.
The number of elliptical nanoscale bulges observed on one screen (600 nm × 600 nm) of the surface shape image is visually counted from the grayscale image, and the number of elliptical nanoscale bulges per square μm is obtained. Converted. Also, from the ellipsoidal nanoscale bulges, select five large bottoms from one screen, find the maximum ferret diameter and the area of the bottom of the bulge, and determine the maximum ferret diameter as an elliptical nanoscale bulge. The length of the ellipsoidal nanoscale bulge was defined as the width of the ellipsoidal nanoscale bulge. Five ellipsoidal nanoscale bulges selected from each screen were overlaid on each grayscale image.
The height of the ellipsoidal nanoscale bulge is the average of the heights at both ends of the maximum ferret diameter at the bottom of the bulge (the height of the midpoint of the line segment connecting both ends) and the height of the ellipsoidal nanoscale bulge. It was calculated as the difference in apex height.

"Example 1"
<Manufacture of precursor fibers>
Acrylonitrile-based polymer (acrylonitrile unit content: 96% by mass, acrylamide unit content: 3% by mass, methacrylic acid unit content: 1% by mass) was added to dimethylacetamide (concentration of 22% by mass). In order to prepare a spinning dope. The spinning solution was passed through a spinneret having a pore diameter of 75 μm and a pore number of 3000, and coagulated in a coagulation bath filled with a DMAC aqueous solution having a temperature of 35 ° C. and a concentration of 67% by mass to obtain a coagulated yarn. The obtained coagulated yarn was stretched while removing the solvent in warm water, and then an amino-modified silicone oil was applied. Further, after drawing in pressurized steam, they were combined to obtain a precursor fiber made of an organic polymer substance precursor having 3000 single fibers and a single fiber fineness of 1.2 dtex.

<Manufacture of carbon fiber>
The obtained precursor fiber was subjected to a flame resistance treatment by heating in air at a temperature of 260 ° C. under tension for a heating time of 20 minutes, and a precursor fiber having a density (ρ) of 1.34 g / cm ³ (flame resistance). Fiber) was obtained (oxidation step).
Next, a thermogravimetric measurement device (manufactured by Hitachi High-Technologies Corporation, “STA7300”) provided with a mixed gas introduction path was used, and acetylene gas (Taiyo Nippon Oil & Gas) was used as a gaseous substance (A) in this device. Welding Co., Ltd., “Ultra High Purity Acetylene HA-5N”) and a mixed gas comprising nitrogen gas as a non-oxidizing gas (volume concentration of acetylene gas: 20% by volume, volume concentration of nitrogen gas: 80% by volume) ), And the flame resistant fiber was heated under constant tension. Specifically, the temperature is increased from 30 ° C. to 150 ° C. at a rate of temperature increase of 100 ° C./min with the mixed gas introduced, and held at 150 ° C. for 30 minutes, and then from 150 ° C. to 500 ° C. at 50 ° C./min. The temperature rose. After reaching 500 ° C., it was held at 500 ° C. for 20 minutes (first carbonization step).
Subsequently, the atmosphere in the apparatus was replaced with nitrogen gas from the mixed gas, and further maintained at 500 ° C. for 20 minutes, and then heated to a maximum temperature of 1350 ° C. at a rate of temperature increase of 10 ° C./min to obtain carbon fibers.
A gray scale image of the surface shape of the carbon fiber obtained in FIG. 1 is shown, and a 3D perspective view is shown in FIG. Table 1 shows the analysis results of the surface shape of the carbon fibers.

"Example 2"
Flame-resistant fibers were obtained in the same manner as in Example 1.
Subsequently, the flame-resistant fiber was heated in a tension-free state while introducing the mixed gas (volume concentration of acetylene gas: 20 vol%, volume concentration of nitrogen gas: 80 vol%) into the same apparatus as in Example 1. . The specific heating conditions were the same as in the first carbonization step of Example 1. Subsequently, heating in nitrogen was performed in the same manner as in Example 1 to obtain carbon fibers. FIG. 3 shows a gray scale image of the surface shape of the carbon fiber obtained, and FIG. 4 shows a 3D perspective view. Table 1 shows the analysis results of the surface shape of the carbon fibers.

"Comparative Example 1"
Carbon fibers were produced in the same manner as in Example 1 except that nitrogen gas was used instead of the mixed gas in the first carbonization step. FIG. 6 shows a 3D perspective view of the gray scale image of the surface shape of the carbon fiber obtained in FIG. Table 1 shows the analysis results of the surface shape of the carbon fibers.

  The carbon material of the present invention has a characteristic nanoscale elliptical bulge on its surface, and it can be expected to improve the strength of the interface with other materials and the fracture toughness of the interface. In particular, the carbon fiber having such characteristics is useful as a carbon fiber reinforced resin composite material.

Claims (18)

  A carbon material whose surface is covered with an elliptical bulge whose length and width are both in the range of 10 to 120 nm, and the elliptical bulge includes an elliptical bulge having a length greater than 70 nm. Carbon material.   The carbon material according to claim 1, wherein there are 200 or more and 300 or less elliptical bulges per square μm of the surface of the carbon material.   The method for producing a carbon material according to claim 1 or 2, wherein the organic polymer substance is heated to 400 ° C in a non-oxidizing atmosphere containing a gaseous substance (A) made of at least one of acetylene and an acetylene derivative. The manufacturing method of a carbon material including the process of heating and superposing | polymerizing super.   The method for producing a carbon material according to claim 3, wherein the organic polymer substance includes a vinyl polymer.   The method for producing a carbon material according to claim 4, wherein the vinyl polymer includes at least one of an acrylonitrile polymer and a derivative of an acrylonitrile polymer.   The method for producing a carbon material according to claim 4, wherein the vinyl polymer contains at least one of an olefin polymer and a derivative of the olefin polymer.   The method for producing a carbon material according to claim 6, wherein the olefin polymer contains at least one of polyethylene and polypropylene.   The method for producing a carbon material according to claim 3, comprising a step of oxidizing the organic polymer material precursor to obtain the organic polymer material before the carbonizing step.   The method for producing a carbon material according to claim 8, wherein the oxidation treatment is a step of oxidizing the organic polymer substance precursor by heating to 200 to 350 ° C. in an oxidizing atmosphere.   The method for producing a carbon material according to claim 8 or 9, wherein the organic polymer substance precursor includes a vinyl polymer.   The method for producing a carbon material according to claim 10, wherein the vinyl polymer contains at least one of an acrylonitrile polymer and a derivative of an acrylonitrile polymer.   The method for producing a carbon material according to claim 10, wherein the vinyl polymer includes at least one of an olefin polymer and a derivative of the olefin polymer.   The method for producing a carbon material according to claim 12, wherein the olefin polymer contains at least one of polyethylene and polypropylene.   The carbon material production according to any one of claims 3 to 13, wherein the volume concentration of the gaseous substance (A) is 2% by volume or more with respect to the total volume of the gas forming the non-oxidizing atmosphere. Method.   The said non-oxidizing atmosphere is a manufacturing method of the carbon material as described in any one of Claims 3-14 containing nitrogen gas.   The carbon according to any one of claims 3 to 15, further comprising a step of further heating to 1000 ° C or higher in a nitrogen atmosphere after heating the organic polymer substance to more than 400 ° C in the non-oxidizing atmosphere. Material manufacturing method.   The method for producing a carbon material according to any one of claims 3 to 16, wherein the organic polymer substance is fibrous.   The method for producing a carbon material according to any one of claims 1 to 17, wherein in the carbonizing step, tension is applied to the organic polymer substance.