Method for manufacturing carbon-coated components, coating composition, and method for manufacturing carbonaceous materials

Abstract

To provide a method of easily and efficiently producing a carbon coating member with a high flexibility of its shape.SOLUTION: A method of producing a carbon coating member comprises a step of heating a coating composition including a carboxylic acid anhydride and a metal catalyst while the coating composition is in contact with a portion or the whole of a member to be coated.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a method for manufacturing a carbon-coated member, a coating composition, and a method for manufacturing a carbonaceous material.

Background Art

[0002] Carbonaceous materials such as diamond, graphite, and amorphous carbon (glassy carbon) are used as corrosion-resistant coatings because of their high stability against acids and alkalis.

[0003] As a method for coating with a carbonaceous material (carbon coating), for example, a dry method such as CVD (chemical-vapor-deposition) disclosed in Patent Document 1 below, and an electroplating method using a carbon molten salt disclosed in Patent Document 2 below are known.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] The above methods have problems in that the apparatus is complex, a high temperature of 300°C or higher is required to sufficiently apply a carbon coating to the coated member, and it is difficult to coat particles, etc., in terms of manufacturing cost, energy consumption, and the shape of the coated member being restricted.

[0006] Therefore, the present disclosure aims to provide a method and coating composition that allow for a high degree of freedom in the shape of the component and enable the simple and efficient acquisition of a carbon-coated component, as well as a method for producing a carbonaceous material that enables the simple and efficient production of a carbonaceous material. [Means for solving the problem]

[0007] To solve the above problems, one aspect of this disclosure provides a first method for manufacturing a carbon coated member, comprising the step of heating a coating composition containing a carboxylic acid anhydride and a metal catalyst while the coating composition is in contact with a part or all of the surface of a member to be coated.

[0008] According to the first manufacturing method described above, carbon coating can be applied to various shapes of coated members even under low-temperature conditions by a simple process of heating using the coating composition.

[0009] Furthermore, while the methods described in Patent Documents 1 and 2 above make it difficult to coat insulators, the first manufacturing method described above allows for the production of carbon-coated members without being limited by the material of the member to be coated.

[0010] In the first manufacturing method described above, the coating composition may further contain a dehydration catalyst from the viewpoint of improving yield and lowering the reaction temperature.

[0011] The heating temperature in the above process may be between 100 and 300°C.

[0012] The material to be coated may be in particulate form. In this case, carbon-coated particles can be manufactured.

[0013] The material to be coated may be an insulator.

[0014] Another aspect of the present disclosure provides a second method for manufacturing a carbon coated member, comprising the step of heating a coating composition containing a carboxylic acid anhydride while the coating composition is in contact with part or all of the surface of the member to be coated, wherein the surface of the member to be coated contains a metal.

[0015] According to the second manufacturing method described above, carbon coating can be applied to various shapes of coated members even under low-temperature conditions by a simple process of heating using the coating composition.

[0016] In the second manufacturing method described above, the coating composition may further contain a dehydration catalyst from the viewpoint of improving yield and lowering the reaction temperature.

[0017] The heating temperature in the above process may be between 100 and 300°C.

[0018] The material to be coated may be in particulate form. In this case, carbon-coated particles can be manufactured.

[0019] Another aspect of this disclosure provides a first coating composition used for carbon coating the surface of a member to be coated, comprising a carboxylic acid anhydride and a metal catalyst.

[0020] According to the first coating composition described above, carbon coating can be applied to members of various shapes even under low-temperature conditions by a simple process of heating the member to be coated in contact with it.

[0021] Furthermore, the first coating composition described above allows for coating of insulators and enables carbon coating of various materials to be coated.

[0022] The first coating composition described above may further contain a dehydration catalyst.

[0023] Another aspect of the present disclosure provides a second coating composition that is used for carbon coating a metal surface of a coated member having a metal surface and contains a carboxylic anhydride.

[0024] According to the second coating composition, carbon coating can be performed on coated members of various shapes even under low-temperature conditions by a simple process of contacting and heating with the coated member.

[0025] The second coating composition may further contain a dehydration catalyst.

[0026] Another aspect of the present disclosure provides a method for producing a carbonaceous material, which includes a step of heating a carboxylic anhydride in the presence of a metal catalyst in a system.

[0027] According to the above production method, a carbonaceous material can be produced even under low-temperature conditions, and the carbonaceous material can be easily recovered from the system in a sufficient yield.

[0028] In the above step, a dehydration catalyst can be further present in the system, and the carboxylic anhydride can be heated in the presence of a metal catalyst and a dehydration catalyst.

Advantages of the Invention

[0029] According to the present disclosure, it is possible to provide a method and a coating composition that have a high degree of freedom in the shape of the member and enable a carbon-coated member to be obtained simply and efficiently, and a method for producing a carbonaceous material that can produce a carbonaceous material simply and efficiently.

Modes for Carrying Out the Invention

[0030] In this specification, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described stepwise in this specification, the upper or lower limit of one step may be replaced with the upper or lower limit of another step. Also, in numerical ranges described in this specification, the upper or lower limit of that range may be replaced with the values ​​shown in the examples. Furthermore, the upper and lower limits described individually can be combined in any way. Also, "A or B" means that either A or B is included, or both are included. Furthermore, unless otherwise specified, the materials exemplified below may be used individually or in combination of two or more. The content of each component in the composition means the total amount of multiple substances present in the composition if there are multiple substances corresponding to each component in the composition, unless otherwise specified.

[0031] <First method for manufacturing carbon-coated components> The first method for manufacturing the carbon coated member of this embodiment comprises step A-1, in which the first coating composition containing a carboxylic acid anhydride and a metal catalyst is heated while a part or all of the surface of the first member to be coated is in contact with the first coating composition.

[0032] (First coating composition) The first coating composition comprises a carboxylic acid anhydride and a metal catalyst.

[0033] Examples of carboxylic acid anhydrides include carboxylic acid anhydrides derived from aliphatic carboxylic acids or aromatic carboxylic acids. Carboxylic acid anhydrides can be used individually or in combination of two or more.

[0034] The carboxylic acid constituting the carboxylic acid anhydride may be a monocarboxylic acid or a polycarboxylic acid.

[0035] Examples of carboxylic acids include aliphatic carboxylic acids having 2 to 12 carbon atoms, and aromatic carboxylic acids. Specific examples of carboxylic acids include aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, maleic acid, and succinic acid; and aromatic carboxylic acids such as benzoic acid, phthalic acid, and naphthalic acid.

[0036] From the viewpoint of cost and availability, carboxylic acid anhydrides derived from aliphatic carboxylic acids may be used, and from the viewpoint of reactivity, acetic anhydride may be used. Furthermore, since acetic anhydride is liquid at room temperature (25°C), separation and cleaning of the resulting carbon coated material are facilitated.

[0037] The coating composition may contain a solvent. Examples of solvents include ethers, alcohols, ketones, and aldehydes. The solvent can be used alone or in combination of two or more.

[0038] Liquid carboxylic acid anhydrides at room temperature, such as acetic anhydride and propionic anhydride, can also function as solvents in coating compositions. Many carboxylic acid anhydrides are solid at room temperature due to their strong hydrogen bonding and crystallinity (e.g., succinic anhydride and maleic anhydride), but in such cases, the above-mentioned solvent or a solution obtained by dissolving them in a liquid carboxylic acid anhydride at room temperature may be used.

[0039] Carboxylic acid anhydrides, which are solid at room temperature, tend to crystallize and become difficult to handle when returned to room temperature after the reaction treatment in step A-1. However, using the above solution makes it easy to separate and clean the carbon-coated components.

[0040] The content of carboxylic acid anhydride in the coating composition before heating may be 40% by mass or more, 50% by mass or more, 60% by mass or more, or 70% by mass or more, based on the total mass of the coating composition.

[0041] Examples of metals that make up a metal catalyst include transition metals. From the standpoint of chemical stability, it may be one or more of the following metals: copper, gold, platinum, nickel, palladium, iron, and titanium. From an economic standpoint, copper may also be used. The metal catalyst may be these metals in their elemental form or as an alloy of these metals. Examples of alloys include stainless steel, which is mainly composed of iron; copper alloys, which are mainly composed of copper; and aluminum alloys, which are mainly composed of aluminum.

[0042] The shape of the metal catalyst is not particularly limited and may be particulate, plate-shaped, amorphous, or porous.

[0043] The amount of metal catalyst in the coating composition before heating may be 0.1% by mass or more, or 60% by mass or less, based on the total mass of the coating composition.

[0044] From the viewpoint of reducing the temperature and time of the carbon coating treatment, the first coating composition may further contain a dehydration catalyst. Sulfuric acid is an example of a dehydration catalyst.

[0045] The concentration of the dehydration catalyst in the coating composition before heating can be 0.4% by mass or more, based on the total mass of the carboxylic acid anhydride and the dehydration catalyst, and may be 0.5% by mass or more, 0.9% by mass or more, 2% by mass or more, 4% by mass or more, 5% by mass or more, or 9% by mass or more.

[0046] When sulfuric acid is used as the dehydration catalyst, the concentration of sulfuric acid in the coating composition can be adjusted based on the purity and amount of concentrated sulfuric acid added to the coating composition. The purity of concentrated sulfuric acid can be measured by titration with a base.

[0047] From the viewpoint of facilitating the separation of the carbon coating member from the coating composition after treatment, the concentration of the dehydration catalyst in the coating composition before heating may be 30% by mass or less, or 10% by mass or less, based on the total mass of the carboxylic acid anhydride and the dehydration catalyst.

[0048] From the viewpoint of yield, the water content in the coating composition before heating may be 5% by mass or less, 1% by mass or less, or 0.1% by mass or less, based on the total mass of the coating composition (excluding the metal catalyst).

[0049] The coating composition may contain additives such as silane coupling agents and sedimentation inhibitors, to the extent that the carbon coating treatment is not impaired.

[0050] Furthermore, from the viewpoint of improving the peel resistance of the carbon coating, the coating composition may contain a resin component. As the resin component, thermoplastic resins such as phenoxy resin and acrylic rubber can be used.

[0051] The resin component content in the coating composition before heating may be 5 to 20% by mass, based on the total mass of the coating composition (excluding the metal catalyst).

[0052] From the viewpoint of facilitating the separation and cleaning of carbon-coated components, the coating composition may be liquid at room temperature (25°C), and its viscosity at 25°C may be 10,000 mPa·s or less. The viscosity here refers to the value measured with an eta viscometer.

[0053] (First coated member) The coated material may include various materials such as metals, insulators, organic materials, inorganic materials, hydrophilic materials, and hydrophobic materials. For example, it may include metals that require rust prevention treatment, such as iron, aluminum, stainless steel, and titanium.

[0054] Furthermore, the member to be coated may have a fluororesin such as polytetrafluoroethylene, which is generally difficult to coat. In addition, the member to be coated may be composed of materials such as glass and ceramics, which are difficult to coat using the methods described in Patent Documents 1 and 2 above.

[0055] Furthermore, the member to be coated may have a particulate, plate-like, block-like, or other shape, or it may be irregular in shape. If the member to be coated is particulate, carbon coating particles can be manufactured.

[0056] When the material to be coated is particulate, the primary particle size (or average primary particle size) may be 0.05 μm or larger, or it may be between 1 and 10,000 μm. Examples of particulate material to be coated include oxide particles such as silica and alumina; metal particles such as copper, gold, iron, stainless steel, and titanium; and organic particles such as polytetrafluoroethylene, styrene resins, and acrylic resins.

[0057] The material to be coated may be, for example, the negative electrode material of a lithium battery.

[0058] (Process A-1) Contact between the first member to be coated and the first coating composition can be achieved by methods such as immersing the member to be coated in the coating composition.

[0059] The heating temperature of the coating composition may be 100-300°C, 150-250°C, or 180-220°C. From the viewpoint of minimizing the thermal effect on the coated member, the heating temperature may be 180-200°C.

[0060] The coating composition may be heated by directly heating the coating composition, or by heating the member to be coated, thereby heating the coating composition in contact with the member.

[0061] Heating may be carried out under normal pressure (atmospheric pressure) or under pressurized pressure. Heating under pressurized pressure allows the temperature to be raised above the boiling point of the components in the coating composition at normal pressure, thus shortening the heating time compared to heating at normal pressure.

[0062] When pressurizing, a pressure vessel such as an autoclave can be used. Using a pressure vessel makes it easier to heat the carboxylic acid anhydride to a temperature above its boiling point at atmospheric pressure (for example, acetic anhydride is 140°C).

[0063] The pressure applied during pressurization may be between 200 kPa and 5.0 MPa, or between 500 kPa and 2.0 MPa.

[0064] The heating time may be 1 minute to 24 hours, 30 minutes to 15 hours, or 1 hour to 5 hours.

[0065] (Process A-2) In this embodiment, a step A-2 may be added after step A-1 to clean the carbon-coated member (the coated member that has been coated with carbon).

[0066] In step A-2, for example, the treated coating composition can be removed by washing the carbon coated member with one or more of the following: water and an organic solvent. Examples of organic solvents include alcohols such as ethanol and hydrocarbon compounds such as toluene.

[0067] According to the first method for manufacturing the carbon-coated member described above, a member can be obtained in which the carbon coating is a carbon film containing graphene.

[0068] <Second method for manufacturing carbon-coated components> The second method for manufacturing the carbon coated member of this embodiment comprises step B-1, in which the second coating composition containing a carboxylic acid anhydride is heated while the second coating composition is in contact with a part or all of the metal surface of the second member to be coated, which has a metal surface.

[0069] (Second coating composition) The second coating composition contains a carboxylic acid anhydride.

[0070] The second coating composition can have the same configuration as the first coating composition, except that it contains a metal catalyst.

[0071] For example, the second coating composition may contain a carboxylic acid anhydride under the same conditions as the first coating composition. Furthermore, the second coating composition may contain the aforementioned solvent, dehydration catalyst, additives, or resin components under the aforementioned conditions. Additionally, the second coating composition may be liquid at room temperature (25°C), and its viscosity at 25°C may be within the range described above.

[0072] (Second coated member) The metal surface may be made of a metal that requires rust prevention treatment, such as iron, aluminum, stainless steel, or titanium. The metal surface of the second coated member may be a part of the member's surface or the entire surface.

[0073] Furthermore, the coated member may be composed solely of metal, or it may be composed of metal and materials other than metal.

[0074] Furthermore, the member to be coated may have a particulate, plate-like, block-like, or other shape, or it may be irregular in shape. If the member to be coated is particulate, carbon coating particles can be manufactured.

[0075] When the material to be coated is particulate, the primary particle size (or average primary particle size) may be 0.05 μm or larger, or it may be between 1 and 10,000 μm. Examples of particulate material to be coated include metal particles such as copper, gold, iron, stainless steel, and titanium.

[0076] When the second coated member is in contact with the second coating composition, the metal surface is thought to function as a metal catalyst, thereby allowing the second coated member, which has at least a carbon coating on its metal surface, to be obtained as a carbon coated member.

[0077] (Process B-1) Contact between the second member to be coated and the second coating composition can be achieved by methods such as immersing the member to be coated in the coating composition.

[0078] Process B-1 can be carried out in the same manner as process A-1 described above.

[0079] A second method for manufacturing a carbon-coated member may further include a step B-2 after step B-1, in which the carbon-coated member (the coated member to be coated with carbon) is cleaned. Step B-2 can be carried out in the same manner as step A-2 described above.

[0080] According to the second method for manufacturing the carbon-coated member described above, a member can be obtained in which the carbon coating is a carbon film containing graphene.

[0081] <Method for manufacturing carbonaceous materials> The method for producing the carbonaceous material of this embodiment comprises step C-1, in which a carboxylic acid anhydride is heated in the presence of a metal catalyst within the system.

[0082] The reaction system in the above method may be a solution or a dispersion in which solid carboxylic acid anhydrides are dispersed. The solution may be the same as the coating composition described above. Furthermore, when heating under pressure, a sealed system such as an autoclave can be used.

[0083] As for the carboxylic acid anhydride, the one described in the first coating composition above can be used.

[0084] In step C-1 described above, a dehydration catalyst can be further added to the system, allowing the carboxylic acid anhydride to be heated in the presence of both a metal catalyst and a dehydration catalyst. Sulfuric acid can be used as the dehydration catalyst.

[0085] The concentration of the dehydration catalyst in the system before heating may be 0.4% by mass or more, based on the total mass of the carboxylic acid anhydride and the dehydration catalyst, and may be 0.5% by mass or more, 0.9% by mass or more, 2% by mass or more, 4% by mass or more, 5% by mass or more, or 9% by mass or more, and may be 30% by mass or less, 10% by mass or less, or 2 to 10% by mass, or 5 to 30% by mass.

[0086] If the system is a solution, the amount of dehydration catalyst present can be set in the same way as the amount of dehydration catalyst in the first coating composition described above.

[0087] If the system is a solution, the heating temperature and heating time, as well as the pressure when pressurizing, can be set in the same way as in step A-1 of the first method for manufacturing the carbon coated member described above.

[0088] In step C-1, a carbonaceous material is produced using carboxylic acid anhydride as the carbon source. Examples of carbonaceous materials include graphene, graphite, amorphous carbon, and diamond.

[0089] The method for producing the carbonaceous material of this embodiment may further include a step C-2 after step C-1, in which the carbonaceous material is separated from the system.

[0090] Step C-2 may include, for example, washing with one or more organic solvents such as water, alcohol, and toluene, followed by separation by centrifugation or a filter with a predetermined mesh size.

[0091] The carbonaceous material obtained by the manufacturing method of this embodiment can be used as a raw material for electromagnetic wave absorbers, antibacterial agents, light-emitting materials, battery electrode materials, thermal conductive materials, electrical conductive materials, and the like. [Examples]

[0092] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples.

[0093] (Example 1) In a 100ml Teflon® container, 19.8g of acetic anhydride, 0.2g of concentrated sulfuric acid, a stirring bar coated with Teflon® (first coated component), and 0.3g of a copper plate (size: 1.0mm x 1.0mm x 1.0mm) (metal catalyst / second coated component) were placed. Next, this Teflon® container was placed in a stainless steel pressure vessel, and the pressure vessel was sealed.

[0094] In a sealed pressure-resistant container, the solution in a Teflon® container was heated with a heater to a temperature of 180°C while being stirred at 300 rpm using a magnetic stirrer. After reaching 180°C, the solution was subjected to heating and pressurizing treatment at 180°C and 0.5 MPa for 1 hour while continuing to stir.

[0095] Afterward, heating and stirring were stopped, and the mixture was allowed to cool naturally to room temperature (25°C). The highest temperature reached during the process was 181°C. After cooling, the coated material, solution, and solids from the Teflon® container were transferred to a beaker.

[0096] Furthermore, concentrated sulfuric acid with a concentration of 95% or higher was used.

[0097] (Examples 2-5) The procedure was the same as in Example 1, except that the heating temperature was changed to the temperatures shown in Table 1.

[0098] (Examples 6-9) The procedure was the same as in Example 1, except that the heating time was changed to the time shown in Table 2.

[0099] (Examples 10-12) The procedure was carried out in the same manner as in Example 1, except that the amounts of acetic anhydride and concentrated sulfuric acid were changed to the amounts shown in Table 2 or Table 3.

[0100] (Example 13) The procedure was the same as in Example 1, except that instead of a copper plate, 0.04 g of a SUS316 plate (size: 1.0 mm x 1.0 mm x 0.5 mm) (metal catalyst / second coated material) was placed in a Teflon® container.

[0101] (Example 14) The procedure was the same as in Example 1, except that instead of a copper plate, 3.0g of an iron plate (size: 0.7mm x 0.7mm x 0.7mm) (metal catalyst / second coated material) was placed in a Teflon® container.

[0102] (Example 15) The procedure was the same as in Example 1, except that 0.04 g of a titanium plate (size: 1.0 mm x 1.0 mm x 0.01 mm) (metal catalyst / second coated material) was placed in a Teflon® container instead of a copper plate.

[0103] (Example 16) The procedure was the same as in Example 1, except that 0.05 g of a nickel plate (size: 1.0 mm x 1.0 mm x 0.01 mm) (metal catalyst / second coated material) was placed in a Teflon® container instead of a copper plate.

[0104] (Example 17) The procedure was carried out in the same manner as in Example 1, except that 1 g of copper particles (average primary particle size: 2 μm) was added as a second metal catalyst (third coated material) inside the Teflon® container.

[0105] (Example 18) The process was carried out in the same manner as in Example 1, except that 0.2g of a glass plate (size: 2mm x 5mm x 0.1mm) was added as a third material to be coated in the Teflon® container.

[0106] (Example 19) The procedure was the same as in Example 1, except that 1 g of silica particles (average particle size: 1.5 μm) was added as a third material to be coated in the Teflon® container.

[0107] (Example 20) The process was carried out in the same manner as in Example 1, except that 1 g of a 0.1 mm thick polyimide film (size: 5 mm x 5 mm) was added as a third material to be coated inside the Teflon® container.

[0108] (Example 21) The procedure was the same as in Example 1, except that 1 g of phenoxy resin "Phenotote ZX1356-2" (manufactured by Toto Kasei Co., Ltd., product name) was added as a resin component to the Teflon® container.

[0109] (Example 22) The process was carried out in the same manner as in Example 1, except that 1 g of acrylic rubber "HTR-708-6T" (manufactured by Nagase ChemteX Corporation, product name) was added as a resin component to the Teflon® container.

[0110] (Examples 23-24) The procedure was carried out in the same manner as in Example 1, except that the amount of acetic anhydride was changed to the amount shown in Table 5, and water was added to the Teflon® container in the amount shown in the same table.

[0111] (Examples 25-29) The treatment was carried out in the same manner as in Example 1, except that acetic anhydride was replaced with a carboxylic acid anhydride shown in Table 5 or Table 6 (succinic anhydride, maleic anhydride, phthalic anhydride, propionic anhydride, or propionic anhydride and succinic anhydride). In Example 29, 17.8 g of propionic anhydride and 2 g of succinic anhydride were added.

[0112] (Examples 30-34) The treatment was carried out in the same manner as in Example 1, except that the amounts of acetic anhydride and concentrated sulfuric acid, the heating temperature, and the heating time were as shown in Table 6 or Table 7.

[0113] (Example 35) The treatment was carried out in the same manner as in Example 1, except that concentrated sulfuric acid was not added, and the amount of acetic anhydride, heating temperature, and heating time were set to the conditions shown in Table 8.

[0114] (Example 36) The process was carried out in the same manner as in Example 35, except that five copper plates (size: 1.0 mm x 1.0 mm x 1.0 mm) (metal catalyst / second coated material) (1.5 g) were placed inside a Teflon® container.

[0115] (Comparative Example 1) The process was carried out in the same manner as in Example 1, except that the copper plate was omitted and the amount of acetic anhydride was changed to 20g.

[0116] (Comparative Examples 2-6) The treatment was carried out in the same manner as in Example 1, except that instead of acetic anhydride, one of the compounds shown in Table 9 (ethanol, cyclohexanone, acetic acid, malic acid, or maleic acid) was used as a carbon source compound other than a carboxylic acid anhydride.

[0117] <Rating> In the examples and comparative examples, after cooling, the coated material and the solution (including solids) in the Teflon® container were removed into a beaker. For these, carbon coating was confirmed, the carbon content was measured, the supernatant yield was measured, and graphene formation was confirmed according to the following methods.

[0118] [Checking the carbon coating] The carbon coating was evaluated by visually checking whether a new black coating had formed on the surface of the coated material, according to the following criteria. A: The entire surface of the component is covered with a black coating. B: The component is covered with a black coating, but the base color (the color of the component) is exposed in some areas. C: No black coating is observed.

[0119] [Measurement of carbon content] If carbon coating was confirmed on the coated component, the percentage of carbon content on the component surface was measured using an energy-dispersive X-ray spectrometer (EDX, manufactured by Hitachi High-Tech Corporation).

[0120] [Measurement of supernatant yield] 1 L of water was added to the solution (the reaction solution from which the material to be coated (excluding powder) had been removed), and the mixture was treated in a centrifuge at 10,000 rpm for 30 minutes to separate the supernatant (supernatant A). 1 L of water was added to the settled solids and stirred, and the centrifugation process was repeated twice. The weight of the resulting solids was measured after drying in an oven at 100°C for 6 hours. The weight ratio to the carboxylic acid anhydride before treatment (before heating) (or "carbon source compounds other than carboxylic acid anhydrides" for Comparative Examples 2-6) was defined as the supernatant yield (%).

[0121] [Confirmation of graphene generation] The supernatant A was diluted 400-fold with acetic anhydride to obtain a diluted solution. This diluted solution was irradiated with 365 nm ultraviolet light using AS ONE's "Handy UV Lump LUV-4," and the presence or absence of emission and its color were observed visually. If blue to yellow emission was observed, it was considered that graphene had been formed and was indicated as "present," and if no blue to yellow emission was observed, it was considered that graphene had not been formed and was indicated as "absent."

[0122] [Table 1]

[0123] [Table 2]

[0124] [Table 3]

[0125] [Table 4]

[0126] Table 5

[0127] Table 6

[0128] Table 7

[0129] Table 8

[0130] Table 9

Claims

1. The process includes a step of heating a coating composition containing a carboxylic acid anhydride and a metal catalyst while the coating composition is in contact with a part or all of the surface of the member to be coated, The coating composition further comprises a dehydration catalyst, wherein the dehydration catalyst is sulfuric acid. The carboxylic acid anhydride is acetic anhydride or propionic anhydride. The aforementioned metal catalyst is a single element of copper, nickel, iron, or titanium, or stainless steel. The content of the carboxylic acid anhydride in the coating composition is 40% by mass or more, based on the total mass of the coating composition. The content of the metal catalyst in the coating composition is 0.1% by mass or more and 60% by mass or less, based on the total mass of the coating composition. The content of the dehydration catalyst in the coating composition is 0.1% by mass or more and 30% by mass or less, based on the total mass of the carboxylic acid anhydride and the dehydration catalyst. A method for manufacturing carbon-coated components.

2. The method for manufacturing a carbon coated member according to Claim 1, wherein the heating temperature in the step is 100 to 300°C.

3. The process includes a step of heating a coating composition containing a carboxylic acid anhydride and a metal catalyst while the coating composition is in contact with a part or all of the surface of the member to be coated, The coating composition further comprises a dehydration catalyst, wherein the dehydration catalyst is sulfuric acid. The carboxylic acid anhydride is maleic anhydride. The aforementioned metal catalyst is a single element of copper, nickel, iron, or titanium, or stainless steel. The content of the carboxylic acid anhydride in the coating composition is 40% by mass or more, based on the total mass of the coating composition. The content of the metal catalyst in the coating composition is 0.1% by mass or more and 60% by mass or less, based on the total mass of the coating composition. The content of the dehydration catalyst in the coating composition is 0.4% by mass or more and 30% by mass or less, based on the total mass of the carboxylic acid anhydride and the dehydration catalyst. A method for manufacturing a carbon-coated member, wherein the heating temperature in the above step is 100 to 300°C.

4. The process includes a step of heating a coating composition containing a carboxylic acid anhydride and a metal catalyst while the coating composition is in contact with a part or all of the surface of the member to be coated, The coating composition further comprises a dehydration catalyst, wherein the dehydration catalyst is sulfuric acid. The carboxylic acid anhydride is succinic anhydride or phthalic anhydride. The aforementioned metal catalyst is a single element of copper, nickel, iron, or titanium, or stainless steel. The content of the carboxylic acid anhydride in the coating composition is 40% by mass or more, based on the total mass of the coating composition. The content of the metal catalyst in the coating composition is 0.1% by mass or more and 60% by mass or less, based on the total mass of the coating composition. The content of the dehydration catalyst in the coating composition is 0.4% by mass or more and 30% by mass or less, based on the total mass of the carboxylic acid anhydride and the dehydration catalyst. A method for manufacturing a carbon-coated member, wherein the heating temperature in the above step is 150 to 250°C.

5. The process includes a step of heating a coating composition containing a carboxylic acid anhydride and a metal catalyst while the coating composition is in contact with a part or all of the surface of the member to be coated, The carboxylic acid anhydride is acetic anhydride, The aforementioned metal catalyst is copper. The content of the carboxylic acid anhydride in the coating composition is 40% by mass or more, based on the total mass of the coating composition. A method for manufacturing a carbon coated member, wherein the content of the metal catalyst in the coating composition is 0.1% by mass or more and 60% by mass or less, based on the total mass of the coating composition.

6. The method for manufacturing a carbon coated member according to claim 5, wherein the heating temperature in the step is 100 to 300°C.

7. The process includes a step of heating a coating composition containing a carboxylic acid anhydride while the coating composition is in contact with a part or all of the surface of the member to be coated, The surface of the member to be coated contains copper, The coating composition further comprises a dehydration catalyst, wherein the dehydration catalyst is sulfuric acid. The carboxylic acid anhydride is acetic anhydride or propionic anhydride. The content of the carboxylic acid anhydride in the coating composition is 40% by mass or more, based on the total mass of the coating composition. A method for producing a carbon coated member, wherein the content of the dehydration catalyst in the coating composition is 0.1% by mass or more and 30% by mass or less, based on the total mass of the carboxylic acid anhydride and the dehydration catalyst.

8. The method for manufacturing a carbon coated member according to claim 7, wherein the heating temperature in the step is 100 to 300°C.

9. The process includes a step of heating a coating composition containing a carboxylic acid anhydride while the coating composition is in contact with a part or all of the surface of the member to be coated, The surface of the member to be coated contains copper, The coating composition further comprises a dehydration catalyst, wherein the dehydration catalyst is sulfuric acid. The carboxylic acid anhydride is maleic anhydride. The content of the carboxylic acid anhydride in the coating composition is 40% by mass or more, based on the total mass of the coating composition. The content of the dehydration catalyst in the coating composition is 0.4% by mass or more and 30% by mass or less, based on the total mass of the carboxylic acid anhydride and the dehydration catalyst. A method for manufacturing a carbon-coated member, wherein the heating temperature in the above step is 100 to 300°C.

10. The process includes a step of heating a coating composition containing a carboxylic acid anhydride while the coating composition is in contact with a part or all of the surface of the member to be coated, The surface of the member to be coated contains copper, The coating composition further comprises a dehydration catalyst, wherein the dehydration catalyst is sulfuric acid. The carboxylic acid anhydride is succinic anhydride or phthalic anhydride. The content of the carboxylic acid anhydride in the coating composition is 40% by mass or more, based on the total mass of the coating composition. The content of the dehydration catalyst in the coating composition is 0.4% by mass or more and 30% by mass or less, based on the total mass of the carboxylic acid anhydride and the dehydration catalyst. A method for manufacturing a carbon-coated member, wherein the heating temperature in the above step is 150 to 250°C.

11. The process includes a step of heating a coating composition containing a carboxylic acid anhydride while the coating composition is in contact with a part or all of the surface of the member to be coated, The surface of the member to be coated contains copper, The carboxylic acid anhydride is acetic anhydride, The content of the carboxylic acid anhydride in the coating composition is 40% by mass or more, based on the total mass of the coating composition. A method for manufacturing a carbon-coated member, wherein the heating temperature in the above step is 100 to 300°C.

12. A method for manufacturing a carbon coated member according to any one of claims 7 to 11, wherein the member to be coated is in particulate form.

13. Used to carbon coat the surface of the material to be coated, A coating composition comprising a carboxylic acid anhydride, a metal catalyst, and a dehydration catalyst, The dehydration catalyst is sulfuric acid, The carboxylic acid anhydride is acetic anhydride, propionic anhydride, maleic anhydride, succinic anhydride, or phthalic anhydride. The aforementioned metal catalyst is a single element of copper, nickel, iron, or titanium, or stainless steel. The content of the carboxylic acid anhydride in the coating composition is 40% by mass or more, based on the total mass of the coating composition. The content of the metal catalyst in the coating composition is 0.1% by mass or more and 60% by mass or less, based on the total mass of the coating composition. The coating composition wherein the content of the dehydration catalyst in the coating composition is 0.1% by mass or more and 30% by mass or less, based on the total mass of the carboxylic acid anhydride and the dehydration catalyst.

14. Used to carbon coat the metal surface of a coated member having a copper-containing metal surface, A coating composition comprising a carboxylic acid anhydride and a dehydration catalyst, The dehydration catalyst is sulfuric acid, The carboxylic acid anhydride is acetic anhydride, propionic anhydride, maleic anhydride, succinic anhydride, or phthalic anhydride. The content of the carboxylic acid anhydride in the coating composition is 40% by mass or more, based on the total mass of the coating composition. The coating composition wherein the content of the dehydration catalyst in the coating composition is 0.1% by mass or more and 30% by mass or less, based on the total mass of the carboxylic acid anhydride and the dehydration catalyst.

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