JP7437924B2 - Method for producing carbon material, carbon material, method for producing carbon material-containing material, carbon material-containing material, and organic-inorganic composite - Google Patents

Description

Article 30, Paragraph 2 of the Patent Act applies Meeting name: 45th Annual Meeting of the Carbon Materials Society Date: December 5, 2018 [Publications, etc.] Meeting name: 12th Graphene Oxide Symposium Date: Reiwa 1 June 21, 2020 [Publications, etc.] Meeting name: 46th Annual Meeting of the Carbon Materials Society Date: November 28 to November 29, 2020

The present invention relates to a method for producing a carbon material, a carbon material, a method for producing a carbon material-containing material, a carbon material-containing material, and an organic-inorganic composite.

In recent years, carbon materials such as carbon nanotubes, fullerenes, graphite, graphene, graphene oxide, reduced graphene oxide, artificial graphite, and carbon black have been used as novel functional materials in various fields due to their characteristic physical properties. (For example, non-patent documents 1 to 3).

Graphene is a two-dimensional sheet-like carbon material, and has a structure covered with six-membered rings made of sp2 carbon. Graphite usually refers to a layered structure in which two-dimensional sheets of graphene are bonded together by van der Waals forces, but a single-layer graphene is referred to as graphene. A material in which 2 to 10 layers of graphene are stacked is called multilayer graphene, and a material in which 2 to 5 layers of graphene are stacked is called few-layer graphene. In a single layer of graphene, the properties and shape of the graphene itself change significantly by introducing functional groups into the basal plane. When there are three or more layers, even if a functional group is introduced into the basal plane of graphene, the graphene in the center is less likely to be directly affected. Therefore, in graphene with three or more layers, the number of layers basically increases, and other than a decrease in specific surface area, it becomes difficult to see any noticeable difference in properties.

Although the existence of graphene has been known for a long time, a method for extracting a single graphene sheet from graphite had not been established until recently. In 2004, it was discovered that graphene flakes could be extracted by peeling off the surface of highly oriented anhydrous graphite with adhesive tape and pasting the peeled material onto a substrate. Aiming for cost-effective production, we are developing graphene manufacturing methods using vapor-phase film forming methods such as CVD (chemical vapor deposition), and graphene (reduced graphene oxide: RGO) using graphene oxide (GO) reduction methods. Methods are being considered.

However, methods for producing graphene using vapor phase film forming methods such as CVD (chemical vapor deposition film forming method) have problems such as the inability to obtain graphene in a form other than a film (typically, a bulk form), and combustible gas. There is a problem that metal must be used as an impurity because the film is formed on a metal substrate having catalytic performance such as Cu.

Furthermore, a method for producing a carbon material by heating a compound in which a condensation reaction occurs between the same molecules and/or between different molecules is disclosed (Patent Document 1). This technology has been shown to be able to synthesize carbon materials under mild conditions.

Industrially manufactured carbon materials have various functional groups. Therefore, it is difficult to precisely control the structure of the carbon material, resulting in variations in physical properties. In recent years, there has been a demand for carbon materials that can reliably exhibit targeted physical properties, and for this reason, there is a need for the development of carbon materials whose structures are precisely controlled.

Furthermore, in light of recent trends in resource and energy conservation, lightweight carbon materials have been developed and are being used in various fields. Carbon material-containing materials such as carbon-coated inorganic particles and hollow carbon fine particles have been reported as compounds containing such lightweight carbon materials that are useful in various fields (for example, Patent Documents 2 to 5, Non-Patent Documents References 3-6). Additionally, activated carbon, carbon black, and the like are known as industrially produced carbon material-containing materials.

However, with conventional carbon-containing materials such as carbon-coated inorganic particles and hollow carbon fine particles, a carbon material film is formed on the surface of the inorganic particles to be coated with carbon or the fine particles that serve as the base of the hollow structure by a gas phase reaction or a high-temperature vapor deposition reaction. It is difficult to apply it to industrial manufacturing that involves mass production at low cost because it must be formed and manufactured.

Furthermore, the above carbon material-containing materials, including industrially produced activated carbon and carbon black, have various functional groups. For this reason, it is difficult to precisely control the structure of the carbon material-containing material, resulting in variations in physical properties. In recent years, there has been a demand for carbon material-containing materials that can reliably exhibit targeted physical properties, and for this reason, there is a demand for the development of carbon material-containing materials whose structures are precisely controlled.

JP2019-085298A Japanese Unexamined Patent Publication No. 7-187849 Japanese Patent Application Publication No. 7-267618 Japanese Patent Application Publication No. 2005-281065 Japanese Patent Application Publication No. 2010-168251

Nature, 354, p. 56-58 (1991) Science, 306, p. 666-669 (2004) H. Nishihara et. al. , Adv. Funct. Mater. , 26, 6418-6427 (2016) Riichiro Saito, “Cutting-edge technology and expanding applications of graphene”, Chapter 2. Basic physical properties of graphene, 3. Photoelectronic properties of graphene Dawei Pan et. al. , Langmuir, 22, 5872-5876 (2006) V. Ruiz et. al. , Electrochemistry Communications, 24, 35-38 (2012)

An object of the present invention is to provide a method for easily producing a carbon material whose structure is precisely controlled under mild conditions. Another object of the present invention is to provide a carbon material whose structure is precisely controlled. Another object of the present invention is to provide a method for easily producing a carbon material-containing material that is soluble in a solvent or a carbon material-containing material whose structure is precisely controlled under mild conditions. Another object of the present invention is to provide a carbon material-containing material whose structure is precisely controlled and in which a carbon material and an inorganic substance are bonded by covalent bonds. Another object of the present invention is to provide an organic-inorganic composite that can be industrially produced under mild conditions and is useful for industrially producing carbon material-containing materials such as carbon-coated inorganic particles and hollow carbon fine particles.

The method for producing a carbon material of the present invention includes:
Including a heating step (i) of heating a composition containing a compound (A) in which a condensation reaction occurs between the same molecules and/or between different molecules by heating,
The heating temperature in the heating step (i) is (T-150) °C or higher when the condensation reaction temperature of the compound (A) is T °C,
The compound (A) is a compound having two or more phenolic OH groups in the molecule,
The heating step (i) includes a condensation reaction between the two phenolic OH groups of the compound (A) between the same molecules and/or between different molecules.

The carbon material of the present invention is
The content ratio of carbon atoms, hydrogen atoms, and oxygen atoms in elemental analysis is that when the content ratio of carbon atoms is 6.0 atom%, the content ratio of hydrogen atoms is 1.0 atom% to 8.0 atom%, and oxygen The content ratio of atoms is 0.1 atom% to 4 atom%.

The method for producing a carbon material-containing material of the present invention includes:
A method of manufacturing a carbon material-containing material, the method comprising:
Including a heating step (I) of heating a composition containing a compound (A) and an inorganic substance in which a condensation reaction occurs between the same molecules and/or between different molecules by heating,
The heating temperature in the heating step (I) is (T-150) °C or higher when the condensation reaction temperature of the compound (A) is T °C,
The compound (A) is a compound having two or more phenolic OH groups in the molecule,
The heating step (I) includes a condensation reaction between the two phenolic OH groups of the compound (A) between the same molecules and/or between different molecules.

In one embodiment, after the heating step (I), a carbon material removing step is included in which at least a part of the carbon material generated by heating the compound (A) is removed.

In one embodiment, after the carbon material removal step, a heating step (II) of further heating is included.

In one embodiment, after the heating step (I), an inorganic substance removal step of removing the inorganic substance is included.

In one embodiment, a heating step (II) of further heating is included after the inorganic substance removal step.

In one embodiment, the molecular weight of the compound (A) is 500 or less.

In one embodiment, the condensation reaction temperature of the compound (A) is 450°C or lower.

In one embodiment, the condensation reaction temperature of the compound (A) is 400°C or less.

In one embodiment, the initial weight M50 of the compound (A) at a temperature of 50°C when TG-DTA analysis is performed under nitrogen gas atmosphere from 40°C under heating conditions of 10°C/min. The weight ratio (M500/M50) of weight M500 at a temperature of 500° C. is 0.2 or more.

In one embodiment, the condensation reaction is facilitated by an acid catalyst.

In one embodiment, the inorganic substance is at least one selected from the group consisting of inorganic oxides, inorganic nitrides, inorganic sulfides, inorganic carbides, and insoluble salts.

In one embodiment, the inorganic oxide is an inorganic oxide particle having a functional group on its surface.

In one embodiment, the inorganic oxide particles include silica particles, alumina particles, titania particles, magnesium oxide particles, polyacid particles, metal particles whose surfaces are at least partially oxidized, composite oxide particles, and solid solutions. At least one kind selected from the group consisting of oxide particles.

In one embodiment, the metal constituting the polyacid particles is at least one metal selected from the group consisting of molybdenum, vanadium, tungsten, niobium, titanium, and tantalum.

In one embodiment, the decomposition temperature of the inorganic oxide is 800°C or higher.

The carbon material-containing material of the present invention is
A carbon material-containing material containing a carbon material and an inorganic substance,
At least a part of the carbon material and at least a part of the inorganic substance are bonded by a covalent bond,
The content ratio of carbon atoms, hydrogen atoms, and oxygen atoms in the elemental analysis of the carbon material is such that when the content ratio of carbon atoms is 6.0 atom%, the content ratio of hydrogen atoms is 1.0 atom% to 8.0 atom%. The content of oxygen atoms is 0.1 atom% to 4 atom%.

In one embodiment, the carbon material-containing material of the present invention exhibits a peak between 125 ppm and 135 ppm in ¹³ C-NMR analysis.

In one embodiment, the carbon material-containing material of the present invention exhibits a peak between 140 ppm and 160 ppm in ¹³ C-NMR analysis.

The organic-inorganic composite of the present invention is
An organic-inorganic composite containing a carbon material and an inorganic substance,
the carbon material is soluble in a solvent,
The content ratio of carbon atoms, hydrogen atoms, and oxygen atoms in the elemental analysis of the carbon material is such that when the content ratio of carbon atoms is 6.0 atom%, the content ratio of hydrogen atoms is 1.0 atom% to 8.0 atom%. The content of oxygen atoms is 0.1 atom% to 4 atom%.

In one embodiment, the solvent is N-methylpyrrolidone.

In one embodiment, the inorganic substance is at least one selected from the group consisting of inorganic oxides, inorganic nitrides, inorganic sulfides, inorganic carbides, and insoluble salts.

In one embodiment, the inorganic oxide is an inorganic oxide particle having a functional group on its surface.

In one embodiment, the inorganic oxide particles include silica particles, alumina particles, titania particles, magnesium oxide particles, polyacid particles, metal particles whose surfaces are at least partially oxidized, composite oxide particles, and solid solutions. At least one kind selected from the group consisting of oxide particles.

In one embodiment, the metal constituting the polyacid particles is at least one metal selected from the group consisting of molybdenum, vanadium, tungsten, niobium, titanium, and tantalum.

According to the present invention, it is possible to provide a method for easily producing a carbon material whose structure is precisely controlled under mild conditions. Furthermore, a carbon material whose structure is precisely controlled can be provided. Further, it is possible to provide a method for easily producing a carbon material-containing material that is soluble in a solvent or a carbon material-containing material whose structure is precisely controlled under mild conditions. Further, according to the present invention, it is possible to provide a carbon material-containing material whose structure is precisely controlled and in which a carbon material and an inorganic substance are bonded by covalent bonds. Furthermore, the present invention provides an organic-inorganic composite that can be industrially manufactured under mild conditions and is useful for industrially manufacturing carbon material-containing materials such as carbon-coated inorganic particles and hollow carbon fine particles. can do.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic cross-sectional view showing an organic-inorganic composite that is one embodiment of a carbon material-containing material obtained by the production method of the present invention, and a preferred embodiment of the organic-inorganic composite of the present invention. A schematic cross-sectional view showing core-shell particles that are an example of carbon material-containing particles that are one embodiment of the carbon material-containing material obtained by the production method of the present invention, and core-shell particles that can be obtained from the organic-inorganic composite of the present invention. It is. 1 is an XPS spectrum (C1s) diagram of organic-inorganic composites (1) to (4) obtained in Examples 1 to 4. FIG. FIG. 2 is a measurement diagram showing the results of DTA analysis in TG-DTA analysis of organic-inorganic composites (1) to (4) obtained in Examples 1 to 4. FIG. 2 is an IR spectrum diagram of organic-inorganic composites (1) to (4) obtained in Examples 1 to 4. 1 is a Raman spectrum diagram of organic-inorganic composites (1) to (4) obtained in Examples 1 to 4. FIG. FIG. 2 is an XPS spectrum (C1s) diagram of organic-inorganic composites (5) to (8) obtained in Examples 5 to 8. FIG. 2 is an IR spectrum diagram of organic-inorganic composites (5) to (8) obtained in Examples 5 to 8. FIG. 3 is a Raman spectrum diagram of an organic-inorganic composite (9) obtained in Example 9. FIG. 3 is a SEM photograph of highly carbonized core-shell particles (9) obtained in Example 9. FIG. 3 is a Raman spectrum diagram of the surface of highly carbonized core-shell particles (9) obtained in Example 9. ^13C -NMR images of highly carbonized core-shell particles (9) obtained in Example 9 and particles obtained in Comparative Example 3. FIG. 29 is a ²⁹ Si-NMR image of highly carbonized core-shell particles (9) obtained in Example 9, particles obtained in Comparative Example 3, and silica particles. FIG. FIG. 2 is a Raman spectrum diagram of the surface of highly carbonized core-shell particles (10) obtained in Example 10. FIG. 2 is a Raman spectrum diagram of the surface of highly carbonized core-shell particles (11) obtained in Example 11. It is a comparative graph of the Vickers hardness of a sintered body obtained by SPS sintering of highly carbonized core-shell particles (11) and a sintered body obtained by SPS sintering of aluminum. FIG. 3 is a Raman spectrum diagram of the surface of highly carbonized core-shell particles (12) obtained in Example 12. FIG. 3 is a Raman spectrum diagram of the surface of highly carbonized core-shell particles (13) obtained in Example 13. FIG. 3 is a Raman spectrum diagram of the surface of highly carbonized core-shell particles (14) obtained in Example 14. FIG. 3 is a Raman spectrum diagram of the surface of highly carbonized core-shell particles (15) obtained in Example 15. FIG. 3 is a Raman spectrum diagram of the surface of highly carbonized core-shell particles (16) obtained in Example 16. FIG. 3 is a Raman spectrum diagram of the surface of highly carbonized core-shell particles (17) obtained in Example 17. FIG. 3 is a Raman spectrum diagram of the surface of highly carbonized core-shell particles (18) obtained in Example 18. FIG. 3 is a Raman spectrum diagram of the surface of highly carbonized core-shell particles (19) obtained in Example 19. 3 is a Raman spectrum diagram of the surface of highly carbonized core-shell particles (20) obtained in Example 20. FIG. FIG. 3 is a Raman spectrum diagram of the surface of the organic-inorganic composite (21) obtained in Example 21. FIG. 3 is a Raman spectrum diagram of the surface of highly carbonized core-shell particles (21) obtained in Example 21. FIG. 3 is a Raman spectrum diagram of the surface of the organic-inorganic composite (22) obtained in Example 22. FIG. 3 is a Raman spectrum diagram of the surface of highly carbonized core-shell particles (22) obtained in Example 22. FIG. 3 is a Raman spectrum diagram of the surface of the organic-inorganic composite (23) obtained in Example 23. FIG. 3 is a Raman spectrum diagram of the surface of highly carbonized core-shell particles (23) obtained in Example 23. FIG. 3 is a Raman spectrum diagram of the surface of the organic-inorganic composite (24) obtained in Example 24. FIG. 3 is a Raman spectrum diagram of the surface of highly carbonized core-shell particles (24) obtained in Example 24. ^13C -NMR analysis results of carbon materials obtained in Examples 1 to 8.

≪≪1. Manufacturing method of carbon material≫≫
The method for producing a carbon material of the present invention includes a heating step (i) of heating a composition containing a compound (A) in which a condensation reaction occurs between the same molecules and/or between different molecules by heating, and the heating step (i) ), when the condensation reaction temperature of the compound (A) is T°C, the heating temperature is at least (T-150)°C, and the compound (A) has two or more phenolic OH groups in the molecule. The heating step (i) includes a condensation reaction between the two phenolic OH groups of the compound (A) between the same molecules and/or between different molecules.

The content of the compound (A) in a composition containing the compound (A) in which a condensation reaction occurs between the same molecules and/or between different molecules upon heating is preferably 50% by weight to 100% by weight, more preferably is 80% to 100% by weight, more preferably 90% to 100% by weight, particularly preferably 95% to 100% by weight, and most preferably substantially 100% by weight.

The term "substantially" as used herein means that compound (A) is actively provided with another component to produce an effect other than that caused by compound (A), or that compound (A) This means excluding forms that are actively used in combination; for example, the inclusion of impurities that are unavoidably mixed in during the manufacturing process etc. is permitted within a range that does not impair the effects of the present invention.

The composition containing the compound (A) in which a condensation reaction occurs between the same molecules and/or between different molecules upon heating may contain any other appropriate components as long as the effects of the present invention are not impaired. Good too. Examples of such other components include a solvent, a catalyst, a base material, a carrier, and the like.

Note that the above-mentioned arbitrary appropriate other components exclude inorganic substances contained in the composition containing the compound (A) used when manufacturing the carbon material-containing material described below.

The heating temperature in the heating step (i) is at least (T-150)°C, preferably (T-150 to T+50)°C, when the condensation reaction temperature of compound (A) is T°C, and more preferably Preferably (T-130 to T+45)°C, more preferably (T-100 to T+40)°C, particularly preferably (T-80 to T+35)°C, most preferably (T-50 to T+30) )℃. By adjusting the heating temperature within the above range, a carbon material whose structure is precisely controlled can be easily produced under mild conditions.

The condensation reaction temperature of compound (A) can be determined by TG-DTA analysis. Specifically, it is as follows.
(1) When one type of compound is used as compound (A), TG-DTA analysis of compound (A) is performed by heating from 40°C at a temperature increase rate of 10°C/min in a nitrogen gas atmosphere, The peak top temperature on the lowest temperature side of DTA is determined as the condensation reaction temperature (T° C.) of compound (A).
(2) When using a mixture of two or more compounds as compound (A), perform TG-DTA analysis of the mixture by increasing the temperature from 40°C at a heating rate of 10°C/min in a nitrogen gas atmosphere. , the peak top temperature at the lowest temperature side of DTA is determined as the condensation reaction temperature (T° C.) of compound (A) (a mixture of two or more compounds).
(3) However, if compound (A) as one type of compound or a mixture of two or more types of compounds contains impurities such as a solvent, water, or water of hydration, the impurities can be removed. A DTA peak (sometimes referred to as an impurity peak) accompanying the condensation reaction may be observed at a temperature lower than the condensation reaction temperature. In such a case, the above impurity peak is ignored and the condensation reaction temperature of the compound (A) is determined. Usually, the peak top temperature on the lowest temperature side of DTA is determined as the condensation reaction temperature of the compound (A), ignoring the impurity peaks mentioned above.

The specific heating temperature in the heating step (i) is preferably 100°C to 800°C, more preferably 150°C to 700°C, still more preferably 200°C to 650°C, and most preferably is 250°C to 600°C. By adjusting the heating temperature within the above range, a carbon material whose structure is precisely controlled can be easily produced under mild conditions.

In addition, considering the solubility of the obtained carbon material, the heating temperature in the heating step (i) is preferably 200°C or higher and lower than 500°C, more preferably 220°C or higher and lower than 400°C, and even more preferably 230°C or higher and lower than 400°C. ℃~350℃, particularly preferably 250℃~300℃.

The specific heating time in the heating step (i) is preferably 0.1 to 120 hours, more preferably 0.5 to 100 hours, and even more preferably 1 to 50 hours. and most preferably from 2 hours to 24 hours. By adjusting the heating time within the above range, a carbon material whose structure is precisely controlled can be easily produced under mild conditions.

In the method for producing a carbon material of the present invention, preferably a composition containing a compound having two or more phenolic OH groups in the molecule (preferably a compound having two or more phenolic OH groups in the molecule) is used. ) is fired without contact with metal. By firing a composition containing a compound having two or more phenolic OH groups in the molecule (preferably a compound having two or more phenolic OH groups in the molecule) without contacting with metal, It is possible to suppress metal from being contained as an impurity in the obtained carbon material. However, as mentioned above, not coming into contact with metal means not actively coming into contact with metal, and does not include cases where it comes into contact with, for example, the bottom or wall of the firing furnace during the manufacturing process. Actively contacting refers to a composition containing a compound having two or more phenolic OH groups in the molecule (preferably a compound having two or more phenolic OH groups in the molecule), as described below. ) into a thin film to actively increase the contact area with metal.

In the method for producing a carbon material of the present invention, preferably a composition containing a compound having two or more phenolic OH groups in the molecule (preferably a compound having two or more phenolic OH groups in the molecule) is used. ) is calcined without catalytic reaction. By baking a composition containing a compound having two or more phenolic OH groups in the molecule (preferably a compound having two or more phenolic OH groups in the molecule) without using a catalytic reaction, This can prevent the reaction catalyst from existing in the carbon material and becoming a fatal impurity.

In the method for producing a carbon material of the present invention, preferably a composition containing a compound having two or more phenolic OH groups in the molecule (preferably a compound having two or more phenolic OH groups in the molecule) is used. ) is fired in bulk. Calcining a composition containing a compound having two or more phenolic OH groups in the molecule (preferably a compound having two or more phenolic OH groups in the molecule) in a bulk state means, for example, (i) (ii) firing particles (powder) made of a composition containing a compound having two or more phenolic OH groups in the molecule (preferably a compound having two or more phenolic OH groups in the molecule); ) Compression molding of particles (e.g., powder) consisting of a composition containing a compound having two or more phenolic OH groups in the molecule (preferably a compound having two or more phenolic OH groups in the molecule) It includes actions such as molding the molded product into a pellet or film shape using a method such as the above, and then firing the molded product. When firing particles (for example, powder) or molded bodies, they may be placed in a container and heated, for example. Any suitable container can be used as the container. Such a container is preferably made of a material that does not substantially change in quality at heating temperatures, for example. In addition, when the surface of the particles (e.g., powder) or molded body comes into contact with is a composition containing a compound having two or more phenolic OH groups in the molecule (preferably two or more phenolic OH groups in the molecule). It is preferable that the material is one that does not chemically react with the above-mentioned compounds having a phenolic OH group. By firing particles (e.g. powder) or molded bodies under favorable conditions, it is possible to obtain a carbon material, and in the heating process, the melting point of a compound having two or more phenolic OH groups in the molecule can be reduced. The compound (a) may melt in the vicinity and become liquid. Even if such a process occurs, "a composition containing a compound having two or more phenolic OH groups in the molecule (preferably a compound having two or more phenolic OH groups in the molecule)" in a bulk state. Included in ``baking''. On the other hand, examples of compositions that are not "calcined in bulk" within the meaning of the present invention include, for example, compositions containing a compound having two or more phenolic OH groups in the molecule (preferably, two or more phenolic OH groups in the molecule). A method of forming a thin film by dissolving the above-mentioned compound having a phenolic OH group in a solvent and applying it to an arbitrary base material to form a film and heating it together with the base material, chemical vapor deposition method (CVD) ) method, physical vapor deposition method (PVD), thin film deposition heating method, and the like. A thin film generally means a film thickness of 1 μm or less.

The method of heating (sometimes referred to as calcination) in the heating step (i) includes a tube furnace, a calcination furnace such as a box furnace, a heating reaction device using a heating medium, a heating reaction device using microwaves, etc. Can be used. Heating can be carried out under vacuum, normal pressure, pressurization, or the like. The heating atmosphere may be in the atmosphere, in an inert gas atmosphere, or the like. The heating atmosphere is preferably an atmosphere of an inert gas such as nitrogen or argon.

≪1-1. Compound (A)≫
When compound (A) is heated, a condensation reaction occurs between the same molecules and/or between different molecules. Then, by the heating step (i) of heating the composition containing compound (A), compound (A) can be turned into a carbon material.

Compound (A) is a compound having two or more phenolic OH groups in the molecule. The number of compounds having two or more phenolic OH groups in the molecule may be one, or two or more.

In the method for producing a carbon material of the present invention, by employing a compound having two or more phenolic OH groups in the molecule as the compound (A), the heating step (i) It involves a condensation reaction between two phenolic OH groups in the same molecule and/or in different molecules. In addition, in the heating step (i), in addition to the above-mentioned condensation reaction between the same molecules and/or between the two phenolic OH groups between the same molecules and/or different types of molecules, reactions between the same molecules and between the same molecules and/or between different types of molecules are carried out within the range that does not impair the effects of the present invention. It may also include a condensation reaction between any other suitable two groups between different molecules.

A condensation reaction between two phenolic OH groups of a compound having two or more phenolic OH groups in the molecule, between the same molecules and/or between different molecules, preferably by at least a C-O-C bond. A structure in which two aromatic rings are bonded is formed. Furthermore, new bonds (for example, C--C bonds, etc.) are formed between two or more aromatic rings by the above condensation reaction and other reactions that occur following or in parallel with the condensation reaction. or polymerization may proceed.

Note that the formation of the above C--C bond is, for example, a deoxygenation reaction from a C--O--C bond, a dehydration reaction between an H group directly bonded to an aromatic ring and an OH group, a H group directly bonded to an aromatic ring, etc. This can occur due to a dehydrogenation reaction between the group and the H group.

Further, depending on the selection of the compound (A) and the selection of various conditions in the heating step (i), a ring condensation reaction between two or more aromatic rings may also occur.

Examples of compounds having two or more phenolic OH groups in the molecule include compounds represented by general formulas (1) to (11).

In each of the general formulas (1) to (11), X represents a hydrogen atom or a hydroxyl group, and two or more of X are phenolic OH groups.

Here, the phenolic OH group means a hydroxyl group bonded to an aromatic ring. That is, in general formula (1), two or more of the six Xs bonded to the aromatic ring are phenolic OH groups, and in general formula (2), two or more of the six Xs bonded to the aromatic ring are phenolic OH groups. In general formula (3), two or more of the 10 X bonded to the aromatic ring are phenolic OH groups, and in general formula (4), two or more of , two or more of the 11 Xs bonded to the aromatic ring are phenolic OH groups, and in general formula (5), two or more of the 9 Xs bonded to the aromatic ring are phenolic OH groups. In the general formula (6), two or more of the nine Xs bonded to the aromatic ring are phenolic OH groups, and in the general formula (7), two or more of the nine Xs bonded to the aromatic ring are Two or more of the Xs are phenolic OH groups, and in the general formula (8), two or more of the 11 Xs bonded to the aromatic ring are phenolic OH groups, and the general formula (9 ), two or more of the nine Xs bonded to the aromatic ring are phenolic OH groups, and in general formula (10), two or more of the nine Xs bonded to the aromatic ring are phenol. In general formula (11), two or more of the 12 Xs bonded to the aromatic ring are phenolic OH groups.

Among compounds that have two or more phenolic OH groups in the molecule, it is assumed that condensation reactions between two phenolic OH groups between the same molecule and/or different molecules are likely to occur, and the reaction tends to proceed easily. As expected, preferred examples include phloroglucinol, hexahydroxytriphenylene, polyphenols, dihydroxybenzenes (e.g., hydroquinone, resorcinol, catechol, etc.), dihydroxynaphthalene, dihydroxyanthracene, dihydroxyphenanthrene, dihydroxypyrene, dihydroxytriphenylene, etc. . Further, the above-mentioned compounds further include those having a substituent and those having a hetero element-containing ring. Among these, phloroglucinol, hexahydroxytriphenylene, and polyphenol are more preferred in that they can more effectively exhibit the effects of the present invention.

As the polyphenol, any suitable polyphenol may be employed as long as it does not impair the effects of the present invention. Examples of such polyphenols include ginkgo biloba extract, mangosteen extract, strawberry seed extract, walnut polyphenols, guarana extract, Java ginger extract, nobiletin, blueberry leaf extract, melinjo extract, grape resveratrol, lingonberry extract, and lingonberry extract. Extract, gnetin C, ε-viniferin, resveratrol, grape seed extract, black soybean seed coat polyphenols, black bean seed coat polyphenols, blackcurrant extract, curcumin, white curcuminoids, polymethoxyflavonoids (PMF), dihydroquercetin, milk thistle extract, silymarin, Silibinin, αG hesperidin, hesperidin, methylhesperidin, orange-derived rutinoside, hesperetin, pycnogenol, oligonol, flaxseed lignan, parsley extract, maqui berry extract, kiwi seed extract, perilla extract, red perilla extract, perilla leaf, aronia extract, haskap Extract, cyanidin-3-glucoside, Urticaria extract, Acai extract, Camu Camu extract, Maron polyphenol, Soy isoflavone, Citrus fruit extract, Seaweed polyphenol, Pumice extract, Olive fruit extract, Sudachi pericarp extract, Lotus root extract, Turmeric extract, Echinacea ), lotus leaf extract (lotus leaf), citrus citrus, guava leaf extract, mulberry leaf extract, safflower extract, corn silk extract, salacia extract, chambo extract (plantain), hawthorn extract, chimpi extract, ginseng Extract, sweet tea extract, spruce extract, Hokudami extract, Yacon extract, Lafuma extract, green tea extract, etc. The number of polyphenols may be one, or two or more.

The compound having two or more phenolic OH groups in the molecule is preferably solid and has a melting point in an environment of 23°C. Because it has a melting point, it melts during the firing process, and reactions between molecules proceed smoothly. If it does not have a melting point, it will not melt during the firing process, so the position of the molecules will be fixed, and reactions between molecules will be difficult to promote, making it difficult to turn into a carbon material. By employing such a compound, the condensation reaction can be promoted and the decomposition reaction can be suppressed.

≪≪2. Carbon material≫≫
The carbon material of the present invention may be produced by any appropriate method as long as the effects of the present invention are not impaired. Preferably, <<<1. It can be manufactured by the manufacturing method explained in ≫≫ Manufacturing method of carbon material.

In the carbon material of the present invention, the content ratio of carbon atoms, hydrogen atoms, and oxygen atoms in elemental analysis is 1.0 atom% to 8.0 atom%, when the content ratio of carbon atoms is 6.0 atom%. .0atom%, and the content of oxygen atoms is 0.1atom% to 4atom%.

In the carbon material of the present invention, the content ratio of carbon atoms, hydrogen atoms, and oxygen atoms in elemental analysis is preferably such that the lower limit of the content ratio of hydrogen atoms is 1 when the content ratio of carbon atoms is 6.0 atom%. The upper limit of the hydrogen atom content is preferably 7.0 atom % or less, more preferably 5.0 atom % or less.

In the carbon material of the present invention, the content ratio of carbon atoms, hydrogen atoms, and oxygen atoms in elemental analysis is preferably such that the lower limit of the content ratio of oxygen atoms is 1 when the content ratio of carbon atoms is 6.0 atom%. .0 atom% or more, more preferably 1.2 atom% or more, still more preferably 1.5 atom% or more, and the upper limit of the oxygen atom content is preferably 3.5 atom% or less, more preferably is 3.2 atom% or less, more preferably 2.5 atom% or less.

If the content ratio of carbon atoms, hydrogen atoms, and oxygen atoms in the carbon material of the present invention in elemental analysis is within the above range, a carbon material whose structure is precisely controlled can be provided. Moreover, the solubility of the provided carbon material can be improved. Note that the content ratios of carbon atoms, hydrogen atoms, and oxygen atoms can be determined based on the results obtained by performing elemental analysis of C, H, and O using a commercially available elemental analyzer. As such an analyzer, for example, Exeter Analytical, Inc. An elemental analyzer (CE-440F), etc. manufactured by the company can be used.

The carbon material of the present invention preferably has a C--O--C bond and a C--C bond. The carbon atom (C) of the bond here is preferably a carbon atom of an aromatic ring.

The C-O-C bond that the carbon material of the present invention has preferably refers to two phenolic OH groups between the same molecule and/or between different molecules of a compound having two or more phenolic OH groups in the molecule. Formed by a condensation reaction between groups.

The C-C bond that the carbon material of the present invention has preferably includes a deoxygenation reaction from the C-O-C bond, a dehydration reaction between an H group and an OH group directly bonded to an aromatic ring, and a dehydration reaction directly to an aromatic ring. It is formed by a dehydrogenation reaction between bonded H groups.

The ratio of C-O-C bonds and C-C bonds that the carbon material of the present invention has is such that the number of C-C bonds is preferably 0.1 to 2.0 to 1 C-O-C bond. It is more preferably 0.1 to 1.2, still more preferably 0.1 to 0.6, particularly preferably 0.1 to 0.3. If the ratio of C--O--C bonds and C--C bonds in the carbon material of the present invention is within the above range, it is possible to provide a carbon material whose structure is precisely controlled. Moreover, the solubility of the provided carbon material can be improved. The ratio of such C--O--C bonds and C--C bonds can be evaluated by, for example, XPS analysis.

The carbon material of the present invention preferably has at least one embodiment selected from the group consisting of (1) to (6) below.

(1) All bonds by C1sXPS analysis, that is, C-C bonds, C=C bonds, C-H bonds, and C-O bonds (C-O bonds derived from alcohol, C-O bonds derived from ether, and C-O bonds derived from epoxy) ) and C=O bonds (including carbonyl-derived C=O bonds, carboxyl-derived C=O bonds, ester-derived C=O bonds, lactone-derived C=O bonds, etc.) The ratio of all carbon-oxygen bonds, that is, the total amount of C--O bonds and C=O bonds, to the amount is preferably 10% or more, more preferably 20% or more, and still more preferably 25% or more. The upper limit of the above ratio is preferably 35% or less. In carbon materials, the total amount of C-O bonds and C=O bonds relative to the total amount of C-C bonds, C=C bonds, C-H bonds, C-O bonds, and C=O bonds, according to C1sXPS analysis. If the ratio is within the above range, the carbon material of the present invention can be a novel carbon material having various physical properties such as solubility, unlike conventionally known simple carbon materials.

(2) All carbon-oxygen bonds by C1sXPS analysis, that is, C-O bonds (including alcohol-derived C-O bonds, ether-derived C-O bonds, epoxy-derived C-O bonds, etc.) and C=O bonds (Including C=O bonds derived from carbonyl, C=O bonds derived from carboxyl, C=O bonds derived from esters, C=O bonds derived from lactones, etc.) The ratio of the total amount of C-O-C bonds) and alcohol-derived C-O bonds (i.e., C-OH bonds) is preferably 50% or more, more preferably 60% or more, and even more preferably It is 65% or more, particularly preferably 70% or more, and most preferably 75% or more. The upper limit of the above ratio is preferably 90% or less. In the carbon material, if the ratio of the total amount of ether-derived C-O bonds and alcohol-derived C-O bonds to the total amount of C-O bonds and C=O bonds is within the above range according to C1sXPS analysis. , the carbon material of the present invention can increase the structural control rate of the carbon material portion, and the structure can be controlled more precisely. That is, the smaller the ratio of C═O bonds originating from the decomposition reaction, the more suppressed the decomposition reaction is, and it can be said that such a carbon material is a carbon material whose structure is more precisely controlled.

(3) All bonds by C1sXPS analysis, that is, C-C bonds, C=C bonds, C-H bonds, and C-O bonds (C-O bonds derived from alcohol, C-O bonds derived from ether, and C-O bonds derived from epoxy) ) and C=O bonds (including carbonyl-derived C=O bonds, carboxyl-derived C=O bonds, ester-derived C=O bonds, lactone-derived C=O bonds, etc.) The ratio of the total amount of ether-derived C-O bonds (i.e., C-O-C bonds) and alcohol-derived C-O bonds (i.e., C-OH bonds) to the amount is preferably 15% or more. , more preferably 17% or more, still more preferably 20% or more. The upper limit of the above ratio is preferably 30% or less. In carbon materials, the sum of ether-derived C-O bonds (i.e., C-O-C bonds) and alcohol-derived C-O bonds (i.e., C-OH bonds) relative to the total amount of all bonds by C1sXPS analysis If the amount ratio is within the above range, it can be said that the carbon material of the present invention is a carbon material-containing material whose structure is more precisely controlled.

(4) All bonds by C1sXPS analysis, that is, C-C bond, C=C bond, C-H bond, and C-O bond (C-O bond derived from alcohol, C-O bond derived from ether, C-O bond derived from epoxy ) and C=O bonds (including carbonyl-derived C=O bonds, carboxyl-derived C=O bonds, ester-derived C=O bonds, lactone-derived C=O bonds, etc.) The ratio of total carbon-oxygen bonds, that is, the total amount of CO bonds and C═O bonds to the amount, is within the range described in (1) above, and the total carbon-oxygen bonds are determined by C1sXPS analysis, That is, C-O bonds (including alcohol-derived C-O bonds, ether-derived C-O bonds, epoxy-derived C-O bonds, etc.) and C=O bonds (carbonyl-derived C=O bonds, carboxyl-derived C=O bonds, etc.) ether-derived C-O bonds (i.e., C-O-C bonds) and alcohol-derived C-C bonds, relative to the total amount of C=O bonds, C=O bonds derived from esters, C=O bonds derived from lactones, etc.) This is an embodiment in which the ratio of the total amount of -O bonds (ie, C-OH bonds) is within the range described in (2) above. In such an embodiment, the carbon material of the present invention can further improve the solubility of the carbon material portion, and can further increase the structural control rate of the carbon material portion. Further, in such an embodiment, the structure of the carbon material of the present invention can be controlled even more precisely.

(5) In IR analysis, preferably no peak due to C=O stretching vibration is observed between 1660 cm ^-1 and 1800 cm ^-1 . If a peak due to C═O stretching vibration is not observed between 1660 cm ⁻¹ and 1800 cm ⁻¹ in the IR analysis of the carbon material-containing material, the structure of the carbon material-containing material can be controlled more precisely. The reason why the structure of the carbon material can be controlled more precisely when no peak due to C=O stretching vibration is observed between 1660 cm ^-1 and 1800 cm ^-1 in the IR analysis of the carbon material-containing material is as described above. It is as follows.

(6) The carbon material of the present invention is soluble in a solvent.

The presence of carbon components in the carbon material of the present invention can be easily confirmed by C1sXPS analysis. Further, the carbon material of the present invention preferably has a honeycomb structure (graphene structure) derived from a benzene ring in its structure. The presence or absence of a graphene structure can be confirmed by Raman spectroscopy (Non-Patent Document 4).

In the carbon material of the present invention, the total content of metal components serving as impurities is usually preferably 0.1 atomic % or less, more preferably 0.01 atomic % or less, based on 100 atomic % of carbon atoms. Yes, particularly preferably substantially zero. These can be confirmed by analyzing the carbon material of the present invention by X-ray fluorescence elemental analysis (XRF).

The carbon material of the present invention includes carbon as an essential constituent element, and may contain elements other than carbon. Such elements other than carbon are preferably at least one element selected from oxygen, hydrogen, nitrogen, sulfur, fluorine, chlorine, bromine, and iodine, and more preferably oxygen, hydrogen, nitrogen, and sulfur. More preferably, it is at least one element selected from oxygen, hydrogen, and nitrogen, and particularly preferably at least one element selected from oxygen and hydrogen. When the total amount of elements other than hydrogen among the elements constituting the carbon material of the present invention is 100 atom%, carbon preferably accounts for 60 atom% or more, more preferably 70 atom% or more, and still more preferably It is 75 atomic % or more. Further, the content of elements other than carbon is preferably 10 atomic % or more. When the ratio of each element falls within this range, it becomes possible to exhibit good solubility even though it is a carbon material. These can be confirmed by quantifying the carbon material using X-ray photoelectron spectroscopy (C1sXPS).

The carbon material of the present invention is preferably soluble in a solvent.

Here, the case where the carbon material of the present invention is soluble in a solvent is the case where it has better solubility in a solvent than conventional carbon materials and can realize good handling properties.

As an embodiment in which the carbon material of the present invention is soluble in a solvent, the following embodiments can be preferably adopted.
(Embodiment 1) An embodiment in which all of the carbon material is dissolved in the solvent. That is, an embodiment in which the carbon material consists only of a component (component A) that dissolves in a solvent.
(Embodiment 2) An embodiment in which a part of the carbon material is dissolved in a solvent. That is, an embodiment in which the carbon material consists of a component that dissolves in a solvent (component A) and a component that does not dissolve in a solvent (component B).

In the present invention, "soluble in a solvent" means an embodiment in which a component is soluble in any solvent, and the solvent preferably includes N,N-dimethylformamide, N,N-dimethylacetamide, N- Examples include methylpyrrolidone, dimethylsulfoxide, acetone, methylethylketone, methylisobutylketone, tetrahydrofuran, methanol, ethanol, 2-propanol, butanol, chloroform, dichloromethane and the like. Namely, the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, acetone, methylethylketone, methylisobutylketone, tetrahydrofuran, methanol, ethanol, 2-propanol, butanol, chloroform, dichloromethane. Preferably, there is a component soluble in at least one solvent selected from the following. More preferred is an embodiment in which there is a component soluble in at least one solvent selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and chloroform. is an embodiment in which there is a component soluble in at least one solvent selected from the group consisting of N,N-dimethylformamide and N-methylpyrrolidone, and particularly preferably an embodiment in which there is a component soluble in N-methylpyrrolidone. be.

One embodiment in which the carbon material of the present invention is soluble in a solvent is, for example, an embodiment in which the carbon material of the present invention contains a carbon-based compound that is soluble in a solvent.

As a method for determining whether or not it is soluble in a solvent, for example, the carbon material is mixed at a concentration of 0.001% by mass with respect to the above solvent, and then subjected to ultrasonic treatment for 1 hour. When the liquid is passed through a PTFE filter paper (pore size: 0.45 μm), the determination can be made by whether or not the liquid that has passed through the filter paper contains carbon-based compounds. If the liquid that has passed through the filter paper contains a carbon-based compound, it is determined that the carbon material of the present invention contains a carbon-based compound that is soluble in the solvent. As the PTFE filter paper, for example, GL Chromato Disc (Model 13P) manufactured by GL Sciences, Inc. can be used.

The carbon material of the present invention preferably exhibits a peak in the G band (generally within the range of 1550 cm ^-1 to 1650 cm ^-1 ) in a Raman spectrum obtained by (i) Raman spectroscopy. Therefore, the fact that the carbon material of the present invention has a peak in the G band (generally within the range of 1550 cm ^-1 to 1650 cm ^-1 ) in the Raman spectrum obtained by Raman spectroscopy means that the carbon material of the present invention has a graphene structure. Or it means that it has a structure similar to graphene structure. If the G band has high intensity and is sharp, it can be said that the G band has a more beautiful graphene structure or a structure similar to a graphene structure.

The carbon material of the present invention preferably exhibits a peak in the D band (generally within the range of 1300 cm ⁻¹ to 1400 cm ⁻¹ ) in a Raman spectrum obtained by (ii) Raman spectrometry. A carbon material having a structure derived from defects in the graphene structure exhibits a peak in the D band (generally within the range of 1300 cm ⁻¹ to 1400 cm ⁻¹ ) in a Raman spectrum obtained by Raman spectroscopy. Therefore, the fact that the carbon material of the present invention has a peak in the D band (generally within the range of 1300 cm ^-1 to 1400 cm ^-1 ) in the Raman spectrum obtained by Raman spectroscopy means that the carbon material of the present invention has a functional group. This means that it contains a structure derived from a defect in the graphene structure or a structure similar to a structure derived from a defect in the graphene structure. If the intensity of the D band is low, it can be said that the D band has a more beautiful graphene structure or a structure similar to a graphene structure. Furthermore, the fact that the D band can be confirmed means that the carbon material of the present invention has a functional group, which can improve its solubility in a solvent.

The carbon material of the present invention preferably exhibits (i) a peak in the G band (generally within the range of 1550 cm ^-1 to 1650 cm ^-1 ) in a Raman spectrum obtained by Raman spectroscopy, and (ii) a Raman spectrum obtained by Raman spectroscopy. A Raman spectrum obtained by spectroscopic analysis shows a peak in the D band (generally within the range of 1300 cm ^-1 to 1400 cm ^-1 ).

The carbon material of the present invention preferably exhibits a peak in the G' band (generally within the range of 2650 cm ^-1 to 2750 cm ^-1 ) in the Raman spectrum obtained by (iii) Raman spectroscopy. Therefore, the carbon material of the present invention has a peak in the G' band (generally within the range of 2650 cm ^-1 to 2750 cm ^-1 ) in the Raman spectrum obtained by Raman spectroscopy. structure or a structure similar to that of graphene. The intensity of the G' band is strongest when the graphene structure has one layer, and gradually decreases as the number of stacked graphene structures increases. However, even though the intensity of the G' band gradually decreases as the number of stacked graphene structures increases, the peak can be observed. Therefore, having a peak in the G' band means that the carbon material of the present invention has a graphene structure or a structure similar to a graphene structure. The G' band is also sometimes called the 2D band.

The carbon material of the present invention preferably (i) exhibits a peak in the G band (generally within the range of 1550 cm ^-1 to 1650 cm ^-1 ) in a Raman spectrum obtained by Raman spectroscopy, and (ii) Raman The Raman spectrum obtained by spectroscopic analysis shows a peak in the D band (generally within the range of 1300 cm ^-1 to 1400 cm ^-1 ), and (iii) the Raman spectrum obtained by Raman spectrometry shows a peak in the G' band (generally shows a peak within the range of 2650 cm ^-1 to 2750 cm ^-1 ).

The carbon material of the present invention preferably exhibits a peak in the D+D' band (generally within the range of 2800 cm ^-1 to 3000 cm ^-1 ) in a Raman spectrum obtained by (iv) Raman spectroscopy. A carbon material having a structure derived from defects in the graphene structure exhibits a peak in the D+D' band (generally within the range of 2800 cm ⁻¹ to 3000 cm ⁻¹ ) in a Raman spectrum obtained by Raman spectroscopy. Therefore, the carbon material of the present invention has a peak in the D+D' band (generally within the range of 2800 cm ^-1 to 3000 cm ^-1 ) in the Raman spectrum obtained by Raman spectroscopy. It means that it contains a group or has a structure derived from a defect in the graphene structure or a structure similar to a structure derived from a defect in the graphene structure. If the intensity of the D+D' band is low, it can be said that the band has a more beautiful graphene structure or a structure similar to a graphene structure. The D+D' band is also sometimes called the D+G band. Furthermore, the fact that the D+D' band can be confirmed also means that the carbon material of the present invention has a functional group, which can improve its solubility in a solvent.

The carbon material of the present invention preferably (i) exhibits a peak in the G band (generally within the range of 1550 cm ^-1 to 1650 cm ^-1 ) in a Raman spectrum obtained by Raman spectroscopy, and (ii) Raman The Raman spectrum obtained by spectroscopic analysis shows a peak in the D band (generally within the range of 1300 cm ^-1 to 1400 cm ^-1 ), and (iii) the Raman spectrum obtained by Raman spectrometry shows a peak in the G' band (generally (iv) a peak in the D+D' band (generally within the range of 2800 ^{cm -1 to} 3000 ^{cm -1 )} in the Raman spectrum obtained by Raman spectroscopy. Indicates peak.

The carbon material of the present invention preferably contains a carbon-based compound that is soluble in a solvent.

As one embodiment, the carbon material of the present invention exhibits a peak in the G band (generally within the range of 1550 cm ^-1 to 1650 cm ^-1 ) in a Raman spectrum obtained by (i) Raman spectroscopy, and further , (ii) exhibits a peak in the D band (generally within the range of 1300 cm ⁻¹ to 1400 cm ⁻¹ ) in a Raman spectrum obtained by Raman spectroscopy, and further contains a carbon-based compound that is soluble in a solvent.

When the carbon material of the present invention contains a functional group and also has defects in a part of the graphene structure, these defects may contribute to the solubility of the carbon material of the present invention in a solvent.

As mentioned above, unlike conventionally known carbon materials, the carbon material of the present invention has a graphene structure or a structure similar to a graphene structure, and has better solubility in a solvent (for example, carbon (The material has more components and can be dissolved in more types of solvents.)

The molecular weight of the carbon-based compound contained in the carbon material of the present invention is preferably 1,000 to 1,300,000, more preferably 5,000 to 1,000,000, still more preferably 10,000 to 700,000, particularly preferably 15,000 to 500,000, The most preferred range is 20,000 to 300,000. If the molecular weight of the carbon-based compound contained in the carbon material of the present invention is within the above range, in combination with the feature (i) above, the carbon material of the present invention has better solubility in a solvent (for example, (This increases the number of carbon material components that can be dissolved, and increases the number of types of solvents that can be dissolved.) If the molecular weight of the carbon-based compound contained in the carbon material exceeds 1,300,000, the solubility of the carbon material in a solvent may deteriorate. If the molecular weight of the carbon-based compound contained in the carbon material is less than 1000, the characteristics as a carbon material may be weakened. These molecular weights can be analyzed by the method described below.

The content of the carbon-based compound in the carbon material of the present invention is preferably 50% to 100% by mass, more preferably 70% to 100% by mass, and even more preferably 90% to 100% by mass. It is particularly preferably 95% by weight to 100% by weight, most preferably substantially 100% by weight. If the content ratio of the carbon-based compound in the carbon material of the present invention is within the above range, in combination with the features (i) and (ii) above, the carbon material of the present invention has better solubility in a solvent (e.g. , the number of carbon material components that can be dissolved in a solvent increases, and the types of solvents that can be dissolved increase.)

The carbon material of the present invention preferably shows a peak within the range of 20° to 30° in an XRD spectrum chart obtained by XRD analysis. That is, one of the preferred embodiments is that the carbon material of the present invention has a structure in which graphene structures are stacked (graphene stacked structure). By having a laminated structure, the carbon material of the present invention can be made stronger and more stable.

A more preferable form of the carbon material of the present invention is any of the forms (i) to (iv) described above in the Raman spectrum obtained by Raman spectroscopy, or a combination of forms; (i) and (ii), (i) ), (ii) and (iii), (i), (ii), (iii) and (iv), and within the range of 20° to 30° in the XRD spectrum chart obtained by XRD analysis. This is a form that shows a peak.

≪≪3. Manufacturing method of carbon material-containing material≫≫
The method for producing a carbon material-containing material of the present invention includes a heating step (I) of heating a composition containing an inorganic substance and a compound (A) in which a condensation reaction occurs between the same molecules and/or different molecules when heated; The heating temperature in the heating step (I) is at least (T-150)°C when the condensation reaction temperature of the compound (A) is T°C, and the compound (A) has two or more molecules in the molecule. It is a compound having a phenolic OH group, and the heating step (I) includes a condensation reaction between two of the phenolic OH groups of the compound (A) between the same molecules and/or between different molecules.

In the heating step (I), a composition containing an inorganic substance and a compound (A) that causes a condensation reaction between the same molecules and/or between different molecules upon heating is heated. The blending ratio of compound (A) and inorganic substance is preferably 0.01% by mass to 1,000,000% by mass, more preferably 0.1% by mass to 100,000% by mass, relative to 100% by mass of inorganic matter. It is % by mass, particularly preferably 1% by mass to 1000% by mass. If the blending ratio of the compound (A) and the inorganic substance is within the above range, a carbon material-containing material whose structure is more precisely controlled can be manufactured more easily under milder conditions. The blending ratio of these inorganic substances and compound (A) can be arbitrarily adjusted depending on the physical properties of the intended composite. For example, by adjusting the blending ratio of the inorganic substance and the compound (A), the physical properties and form of the resulting carbon material-containing material (for example, solubility in a solvent, the shape of the carbon component or inorganic component (particulate or non-particulate), (such as the size of the carbon component or inorganic component).

The composition containing the compound (A), which undergoes a condensation reaction between the same molecules and/or different molecules upon heating, and an inorganic substance may not contain any other appropriate components as long as the effects of the present invention are not impaired. You can leave it there. Examples of such other components include a solvent, a catalyst, a base material, a carrier, and the like.

The composition to be heated in the heating step (I) may be prepared by any appropriate method as long as the effects of the present invention are not impaired. Examples of such a method include a method of mixing compound (A) and an inorganic substance in a solid state by any appropriate method (eg, crushing, pulverization, etc.). Alternatively, the compound (A), the inorganic substance, the solvent, and, if necessary, other components other than the solvent may be mixed by any appropriate method (for example, ultrasonication, etc.), Examples include a method of removing the solvent by vacuum drying). Further, crushing may be performed as necessary.

The heating temperature in the heating step (I) is (T-150)°C or higher, preferably (T-150 to T+50)°C, when the condensation reaction temperature of compound (A) is T°C, and more preferably Preferably (T-130 to T+45)°C, more preferably (T-100 to T+40)°C, particularly preferably (T-80 to T+35)°C, most preferably (T-50 to T+30) )℃. In the method for producing a carbon material-containing material of the present invention, since the catalytic ability of the inorganic material and the reactivity of the functional group on the inorganic material and the carbon material are high, the temperature is lower than the condensation reaction temperature of the compound (A) as described above. The reaction can proceed from a relatively low temperature and carbonization can proceed. By adjusting the heating temperature within the above range, a carbon material-containing material that is soluble in a solvent or a carbon material-containing material whose structure is more precisely controlled can be manufactured more easily under milder conditions.

The condensation reaction temperature of compound (A) can be determined by TG-DTA analysis. Specifically, it is as follows.
(1) When one type of compound is used as compound (A), TG-DTA analysis of compound (A) is performed by heating the compound (A) from 40°C at a heating rate of 10°C/min in a nitrogen gas atmosphere, The peak top temperature on the lowest temperature side of DTA is determined as the condensation reaction temperature (T° C.) of compound (A).
(2) When using a mixture of two or more compounds as compound (A), perform TG-DTA analysis of the mixture by increasing the temperature from 40°C at a heating rate of 10°C/min in a nitrogen gas atmosphere. , the peak top temperature at the lowest temperature side of DTA is determined as the condensation reaction temperature (T° C.) of compound (A) (a mixture of two or more compounds).
(3) However, if compound (A) as one type of compound or a mixture of two or more types of compounds contains impurities such as a solvent, water, or water of hydration, the impurities can be removed. A DTA peak (sometimes referred to as an impurity peak) accompanying the condensation reaction may be observed at a temperature lower than the condensation reaction temperature. In such a case, the above impurity peak is ignored and the condensation reaction temperature of the compound (A) is determined. Usually, the peak top temperature on the lowest temperature side of DTA is determined as the condensation reaction temperature of the compound (A), ignoring the impurity peaks mentioned above.

The specific heating temperature in the heating step (I) is preferably 200°C to 500°C, more preferably 220°C to 400°C, still more preferably 230°C to 350°C, and most preferably Preferably it is 250°C to 300°C. By adjusting the heating temperature within the above range, a carbon material-containing material that is soluble in a solvent or a carbon material-containing material whose structure is more precisely controlled can be manufactured more easily under milder conditions. In particular, since the heating temperature in the heating step (I) is so low, the carbon material-containing material can be industrially manufactured under milder conditions.

The specific heating time in the heating step (I) is preferably 0.1 to 120 hours, more preferably 0.5 to 100 hours, and even more preferably 1 to 50 hours. and most preferably from 2 hours to 24 hours. By adjusting the heating time within the above range, a carbon material-containing material that is soluble in a solvent or a carbon material-containing material whose structure is more precisely controlled can be produced more easily under milder conditions.

≪3-1. Compound (A)≫
When compound (A) is heated, a condensation reaction occurs between the same molecules and/or between different molecules. Then, through the heating step (I) of heating the composition containing the compound (A) and the inorganic substance, the compound (A) can be turned into a carbon material.

Compound (A) is a compound having two or more phenolic OH groups in the molecule. The number of compounds having two or more phenolic OH groups in the molecule may be one, or two or more.

In the method for producing a carbon material-containing material of the present invention, by employing a compound having two or more phenolic OH groups in the molecule as the compound (A), the heating step (I) It involves a condensation reaction between the two phenolic OH groups between the same molecules and/or between different molecules. In addition, in the heating step (I), in addition to the above-mentioned condensation reaction between the same molecules and/or between the two phenolic OH groups between the same molecules and/or different molecules, reactions between the same molecules and between the same molecules and/or between different types of molecules are carried out within the range that does not impair the effects of the present invention. It may also include a condensation reaction between any other suitable two groups between different molecules.

A condensation reaction between two phenolic OH groups of a compound having two or more phenolic OH groups in the molecule, between the same molecules and/or between different molecules, preferably by at least a C-O-C bond. A structure in which two aromatic rings are bonded is formed. Furthermore, new bonds (for example, C--C bonds, etc.) are formed between two or more aromatic rings by the above condensation reaction and other reactions that occur following or in parallel with the condensation reaction. or polymerization may proceed.

Note that the formation of the above C--C bond is, for example, a deoxygenation reaction from a C--O--C bond, a dehydration reaction between an H group directly bonded to an aromatic ring and an OH group, a H group directly bonded to an aromatic ring, etc. This can occur due to a dehydrogenation reaction between the group and the H group.

Further, depending on the selection of the compound (A) and the selection of various conditions in the heating step (I), a ring condensation reaction between two or more aromatic rings may also occur.

Regarding compound (A), <<1-1. The explanation in Compound (A)>> can be referred to.

≪3-2. Inorganic substances≫
Any suitable inorganic material may be used as the inorganic material as long as the effects of the present invention are not impaired. As such an inorganic substance, for example, a particulate inorganic substance (inorganic particle), a non-particulate inorganic substance (for example, a fibrous inorganic substance, a thin film inorganic substance, etc.) can be employed. As the inorganic substance, particulate inorganic substances (inorganic particles) are preferable.

The number of inorganic substances may be one type or two or more types.

The inorganic substance is preferably at least one selected from the group consisting of inorganic oxides, inorganic nitrides, inorganic sulfides, inorganic carbides, and insoluble salts.

Examples of the "inorganic oxide" referred to in the present invention include metals whose surfaces are partially oxidized, preferably metals whose surfaces are at least partially oxidized. This is because, as will be described later, a portion of the metal, preferably at least a portion of its surface, is generally oxidized. Such metals are preferably metals that are easily oxidized, such as magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), titanium (Ti), zirconium (Zr), and hafnium. (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), indium (In), gallium (Ga), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), cadmium (Cd), aluminum (Al), tin (Sn), lanthanum (La), yttrium (Y), cerium (Ce), silicon (Si), etc., and more preferably copper (Cu), aluminum (Al), and silicon (Si). That is, such a metal is easily oxidized, and a portion thereof, preferably at least a portion of its surface, is oxidized, and is included in the "inorganic oxide" referred to in the present invention.

Specifically, the "inorganic oxide" referred to in the present invention includes, for example, silica, alumina, titania, polyacid, and metals whose surfaces are partially oxidized (preferably, whose surfaces are at least partially oxidized. Examples include metals), composite oxides, and solid solution oxides. That is, the "inorganic oxide" referred to in the present invention may be an oxide consisting of one kind of metal element, or a composite oxide of two or more kinds of metal elements. The oxide may be a so-called solid solution oxide in which a different element is dissolved in an oxide (also referred to as a single metal oxide) or a composite oxide consisting of one type of metal element. Note that the different element in the solid solution oxide may be a metallic element or a nonmetallic element other than oxygen, such as nitrogen or fluorine.

The number of inorganic oxides may be one, or two or more. Examples of cases in which two or more types of inorganic oxides are employed include cases in which two or more types of inorganic oxides are simply used together (mixed, etc.), or cases in which two or more types of inorganic oxides are combined. For example, when

Examples of the above-mentioned "oxides consisting of one metal element" include magnesium oxide, calcium oxide, strontium oxide, barium oxide, titanium oxide, zirconium oxide, hafnium oxide, vanadium oxide, niobium oxide, tantalum oxide, Chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide, indium oxide, gallium oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, cadmium oxide, aluminum oxide, tin oxide, lanthanum oxide, yttrium oxide, cerium oxide , silicon oxide, etc., and preferred are magnesium oxide, titanium oxide (titania), aluminum oxide (alumina), and silicon oxide (silica).

As the above-mentioned "composite oxide consisting of two or more types of metal elements", any suitable composite oxide may be employed as long as the effects of the present invention are not impaired. Such a complex oxide is typically an oxide containing two or more metals, such as a perovskite-structured complex oxide, a spinel-structured complex oxide, and the like.

The perovskite structure double oxide is typically an oxide represented by ABO ₃ (A and B represent different elements), such as perovskite (CaTiO ₃ ), barium titanate, etc. (BaTiO ₃ ), strontium titanate (SrTiO ₃ ), lead zirconate titanate (Pb(Zr,Ti)O ₃ ), barium zirconate (BaZrO ₃ ), lithium niobate (LiNbO ₃ ), and the like.

Examples of the spinel-structured double oxide include spinel (MgAl ₂ O ₄ ), lithium titanate (LiTi ₂ O ₄ ), and chrysoberyl (BeAl ₂ O ₄ ).

As the above-mentioned "solid solution oxide", any suitable solid solution oxide may be employed as long as the effects of the present invention are not impaired. Such a solid solution oxide is typically a single metal oxide or a composite oxide in which a different metal element and/or a nonmetallic element other than oxygen, such as nitrogen or fluorine, is dissolved in solid solution.

The "inorganic oxide" referred to in the present invention is an inorganic oxide as a whole, regardless of its shape (i.e., for example, whether it is an inorganic oxide particle or a non-particulate inorganic oxide). It may be an embodiment, or it may be an embodiment in which a part is an inorganic oxide. The embodiment in which a portion is an inorganic oxide is preferably an embodiment in which the surface has an inorganic oxide.

An embodiment in which a part is an inorganic oxide (preferably an embodiment having an inorganic oxide on the surface) may be any shape, for example, a metal in which a part of the part is oxidized (preferably an embodiment having an inorganic oxide on the surface). metals that are at least partially oxidized. A portion of the metal (preferably at least a portion of its surface) can be oxidized in the presence of oxygen. Therefore, the "embodiment having an inorganic oxide on the surface" which is one form of the inorganic oxide in the present invention includes a metal whose surface is at least partially oxidized, regardless of its shape.

When inorganic oxide particles are used as the inorganic oxide, the heating step (I) of heating a composition containing the compound (A) and the inorganic oxide typically produces a lumpy carbon material containing a large number of inorganic oxide particles. A containing material may be obtained (in this case, a particulate carbon material-containing material may be obtained by crushing or the like). However, by adjusting the blending ratio of the compound (A) and the inorganic oxide, a particulate carbon material-containing material can be obtained by the heating step (I) of heating a composition containing the compound (A) and the inorganic oxide. In some cases,

When a fibrous inorganic oxide is used as the inorganic oxide, for example, fibrous core-shell fibers can be obtained instead of the core-shell particles described below. Moreover, when using a fibrous inorganic oxide, for example, a tube-shaped hollow carbon material can be obtained instead of the hollow carbon fine particles described below.

When using a thin film-like inorganic oxide as the inorganic oxide, a laminated carbon material-containing material can be obtained, for example, by the heating step (I) of heating the composition containing the compound (A) and the inorganic oxide. . Further, by further performing a heating process (II), a carbon material removal process, an inorganic oxide removal process, etc. to be described later on such a laminated carbon material-containing material, for example, various carbon materials in a thin film form can be formed. can be obtained.

The decomposition temperature of the inorganic oxide is preferably 800° C. or higher, more preferably 850° C. or higher, still more preferably 900° C. or higher, and particularly preferably 950° C. or higher, in order to better express the effects of the present invention. ℃ or higher.

In the present invention, inorganic oxide particles are preferable as the inorganic oxide in that the effects of the present invention can be more fully expressed.

The "inorganic oxide particles" as used herein are preferably particles in which the entire particle is an inorganic oxide, or particles in which a part of the particle is an inorganic oxide. As particles in which part of the particles is an inorganic oxide, particles having an inorganic oxide on the surface are preferable. More preferably, the "inorganic oxide particles" referred to in this specification are particles in which the entire particle is an inorganic oxide.

Examples of particles whose part is an inorganic oxide (preferably particles having an inorganic oxide on their surface) include, for example, metal particles whose part is oxidized (preferably at least part of their surface). oxidized metal particles). A part of the metal particle (preferably at least a part of its surface) can be oxidized in the presence of oxygen. Therefore, "particles having an inorganic oxide on their surfaces", which is one form of inorganic oxide particles as used in the present invention, includes metal particles whose surfaces are at least partially oxidized.

Inorganic oxide particles other than metal particles (for example, silica particles, alumina particles, titania particles, etc.) include not only particles in which the entire particle is an inorganic oxide, but also particles in which a part of the particle is an inorganic oxide. (preferably particles having an inorganic oxide on the surface). That is, for example, taking silica particles as an example, silica particles include not only cases in which the entire particle is silica, but also particles in which part of the particle is silica (preferably particles having silica on the surface). It is also possible.

The average particle diameter of the inorganic oxide particles can be appropriately set depending on the purpose. The average particle diameter of the inorganic oxide particles is preferably from 0.01 μm to 100 μm, particularly preferably from 0.1 μm to 10 μm, in order to better exhibit the effects of the present invention.

The average particle diameter of the inorganic oxide particles is the average particle diameter in a volume-based particle size distribution, and is preferably measured by a laser diffraction scattering method.

The inorganic oxide particles are preferably inorganic oxide particles having a functional group on the surface so that the effects of the present invention can be more fully expressed. Such functional groups include, for example, hydroxyl functional groups such as M-OH; oxygen functional groups including ether functional groups such as M- _O -M; Nitrogen functional groups including amine functional groups such as; sulfur functional groups including thiol functional groups such as M-SH and M-SM; silicon functional groups, boron functional groups, phosphorus functional groups, etc. (M conceptually indicates the object to which the functional group is bonded, and is any suitable object to which the functional group can bond, such as the inorganic oxide itself, for example, the metal element or organic group that constitutes the inorganic oxide. ). These functional groups can be easily formed by surface treating an inorganic oxide with various compounds. Among these, preferred inorganic oxide particles are inorganic oxide particles having an oxygen functional group on the surface.

If inorganic oxide particles having a functional group on the surface are used as the inorganic oxide, the functional group present on the surface of the inorganic oxide particle can form a bond with the carbon material in the carbon material-containing material. The region of the carbon material contributing to such bonding (carbon material bonding region) is not the carbon material itself. That is, as shown in FIG. 1, an organic-inorganic composite (details will be described later) 100 in one preferred embodiment of the carbon material-containing material includes a plurality of inorganic particles 20 (in this case, At the interface between the carbon material 10 and the inorganic particles 20, there is a carbon material formed by the carbon material forming a bond with a functional group present on the surface of the inorganic particle 20. A region (carbon material bonding region) 30 exists. Then, for example, when the carbon material is soluble in a solvent, when the organic-inorganic composite 100 is treated with a solvent that dissolves the carbon material, as shown in FIG. A core-shell particle (core part: inorganic oxide particle, shell part: carbon material binding region) 200 coated with a region (region not dissolved by a solvent) 30 can be obtained. By removing the inorganic particles 20 as the core portion from the core-shell particles 200 thus obtained, hollow carbon fine particles having a carbon material can be obtained.

Inorganic oxide particles having functional groups on their surfaces are preferably silica particles, alumina particles, titania particles, magnesium oxide particles, polyacid particles, metal particles whose surfaces are at least partially oxidized, and composite oxide particles. , solid solution oxide particles. Examples of inorganic oxide particles having a functional group on the surface include silica particles, alumina particles, titania particles, magnesium oxide particles, polyacid particles, metal particles whose surfaces are at least partially oxidized, composite oxide particles, and solid solution oxides. By employing at least one kind selected from the group consisting of particles, the functional groups present on the surface of the inorganic oxide particles can more easily form bonds with the carbon material.

More preferably, the inorganic oxide particles having a functional group on the surface are polyacid particles. Examples of the polyacid constituting the polyacid particles include isopolyacid and heteropolyacid. As mentioned above, when compound (A) is used, a carbon material-containing material can be obtained without using the catalytic effect. However, in particular, when polyacid particles are used as inorganic oxide particles having functional groups on the surface, strong acid Due to the combination of the catalytic effect of carbon and the presence of surface functional groups, the dehydration condensation reaction is promoted in the case of a carbon material-containing material, and the ratio of the total amount of -OH groups and -O- groups to the total amount of C-O bonds increases. and can have a high structural control rate.

As the isopoly acid, any suitable isopoly acid may be employed as long as the effects of the present invention are not impaired. Examples of such isopolyacids include molybdenum, vanadium, tungsten, niobium, titanium, tantalum, chromium, manganese, rhenium, iron, ruthenium, cobalt, nickel, palladium, platinum, copper, silver, gold, tin, titanium, Examples include inorganic acids and their salts mainly composed of inorganic elements such as zirconium, rhodium, iridium, osmium, zinc, etc. Typical examples include molybdic acid, vanadate acid, tungstic acid, niobic acid, titanic acid, tantalic acid, etc. can be mentioned.

As the heteropolyacid, any suitable heteropolyacid may be employed as long as the effects of the present invention are not impaired. Examples of such heteropolyacids include isopolyacids or metal salts thereof into which heteroatoms are introduced. Examples of the heteroatom include oxygen, sulfur, phosphorus, ammonium, potassium, sodium, and silicon. The heteropolyacid may be a hydrate.

Specific examples of the heteropolyacid include, for example, a tungsten-based heteropolyacid obtained by introducing a heteroatom into an isopolyacid containing tungsten, and a molybdenum-based heteropolyacid obtained by introducing a heteroatom into an isopolyacid containing molybdenum. Can be mentioned.

Examples of the tungsten-based heteropolyacid include phosphotungstic acid, silicotungstic acid, cobalt tungstic acid, germanotungstic acid, borotungstic acid, phosphotungstic acid, phosphotungstomolybdic acid, and the like.

Examples of molybdenum-based heteropolyacids include phosphomolybdic acid, silicomolybdic acid, and phosphovanadomolybdic acid.

Any suitable inorganic nitride may be used as the inorganic nitride as long as the effects of the present invention are not impaired. Examples of such inorganic nitrides include boron nitride, carbon nitride, aluminum nitride, and gallium nitride, with boron nitride and aluminum nitride being preferred.

The number of inorganic nitrides may be one, or two or more.

In the present invention, inorganic nitride particles are preferable as the inorganic nitride, similar to the above-mentioned inorganic oxides, in that they can better exhibit the effects of the present invention.

The average particle diameter of the inorganic nitride particles can be appropriately set depending on the purpose. The average particle diameter of the inorganic nitride particles is preferably 0.01 μm to 100 μm, particularly preferably 0.1 μm to 10 μm, so that the effects of the present invention can be more fully expressed.

The average particle diameter of the inorganic nitride particles is the average particle diameter in a volume-based particle size distribution, and is preferably measured by a laser diffraction scattering method.

The inorganic nitride particles are preferably inorganic nitride particles having a functional group on the surface so that the effects of the present invention can be more fully expressed. Such functional groups include, for example, hydroxyl functional groups such as M-OH; oxygen functional groups including ether functional groups such as M- _O -M; Nitrogen functional groups including amine functional groups such as; sulfur functional groups including thiol functional groups such as M-SH and M-SM; silicon functional groups, boron functional groups, phosphorus functional groups, etc. (M conceptually indicates the object to which the functional group is bonded, and is any suitable object to which the functional group can bond, such as the inorganic nitride itself, for example, the metal element or organic group that constitutes the inorganic nitride. ). These functional groups can be easily formed by surface treating the inorganic nitride with various compounds.

If inorganic nitride particles having a functional group on the surface are used as the inorganic nitride, the functional group present on the surface of the inorganic nitride particle can form a bond with the carbon material in the carbon material-containing material. The region of the carbon material contributing to such bonding (carbon material bonding region) is not the carbon material itself. That is, similar to the above-mentioned inorganic oxide particles having functional groups on the surface, as shown in FIG. A plurality of inorganic particles 20 (in this case, inorganic nitride particles) are dispersed in a carbon material 10, and at the interface between the carbon material 10 and the inorganic particles 20, the carbon material is disposed on the surface of the inorganic particles 20. There is a region (carbon material bonding region) 30 of the carbon material formed by forming a bond with a functional group present in the carbon material. Then, for example, when the carbon material is soluble in a solvent, when the organic-inorganic composite 100 is treated with a solvent that dissolves the carbon material, as shown in FIG. A core-shell particle (core part: inorganic nitride particle, shell part: carbon material binding region) 200 coated with a region (region not dissolved by a solvent) 30 can be obtained. By removing the inorganic particles 20 as the core portion from the core-shell particles 200 thus obtained, hollow carbon fine particles having a carbon material can be obtained.

As the inorganic sulfide, any suitable inorganic sulfide may be employed as long as the effects of the present invention are not impaired. Examples of such inorganic sulfides include copper sulfide, zinc sulfide, and cadmium sulfide.

The number of inorganic sulfides may be one, or two or more.

In the present invention, inorganic sulfide particles are preferable as the inorganic sulfide, similar to the above-mentioned inorganic oxides, in that the effects of the present invention can be more fully expressed.

The average particle diameter of the inorganic sulfide particles can be appropriately set depending on the purpose. The average particle diameter of the inorganic sulfide particles is preferably from 0.01 μm to 100 μm, particularly preferably from 0.1 μm to 10 μm, in order to better exhibit the effects of the present invention.

The average particle diameter of the inorganic sulfide particles is the average particle diameter in a volume-based particle size distribution, and is preferably measured by a laser diffraction scattering method.

The inorganic sulfide particles are preferably inorganic sulfide particles having a functional group on the surface, in order to more effectively exhibit the effects of the present invention. Such functional groups include, for example, hydroxyl functional groups such as M-OH; oxygen functional groups including ether functional groups such as M- _O -M; Nitrogen functional groups including amine functional groups such as; sulfur functional groups including thiol functional groups such as M-SH and M-SM; silicon functional groups, boron functional groups, phosphorus functional groups, etc. (M conceptually indicates the object to which the functional group is bonded, and is any suitable object to which the functional group can bond, such as the inorganic sulfide itself, for example, the metal element or organic group that constitutes the inorganic sulfide. ). These functional groups can be easily formed by surface treating an inorganic sulfide with various compounds.

If inorganic sulfide particles having a functional group on the surface are used as the inorganic sulfide, the functional group present on the surface of the inorganic sulfide particle can form a bond with the carbon material in the carbon material-containing material. The region of the carbon material contributing to such bonding (carbon material bonding region) is not the carbon material itself. That is, similar to the above-mentioned inorganic oxide particles having functional groups on the surface, as shown in FIG. A plurality of inorganic particles 20 (in this case, inorganic sulfide particles) are dispersed in a carbon material 10, and at the interface between the carbon material 10 and the inorganic particles 20, the carbon material is formed on the surface of the inorganic particles 20. There is a region (carbon material bonding region) 30 of the carbon material formed by forming a bond with a functional group present in the carbon material. Then, for example, when the carbon material is soluble in a solvent, when the organic-inorganic composite 100 is treated with a solvent that dissolves the carbon material, as shown in FIG. A core-shell particle (core part: inorganic nitride particle, shell part: carbon material binding region) 200 coated with a region (region not dissolved by a solvent) 30 can be obtained. By removing the inorganic particles 20 as the core portion from the core-shell particles 200 thus obtained, hollow carbon fine particles having a carbon material can be obtained.

As the inorganic carbide, any suitable inorganic carbide may be employed as long as the effects of the present invention are not impaired. Examples of such inorganic carbides include silicon carbide, tungsten carbide, and calcium carbide.

The number of inorganic carbides may be one, or two or more.

In the present invention, inorganic carbide particles are preferable as the inorganic carbide, similar to the above-mentioned inorganic oxides, in that the effects of the present invention can be more fully expressed.

The average particle diameter of the inorganic carbide particles can be appropriately set depending on the purpose. The average particle diameter of the inorganic carbide particles is preferably from 0.01 μm to 100 μm, particularly preferably from 0.1 μm to 10 μm, in order to better exhibit the effects of the present invention.

The average particle diameter of the inorganic carbide particles is the average particle diameter in a volume-based particle size distribution, and is preferably measured by a laser diffraction scattering method.

The inorganic carbide particles are preferably inorganic carbide particles having a functional group on the surface so that the effects of the present invention can be more fully expressed. Such functional groups include, for example, hydroxyl functional groups such as M-OH; oxygen functional groups including ether functional groups such as M- _O -M; Nitrogen functional groups including amine functional groups such as; sulfur functional groups including thiol functional groups such as M-SH and M-SM; silicon functional groups, boron functional groups, phosphorus functional groups, etc. (M conceptually indicates the object to which the functional group is bonded, and may be any suitable object to which the functional group can bond, such as the inorganic carbide itself, for example, the metal element or organic group that constitutes the inorganic carbide. ). These functional groups can be easily formed by surface treating an inorganic carbide with various compounds.

If inorganic carbide particles having a functional group on the surface are used as the inorganic carbide, the functional group present on the surface of the inorganic carbide particle can form a bond with the carbon material in the carbon material-containing material. The region of the carbon material contributing to such bonding (carbon material bonding region) is not the carbon material itself. That is, similar to the above-mentioned inorganic oxide particles having functional groups on the surface, as shown in FIG. A plurality of inorganic particles 20 (in this case, inorganic carbide particles) are dispersed in the carbon material 10, and at the interface between the carbon material 10 and the inorganic particles 20, the carbon material is on the surface of the inorganic particles 20. There is a region 30 of carbon material formed by forming a bond with an existing functional group (carbon material bonding region). Then, for example, when the carbon material is soluble in a solvent, when the organic-inorganic composite 100 is treated with a solvent that dissolves the carbon material, as shown in FIG. A core-shell particle (core part: inorganic nitride particle, shell part: carbon material binding region) 200 coated with a region (region not dissolved by a solvent) 30 can be obtained. By removing the inorganic particles 20 as the core portion from the core-shell particles 200 thus obtained, hollow carbon fine particles having a carbon material can be obtained.

As the insoluble salt, any suitable insoluble salt may be employed as long as it does not impair the effects of the present invention. Such insoluble salts are preferably metal-containing salts that are insoluble in organic solvents, such as metal phosphates such as lithium iron phosphate, metal sulfates, etc., and preferably lithium iron phosphate. It is.

The number of insoluble salts may be one, or two or more.

The insoluble salt only needs to be insoluble in the solvent used in the method for producing a carbon material-containing material in the embodiment of the present invention. For example, when a solvent is used in the step of mixing compound (A) and an inorganic substance, any inorganic substance that is insoluble in the solvent may be used. In other words, an appropriate solvent that does not dissolve the inorganic substance may be selected depending on the inorganic substance. The same applies to the carbon material removal step when the method for producing a carbon material-containing material in the embodiment of the present invention includes the carbon material removal step. In addition, in the manufacturing method of a carbon material-containing material according to an embodiment of the present invention, when manufacturing hollow carbon fine particles etc., it is preferable to include a step of dissolving an inorganic substance; In this case, an inorganic substance that does not dissolve in the solvent may be selected in the step before this step. Insoluble salt means that it is soluble in a solvent under certain conditions, but is insoluble in a solvent in the production method that can exhibit the effects of the present invention. Furthermore, the insoluble salt is preferably in the form of particles, and the preferable range of the average particle diameter is also the same as that of the oxide.

In addition, when at least one type selected from the group consisting of silica particles and polyacid particles is employed as the inorganic oxide particles having functional groups on the surface, the functional groups present on the surface of the inorganic oxide particles bond with the carbon material. The resulting carbon material-containing material preferably shows no peak due to C=O stretching vibration between 1660 cm ^-1 and 1800 cm ^-1 in IR analysis. If a peak due to C═O stretching vibration is not observed between 1660 cm ⁻¹ and 1800 cm ⁻¹ in the IR analysis of the carbon material-containing material, the structure of the carbon material-containing material can be controlled more precisely.

≪≪4. Typical example of manufacturing method of carbon material-containing material≫≫
The carbon material-containing materials that can be produced by the method for producing carbon material-containing materials of the present invention include a wide variety of materials, including granular, non-particulate (e.g., fibrous, thin film, etc.) shapes. , can take various shapes. The shape is preferably particulate.

As mentioned above, for example, as the inorganic substance, inorganic substances in various shapes such as particulate inorganic substances (inorganic particles) and non-particulate inorganic substances (for example, fibrous inorganic substances, thin film-like inorganic substances, etc.) are employed. In this case, a wide variety of carbon material-containing materials can be obtained depending on the respective shapes. As the inorganic substance, particulate inorganic substances (inorganic particles) are preferable.

When inorganic particles are used, the method for producing a carbon material-containing material of the present invention can typically yield a lumpy carbon material-containing material containing a large number of inorganic particles. In this case, a particulate carbon material-containing material may be obtained by crushing or the like. Further, by adjusting the blending ratio of compound (A) and inorganic material, a particulate carbon material-containing material may be obtained by the method for producing a carbon material-containing material of the present invention.

When a fibrous inorganic material is used, fibrous core-shell fibers can be obtained instead of core-shell particles described below by the method for producing a carbon material-containing material of the present invention. Furthermore, when using a fibrous inorganic material, a tubular hollow carbon material can be obtained instead of the hollow carbon fine particles described below by the method for producing a carbon material-containing material of the present invention.

When using a thin film-like inorganic material, a laminated carbon material-containing material can be obtained by the method for producing a carbon material-containing material of the present invention. Further, by further subjecting such a laminated carbon material-containing material to a heating step (II), a carbon material removal step, an inorganic matter removal step, etc., which will be described later, various thin film carbon materials can be obtained. .

In the carbon material-containing material that can be produced by the method for producing a carbon material-containing material of the present invention, the film thickness of the carbon material portion can be adapted to various uses by controlling its size. As for the film thickness of such a carbon material part, for example, to explain a specific aspect as a typical example,
(Aspect 1) A carbon material in a carbon material-containing material obtained by removing all carbon materials other than the carbon material that strongly interacts with the outermost surface of an inorganic material and is present on the surface of the inorganic material in a carbon material removal step. Part film thickness,
(Aspect 2) The film thickness of the carbon material portion of the carbon material-containing material with all or part of the carbon material portion of the carbon material-containing material remaining;
can be mentioned.

More specifically, the carbon material portion in the above (aspect 1) is a carbon material other than the carbon material (representative Specifically, it is a carbon material portion that is obtained by removing all of the soluble carbon material and that strongly interacts with the outermost surface of the inorganic material. The film thickness of such a carbon material portion is thin, and although it depends on the structure of the carbon material, it is preferably 0.3 nm to 10 nm, more preferably 0.4 nm to 3 nm. By controlling the film thickness of the carbon material portion within such a range, the carbon component that has strongly interacted with the inorganic substance can be fully utilized for various purposes.

In addition, in the above (aspect 1), although the film thickness of the carbon material portion is typically thin, it is also possible to adjust the thickness without an upper limit by using an appropriate carbon material removal method.

The film thickness of the carbon material portion in the above (aspect 2) is typically thicker than the film thickness of the carbon material portion in the above (aspect 1), but is preferably is 100 μm or less, more preferably 50 μm or less, even more preferably 10 μm or less, and most preferably 1 μm or less. In the above (aspect 2), if the film thickness of the carbon material portion is controlled within such a range, the function as a film can be fully exhibited.

Note that the film thickness of the carbon material portion can also be appropriately controlled by the type of raw material compound (for example, compound (A)) used in the method for manufacturing a carbon material-containing material and the manufacturing conditions.

The film thickness of such a carbon material portion can be confirmed by various analytical methods. Such analysis methods include, for example, direct observation using an electron microscope (Method A), carbon content calculated from elemental analysis and thermogravimetric analysis, and macroscopic surface area of inorganic substances (organic molecules such as the present invention). (Excluding the surface area of microstructures that cannot be penetrated) and a method of estimating from the density of carbon material (Method B).

More specifically, in the above (method A), for example, a cross section of a carbon material-containing material to be a sample is examined using a transmission electron microscope or a scanning electron microscope, preferably a transmission electron microscope equipped with an energy dispersive X-ray analyzer. Examples include a method using a scanning electron microscope or a scanning electron microscope.

In the above (method B), the macroscopic surface area of the inorganic substance can be estimated from the shape of the carbon material-containing material serving as a sample, the shape of the contained inorganic substance, and the like.

In the above (Method A), for example, when the sample is a particle, it is preferable to measure the thickness of each particle contained in the sample at three or more locations, and take the simple average value as the film thickness of the particle. More preferably, the film thickness of 10 or more particles can be determined, and the simple average value thereof can be taken as the average film thickness of the sample. It is preferable that the film thickness (average film thickness) obtained in this way falls within the desired film thickness range to be controlled, for example.

In the above (method B), the analyzed film thickness can be regarded as the average film thickness of the sample. It is preferable that the film thickness analyzed by this (method B) falls within the desired film thickness range to be controlled, for example.

Typical embodiments of such carbon material-containing materials include organic-inorganic composites, carbon material-containing particles, and the like. Examples of the carbon material-containing particles include core-shell particles, highly carbonized core-shell particles, hollow carbon fine particles, and highly carbonized hollow carbon fine particles. Hereinafter, the manufacturing method of typical and specific carbon material-containing materials will be explained.

≪4-1. Method for producing organic-inorganic composite≫
One embodiment of the carbon material-containing material obtained by the production method of the present invention is an organic-inorganic composite.

The organic-inorganic composite can typically be obtained by a heating step (I) of heating a composition containing an inorganic substance and a compound (A) in which a condensation reaction occurs between the same molecules and/or between different molecules upon heating.

The organic-inorganic composite includes a carbon material and an inorganic material. The carbon material is typically produced by a heating step (I) of heating a composition containing an inorganic substance and a compound (A) that causes a condensation reaction between the same molecules and/or between different molecules when heated. It can be produced by heating compound (A).

Only one type of carbon material may be used, or two or more types may be used. The number of inorganic substances may be one type or two or more types. Regarding "inorganic substances", see <<3-2. The explanation in ``Inorganic substances'' can be referred to.

The content ratio of the carbon material in the organic-inorganic composite is preferably 0.01% by mass to 99.99% by mass, particularly preferably 0.1% by mass to 99.9% by mass. If the content of the carbon material in the organic-inorganic composite is within the above range, the organic-inorganic composite can be industrially manufactured under mild conditions. It can be manufactured industrially. The content ratio of these carbon materials can be easily adjusted to any desired ratio by various removal steps described below, depending on the desired physical properties.

The content of the inorganic substance in the organic-inorganic composite is preferably 0.01% by mass to 99.99% by mass, particularly preferably 0.1% by mass to 99.9% by mass. If the content of inorganic substances in the organic-inorganic composite is within the above range, the organic-inorganic composite can be industrially manufactured under mild conditions, and hollow carbon particles etc. can be manufactured industrially using the organic-inorganic composite as a material. It can be manufactured as follows. The content ratio of these inorganic substances can be easily adjusted to an arbitrary ratio according to the desired physical properties by various removal steps described below.

The organic-inorganic complex was analyzed by C1sXPS analysis to determine the total number of bonds, that is, C-C bonds, C=C bonds, C-H bonds, and C-O bonds (C-O bonds derived from alcohols, C-O bonds derived from ethers). , epoxy-derived C-O bonds, etc.) and C=O bonds (including carbonyl-derived C=O bonds, carboxyl-derived C=O bonds, ester-derived C=O bonds, lactone-derived C=O bonds, etc.) ) The ratio of all carbon-oxygen bonds, that is, the total amount of C--O bonds and C=O bonds, is preferably 10% or more, more preferably 20% or more, and even more preferably 25 % or more. The upper limit of the above ratio is preferably 35% or less. In organic-inorganic composites, the sum of C-O bonds and C=O bonds relative to the total amount of C-C bonds, C=C bonds, C-H bonds, C-O bonds, and C=O bonds, by C1sXPS analysis If the amount ratio is within the above range, the organic-inorganic composite can become a novel carbon material-containing material that has various physical properties such as solubility, unlike conventionally known simple carbon materials.

The organic-inorganic composite has all carbon-oxygen bonds, that is, C-O bonds (including alcohol-derived C-O bonds, ether-derived C-O bonds, epoxy-derived C-O bonds, etc.) and C-O bonds, as determined by C1sXPS analysis. Ether-derived C-O bonds relative to the total amount of =O bonds (including carbonyl-derived C=O bonds, carboxyl-derived C=O bonds, ester-derived C=O bonds, lactone-derived C=O bonds, etc.) (i.e., C-O-C bonds) and alcohol-derived C-O bonds (i.e., C-OH bonds), the ratio of the total amount is preferably 50% or more, more preferably 60% or more, More preferably, it is 65% or more, particularly preferably 70% or more, and most preferably 75% or more. The upper limit of the above ratio is preferably 90% or less. In the organic-inorganic composite, the ratio of the total amount of ether-derived C-O bonds and alcohol-derived C-O bonds to the total amount of C-O bonds and C=O bonds is within the above range according to C1sXPS analysis. If so, the organic-inorganic composite can increase the structural control rate of the carbon material portion, and the structure can be controlled more precisely. In other words, the smaller the ratio of C=O bonds derived from the decomposition reaction, the more suppressed the decomposition reaction is, and it can be said that such an organic-inorganic composite is a carbon material-containing material whose structure is more precisely controlled.

The organic-inorganic complex was analyzed by C1sXPS analysis to determine the total number of bonds, that is, C-C bonds, C=C bonds, C-H bonds, and C-O bonds (C-O bonds derived from alcohols, C-O bonds derived from ethers). , epoxy-derived C-O bonds, etc.) and C=O bonds (including carbonyl-derived C=O bonds, carboxyl-derived C=O bonds, ester-derived C=O bonds, lactone-derived C=O bonds, etc.) ), the ratio of the total amount of ether-derived C-O bonds (i.e., C-O-C bonds) and alcohol-derived C-O bonds (i.e., C-OH bonds) is preferably 15%. or more, more preferably 17% or more, still more preferably 20% or more. The upper limit of the above ratio is preferably 30% or less. In carbon material-containing materials, ether-derived C-O bonds (i.e., C-O-C bonds) and alcohol-derived C-O bonds (i.e., C-OH bonds) with respect to the total amount of all bonds, as determined by C1sXPS analysis. If the ratio of the total amount of is within the above range, it can be said that the organic-inorganic composite is an organic-inorganic composite whose structure is more precisely controlled.

Particularly preferably, the organic-inorganic composite has all bonds determined by C1s (C-O bond, C-O bond derived from epoxy, etc.) and C=O bond (C=O bond derived from carbonyl, C=O bond derived from carboxyl, C=O bond derived from ester, C= derived from lactone) The ratio of all carbon-oxygen bonds, that is, the total amount of C-O bonds and C=O bonds, to the total amount of carbon-oxygen bonds (including O bonds, etc.) is within the above range, and the total carbon-oxygen bonds are determined by C1sXPS analysis. That is, C-O bonds (including alcohol-derived C-O bonds, ether-derived C-O bonds, epoxy-derived C-O bonds, etc.) and C=O bonds (carbonyl-derived C=O bonds, carboxyl-derived C=O bonds, etc.) ether-derived C-O bonds (i.e., alcohol-derived C=O bonds) and alcohol-derived C=O bonds (including C=O bonds derived from esters, C=O bonds derived from esters, C=O bonds derived from lactones, etc.) This is an embodiment in which the ratio of the total amount of C--O bonds (ie, C--OH bonds) is within the above range. In such an embodiment, the organic-inorganic composite can further improve the solubility of the carbon material portion, and can further increase the structural control rate of the carbon material portion. Moreover, in such an embodiment, the structure of the organic-inorganic composite can be controlled even more precisely.

Particularly preferably, the organic-inorganic composite has all bonds determined by C1s (C-O bond, C-O bond derived from epoxy, etc.) and C=O bond (C=O bond derived from carbonyl, C=O bond derived from carboxyl, C=O bond derived from ester, C= derived from lactone) The ratio of the total amount of all carbon-oxygen bonds, that is, the total amount of C--O bonds and C=O bonds, to the total amount of carbon-oxygen bonds (including O bonds, etc.) is within the above range, and the total amount of bonds, that is, as determined by C1sXPS analysis C-C bond, C=C bond, C-H bond, C-O bond (including alcohol-derived C-O bond, ether-derived C-O bond, epoxy-derived C-O bond, etc.) and C=O ether-derived C--O bonds (i.e., ether-derived C--O bonds (i.e., , C--O--C bond) and alcohol-derived C--O bond (ie, C--OH bond) is within the above range. In such an embodiment, the organic-inorganic composite can further improve the solubility of the carbon material portion, and can further increase the structural control rate of the carbon material portion. Moreover, in such an embodiment, the structure of the organic-inorganic composite can be controlled even more precisely.

Most preferably, the organic-inorganic complex has all the bonds determined by C1s (C-O bond, C-O bond derived from epoxy, etc.) and C=O bond (C=O bond derived from carbonyl, C=O bond derived from carboxyl, C=O bond derived from ester, C= derived from lactone) The ratio of all carbon-oxygen bonds, that is, the total amount of C-O bonds and C=O bonds, to the total amount of carbon-oxygen bonds (including O bonds, etc.) is within the above range, and the total carbon-oxygen bonds are determined by C1sXPS analysis. That is, C-O bonds (including alcohol-derived C-O bonds, ether-derived C-O bonds, epoxy-derived C-O bonds, etc.) and C=O bonds (carbonyl-derived C=O bonds, carboxyl-derived C=O bonds, etc.) ether-derived C-O bonds (i.e., alcohol-derived C=O bonds) and alcohol-derived C=O bonds (including C=O bonds derived from esters, C=O bonds derived from esters, C=O bonds derived from lactones, etc.) The ratio of the total amount of C-O bonds (i.e., C-OH bonds) is within the above range, and all bonds, that is, C-C bonds, C=C bonds, and C-H bonds, are determined by C1sXPS analysis. and C-O bonds (including alcohol-derived C-O bonds, ether-derived C-O bonds, epoxy-derived C-O bonds, etc.) and C=O bonds (carbonyl-derived C=O bonds, carboxyl-derived C-O bonds, etc.) ether-derived C-O bonds (i.e., C-O-C bonds) and alcohol-derived C- This is an embodiment in which the ratio of the total amount of O bonds (ie, C—OH bonds) is within the above range. In such an embodiment, the organic-inorganic composite can further increase the solubility of the carbon material portion, and can further increase the structural control rate of the carbon material portion. Moreover, in such an embodiment, the structure of the organic-inorganic composite can be controlled even more precisely.

The organic-inorganic composite preferably shows no peak due to C=O stretching vibration between 1660 cm ^-1 and 1800 cm ^-1 in IR analysis. If no peak due to C═O stretching vibration is observed between 1660 cm ⁻¹ and 1800 cm ⁻¹ in the IR analysis of the organic-inorganic composite, the structure of the organic-inorganic composite can be controlled more precisely.

The reason why the structure of the organic-inorganic composite can be controlled more precisely when no peak due to C=O stretching vibration is observed between 1660 cm ^-1 and 1800 cm ^-1 in the IR analysis of the organic-inorganic composite is It can be considered as follows. That is, when an organic-inorganic composite is formed using a compound and a production method as described below, the aromatic skeleton and the oxygen functional group remain in the product after the reaction due to the condensation reaction. At this time, if the aromatic structure is maintained (in other words, if the structure is controlled), the C-O bond of the ether bridge or the C-O bond derived from the alcohol, as well as the oxygen functional group, are eliminated and condensed. It is thought that C--C bonds are formed between aromatic skeletons. On the other hand, if an undesired decomposition reaction occurs and the aromatic structure of the skeleton is cleaved, a C=O bond resulting from the decomposition reaction is generated. Therefore, the fact that no peak due to C=O stretching vibration is observed between 1660 cm ^-1 and 1800 cm ^-1 in IR analysis means that the decomposition reaction is suppressed, and such organic-inorganic composites can be said to be a carbon material-containing material whose structure is more precisely controlled. The above range is particularly preferably from 1700 cm ⁻¹ to 1800 cm ⁻¹ .

The organic-inorganic composite preferably has an oxidation start temperature of 200°C or higher, as indicated by the rise temperature of DTA when TG-DTA analysis is performed under heating conditions of 10°C/min from 40°C in an air atmosphere. The temperature is more preferably 250°C or higher, and most preferably 300°C or higher. When TG-DTA analysis is performed on an organic-inorganic composite under heating conditions of 10°C/min from 40°C in an air atmosphere, the oxidation start temperature indicated by the rise temperature of DTA is within the above range. For example, the carbon material-containing material of the present invention has high oxidation stability, that is, the structure is controlled and the skeleton structure is maintained, so the oxidation resistance (decomposition resistance) is high. If the skeleton is cleaved to form a C═O bond, there is a risk that the stability of the skeleton will decrease and the oxidation resistance (decomposition resistance) will decrease.

As described above, the organic-inorganic composite, which is one embodiment of the carbon material-containing material obtained by the production method of the present invention, contains a carbon material and an inorganic substance. The organic-inorganic composite, which is one embodiment of the carbon material-containing material obtained by the production method of the present invention, includes the "carbon material" as described above, and typically, as described above, heating causes the formation of molecules between the same molecules. And/or it can be produced by heating the compound (A) in the composition in the heating step (I) of heating a composition containing the compound (A) and an inorganic substance in which a condensation reaction occurs between different molecules. Note that the following description of the "carbon material" included in the organic-inorganic composite, which is one embodiment of the carbon material-containing material obtained by the production method of the present invention, is based on the previous <<<3. The "carbon material" mentioned in the explanation in the item ``Method for producing carbon material-containing material'', this ``4-1.'' <<<3. Method for producing organic-inorganic composite>> other than <<<<3. Typical examples of manufacturing methods for carbon material-containing materials ≫≫ “Carbon materials” mentioned in the explanation in the section ≪≪5. "Carbon material" mentioned in the explanation in the item "Carbon material-containing material", "Carbon material", <<<6. "Carbon material" mentioned in the explanation in the section of "Organic-inorganic composite", "7. It can be used as an explanation of the "carbon material" mentioned in the explanation in the section ``Applications of organic-inorganic composites''.

The presence of carbon components in the carbon material can be easily confirmed by C1sXPS analysis. Further, the carbon material preferably has a honeycomb structure (graphene structure) derived from a benzene ring in its structure. The presence or absence of a graphene structure can be confirmed by Raman spectroscopy (Non-Patent Document 4).

In the carbon material, the total content of metal components that become impurities is usually preferably 0.1 atomic % or less, more preferably 0.01 atomic % or less, based on 100 atomic % of carbon atoms, and particularly Preferably it is substantially zero. These can be confirmed by analyzing the carbon material using X-ray fluorescence elemental analysis (XRF). In addition, when a carbon material-containing material (organic-inorganic composite in this item) is analyzed by X-ray fluorescence elemental analysis (XRF), it is found that The content of metal components other than metal components is preferably 0.1 atomic % or less, more preferably 0.01 atomic % or less, and particularly preferably substantially zero, based on 100 atomic % of carbon atoms. be. For example, when a carbon material-containing material (organic-inorganic composite in this item) that uses alumina as an inorganic substance is analyzed by X-ray fluorescence elemental analysis (XRF), if the only metal component contained in alumina is aluminum, The content of other metal components is preferably 0.1 atomic % or less, more preferably 0.01 atomic % or less, and particularly preferably substantially zero based on 100 atomic % of carbon atoms.

The carbon material includes carbon as an essential element, and may contain elements other than carbon. Such elements other than carbon are preferably at least one element selected from oxygen, hydrogen, nitrogen, sulfur, fluorine, chlorine, bromine, and iodine, and more preferably oxygen, hydrogen, nitrogen, and sulfur. More preferably, it is at least one element selected from oxygen, hydrogen, and nitrogen, and particularly preferably at least one element selected from oxygen and hydrogen. When the total amount of elements other than hydrogen among the elements constituting the carbon material is 100 atom%, carbon is preferably 60 atom% or more, more preferably 70 atom% or more, and even more preferably 75 atom%. That's all. Further, the content of elements other than carbon is preferably 10 atomic % or more. When the ratio of each element falls within this range, it becomes possible to exhibit good solubility even though it is a carbon material. These can be confirmed by quantifying the carbon material using X-ray photoelectron spectroscopy (C1sXPS). In addition, when a carbon material-containing material (organic-inorganic composite in this item) is quantified by X-ray photoelectron spectroscopy (C1s When the total amount of other elements is 100 atomic %, carbon is preferably 60 atomic % or more, more preferably 70 atomic % or more, still more preferably 75 atomic % or more. Further, the content of elements other than carbon is preferably 10 atomic % or more. For example, when a carbon material-containing material (organic-inorganic composite in this item) using phosphotungstic acid as an inorganic substance is analyzed by X-ray photoelectron spectroscopy (C1sXPS), phosphorus and tungsten are detected; , and the ratio of the amount of carbon to the total amount of elements other than oxygen (excluding hydrogen) constituting phosphotungstic acid calculated from the content of phosphorus and tungsten, and the ratio of elements other than carbon is within the above range Preferably inside.

The carbon material is preferably soluble in a solvent.

Here, the case where the carbon material is soluble in a solvent is the case where it has better solubility in a solvent than conventional carbon materials and can realize good handling properties.

As an embodiment in which the carbon material is soluble in a solvent, the following embodiments can be preferably adopted.
(Embodiment 1) An embodiment in which all of the carbon material is dissolved in the solvent. That is, an embodiment in which the carbon material consists only of a component (component A) that dissolves in a solvent.
(Embodiment 2) An embodiment in which a part of the carbon material is dissolved in a solvent. That is, an embodiment in which the carbon material consists of a component that dissolves in a solvent (component A) and a component that does not dissolve in a solvent (component B).

In the present invention, "soluble in a solvent" means an embodiment in which a component is soluble in any solvent, and the solvent preferably includes N,N-dimethylformamide, N,N-dimethylacetamide, N- Examples include methylpyrrolidone, dimethylsulfoxide, acetone, methylethylketone, methylisobutylketone, tetrahydrofuran, methanol, ethanol, 2-propanol, butanol, chloroform, dichloromethane and the like. Namely, the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, acetone, methylethylketone, methylisobutylketone, tetrahydrofuran, methanol, ethanol, 2-propanol, butanol, chloroform, dichloromethane. Preferably, there is a component soluble in at least one solvent selected from the following. More preferred is an embodiment in which there is a component soluble in at least one solvent selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and chloroform. is an embodiment in which there is a component soluble in at least one solvent selected from the group consisting of N,N-dimethylformamide and N-methylpyrrolidone, and particularly preferably an embodiment in which there is a component soluble in N-methylpyrrolidone. be.

One embodiment in which the carbon material is soluble in a solvent is, for example, an embodiment in which the carbon material includes a carbon-based compound that is soluble in the solvent.

As a method for determining whether or not it is soluble in a solvent, for example, after mixing a carbon material-containing material (organic-inorganic composite in this item) to the above solvent to a concentration of 0.001% by mass, When sonication is performed for 1 hour and the resulting liquid is passed through a PTFE filter paper (pore size: 0.45 μm), it can be determined whether or not the liquid that has passed through the filter paper contains carbon-based compounds. If the liquid that has passed through the filter paper contains a carbon-based compound, it is determined that the carbon material contains a carbon-based compound that is soluble in the solvent. As the PTFE filter paper, for example, GL Chromato Disc (Model 13P) manufactured by GL Sciences, Inc. can be used.

The carbon material preferably exhibits a peak in the G band (generally within the range of 1550 cm ⁻¹ to 1650 cm ⁻¹ ) in a Raman spectrum obtained by (i) Raman spectroscopy. Therefore, the fact that the carbon material has a peak in the G band (generally within the range of 1550 cm ^-1 to 1650 cm ^-1 ) in the Raman spectrum obtained by Raman spectroscopy means that the carbon material has a graphene structure or a structure similar to graphene. It means that it has a structure. If the G band has high intensity and is sharp, it can be said that the G band has a more beautiful graphene structure or a structure similar to a graphene structure.

The carbon material preferably exhibits a peak in the D band (generally within the range of 1300 cm ⁻¹ to 1400 cm ⁻¹ ) in a Raman spectrum obtained by (ii) Raman spectroscopy. A carbon material having a structure derived from defects in the graphene structure exhibits a peak in the D band (generally within the range of 1300 cm ⁻¹ to 1400 cm ⁻¹ ) in a Raman spectrum obtained by Raman spectroscopy. Therefore, the fact that a carbon material has a peak in the D band (generally within the range of 1300 cm ^-1 to 1400 cm ^-1 ) in the Raman spectrum obtained by Raman spectroscopy means that the carbon material contains a functional group, This means that it has a structure derived from defects in the graphene structure or a structure similar to a structure derived from defects in the graphene structure. If the intensity of the D band is low, it can be said that the D band has a more beautiful graphene structure or a structure similar to a graphene structure. Furthermore, the fact that the D band can be confirmed means that the carbon material-containing material obtained by the production method of the present invention has a functional group, which can improve the solubility in a solvent.

The carbon material preferably exhibits (i) a peak in the G band (generally within the range of 1550 cm -1 to 1650 cm -1) in a Raman spectrum obtained by Raman spectroscopy, and (ii) a peak in the G band (generally within the range of 1550 cm ^-1 to 1650 cm ^-1 ). The resulting Raman spectrum shows a peak in the D band (generally within the range of 1300 cm ^-1 to 1400 cm ^-1 ).

The carbon material preferably exhibits a peak in the G' band (generally within the range of 2650 cm ^-1 to 2750 cm ^-1 ) in a Raman spectrum obtained by (iii) Raman spectroscopy. Therefore, the fact that a carbon material has a peak in the G' band (generally within the range of 2650 cm ^-1 to 2750 cm ^-1 ) in a Raman spectrum obtained by Raman spectroscopy means that the carbon material has a graphene structure or a structure similar to graphene. This means that it has the structure of The intensity of the G' band is strongest when the graphene structure has one layer, and gradually decreases as the number of stacked graphene structures increases. However, even though the intensity of the G' band gradually decreases as the number of stacked graphene structures increases, the peak can be observed. Therefore, having a peak in the G' band means that the carbon material has a graphene structure or a structure similar to a graphene structure. The G' band is also sometimes called the 2D band.

The carbon material preferably exhibits (i) a peak in the G band (generally within the range of 1550 cm ^{-1 to 1650 cm -1) in a Raman spectrum obtained by Raman spectroscopy, and (ii) a peak in the G band (generally within the range of 1550 cm -1} to 1650 cm ^-1 ). The Raman spectrum obtained shows a peak in the D band (generally within the range of 1300 cm ^-1 to 1400 cm ^-1 ), and (iii) the Raman spectrum obtained by Raman spectroscopy shows a peak in the G' band (generally within the range of 2650 cm ^{-1). 1} to 2750 cm ^-1 ).

The carbon material preferably exhibits a peak in the D+D' band (generally within the range of 2800 cm ^-1 to 3000 cm ^-1 ) in a Raman spectrum obtained by (iv) Raman spectroscopy. A carbon material having a structure derived from defects in the graphene structure exhibits a peak in the D+D′ band (generally within the range of 2800 cm ⁻¹ to 3000 cm ⁻¹ ) in a Raman spectrum obtained by Raman spectroscopy. Therefore, the fact that a carbon material has a peak in the D+D' band (generally within the range of 2800 cm ^-1 to 3000 cm ^-1 ) in the Raman spectrum obtained by Raman spectroscopy means that the carbon material contains a functional group. , means that it has a structure derived from defects in the graphene structure or a structure similar to a structure derived from defects in the graphene structure. If the intensity of the D+D' band is low, it can be said that the band has a more beautiful graphene structure or a structure similar to a graphene structure. The D+D' band is also sometimes called the D+G band. Furthermore, the fact that the D+D' band can be confirmed also means that the carbon material-containing material obtained by the production method of the present invention has a functional group, which can improve its solubility in a solvent.

The carbon material preferably exhibits (i) a peak in the G band (generally within the range of 1550 cm -1 to 1650 cm -1) in a Raman spectrum obtained by Raman spectroscopy, and (ii) a peak in the G band (generally within the range of 1550 cm ^-1 to 1650 cm ^-1 ). The Raman spectrum obtained shows a peak in the D band (generally within the range of 1300 cm ^-1 to 1400 cm ^-1 ), and (iii) the Raman spectrum obtained by Raman spectroscopy shows a peak in the G' band (generally within the range of 2650 cm ^-1). (iv) Shows a peak in the D+D' band (generally within the range of 2800 cm ^-1 to 3000 cm ^-1 ) in the Raman spectrum obtained ^by Raman spectroscopy ^. .

The carbon material preferably includes a carbon-based compound that is soluble in a solvent.

In one embodiment, the carbon material exhibits a peak in the G band (generally within the range of 1550 cm ^-1 to 1650 cm ^-1 ) in a Raman spectrum obtained by (i) Raman spectroscopy, and further (ii) ) It shows a peak in the D band (generally within the range of 1300 cm ^-1 to 1400 cm ^-1 ) in a Raman spectrum obtained by Raman spectroscopic analysis, and further contains a carbon-based compound that is soluble in a solvent.

When a carbon material contains a functional group and also has defects in a part of the graphene structure, these defects can contribute to the solubility of the carbon material in a solvent.

As mentioned above, unlike conventionally known carbon materials, carbon materials have a graphene structure or a structure similar to a graphene structure, and the solubility of carbon materials in solvents is better (for example, the carbon material dissolves in the solvent). The number of components in the material increases, and the types of solvents in which the carbon material can be dissolved also increase).

The molecular weight of the carbon-based compound contained in the carbon material is preferably 1,000 to 1,300,000, more preferably 5,000 to 1,000,000, still more preferably 10,000 to 700,000, particularly preferably 15,000 to 500,000, and most preferably It is between 20,000 and 300,000. If the molecular weight of the carbon-based compound contained in the carbon material is within the above range, in combination with the feature (i) above, the solubility of the carbon material in the solvent will be better (for example, if the components of the carbon material that dissolve in the solvent are (or the types of solvents in which carbon materials can be dissolved will increase). If the molecular weight of the carbon-based compound contained in the carbon material exceeds 1,300,000, the solubility of the carbon material in a solvent may deteriorate. If the molecular weight of the carbon-based compound contained in the carbon material is less than 1000, the characteristics as a carbon material may be weakened. These molecular weights can be analyzed by the method described below.

The content ratio of the carbon-based compound in the carbon material is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, even more preferably 90% by mass to 100% by mass, Particularly preferably from 95% to 100% by weight, most preferably substantially 100% by weight. If the content ratio of the carbon-based compound in the carbon material is within the above range, in combination with the characteristics (i) and (ii) above, the solubility of the carbon material in the solvent will be better (for example, the solubility of the carbon material in the solvent will be better). The number of components in the material increases, and the types of solvents in which the carbon material can be dissolved also increase).

The carbon material preferably exhibits a peak within the range of 20° to 30° in an XRD spectrum chart obtained by XRD analysis. That is, in one preferred embodiment, the carbon material has a structure in which graphene structures are stacked (graphene stacked structure). Having a layered structure can make the carbon material stronger and more stable.

More preferable forms of the carbon material include any of the forms (i) to (iv) described above in the Raman spectrum obtained by Raman spectroscopy, or a combination of forms; (i) and (ii), (i), ( ii) and (iii), (i), (ii), (iii) and (iv), and exhibits a peak within the range of 20° to 30° in the XRD spectrum chart obtained by XRD analysis. It is a form.

The carbon material may preferably be present in bulk. Generally, the properties of a substance in its bulk state are its inherent properties. That is, the fundamental properties of a substance in its bulk state, such as its boiling point, melting point, viscosity, and density, can be determined. When we talk about the physical properties of a substance, we mean the properties that its bulk part has. Examples of bulk states are particles, pellets, films, etc. Examples of the state of existence of particles include powder. The film is preferably a self-supporting film.

≪4-2. Method for manufacturing carbon material-containing particles≫
One embodiment of the carbon material-containing material obtained by the production method of the present invention is carbon material-containing particles. Typically, the carbon material-containing particles include core-shell particles, highly carbonized core-shell particles, hollow carbon fine particles, and highly carbonized hollow carbon fine particles.

<4-2-1. Method for producing core-shell particles>
In the method for producing a carbon material-containing material of the present invention, the core-shell particles are produced by including a carbon material removal step of removing at least a part of the carbon material produced by heating the compound (A) after the heating step (I). Can be manufactured. That is, after producing an organic-inorganic composite which is one embodiment of a carbon material-containing material through the heating step (I), a carbon material removal step of removing at least a portion of the carbon material contained in the organic-inorganic composite. It can be produced by subjecting it to In the carbon material removal step, treatment is performed using a solvent that dissolves the carbon material contained in the organic-inorganic composite. As a result, as shown in FIG. 2, a core-shell particle (core part: inorganic particle, shell part: carbon material binding region) 200 in which the surface of the inorganic particle 20 is coated with a carbon material binding region (region not dissolved by a solvent) 30 can be obtained. Such core-shell particles are also carbon material-containing materials.

Examples of the solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, acetone, methylethylketone, methylisobutylketone, tetrahydrofuran, methanol, ethanol, 2-propanol, butanol, chloroform, Examples include dichloromethane, preferably N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and chloroform, and more preferably N,N-dimethylformamide and N-methylpyrrolidone. N-methylpyrrolidone is particularly preferred.

<4-2-2. Method for producing highly carbonized core-shell particles>
Highly carbonized core-shell particles can be manufactured by including a heating step (II) of further heating after the heating step (I) and the subsequent carbon material removal step in the method for manufacturing a carbon material-containing material of the present invention. . That is, the above-mentioned core-shell particles (core part: inorganic particles, shell part: carbon material bonding region) are further heated. This heating step (II) allows the shell portion to be highly carbonized. Thereby, highly carbonized core-shell particles (core part: inorganic particles, shell part: highly carbonized material) can be obtained. By increasing the carbon content, the strength and heat resistance of the obtained carbon material or carbon material composite can be improved. Highly carbonized core-shell particles are also carbon material-containing materials.

The heating temperature in the heating step (II) may be within a temperature range that the inorganic components of the core can withstand, but the specific heating temperature is preferably 500°C to 3000°C, more preferably 600°C to 2500°C. The temperature is most preferably 700°C to 2000°C. By adjusting the heating temperature in the heating step (II) within the above range, the shell portion can be effectively carbonized.

The specific heating time in the heating step (II) is preferably 0.1 to 120 hours, more preferably 0.5 to 100 hours, and even more preferably 1 to 50 hours. and most preferably from 2 hours to 24 hours. By adjusting the heating time within the above range, the shell portion can be effectively carbonized.

<4-2-3. Method for manufacturing hollow carbon particles>
Hollow carbon fine particles can be produced by including an inorganic matter removal step of removing inorganic matter after the heating step (I) in the method for producing a carbon material-containing material of the present invention (manufacturing mode 1). That is, after producing an organic-inorganic composite which is one embodiment of the carbon material-containing material through the heating step (I), it is produced by subjecting it to an inorganic matter removal step of removing inorganic matter contained in the organic-inorganic composite. obtain.

Hollow carbon fine particles can also be produced by including an inorganic matter removal step of removing inorganic matter after the heating step (I) and the subsequent carbon material removal step in the method for producing a carbon material-containing material of the present invention. (Manufacturing form 2). That is, after producing core-shell particles, which are one embodiment of a carbon material-containing material, through the heating step (I) and the subsequent carbon material removal step, the core-shell particles are subjected to an inorganic matter removal step of removing inorganic matter contained in the core-shell particles. It can be manufactured by

Examples of the method for removing inorganic substances in the inorganic substance removal step include a method of removing the inorganic substances using a solvent that can dissolve the inorganic substances without dissolving the carbon material. The solvent having the above-mentioned solubility characteristics is not particularly limited, but aqueous solvents are preferred. The reason why an aqueous solvent is preferable is that the carbon material contained in the carbon material-containing material produced by the production method of the present invention is difficult to dissolve in water, while inorganic substances are soluble in water (especially acidic water and basic water). This is because there are many things that can be dissolved. Examples of the aqueous solvent include acidic aqueous solutions such as sulfuric acid, hydrochloric acid, and nitric acid; basic aqueous solutions such as sodium hydroxide, potassium hydroxide, and ammonia; and the like. In addition, in the removal step, the temperature is not particularly limited, but is preferably 0°C to 150°C, more preferably 20°C to 100°C, since it can effectively express the dissolution characteristics of the aqueous solvent. . Further, the physical treatment in the removal step is not particularly limited, but in terms of effectively achieving removability, it is preferably left standing, stirring, ultrasonication, or shearing, and more preferably , stirring, sonication, and shearing operations.

<4-2-4. Method for producing highly carbonized hollow carbon particles>
Highly carbonized hollow carbon fine particles can be manufactured by including a heating step (II) of further heating after the heating step (I) and the subsequent inorganic matter removal step in the method for manufacturing a carbon material-containing material of the present invention. . That is, the hollow carbon fine particles obtained in the above-mentioned production mode 1 are further heated. By this heating step (II), the carbon material portion can be highly carbonized. Thereby, highly carbonized hollow carbon fine particles can be obtained. By increasing the carbon content, the strength and heat resistance of the obtained carbon material or carbon material composite can be improved. Highly carbonized hollow carbon fine particles are also carbon material-containing materials.

The highly carbonized hollow carbon fine particles can also be further heated after the heating step (I), the subsequent carbon material removal step, and the subsequent inorganic matter removal step in the method for producing a carbon material-containing material of the present invention. (II). That is, the hollow carbon fine particles obtained in the above-mentioned production mode 2 are further heated. By this heating step (II), the carbon material portion can be highly carbonized.

≪≪5. Materials containing carbon materials≫≫
The carbon material-containing material of the present invention is a carbon material-containing material containing a carbon material and an inorganic substance, in which at least a part of the carbon material and at least a part of the inorganic substance are bonded by a covalent bond, and the carbon material The content ratio of carbon atoms, hydrogen atoms, and oxygen atoms in the elemental analysis of is 1.0 atom% to 8.0 atom% when the content ratio of carbon atoms is 6.0 atom%, The content of oxygen atoms is 0.1 atom% to 4 atom%.

In the carbon material-containing material of the present invention, at least a portion of the carbon material and at least a portion of the inorganic material are bonded by a covalent bond. Preferably, at least a portion of the carbon material is covalently bonded to at least a portion of the outermost surface of the inorganic material. More preferably, at least a portion of the carbon material is covalently bonded to at least a portion of the outermost surface of the inorganic particle.

In the description of the carbon material-containing material of the present invention, "carbon material" refers to <<<2. The explanation in Carbon Material≫≫ can be referred to. In the description of the carbon material-containing material of the present invention, "inorganic material" refers to <<<3. Method for producing carbon material-containing material≫≫, ≪≪4. The explanation in ≫≫ representative examples of methods for manufacturing carbon material-containing materials may be referred to.

The carbon material-containing material of the present invention can be manufactured by any suitable method. The carbon material-containing material of the present invention can be preferably produced by the method for producing a carbon material-containing material of the present invention.

The carbon material-containing material of the present invention includes a wide variety of materials, and can take various shapes such as particulate and non-particulate (for example, fibrous, thin film, etc.). The shape is preferably particulate.

Previous ≪≪3. Method for producing carbon material-containing material≫≫ and ≪≪4. As explained in ≫≫ Typical Examples of Manufacturing Methods for Carbon Material-Containing Materials, examples of inorganic substances include particulate inorganic substances (inorganic particles), non-particulate inorganic substances (for example, fibrous inorganic substances, thin film-like inorganic substances, etc.). When employing inorganic substances of various shapes such as inorganic substances, a wide variety of carbon material-containing materials can be obtained depending on the respective shapes. As the inorganic substance, particulate inorganic substances (inorganic particles) are preferable.

Previous ≪≪3. Method for producing carbon material-containing material≫≫ and ≪≪4. As explained in ≫≫ representative examples of methods for manufacturing carbon material-containing materials, when inorganic particles are used, the carbon material-containing material of the present invention is typically a lumpy carbon material-containing material containing a large number of inorganic particles. can be mentioned. In this case, it can be made into particulate carbon material-containing material by crushing or the like. Furthermore, by adjusting the blending ratio of compound (A) and inorganic matter, a particulate carbon material-containing material can be obtained. Furthermore, when using a fibrous inorganic material, examples of the carbon material-containing material of the present invention include fibrous core-shell fibers and tubular hollow carbon materials. Furthermore, when using a thin film-like inorganic material, the carbon material-containing material of the present invention includes a laminated carbon material-containing material. Further, by further subjecting such a laminated carbon material-containing material to the above-described heating step (II), carbon material removal step, inorganic substance removal step, etc., various thin film-like carbon materials can be obtained.

Typical embodiments of the carbon material-containing material of the present invention include <<<4. Typical Examples of Manufacturing Methods for Carbon Material-Containing Materials Examples of carbon material-containing materials obtained by the manufacturing method described in ≫≫ include organic-inorganic composites, carbon material-containing particles, and the like. Examples of the carbon material-containing particles include core-shell particles, highly carbonized core-shell particles, hollow carbon fine particles, and highly carbonized hollow carbon fine particles.

The carbon material-containing material of the present invention preferably exhibits a peak between 125 ppm and 135 ppm in ¹³ C-NMR analysis. In ^{the 13} C-NMR analysis, showing a peak between 125 ppm and 135 ppm means that the carbon material-containing material contains a carbon material containing at least sp2 carbon.

The carbon material-containing material of the present invention preferably exhibits a peak between 140 ppm and 160 ppm in ¹³ C-NMR analysis. In ¹³ C-NMR analysis, a peak between 140 ppm and 160 ppm means the presence of a C--O bond. Therefore, in ¹³ C-NMR analysis, showing a peak between 140 ppm and 160 ppm typically means that there is an "oxygen-containing group" on the outermost surface of the inorganic material (for example, an oxygen-containing group derived from an inorganic oxide, metal hydroxyl group, etc.), which means that the oxygen and carbon of the carbon material are covalently bonded.

Further, when the carbon material-containing material of the present invention has a peak derived from a C-O-Si bond in ²⁹ Si-NMR analysis, at least a part of the carbon material and at least a part of the inorganic substance containing Si are It means that they are bonded by a covalent bond. Typically, it means that at least a portion of the carbon material is covalently bonded to at least a portion of the outermost surface of the silica particle.

Regarding the film thickness of the carbon material portion of the carbon material-containing material of the present invention, please refer to <<<4. The content explained in the section ≫≫ representative example of method for producing carbon material-containing material may be used.

≪≪6. Organic-inorganic composite≫≫
The organic-inorganic composite of the present invention is an organic-inorganic composite containing a carbon material and an inorganic substance, and the carbon material is soluble in a solvent.

Regarding the organic-inorganic composite of the present invention, the composition, physical properties, and "carbon material" of the organic-inorganic composite are described in <<<2. Explanation in carbon material≫≫, ≪4-1. The explanation in "Method for producing organic-inorganic composite" can be referred to. In the organic-inorganic composite of the present invention, "compound (A)" is described in <1-1. The explanation in Compound (A)>> can be referred to. In the organic-inorganic composite of the present invention, the "inorganic substance" is described in <<3-2. The explanation in ``Inorganic substances'' can be referred to.

The organic-inorganic composite of the present invention may be produced by any appropriate method as long as the effects of the present invention are not impaired. Such a production method typically includes a heating step (I) of heating a composition containing an inorganic substance and a compound (A) in which a condensation reaction occurs between the same molecules and/or between different molecules upon heating. By this heating step (I), the compound (A) in the composition containing the compound (A) and an inorganic substance is heated and can become a carbon material.

The heating temperature in the heating step (I) when producing the organic-inorganic composite of the present invention is preferably at least (T-150)°C when the condensation reaction temperature of compound (A) is T°C. .

In the heating step (I) when producing the organic-inorganic composite of the present invention, a composition containing an inorganic substance and a compound (A) in which a condensation reaction occurs between the same molecules and/or between different molecules upon heating is heated. The blending ratio of compound (A) and inorganic substance is preferably 0.01% by mass to 1,000,000% by mass, more preferably 0.1% by mass to 100,000% by mass, relative to 100% by mass of inorganic matter. It is % by mass, particularly preferably 1% by mass to 1000% by mass. If the blending ratio of compound (A) and inorganic substance is within the above range, an organic-inorganic composite whose structure is more precisely controlled can be produced more easily under milder conditions. The blending ratio of these inorganic substances and compound (A) can be arbitrarily adjusted depending on the physical properties of the intended composite. For example, by adjusting the blending ratio of the inorganic substance and compound (A), the physical properties and form of the resulting organic-inorganic composite (for example, solubility in a solvent, the shape of the carbon component or inorganic component (particulate or non-particulate), (such as the size of the carbon component or inorganic component).

The composition containing the compound (A), which undergoes a condensation reaction between the same molecules and/or different molecules upon heating, and an inorganic substance may not contain any other appropriate components as long as the effects of the present invention are not impaired. You can leave it there. Examples of such other components include a solvent, a catalyst, a base material, a carrier, and the like.

The composition to be heated in the heating step (I) when producing the organic-inorganic composite of the present invention may be prepared by any appropriate method as long as the effects of the present invention are not impaired. Examples of such a method include a method of mixing compound (A) and an inorganic substance in a solid state by any appropriate method (eg, crushing, pulverization, etc.). Alternatively, the compound (A), the inorganic substance, the solvent, and, if necessary, other components other than the solvent may be mixed by any appropriate method (for example, ultrasonication, etc.), Examples include a method of removing the solvent by vacuum drying). Further, crushing may be performed as necessary.

The heating temperature in the heating step (I) when producing the organic-inorganic composite of the present invention is preferably (T-150) °C or higher when the condensation reaction temperature of compound (A) is T °C, More preferably (T-150 to T+50)°C, further preferably (T-130 to T+45)°C, even more preferably (T-100 to T+40)°C, particularly preferably (T-80 to T+40)°C. T+35)°C, most preferably (T-50 to T+30)°C. When producing the organic-inorganic composite of the present invention, the catalytic ability of the inorganic material and the high reactivity between the functional groups on the inorganic material and the carbon material are higher than the condensation reaction temperature of compound (A) as described above. The reaction can proceed from a relatively low temperature and carbonization can proceed. By adjusting the heating temperature within the above range, an organic-inorganic composite having solubility in a solvent or an organic-inorganic composite whose structure is more precisely controlled can be produced more easily under milder conditions.

The condensation reaction temperature of compound (A) can be determined by TG-DTA analysis. Specifically, it is as follows.
(1) When one type of compound is used as compound (A), TG-DTA analysis of compound (A) is performed by heating the compound (A) from 40°C at a heating rate of 10°C/min in a nitrogen gas atmosphere, The peak top temperature on the lowest temperature side of DTA is determined as the condensation reaction temperature (T° C.) of compound (A).
(2) When using a mixture of two or more compounds as compound (A), perform TG-DTA analysis of the mixture by increasing the temperature from 40°C at a heating rate of 10°C/min in a nitrogen gas atmosphere. , the peak top temperature at the lowest temperature side of DTA is determined as the condensation reaction temperature (T° C.) of compound (A) (a mixture of two or more compounds).
(3) However, if compound (A) as one type of compound or a mixture of two or more types of compounds contains impurities such as a solvent, water, or water of hydration, the impurities can be removed. A DTA peak (sometimes referred to as an impurity peak) accompanying the condensation reaction may be observed at a temperature lower than the condensation reaction temperature. In such a case, the above impurity peak is ignored and the condensation reaction temperature of the compound (A) is determined. Usually, the peak top temperature on the lowest temperature side of DTA is determined as the condensation reaction temperature of the compound (A), ignoring the impurity peaks mentioned above.

The specific heating temperature in the heating step (I) when producing the organic-inorganic composite of the present invention is preferably 200°C to 500°C, more preferably 220°C to 400°C, More preferably the temperature is 230°C to 350°C, most preferably 250°C to 300°C. By adjusting the heating temperature within the above range, an organic-inorganic composite having solubility in a solvent or an organic-inorganic composite whose structure is more precisely controlled can be produced more easily under milder conditions. In particular, since the heating temperature in the heating step (I) is so low, the organic-inorganic composite can be industrially produced under milder conditions.

The heating time in the heating step (I) when producing the organic-inorganic composite of the present invention is preferably 0.1 hour to 120 hours, more preferably 0.5 hour to 100 hours. The time is more preferably 1 hour to 50 hours, and most preferably 2 hours to 24 hours. By adjusting the heating time within the above range, an organic-inorganic composite having solubility in a solvent or an organic-inorganic composite having a more precisely controlled structure can be produced more easily under milder conditions.

In the organic-inorganic composite of the present invention, the film thickness of the carbon material portion is determined in <<<2. The content explained in the section ≫≫ representative example of method for producing carbon material-containing material may be used.

≪≪7. Applications of organic-inorganic composites≫≫
The organic-inorganic composite of the present invention can be used in various applications. A typical product obtained through such application development is carbon material-containing particles. There are a wide variety of carbon material-containing materials, and they can take various shapes, such as particulate and non-particulate (for example, fibrous, thin film, etc.). The shape is preferably particulate. Typically, the carbon material-containing particles include core-shell particles, highly carbonized core-shell particles, hollow carbon fine particles, and highly carbonized hollow carbon fine particles.

≪7-1. Core-shell particles≫
When producing the organic-inorganic composite of the present invention, the core-shell particles are subjected to a carbon material removal step of removing at least a portion of the carbon material produced by heating the compound (A) after the heating step (I). It can be manufactured by That is, after producing the organic-inorganic composite of the present invention through the heating step (I), it is produced by subjecting it to a carbon material removal step of removing at least a part of the carbon material contained in the organic-inorganic composite of the present invention. obtain. In the carbon material removal step, treatment is performed using a solvent that dissolves the carbon material contained in the organic-inorganic composite of the present invention. As a result, as shown in FIG. 2, a core-shell particle (core part: inorganic particle, shell part: carbon material binding region) 200 in which the surface of the inorganic particle 20 is coated with a carbon material binding region (region not dissolved by a solvent) 30 is produced. can be obtained.

Examples of the solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, acetone, methylethylketone, methylisobutylketone, tetrahydrofuran, methanol, ethanol, 2-propanol, butanol, chloroform, Examples include dichloromethane, preferably N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and chloroform, and more preferably N,N-dimethylformamide and N-methylpyrrolidone. N-methylpyrrolidone is particularly preferred.

Regarding the film thickness of the carbon material portion of the core-shell particle, see <<<2. The content explained in the section ≫≫ representative example of method for producing carbon material-containing material may be used.

≪7-2. Highly carbonized core-shell particles≫
When producing the organic-inorganic composite of the present invention, the highly carbonized core-shell particles are subjected to a heating step (II) of further heating after a carbon material removal step after the heating step (I). It can be manufactured by That is, the core-shell particles (core part: inorganic particles, shell part: carbon material bonding region) obtained by the carbon material removal step are further heated. This heating step (II) allows the shell portion to be highly carbonized. Thereby, highly carbonized core-shell particles (core part: inorganic particles, shell part: highly carbonized material) can be obtained. By increasing the carbon content, the strength and heat resistance of the obtained carbon material or carbon material composite can be improved.

The heating temperature in the heating step (II) may be within a temperature range that the inorganic components of the core can withstand, but the specific heating temperature is preferably 500°C to 3000°C, more preferably 600°C to 2500°C. The temperature is most preferably 700°C to 2000°C. By adjusting the heating temperature in the heating step (II) within the above range, the shell portion can be effectively carbonized.

The specific heating time in the heating step (II) is preferably 0.1 to 120 hours, more preferably 0.5 to 100 hours, and even more preferably 1 to 50 hours. and most preferably from 2 hours to 24 hours. By adjusting the heating time within the above range, the shell portion can be effectively carbonized.

Regarding the film thickness of the carbon material portion of the highly carbonized core-shell particles, see <<<2. The content explained in the section ≫≫ representative example of method for producing carbon material-containing material may be used.

≪7-3. Hollow carbon particles≫
Hollow carbon fine particles can be produced by including an inorganic matter removal step of removing inorganic matter after the heating step (I) when producing the organic-inorganic composite of the present invention (manufacturing mode 1). That is, it can be produced by producing an organic-inorganic composite through the heating step (I) and then subjecting it to an inorganic matter removal step of removing inorganic matter contained in the organic-inorganic composite.

Hollow carbon fine particles can also be produced by including an inorganic matter removal step of removing inorganic matter after the heating step (I), followed by a carbon material removal step. can also be produced (manufacturing form 2). That is, it can be produced by producing core-shell particles through a heating step (I) and a subsequent carbon material removal step, and then subjecting the core-shell particles to an inorganic matter removal step of removing inorganic matter contained in the core-shell particles.

Examples of the method for removing inorganic substances in the inorganic substance removal step include a method of removing the inorganic substances using a solvent that can dissolve the inorganic substances without dissolving the carbon material. The solvent having the above-mentioned solubility characteristics is not particularly limited, but aqueous solvents are preferred. The reason why an aqueous solvent is preferable is that the carbon material contained in the organic-inorganic composite produced by the production method of the present invention is difficult to dissolve in water, while the inorganic material is soluble in water (particularly acidic water or basic water). This is because there are many things that can be dissolved. Examples of the aqueous solvent include acidic aqueous solutions such as sulfuric acid, hydrochloric acid, and nitric acid; basic aqueous solutions such as sodium hydroxide, potassium hydroxide, and ammonia; and the like. In addition, in the removal step, the temperature is not particularly limited, but is preferably 0°C to 150°C, more preferably 20°C to 100°C, since it can effectively express the dissolution characteristics of the aqueous solvent. . Further, the physical treatment in the removal step is not particularly limited, but in terms of effectively achieving removability, it is preferably left standing, stirring, ultrasonication, or shearing, and more preferably , stirring, sonication, and shearing operations.

Regarding the film thickness of the carbon material portion of the hollow carbon fine particles, see ≪≪4. The content explained in the section ≫≫ representative example of method for producing carbon material-containing material may be used.

≪7-4. Highly carbonized hollow carbon fine particles≫
When producing the organic-inorganic composite of the present invention, the highly carbonized hollow carbon fine particles may include a heating step (II) of further heating after the heating step (I), followed by an inorganic substance removal step. It can be manufactured by That is, the hollow carbon fine particles obtained in the above-mentioned production mode 1 are further heated. By this heating step (II), the carbon material portion can be highly carbonized. Thereby, highly carbonized hollow carbon fine particles can be obtained. By increasing the carbon content, the strength and heat resistance of the obtained carbon material or carbon material composite can be improved.

In producing the organic-inorganic composite of the present invention, the highly carbonized hollow carbon fine particles may be further subjected to a carbon material removal step after the heating step (I), and then an inorganic substance removal step. After heating, it can be manufactured by including a heating step (II) of further heating. That is, the hollow carbon fine particles obtained in the above-mentioned production mode 2 are further heated. By this heating step (II), the carbon material portion can be highly carbonized.

Regarding the film thickness of the carbon material portion of the highly carbonized hollow carbon fine particles, see <<<2. The content explained in the section ≫≫ representative example of method for producing carbon material-containing material may be used.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. In addition, unless otherwise specified, "part" means "part by mass" and "%" means "% by mass." Moreover, in this specification, "mass" may be read as "weight." However, % in the portion related to C1sXPS in this specification means atomic %. Note that Examples 25 to 32 are to be read as Reference Examples 1 to 8.

<Raman spectroscopy>
Raman spectroscopic analysis was performed using the following equipment and conditions.
Measuring device: Raman microscope (JASCO NRS-3100)
Measurement conditions: 532nm laser used, objective lens 20x, CCD capture time 1 second, 64 times total (resolution = 4cm-1)
Note that in Raman analysis, the G' band and the D+D' band may appear overlapping each other, and the D+D' band may be analyzed as a particularly broad peak with a shoulder. In this case, the inflection point of the shoulder peak is regarded as the peak of the G' band.

<XRD analysis>
The XRD measurement was performed using a fully automatic horizontal X-ray diffraction device (SMART LAB, manufactured by Rigaku Corporation) under the following conditions.
CuKα1 line: 0.15406nm
Scanning range: 10°-90°
X-ray output setting: 45kV-200mA
Step size: 0.020°
Scan speed: 0.5°min ^-1 -4°min ^-1
Note that the XRD measurement was performed in a state where an inert atmosphere was maintained by loading the sample onto an airtight sample stage in a glove box.

<C1sXPS analysis>
The C1sXPS measurement was performed using a photoelectron spectrometer (AXIS-ULTRA, manufactured by Shimadzu Corporation) under the following conditions.
Source: Mg (dual node)
Emission: 10mA
Anode: 10kV
Analyzer: Pass Energy: 40
Measurement range: C1s: 296-270eV
Number of integrations: 10 Analysis conditions: Peaks derived from the C1s orbit were separated for each functional group using the energy described below, and the ratio was calculated from each area. Types of functional groups are (1) -COO-, lactones, and some ketones @288.3eV, (2) C=O and epoxy groups @286.2eV, (3) C-OH and C-O-C It was separated into five peaks: (4) 6-membered cyclic C=C@284.3eV, (5) CC, CH, and 5-membered cyclic C=C@283.6eV. However, for calculating the ratio, (4) and (5) were calculated together. Note that % of the portion related to C1sXPS means atomic %. In addition, in the table, the proportions of peaks corresponding to (1), (2), and (3) are shown as (A), (B), and (C), and the proportions of peaks corresponding to (4) and (5) are shown as (A), (B), and (C). The total percentage of peaks is shown in (D).

<TG-DTA analysis>
TG-DTA analysis was performed using the following equipment and conditions.
Measuring device: Simultaneous thermogravimetric measurement device (Seiko Instruments, TG/DTA6200)
The condensation reaction temperature of compound (A) was determined as follows.
(1) When one type of compound is used as compound (A), TG-DTA analysis of compound (A) is performed by heating from 40°C at a temperature increase rate of 10°C/min in a nitrogen gas atmosphere, The peak top temperature on the lowest temperature side of DTA was determined as the condensation reaction temperature (T° C.) of compound (A).
(2) When using a mixture of two or more compounds as compound (A), perform TG-DTA analysis of the mixture by increasing the temperature from 40°C at a heating rate of 10°C/min in a nitrogen gas atmosphere. The peak top temperature at the lowest temperature side of DTA was determined as the condensation reaction temperature (T° C.) of compound (A) (a mixture of two or more compounds).
(3) However, if compound (A) as one type of compound or a mixture of two or more types of compounds contains impurities such as a solvent, water, or water of hydration, the impurities can be removed. A DTA peak (sometimes referred to as an impurity peak) accompanying the condensation reaction may be observed at a temperature lower than the condensation reaction temperature. In such a case, the above impurity peak was ignored and the condensation reaction temperature of the compound (A) was determined. Specifically, the peak top temperature on the lowest temperature side of DTA was determined as the condensation reaction temperature of the compound (A), ignoring the above impurity peak.
The oxidation start temperature of the organic-inorganic composite was estimated from the temperature rise temperature of the lowest DTA among the DTA rise temperatures, which was carried out from 40°C in an air atmosphere at a heating rate of 10°C/min.

<IR analysis>
FT-IR analysis was performed using the following equipment and conditions.
Measuring device: Fourier transform infrared spectrophotometer (JASCO Corporation FT/IR-4200)
Measurement conditions: Diffuse reflection (DRIFT) method, MCT detector, resolution 4 cm -1, number of integrations 128 times Sample conditions: A mixture of the sample and KBr at a weight ratio of 1:50 was used.

<Measurement of ¹³ C-NMR and ²⁹ Si-NMR>
¹³ C-NMR and ²⁹ Si-NMR measurements were performed using the following equipment and conditions.
Equipment: Bruker Avance NEO 400MHz/263GHz 9.4T DNP system
Probe: 2ch 3.2mm DNP probe Sample tube: 3.2mm sapphire rotor + Teflon insert + zirconia cap Measurement temperature: 105K to 107K
Magic Angle Spinning (MAS): 10kHz
Pulse program: CP (1H- ¹³ C, 1H- ²⁹ Si)
CP contact time: 3ms
Sample preparation conditions: 40mg sample + 20μL TEKPol/1,1,2,2-tetrachloroethane (16mM)

<Measurement of molecular weight>
The molecular weight was measured using gel permeation chromatography (GPC, HLC-8220GPC manufactured by Tosoh Corporation) using N,N-dimethylformamide (containing 0.1% LiBr) so that each carbon material was 0.02% by mass. After 1 hour of ultrasonic treatment, the filtrate was passed through a PTFE filter paper (0.45 μm) for pretreatment, and N,N-dimethylformamide (containing 0.1% LiBr) was used as a developing solvent. The molecular weight was calculated in terms of polystyrene. The maximum molecular weight in the carbon material was calculated from the rising point of the peak.

<Measurement of thermal conductivity properties (thermal diffusivity, thermal conductivity)>
The thermal diffusivity as a thermal conductivity characteristic was measured by measuring the thermal diffusivity in the thickness direction of the film using M3 type 2 manufactured by I-Phase Co., Ltd. Thermal conductivity as a thermal conductive property was calculated from the specific heat of the film×density×thermal diffusivity.

<SPS sintering>
SPS sintering was performed using the following equipment and conditions.
Equipment: Sinterland Co., Ltd. LABOX-125C
Atmosphere: Under vacuum Temperature increase: 10℃/min (temperature increase from ~5Pa)
Sintering temperature: 610℃
Holding time: 5 minutes Pressure: 50MPa (from temperature rise to sintering)
Cooling: No pressure/natural cooling

<Measurement of powder resistance>
Powder resistance was measured by making a 1 cm square hole in a 4 mm Teflon plate, filling the hole with powder, and sandwiching it between copper electrodes from both sides. The device used was a high resistivity meter 6517BJ manufactured by Tektronix, and the measurement was performed at an applied voltage of 10V.

<Element composition ratio>
Exeter Analytical, Inc. Elemental analysis of C, H, and O was performed using an elemental analyzer (CE-440F) manufactured by Co., Ltd., and the atomic ratio was determined based on the obtained results.

<Yield of carbon material in Examples 1 to 8>
When the obtained carbon material (product) was X parts by mass based on 100 parts by mass of phloroglucinol, the yield of the carbon material was defined as X (%).

<Solid ^13C -DD/MAS-NMR analysis>
Bruker Corp. The analysis was performed using an NMR device (Avance III 600) manufactured by Co., Ltd.

[Example 1]: Phloroglucinol + silica particles + 250°C x 1 hour Phloroglucinol (manufactured by Tokyo Kasei Kogyo Co., Ltd., melting point: 220°C, condensation reaction temperature: 330°C): Theoretical specific surface area of 750 m ² /g is silica The particles were thoroughly mixed with silica particles (manufactured by Fuji Silysia Chemical Co., Ltd., trade name "Q-10HT60315", specific surface area 259 m ² /g) so as to form 1.5 layers per particle.
The resulting mixture was vacuum sealed in a quartz ampoule tube, and then heated for 1 hour in an electric furnace that had been previously heated to 250°C.
Thereby, an organic-inorganic composite (1) containing a carbon material (1A) and an inorganic oxide (1B) was obtained.
Analysis of the obtained carbon material revealed that carbon material (1A) mainly undergoes dehydration condensation between phenolic OH groups (C-OH), and condensation reactions between C-H and between C-H and C-OH. It was found that carbonization progressed as the carbonization progressed.
When the organic-inorganic composite (1) was dispersed in NMP (N-methylpyrrolidone) and the solubility of the carbon component was confirmed by the method described above, it was found to be soluble in the solvent.
The results of C1sXPS analysis of the obtained organic-inorganic composite (1) are shown in FIG. 3 (XPS spectrum (C1s)) and Table 1. From Table 1, it can be seen that the organic-inorganic composite (1) is an organic-inorganic composite containing a carbon material and an inorganic oxide, and all carbon bonds (C-C bonds, C=C bonds, C-H bonds, and The ratio of the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) to the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) is 26%. The ratio of the total amount of ether-derived C-O bonds and alcohol-derived C-O bonds to the total amount of all carbon bonds (C-C bonds and C=C bonds) is 62%. The ratio of the total amount of ether-derived C-O bonds and alcohol-derived C-O bonds to the total amount of C--H bonds, C--O bonds, and C=O bonds was 16%. This shows that the structural control rate is high.
The weight ratio of the weight M500 at a temperature of 500°C to the initial weight M50 at a temperature of 50°C (M500/M50 ) was 0.49. This shows that phloroglucinol can sufficiently exist on the inorganic oxide even after carbonization.
The results of DTA analysis in the TG-DTA analysis of the obtained organic-inorganic composite (1) are shown in FIG. According to FIG. 4, the organic-inorganic composite (1) was oxidized as indicated by the rise temperature of DTA when TG-DTA analysis was performed under the conditions of increasing the temperature from 40°C to 10°C/min in an air atmosphere. The starting temperature was 200°C. This shows that the oxidation resistance is high.
Furthermore, the results of IR analysis of the obtained organic-inorganic composite (1) are shown in FIG. According to FIG. 5, in the IR spectrum of the organic-inorganic composite (1), there is no peak at 1660 cm ^-1 to 1800 cm ^-1 derived from the C=O structure, and the structure is highly controlled.
Furthermore, the Raman spectrum of the obtained organic-inorganic composite (1) is shown in FIG. Since the Raman spectrum has peaks at 1365 cm ^-1 , 1590 cm ^-1 , 2650 cm ^-1 , and 2835 cm ^-1 , the carbon material (1A) has a graphene structure and contains a carbon-based compound with a stacked graphene structure. It turned out to be the material.
As described above, according to the production method of the present invention, a carbon material-containing material that is soluble in a solvent and has a precisely controlled structure can be easily produced under mild conditions. Furthermore, as described above, according to the present invention, it is possible to provide an organic-inorganic composite that is soluble in a solvent, has a precisely controlled structure, and can be manufactured industrially under mild conditions.

[Example 2] Phloroglucinol + alumina particles + 250°C x 1 hour Except for changing the silica particles to alumina particles (Japan Catalysis Society free distribution sample "JRC-ALO7", specific surface area 180 m ² /g) The same procedure as in Example 1 was carried out to obtain an organic-inorganic composite (2) containing a carbon material (2A) and an inorganic oxide (2B).
Analysis of the obtained carbon material revealed that carbon material (2A) mainly undergoes dehydration condensation between phenolic OH groups (C-OH), and condensation reactions between C-H and between C-H and C-OH. It was found that carbonization progressed as the carbonization progressed.
When the organic-inorganic composite (2) was dispersed in NMP (N-methylpyrrolidone) and the solubility of the carbon component was confirmed by the method described above, it was found to be soluble in the solvent.
The results of C1sXPS analysis of the obtained organic-inorganic composite (2) are shown in FIG. 3 (XPS spectrum (C1s)) and Table 1. From Table 1, it can be seen that the organic-inorganic composite (2) is an organic-inorganic composite containing a carbon material and an inorganic oxide, and all carbon bonds (C-C bond, C=C bond, C-H bond, The ratio of the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) to the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) is 29%. The ratio of the total amount of ether-derived C-O bonds and alcohol-derived C-O bonds to the total amount of all carbon bonds (C-C bonds and C=C bonds) is 59%. The ratio of the total amount of ether-derived C-O bonds and alcohol-derived C-O bonds to the total amount of C--H bonds, C--O bonds, and C=O bonds was 17%. This shows that the structural control rate is high.
The results of DTA analysis in the TG-DTA analysis of the obtained organic-inorganic composite (2) are shown in FIG. According to FIG. 4, the organic-inorganic composite (2) was oxidized as indicated by the rise temperature of DTA when TG-DTA analysis was performed under the temperature increasing conditions of 10°C/min from 40°C in an air atmosphere. The starting temperature was 230°C. This shows that the oxidation resistance is high.
Furthermore, the results of IR analysis of the obtained organic-inorganic composite (2) are shown in FIG. According to FIG. 5, in the IR spectrum of the organic-inorganic composite (2), there is a peak at 1660 cm ^-1 to 1800 cm ^-1 derived from the C=O structure, and although the structural control rate by C1sXPS is high, The structural control rate by FT-IR analysis is rather low.
Furthermore, the Raman spectrum of the obtained organic-inorganic composite (2) is shown in FIG. Since the Raman spectrum has peaks at 1340 cm ^-1 , 1585 cm ^-1 , 2650 cm ^-1 , and 2835 cm ^-1 , the carbon material (2A) has a graphene structure and contains a carbon-based compound with a stacked graphene structure. It turned out to be the material.
As described above, according to the production method of the present invention, a carbon material-containing material that is soluble in a solvent and has a precisely controlled structure can be easily produced under mild conditions. Further, as described above, according to the present invention, it is possible to provide an organic-inorganic composite that is soluble in a solvent, has a precisely controlled structure, and can be industrially manufactured under mild conditions.

[Example 3] Phloroglucinol + titania particles + 250°C x 1 hour Changed silica particles to titania particles (Japan Catalysis Society free distribution sample "JRC-TIO-4 (2)", specific surface area 50 m ² /g) Except for the above, the same procedure as in Example 1 was carried out to obtain an organic-inorganic composite (3) containing a carbon material (3A) and an inorganic oxide (3B).
Analysis of the obtained carbon material revealed that carbon material (3A) mainly undergoes dehydration condensation between phenolic OH groups (C-OH), and condensation reactions between C-H and between C-H and C-OH. It was found that carbonization progressed as the carbonization progressed.
When the organic-inorganic composite (3) was dispersed in NMP (N-methylpyrrolidone) and the solubility of the carbon component was confirmed by the method described above, it was found to be soluble in the solvent.
The results of C1sXPS analysis of the obtained organic-inorganic composite (3) are shown in FIG. 3 (XPS spectrum (C1s)) and Table 1. From Table 1, it can be seen that the organic-inorganic composite (3) is an organic-inorganic composite containing a carbon material and an inorganic oxide, and all carbon bonds (C-C bonds, C=C bonds, C-H bonds, and The ratio of the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) to the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) is 27%. The ratio of the total amount of ether-derived C-O bonds and alcohol-derived C-O bonds to the total amount of all carbon bonds (C-C bonds and C=C bonds) is 56%. The ratio of the total amount of ether-derived C-O bonds and alcohol-derived C-O bonds to the total amount of C--H bonds, C--O bonds, and C=O bonds was 15%. This shows that the structural control rate is high.
The results of DTA analysis in the TG-DTA analysis of the obtained organic-inorganic composite (3) are shown in FIG. According to FIG. 4, the organic-inorganic composite (3) was oxidized as indicated by the rise temperature of DTA when TG-DTA analysis was performed under heating conditions of 10°C/min from 40°C in an air atmosphere. The starting temperature was 200°C. This shows that the oxidation resistance is high.
Furthermore, the results of IR analysis of the obtained organic-inorganic composite (3) are shown in FIG. According to FIG. 5, in the IR spectrum of the organic-inorganic composite (3), there is a peak at 1660 cm ^-1 to 1800 cm ^-1 derived from the C=O structure, and although the structural control rate by C1sXPS is high, The structural control rate by FT-IR analysis is rather low.
Furthermore, the Raman spectrum of the obtained organic-inorganic composite (3) is shown in FIG. Since the Raman spectrum has peaks at 1340 cm ^-1 , 1580 cm ^-1 , 2650 cm ^-1 , and 2820 cm ^-1 , the carbon material (3A) has a graphene structure and contains a carbon-based compound with a stacked graphene structure. It turned out to be the material.
As described above, according to the production method of the present invention, a carbon material-containing material that is soluble in a solvent and has a precisely controlled structure can be easily produced under mild conditions. Further, as described above, according to the present invention, it is possible to provide an organic-inorganic composite that is soluble in a solvent, has a precisely controlled structure, and can be industrially manufactured under mild conditions.

[Example 4] Phloroglucinol + heteropolyacid particles (HPW) + 250°C x 1 hour HPW (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 12-tungst (VI) phosphate n-hydrate) using silica particles as heteropolyacid particles , specific surface area of 278 m ² /g) was carried out in the same manner as in Example 1 to obtain an organic-inorganic composite (4) containing a carbon material (4A) and an inorganic oxide (4B).
Analysis of the obtained carbon material revealed that carbon material (4A) mainly undergoes dehydration condensation between phenolic OH groups (C-OH), and condensation reactions between C-H and between C-H and C-OH. It was found that carbonization progressed as the carbonization progressed.
When the organic-inorganic composite (4) was dispersed in NMP (N-methylpyrrolidone) and the solubility of the carbon component was confirmed by the method described above, it was found to be soluble in the solvent.
The results of C1sXPS analysis of the obtained organic-inorganic composite (4) are shown in FIG. 3 (XPS spectrum (C1s)) and Table 1. From Table 1, it can be seen that the organic-inorganic composite (4) is an organic-inorganic composite containing a carbon material and an inorganic oxide, and all carbon bonds (C-C bonds, C=C bonds, C-H bonds, and The ratio of the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) to the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) is 29%. The ratio of the total amount of ether-derived C-O bonds and alcohol-derived C-O bonds to the total amount of all carbon bonds (C-C bonds and C=C bonds) is 76%. The ratio of the total amount of ether-derived C--O bonds and alcohol-derived C--O bonds to the total amount of C--H bonds, C--O bonds, and C=O bonds was 22%. This shows that the structural control rate is high.
The results of DTA analysis in the TG-DTA analysis of the obtained organic-inorganic composite (4) are shown in FIG. According to FIG. 4, the organic-inorganic composite (4) was oxidized as indicated by the rise temperature of DTA when TG-DTA analysis was performed under heating conditions of 10°C/min from 40°C in an air atmosphere. The starting temperature was 300°C. This shows that the oxidation resistance is high.
Furthermore, the results of IR analysis of the obtained organic-inorganic composite (4) are shown in FIG. According to FIG. 5, in the IR spectrum of the organic-inorganic composite (4), there is no peak at 1660 cm ^-1 to 1800 cm ^-1 derived from the C=O structure, and the structure is highly controlled.
Furthermore, the Raman spectrum of the obtained organic-inorganic composite (4) is shown in FIG. Since the Raman spectrum has peaks at 1350 cm ^-1 , 1585 cm ^-1 , 2650 cm ^-1 , and 2810 cm ^-1 , the carbon material (4A) has a graphene structure and contains a carbon-based compound with a stacked graphene structure. It turned out to be the material. Further, when the molecular weight of the carbon material (4A) portion was measured, the weight average molecular weight was 8,000 and the maximum molecular weight was 50,000.
As described above, according to the production method of the present invention, a carbon material-containing material that is soluble in a solvent and has a precisely controlled structure can be easily produced under mild conditions. Further, as described above, according to the present invention, it is possible to provide an organic-inorganic composite that is soluble in a solvent, has a precisely controlled structure, and can be industrially manufactured under mild conditions.

[Example 5] Phloroglucinol + heteropolyacid particles (HPMo) + 250°C x 1 hour HPMo (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 12-molybdo(VI) phosphate n-hydrate) using silica particles as heteropolyacid particles ) was carried out in the same manner as in Example 1, to obtain an organic-inorganic composite (5) containing a carbon material (5A) and an inorganic oxide (5B).
Analysis of the obtained carbon material revealed that carbon material (5A) mainly undergoes dehydration condensation between phenolic OH groups (C-OH), and condensation reactions between C-H and between C-H and C-OH. It was found that carbonization progressed as the carbonization progressed.
When the organic-inorganic composite (5) was dispersed in NMP (N-methylpyrrolidone) and the solubility of the carbon component was confirmed by the method described above, it was found to be soluble in the solvent.
The results of C1sXPS analysis of the obtained organic-inorganic composite (5) are shown in FIG. 7 (XPS spectrum (C1s)) and Table 1. From Table 1, it can be seen that the organic-inorganic composite (5) is an organic-inorganic composite containing a carbon material and an inorganic oxide, and all carbon bonds (C-C bonds, C=C bonds, C-H bonds, and The ratio of the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) to the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) is 27%. The ratio of the total amount of ether-derived C-O bonds and alcohol-derived C-O bonds to the total amount of all carbon bonds (C-C bonds and C=C bonds) is 63%. The ratio of the total amount of ether-derived C-O bonds and alcohol-derived C-O bonds to the total amount of C--H bonds, C--O bonds, and C=O bonds was 17%. This shows that the structural control rate is high.
Furthermore, the results of IR analysis of the obtained organic-inorganic composite (5) are shown in FIG. According to FIG. 8, in the IR spectrum of the organic-inorganic composite (5), there is no peak at 1660 cm ^-1 to 1800 cm ^-1 derived from the C=O structure, and the structure is highly controlled.
As described above, according to the production method of the present invention, a carbon material-containing material that is soluble in a solvent and has a precisely controlled structure can be easily produced under mild conditions. Furthermore, as described above, according to the present invention, it is possible to provide an organic-inorganic composite that is soluble in a solvent, has a precisely controlled structure, and can be manufactured industrially under mild conditions.

[Example 6] Phloroglucinol + heteropolyacid particles (HSiW) + 250°C x 1 hour Same as Example 1 except that the silica particles were changed to HSiW (manufactured by Nippon Shinkinzoku Co., Ltd., silicotungstic acid) as heteropolyacid particles. In the same manner, an organic-inorganic composite (6) containing a carbon material (6A) and an inorganic oxide (6B) was obtained.
Analysis of the obtained carbon material revealed that carbon material (6A) mainly undergoes dehydration condensation between phenolic OH groups (C-OH), and condensation reactions between C-H and between C-H and C-OH. It was found that carbonization progressed as the carbonization progressed.
When the organic-inorganic composite (6) was dispersed in NMP (N-methylpyrrolidone) and the solubility of the carbon component was confirmed by the method described above, it was found to be soluble in the solvent.
The results of C1sXPS analysis of the obtained organic-inorganic composite (6) are shown in FIG. 7 (XPS spectrum (C1s)) and Table 1. From Table 1, it can be seen that the organic-inorganic composite (6) is an organic-inorganic composite containing a carbon material and an inorganic oxide, and all carbon bonds (C-C bond, C=C bond, C-H bond, The ratio of the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) to the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) is 29%. The ratio of the total amount of ether-derived C-O bonds and alcohol-derived C-O bonds to the total amount of all carbon bonds (C-C bonds and C=C bonds) is 72%. The ratio of the total amount of ether-derived C-O bonds and alcohol-derived C-O bonds to the total amount of C--H bonds, C--O bonds, and C=O bonds was 21%. This shows that the structural control rate is high.
Furthermore, the results of IR analysis of the obtained organic-inorganic composite (6) are shown in FIG. According to FIG. 8, in the IR spectrum of the organic-inorganic composite (6), there is no peak at 1660 cm ⁻¹ to 1800 cm ⁻¹ derived from the C═O structure, and the structure is highly controlled.
As described above, according to the production method of the present invention, a carbon material-containing material that is soluble in a solvent and has a precisely controlled structure can be easily produced under mild conditions. Further, as described above, according to the present invention, it is possible to provide an organic-inorganic composite that is soluble in a solvent, has a precisely controlled structure, and can be industrially manufactured under mild conditions.

[Example 7] Phloroglucinol + heteropolyacid particles (HPVMo) + 250°C x 1 hour Example 1 except that the silica particles were changed to HPVMo (linvanadomolybdic acid, manufactured by Nippon Shinkin Metal Co., Ltd.) as heteropolyacid particles. In the same manner as above, an organic-inorganic composite (7) containing a carbon material (7A) and an inorganic oxide (7B) was obtained.
Analysis of the obtained carbon material revealed that carbon material (7A) mainly undergoes dehydration condensation between phenolic OH groups (C-OH), and condensation reactions between C-H and between C-H and C-OH. It was found that carbonization progressed as the carbonization progressed.
When the organic-inorganic composite (7) was dispersed in NMP (N-methylpyrrolidone) and the solubility of the carbon component was confirmed by the method described above, it was found to be soluble in the solvent.
The results of C1sXPS analysis of the obtained organic-inorganic composite (7) are shown in FIG. 7 (XPS spectrum (C1s)) and Table 1. From Table 1, it can be seen that the organic-inorganic composite (7) is an organic-inorganic composite containing a carbon material and an inorganic oxide, and all carbon bonds (C-C bond, C=C bond, C-H bond, The ratio of the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) to the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) is 29%. The ratio of the total amount of ether-derived C-O bonds and alcohol-derived C-O bonds to the total amount of all carbon bonds (C-C bonds and C=C bonds) is 55%. The ratio of the total amount of ether-derived C-O bonds and alcohol-derived C-O bonds to the total amount of C--H bonds, C--O bonds, and C=O bonds was 16%. This shows that the structural control rate is high.
Furthermore, the results of IR analysis of the obtained organic-inorganic composite (7) are shown in FIG. According to FIG. 8, in the IR spectrum of the organic-inorganic composite (7), there is no peak at 1660 cm ⁻¹ to 1800 cm ⁻¹ derived from the C═O structure, and the structure is highly controlled.
As described above, according to the production method of the present invention, a carbon material-containing material that is soluble in a solvent and has a precisely controlled structure can be easily produced under mild conditions. Further, as described above, according to the present invention, it is possible to provide an organic-inorganic composite that is soluble in a solvent, has a precisely controlled structure, and can be industrially manufactured under mild conditions.

[Example 8] Phloroglucinol + heteropolyacid particles (HPWMo) + 250°C x 1 hour Example 1 except that the silica particles were changed to HPWMo (phosphotungstomolybdic acid, manufactured by Nippon Shinkinzoku Co., Ltd.) as heteropolyacid particles. In the same manner as above, an organic-inorganic composite (8) containing a carbon material (8A) and an inorganic oxide (8B) was obtained.
Analysis of the obtained carbon material revealed that carbon material (8A) mainly undergoes dehydration condensation between phenolic OH groups (between C-OH), and condensation reactions between C-H and between C-H and C-OH. It was found that carbonization progressed as the carbonization progressed.
When the organic-inorganic composite (8) was dispersed in NMP (N-methylpyrrolidone) and the solubility of the carbon component was confirmed by the method described above, it was found to be soluble in the solvent.
The results of C1sXPS analysis of the obtained organic-inorganic composite (8) are shown in FIG. 7 (XPS spectrum (C1s)) and Table 1. From Table 1, it can be seen that the organic-inorganic composite (8) is an organic-inorganic composite containing a carbon material and an inorganic oxide, and all carbon bonds (C-C bonds, C=C bonds, C-H bonds, and The ratio of the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) to the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) is 27%. The ratio of the total amount of ether-derived C-O bonds and alcohol-derived C-O bonds to the total amount of all carbon bonds (C-C bonds and C=C bonds) is 70%. The ratio of the total amount of ether-derived C-O bonds and alcohol-derived C-O bonds to the total amount of C--H bonds, C--O bonds, and C=O bonds was 19%. This shows that the structural control rate is high.
Furthermore, the results of IR analysis of the obtained organic-inorganic composite (8) are shown in FIG. According to FIG. 8, in the IR spectrum of the organic-inorganic composite (8), there is no peak at 1660 cm ⁻¹ to 1800 cm ⁻¹ derived from the C=O structure, and the structure is highly controlled.
As described above, according to the production method of the present invention, a carbon material-containing material that is soluble in a solvent and has a precisely controlled structure can be easily produced under mild conditions. Further, as described above, according to the present invention, it is possible to provide an organic-inorganic composite that is soluble in a solvent, has a precisely controlled structure, and can be industrially manufactured under mild conditions.

[Example 9]: Phloroglucinol + silica particles + 300°C x 3 hours, hollow carbon fine particles Phloroglucinol (manufactured by Tokyo Kasei Kogyo Co., Ltd., melting point: 220°C, condensation reaction temperature: 330°C): 300 mg to 3 g of isopropyl It was dissolved in alcohol, and 1000 mg of silica spherical fine particles (manufactured by Nippon Shokubai Co., Ltd., average particle diameter: 0.19 μm) was added thereto, and thoroughly mixed by ultrasonication.
Isopropyl alcohol was removed from the resulting mixture by vacuum drying at room temperature, the remaining lumps were crushed, and then heated at 300° C. for 3 hours.
Thereby, an organic-inorganic composite (9) containing a carbon material (9A) and an inorganic oxide (9B) was obtained.
Analysis of the obtained carbon material revealed that carbon material (9A) mainly undergoes dehydration condensation between phenolic OH groups (C-OH), and condensation reactions between C-H and between C-H and C-OH. It was found that carbonization progressed as the carbonization progressed.
The Raman spectrum of the organic-inorganic composite (9) is shown in FIG. Since the Raman spectrum has peaks at 1375 cm ^-1 , 1600 cm ^-1 , 2700 cm ^-1 , and 2890 cm ^-1 , the carbon material (9A) has a graphene structure and contains a carbon-based compound with a stacked graphene structure. It turned out to be the material. Further, when the molecular weight of the carbon material (9A) portion was measured, the weight average molecular weight was 200,000 and the maximum molecular weight was 1,100,000.
The obtained organic-inorganic composite (9) was treated with NMP (N-methylpyrrolidone). As a result, the carbon material (9A) is removed, and the core-shell particles (9) are coated with a carbon material bonding region on the surface of the inorganic oxide (9B) (core part: inorganic oxide particle, shell part: carbon material bonding region). )was gotten.
The core-shell particles (9) were further calcined at 700°C for 1 hour. As a result, the carbon material in the shell portion was highly carbonized, and highly carbonized core-shell particles (9) were obtained. A SEM photograph of the highly carbonized core-shell particles (9) is shown in FIG. 10, and a Raman spectrum of the surface of the highly carbonized core-shell particles (9) is shown in FIG. It can be seen from FIGS. 10 and 11 that the surface (shell portion) of the highly carbonized core-shell particles (9) is made of a highly carbonized carbon material without damaging the shape.
^{The 13} C-NMR and ²⁹ Si-NMR analysis results of the highly carbonized core-shell particles (9) are shown in FIGS. 12 and 13. First, from ¹³ C-NMR, a peak at 129 ppm and a shoulder peak from 140 ppm to 160 ppm were confirmed. This is considered to be due to the presence of sp2 carbon (129 ppm) and the bond between oxygen atoms on the surface of the inorganic substance and carbon atoms derived from the carbon material (140 ppm to 160 ppm). In Comparative Example 3, which will be described later, it is thought that sp2 carbon is not formed and sp3 carbon is the main component, hidden behind the solvent peak. In addition, from ^{the 29} Si-NMR, a peak derived from the Si-O-C bond was confirmed in comparison with the raw material silica spherical fine particles and Comparative Example 3 described later. It was found that covalent bonds are formed with the atoms of Note that, as mentioned above, since the covalent bond was only with the outermost surface of the inorganic substance, the peak intensity was small and was confirmed as a shoulder peak.
When the powder resistance of the highly carbonized core-shell particles (9) was measured, it was 3×10 ⁵ Ωcm. Since the powder resistance of the raw material silica spherical fine particles is on the order of 10 ¹⁴ Ωcm, it was found that the conductivity could be improved by about 9 orders of magnitude by forming core-shell particles.
The film thickness of the carbon portion of the highly carbonized core-shell particles (9) was estimated from TG-DTA analysis. The estimation method is to raise the temperature of silica spherical particles and highly carbonized core-shell particles (9) as raw materials from room temperature to 1000℃ at a rate of 10℃/min in an air atmosphere, burn the carbon component, and separate the silica spherical particles and The amount of carbon component was analyzed by taking the difference using the highly carbonized core-shell particles (9). According to the above method, the carbon content of the highly carbonized core-shell particles (9) was 1.39% by mass. When calculated assuming that the diameter of the spherical silica particles was 0.19 μm and the density of the carbon component was 2, the average film thickness of the carbon component was 0.49 nm.
500 mg of core-shell particles (9) were ultrasonically cleaned in a 10% aqueous sodium hydroxide solution for 5 hours and filtered to obtain 20 mg of hollow carbon fine particles (9). The filtrate was colorless and transparent, and considering the amount removed, only the carbon component remained and the internal inorganic component was removed, so it is thought that the formation of hollow carbon fine particles (9) with a hollow structure was achieved. It will be done.

[Example 10]: Phloroglucinol + copper particles + 300°C x 2 hours, highly carbonized core-shell particles Phloroglucinol (manufactured by Tokyo Kasei Kogyo Co., Ltd., melting point: 220°C, condensation reaction temperature: 330°C): 1 g to 200 g was dissolved in acetone, and 20 g of copper particles (manufactured by ECKA Granules Germany GmbH, particle size: 95 vol% or more is 36 μm or less) were added thereto, and thoroughly mixed by ultrasonication.
Acetone was removed from the resulting mixture by vacuum drying at room temperature, the remaining lumps were crushed, and then heated at 300° C. for 2 hours.
Thereby, an organic-inorganic composite (10) containing a carbon material (10A) and an inorganic oxide (10B) was obtained.
Analysis of the obtained carbon material revealed that the carbon material (10A) mainly undergoes dehydration condensation between phenolic OH groups (C-OH), and condensation reactions between C-H and between C-H and C-OH. It was found that carbonization progressed as the carbonization progressed.
The obtained organic-inorganic composite (10) was treated with DMF (N,N-dimethylformamide). As a result, the carbon material (10A) is removed, and the core-shell particles (10) are coated with a carbon material bonding region on the surface of the inorganic oxide (10B) (core part: inorganic oxide particle, shell part: carbon material bonding region). )was gotten.
The core-shell particles (10) were further calcined at 700°C for 1 hour. As a result, the carbon material in the shell portion was highly carbonized, and highly carbonized core-shell particles (10) were obtained. FIG. 14 shows the Raman spectrum of the surface of the highly carbonized core-shell particles (10). It can be seen from FIG. 14 that the surface (shell portion) of the highly carbonized core-shell particles (10) is made of a highly carbonized carbon material without damaging the shape.

[Example 11]: Phloroglucinol + aluminum particles + 300°C x 2 hours, highly carbonized core-shell particles Phloroglucinol (manufactured by Tokyo Kasei Kogyo Co., Ltd., melting point: 220°C, condensation reaction temperature: 330°C): 0.2 g was dissolved in 200 g of acetone, 2 g of aluminum particles (manufactured by ECKA Granules Germany GmbH, D50 = 5 μm) were added thereto, thoroughly mixed by ultrasonication, and dried to obtain an aluminum particle-phloroglucinol mixture. Ta. This mixture was fired at 300° C. for 2 hours on a Kugelrohr in a nitrogen atmosphere. Thereby, an organic-inorganic composite (11) containing a carbon material (11A) and an inorganic oxide (11B) was obtained.
Analysis of the obtained carbon material revealed that carbon material (11A) mainly undergoes dehydration condensation between phenolic OH groups (C-OH), and condensation reactions between C-H and between C-H and C-OH. It was found that carbonization progressed as the carbonization progressed.
The obtained organic-inorganic composite (11) is treated with ultrasonic waves in DMF (N,N-dimethylformamide), the excess carbon material (11A) is removed and purified by filtration, and the surface of the inorganic oxide (11B) is Core-shell particles (11) coated with a carbon material binding region (core portion: inorganic oxide particle, shell portion: carbon material binding region) were obtained.
The core-shell particles (11) were further calcined at 600°C for 2 hours. As a result, the carbon material in the shell portion was highly carbonized, and highly carbonized core-shell particles (11) were obtained. FIG. 15 shows the Raman spectrum of the surface of the highly carbonized core-shell particles (11). FIG. 15 shows that the surface (shell portion) of the highly carbonized core-shell particles (11) is made of a highly carbonized carbon material without damaging the shape.
Further, the obtained highly carbonized core-shell particles (11) were subjected to SPS sintering to obtain an aluminum-carbon alloy sintered body. For comparison, an aluminum sintered body was also produced by SPS sintering raw material aluminum particles. When the Vickers hardness of each sintered body was confirmed, it was as shown in Figure 16, indicating that the strength (hardness) can be increased when sintered by using the one produced by the carbon coating technology of the present invention. Ta. That is, the carbon material-containing material obtained by the production method of the present invention can be applied to impart strength to a sintered body (as a sintered body strength improver).

[Example 12]: Phloroglucinol + barium titanate particles + 300°C x 2 hours, highly carbonized core-shell particles Phloroglucinol (manufactured by Tokyo Kasei Kogyo Co., Ltd., melting point: 220°C, condensation reaction temperature: 330°C): 0 .2g was dissolved in 200g of acetone, 2g of barium titanate particles (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added thereto, thoroughly mixed by ultrasonication, and dried to form a mixture of barium titanate particles and phloroglucinol. I got a body. This mixture was fired at 300° C. for 2 hours on a Kugelrohr under a nitrogen atmosphere. Thereby, an organic-inorganic composite (12) containing a carbon material (12A) and an inorganic oxide (12B) was obtained.
Analysis of the obtained carbon material revealed that carbon material (12A) mainly undergoes dehydration condensation between phenolic OH groups (C-OH), and condensation reactions between C-H and between C-H and C-OH. It was found that carbonization progressed as the carbonization progressed.
The obtained organic-inorganic composite (12) is treated with ultrasonic waves in DMF (N,N-dimethylformamide), the excess carbon material (12A) is removed and purified by centrifugation, and the surface of the inorganic oxide (12B) is purified. Core-shell particles (12) coated with a carbon material binding region (core portion: inorganic oxide particle, shell portion: carbon material binding region) were obtained.
The core-shell particles (12) were further calcined at 700°C for 2 hours. As a result, the carbon material in the shell portion was highly carbonized, and highly carbonized core-shell particles (12) were obtained. FIG. 17 shows the Raman spectrum of the surface of the highly carbonized core-shell particles (12). It can be seen from FIG. 17 that the surface (shell portion) of the highly carbonized core-shell particles (12) is made of a highly carbonized carbon material without damaging the shape.

[Example 13]: Phloroglucinol + strontium titanate particles + 300°C x 2 hours, highly carbonized core-shell particles Phloroglucinol (manufactured by Tokyo Kasei Kogyo Co., Ltd., melting point: 220°C, condensation reaction temperature: 330°C): 0 .2g was dissolved in 200g of acetone, 2g of strontium titanate particles (manufactured by Aldrich) was added thereto, thoroughly mixed by ultrasonication, and dried to obtain a strontium titanate particle-phloroglucinol mixture. . This mixture was fired at 300° C. for 2 hours on a Kugelrohr under a nitrogen atmosphere. Thereby, an organic-inorganic composite (13) containing a carbon material (13A) and an inorganic oxide (13B) was obtained.
Analysis of the obtained carbon material revealed that carbon material (13A) mainly undergoes dehydration condensation between phenolic OH groups (between C-OH), and condensation reactions between C-H and between C-H and C-OH. It was found that carbonization progressed as the carbonization progressed.
The obtained organic-inorganic composite (13) was treated with ultrasonic waves in DMF (N,N-dimethylformamide), the excess carbon material (13A) was removed and purified by centrifugation, and the surface of the inorganic oxide (13B) was purified. Core-shell particles (13) coated with a carbon material binding region (core portion: inorganic oxide particle, shell portion: carbon material binding region) were obtained.
The core-shell particles (13) were further calcined at 700°C for 2 hours. As a result, the carbon material in the shell portion was highly carbonized, and highly carbonized core-shell particles (13) were obtained. FIG. 18 shows the Raman spectrum of the surface of the highly carbonized core-shell particles (13). It can be seen from FIG. 18 that the surface (shell portion) of the highly carbonized core-shell particles (13) is made of a highly carbonized carbon material without damaging the shape.

[Example 14]: Phloroglucinol + lithium niobate particles + 300°C x 2 hours, highly carbonized core-shell particles Phloroglucinol (manufactured by Tokyo Kasei Kogyo Co., Ltd., melting point: 220°C, condensation reaction temperature: 330°C): 0 .2g was dissolved in 200g of acetone, 2g of lithium niobate particles (manufactured by Aldrich) was added thereto, thoroughly mixed by ultrasonication, and dried to obtain a lithium niobate particle-phloroglucinol mixture. . This mixture was fired at 300° C. for 2 hours on a Kugelrohr under a nitrogen atmosphere. Thereby, an organic-inorganic composite (14) containing a carbon material (14A) and an inorganic oxide (14B) was obtained.
Analysis of the obtained carbon material revealed that carbon material (14A) mainly undergoes dehydration condensation between phenolic OH groups (C-OH), and condensation reactions between C-H and between C-H and C-OH. It was found that carbonization progressed as the carbonization progressed.
The obtained organic-inorganic composite (14) is treated with ultrasound in DMF (N,N-dimethylformamide), the excess carbon material (14A) is removed and purified by filtration, and the surface of the inorganic oxide (14B) is Core-shell particles (14) coated with a carbon material binding region (core portion: inorganic oxide particle, shell portion: carbon material binding region) were obtained.
The core-shell particles (14) were further calcined at 700°C for 2 hours. As a result, the carbon material in the shell portion was highly carbonized, and highly carbonized core-shell particles (14) were obtained. FIG. 19 shows the Raman spectrum of the surface of the highly carbonized core-shell particles (14). FIG. 19 shows that the surface (shell portion) of the highly carbonized core-shell particles (14) is made of a highly carbonized carbon material without damaging the shape.

[Example 15]: Phloroglucinol + silicon particles + 300°C x 2 hours, highly carbonized core-shell particles Phloroglucinol (manufactured by Tokyo Kasei Kogyo Co., Ltd., melting point: 220°C, condensation reaction temperature: 330°C): 0.2 g was dissolved in 200 g of acetone, 2 g of silicon particles (manufactured by Nissin Kasei Co., Ltd.) were added thereto, thoroughly mixed by ultrasonication, and dried to obtain a silicon particle-phloroglucinol mixture. This mixture was fired at 300° C. for 2 hours on a Kugelrohr under a nitrogen atmosphere. Thereby, an organic-inorganic composite (15) containing a carbon material (15A) and an inorganic oxide (15B) was obtained.
Analysis of the obtained carbon material revealed that the carbon material (15A) mainly undergoes dehydration condensation between phenolic OH groups (between C-OH), and condensation reactions between C-H and between C-H and C-OH. It was found that carbonization progressed as the carbonization progressed.
The obtained organic-inorganic composite (15) was treated with ultrasonic waves in DMF (N,N-dimethylformamide), the excess carbon material (15A) was removed and purified by centrifugation, and the surface of the inorganic oxide (15B) was purified. Core-shell particles (15) coated with a carbon material binding region (core portion: inorganic oxide particle, shell portion: carbon material binding region) were obtained.
The core-shell particles (15) were further calcined at 700°C for 2 hours. As a result, the carbon material in the shell portion was highly carbonized, and highly carbonized core-shell particles (15) were obtained. FIG. 20 shows the Raman spectrum of the surface of the highly carbonized core-shell particles (15). It can be seen from FIG. 20 that the surface (shell portion) of the highly carbonized core-shell particles (15) is made of a highly carbonized carbon material without damaging the shape.

[Example 16]: Phloroglucinol + boron nitride particles + 300°C x 2 hours, highly carbonized core-shell particles Phloroglucinol (manufactured by Tokyo Kasei Kogyo Co., Ltd., melting point: 220°C, condensation reaction temperature: 330°C): 0. 2g was dissolved in 200g of acetone, 2g of boron nitride particles (manufactured by Showa Denko) was added thereto, thoroughly mixed by ultrasonication, and dried to obtain a boron nitride particle-phloroglucinol mixture. This mixture was fired at 300° C. for 2 hours on a Kugelrohr under a nitrogen atmosphere. Thereby, an organic-inorganic composite (16) containing a carbon material (16A) and an inorganic oxide (16B) was obtained.
Analysis of the obtained carbon material revealed that carbon material (16A) mainly undergoes dehydration condensation between phenolic OH groups (C-OH), and condensation reactions between C-H and between C-H and C-OH. It was found that carbonization progressed as the carbonization progressed.
The obtained organic-inorganic composite (16) is treated with ultrasonic waves in DMF (N,N-dimethylformamide), the excess carbon material (16A) is removed and purified by filtration, and the surface of the inorganic oxide (16B) is purified. Core-shell particles (16) coated with a carbon material binding region (core portion: inorganic oxide particle, shell portion: carbon material binding region) were obtained.
The core-shell particles (16) were further calcined at 700°C for 2 hours. As a result, the carbon material in the shell portion was highly carbonized, and highly carbonized core-shell particles (16) were obtained. FIG. 21 shows the Raman spectrum of the surface of the highly carbonized core-shell particles (16). FIG. 21 shows that the surface (shell portion) of the highly carbonized core-shell particles (16) is made of a highly carbonized carbon material without damaging the shape.

[Example 17]: Phloroglucinol + alumina particles + 300°C x 2 hours, highly carbonized core-shell particles Phloroglucinol (manufactured by Tokyo Kasei Kogyo Co., Ltd., melting point: 220°C, condensation reaction temperature: 330°C): 0.2 g was dissolved in 200 g of acetone, 2 g of alumina particles (manufactured by Showa Denko) were added thereto, thoroughly mixed by ultrasonication, and dried to obtain an alumina particle-phloroglucinol mixture. This mixture was fired at 300° C. for 2 hours on a Kugelrohr under a nitrogen atmosphere. Thereby, an organic-inorganic composite (17) containing a carbon material (17A) and an inorganic oxide (17B) was obtained.
Analysis of the obtained carbon material revealed that carbon material (17A) mainly undergoes dehydration condensation between phenolic OH groups (between C-OH), and condensation reactions between C-H and between C-H and C-OH. It was found that carbonization progressed as the carbonization progressed.
The obtained organic-inorganic composite (17) is treated with ultrasonic waves in DMF (N,N-dimethylformamide), the excess carbon material (17A) is removed and purified by filtration, and the surface of the inorganic oxide (17B) is Core-shell particles (17) coated with a carbon material binding region (core portion: inorganic oxide particle, shell portion: carbon material binding region) were obtained.
The core-shell particles (17) were further calcined at 700°C for 2 hours. As a result, the carbon material in the shell portion was highly carbonized, and highly carbonized core-shell particles (17) were obtained. FIG. 22 shows the Raman spectrum of the surface of the highly carbonized core-shell particles (17). It can be seen from FIG. 22 that the surface (shell portion) of the highly carbonized core-shell particles (17) is made of a highly carbonized carbon material without damaging the shape.
Further, using the obtained highly carbonized core-shell particles (17) and raw material alumina, PMMA (polymethyl methacrylate): raw material alumina particles and PMMA: highly carbonized core-shell particles (17) were prepared in DMF. By mixing at a volume ratio of 1:2 and drying, PMMA/alumina and PMMA/highly carbonized core-shell particles (17) were obtained. When the thermal conductivity characteristics of each film in the thickness direction were analyzed, as shown in Table 2, it was found that the thermal conductivity was improved when highly carbonized core-shell particles (17) were used. Note that the specific heat and density were calculated from the mixing ratio, and 920 J/kg·K and 3000 kg/m ³ were used, respectively. That is, the organic-inorganic composite of the present invention can be applied to the use of improving thermal conductive properties (as a thermal conductive property improving agent).

[Example 18]: Phloroglucinol + magnesium oxide particles + 300°C x 2 hours, highly carbonized core-shell particles Phloroglucinol (manufactured by Tokyo Kasei Kogyo Co., Ltd., melting point: 220°C, condensation reaction temperature: 330°C): 0. 2g was dissolved in 200g of acetone, 2g of magnesium oxide particles (MgO manufactured by Ube Industries) was added thereto, thoroughly mixed by ultrasonication, and dried to obtain a magnesium oxide particle-phloroglucinol mixture. . This mixture was fired at 300° C. for 2 hours on a Kugelrohr under a nitrogen atmosphere. Thereby, an organic-inorganic composite (18) containing a carbon material (18A) and an inorganic oxide (18B) was obtained.
Analysis of the obtained carbon material revealed that carbon material (18A) mainly undergoes dehydration condensation between phenolic OH groups (C-OH), and condensation reactions between C-H and between C-H and C-OH. It was found that carbonization progressed as the carbonization progressed.
The obtained organic-inorganic composite (18) was treated with ultrasonic waves in DMF (N,N-dimethylformamide), and the excess carbon material (18A) was removed and purified by centrifugation, and the surface of the inorganic oxide (18B) was purified. Core-shell particles (18) coated with a carbon material binding region (core portion: inorganic oxide particle, shell portion: carbon material binding region) were obtained.
The core-shell particles (18) were further calcined at 700°C for 2 hours. As a result, the carbon material in the shell portion was highly carbonized, and highly carbonized core-shell particles (18) were obtained. FIG. 23 shows the Raman spectrum of the surface of the highly carbonized core-shell particles (18). It can be seen from FIG. 23 that the surface (shell portion) of the highly carbonized core-shell particles (18) is made of a highly carbonized carbon material without damaging the shape.

[Example 19]: Phloroglucinol + aluminum nitride particles + 300°C x 2 hours, highly carbonized core-shell particles Phloroglucinol (manufactured by Tokyo Kasei Kogyo Co., Ltd., melting point: 220°C, condensation reaction temperature: 330°C): 0. 2 g was dissolved in 200 g of acetone, 2 g of aluminum nitride particles (manufactured by Tokuyama) were added thereto, thoroughly mixed by ultrasonication, and dried to obtain an aluminum nitride particle-phloroglucinol mixture. This mixture was fired at 300° C. for 2 hours on a Kugelrohr under a nitrogen atmosphere. Thereby, an organic-inorganic composite (19) containing a carbon material (19A) and an inorganic oxide (19B) was obtained.
Analysis of the obtained carbon material revealed that carbon material (19A) mainly undergoes dehydration condensation between phenolic OH groups (C-OH), and condensation reactions between C-H and between C-H and C-OH. It was found that carbonization progressed as the carbonization progressed.
The obtained organic-inorganic composite (19) was treated with ultrasonic waves in DMF (N,N-dimethylformamide), the excess carbon material (19A) was removed and purified by centrifugation, and the surface of the inorganic oxide (19B) was purified. Core-shell particles (19) coated with a carbon material binding region (core portion: inorganic oxide particle, shell portion: carbon material binding region) were obtained.
The core-shell particles (19) were further calcined at 700°C for 2 hours. As a result, the carbon material in the shell portion was highly carbonized, and highly carbonized core-shell particles (19) were obtained. FIG. 24 shows the Raman spectrum of the surface of the highly carbonized core-shell particles (19). FIG. 24 shows that the surface (shell portion) of the highly carbonized core-shell particles (19) is made of a highly carbonized carbon material without damaging the shape.

[Example 20]: Phloroglucinol + lithium iron phosphate particles + 300°C x 2 hours, highly carbonized core-shell particles Phloroglucinol (manufactured by Tokyo Chemical Industry Co., Ltd., melting point: 220°C, condensation reaction temperature: 330°C): Dissolve 0.2 g in 200 g of acetone, add 2 g of lithium iron phosphate particles (manufactured by Toyoshima Seisakusho), mix thoroughly by ultrasonication, dry, and mix lithium iron phosphate particles with phloroglucinol. I got a body. This mixture was fired at 300° C. for 2 hours on a Kugelrohr under a nitrogen atmosphere. Thereby, an organic-inorganic composite (20) containing a carbon material (20A) and an inorganic oxide (20B) was obtained.
Analysis of the obtained carbon material revealed that the carbon material (20A) mainly undergoes dehydration condensation between phenolic OH groups (C-OH), and condensation reactions between C-H and between C-H and C-OH. It was found that carbonization progressed as the carbonization progressed.
The obtained organic-inorganic composite (20) is treated with ultrasonic waves in DMF (N,N-dimethylformamide), the excess carbon material (20A) is removed and purified by centrifugation, and the surface of the inorganic oxide (20B) is purified. Core-shell particles (20) coated with a carbon material binding region (core portion: inorganic oxide particle, shell portion: carbon material binding region) were obtained.
The core-shell particles (20) were further calcined at 700°C for 2 hours. As a result, the carbon material in the shell portion was highly carbonized, and highly carbonized core-shell particles (20) were obtained. FIG. 25 shows the Raman spectrum of the surface of the highly carbonized core-shell particles (20). It can be seen from FIG. 25 that the surface (shell portion) of the highly carbonized core-shell particles (20) is made of a highly carbonized carbon material without damaging the shape.

[Example 21]: Phloroglucinol + silica particles + 250°C x 2 hours, highly carbonized core-shell particles, different solvent Phloroglucinol (manufactured by Tokyo Kasei Kogyo Co., Ltd., melting point: 220°C, condensation reaction temperature: 330°C): 1 g was dissolved in 30 g of acetone, 10 g of silica spherical fine particles (manufactured by Nippon Shokubai Co., Ltd., average particle diameter: 0.19 μm) was added thereto, and thoroughly mixed by ultrasonication.
Acetone was removed from the resulting mixture by vacuum drying at room temperature, the remaining lumps were crushed, and then heated at 250° C. for 2 hours.
Thereby, an organic-inorganic composite (21) containing a carbon material (21A) and an inorganic oxide (21B) was obtained.
Analysis of the obtained carbon material revealed that carbon material (21A) mainly undergoes dehydration condensation between phenolic OH groups (C-OH), and condensation reactions between C-H and between C-H and C-OH. It was found that carbonization progressed as the carbonization progressed.
The Raman spectrum of the organic-inorganic composite (21) is shown in FIG. It was found that the carbon material (21A) is a carbon material containing a carbon-based compound having a graphene structure and a structure in which the graphene structures are stacked.
The obtained organic-inorganic composite (21) is treated with ultrasonic waves in acetone, the excess carbon material (21A) is removed and purified by centrifugation, and the surface of the inorganic oxide (21B) is coated with a carbon material binding region. Core-shell particles (21) (core part: inorganic oxide particle, shell part: carbon material bonding region) were obtained.
The core-shell particles (21) were further fired at 700°C for 1 hour. As a result, the carbon material in the shell portion was highly carbonized, and highly carbonized core-shell particles (21) were obtained. FIG. 27 shows the Raman spectrum of the surface of the highly carbonized core-shell particles (21).

[Example 22]: Phloroglucinol + boron nitride + 250°C x 2 hours, highly carbonized core-shell particles, different solvent Organic-inorganic composite (22), core-shell in the same manner as in Example 21 except that boron nitride was used as the raw material Particles (22) and highly carbonized core-shell particles (22) were obtained. Raman spectra of the organic-inorganic composite (22) and the highly carbonized core-shell particles (22) are shown in FIGS. 28 and 29. As can be seen from Examples 21 and 22, it was found that it was possible to change the solvent used by adjusting the firing temperature, etc.

[Example 23]: Hexahydroxytriphenylene + silica particles + 350°C x 2 hours, highly carbonized core-shell particles, different raw materials 2,3,6,7,10,11-hexahydroxytriphenylene (manufactured by Tokyo Kasei Kogyo Co., Ltd., melting point : None, condensation reaction temperature: 430°C): Dissolve 1 g in 30 g of DMF, add 10 g of silica spherical fine particles (manufactured by Nippon Shokubai Co., Ltd., average particle size: 0.19 μm), and thoroughly dissolve by ultrasonication. mixed with.
DMF was removed from the resulting mixture using an evaporator, the remaining lumps were crushed, and then heated at 350°C for 2 hours.
Thereby, an organic-inorganic composite (23) containing a carbon material (23A) and an inorganic oxide (23B) was obtained.
Analysis of the obtained carbon material revealed that carbon material (23A) mainly undergoes dehydration condensation between phenolic OH groups (C-OH), and condensation reactions between C-H and between C-H and C-OH. It was found that carbonization progressed as the carbonization progressed.
The Raman spectrum of the organic-inorganic composite (23) is shown in FIG. Since the Raman spectrum has peaks at 1340 cm ^-1 , 1590 cm ^-1 , 2700 cm ^-1 , and 2895 cm ^-1 , the carbon material (23A) has a graphene structure and contains a carbon-based compound with a stacked graphene structure. It turned out to be the material.
The obtained organic-inorganic composite (23) is treated with ultrasonic waves in DMF, the excess carbon material (23A) is removed and purified by centrifugation, and the surface of the inorganic oxide (23B) is coated with a carbon material binding region. Core-shell particles (23) (core part: inorganic oxide particle, shell part: carbon material bonding region) were obtained.
The core-shell particles (23) were further calcined at 700°C for 1 hour. As a result, the carbon material in the shell portion was highly carbonized, and highly carbonized core-shell particles (23) were obtained. FIG. 31 shows the Raman spectrum of the surface of the highly carbonized core-shell particles (23).

[Example 24]: (+)-catechin + silica particles + 250°C x 2 hours, highly carbonized core-shell particles, different raw materials (+)-catechin hydrate (manufactured by Tokyo Kasei Kogyo Co., Ltd., melting point: none, condensation reaction Temperature: 270° C.): 1 g was dissolved in 30 g of acetone, 10 g of silica spherical fine particles (manufactured by Nippon Shokubai Co., Ltd., average particle diameter: 0.19 μm) were added thereto, and thoroughly mixed by ultrasonication. Since this catechin is a hydrate, the condensation reaction temperature in TGDTA was checked by ignoring the dehydration peak and checking the temperature at which condensation proceeds after dehydration.
Acetone was removed from the resulting mixture using vacuum drying at room temperature, the remaining lumps were crushed, and then heated at 250° C. for 2 hours.
Thereby, an organic-inorganic composite (24) containing a carbon material (24A) and an inorganic oxide (24B) was obtained.
Analysis of the obtained carbon material revealed that carbon material (24A) mainly undergoes dehydration condensation between phenolic OH groups (C-OH), and condensation reactions between C-H and between C-H and C-OH. It was found that carbonization progressed as the carbonization progressed.
The Raman spectrum of the organic-inorganic composite (24) is shown in FIG. Since the Raman spectrum has peaks at 13 cm ^-1 , 15 cm ^-1 , 27 cm ^-1 and 28 cm ^-1 , the carbon material (24A) has a graphene structure and contains a carbon-based compound with a stacked graphene structure. It turned out to be the material.
The obtained organic-inorganic composite (24) is treated with ultrasonic waves in DMF, the excess carbon material (24A) is removed and purified by centrifugation, and the surface of the inorganic oxide (24B) is coated with a carbon material binding region. Core-shell particles (24) (core part: inorganic oxide particle, shell part: carbon material bonding region) were obtained.
The core-shell particles (24) were further calcined at 700°C for 1 hour. As a result, the carbon material in the shell portion was highly carbonized, and highly carbonized core-shell particles (24) were obtained. FIG. 33 shows the Raman spectrum of the surface of the highly carbonized core-shell particles (24).

[Comparative example 1]
An organic-inorganic composite (C1) was obtained by the method described in Example 9 except that the heating temperature was 170°C. However, no signal from the carbon material could be confirmed by Raman analysis, and only fluorescence derived from low molecular weight compounds was confirmed. In other words, it was found that phloroglucinol was not sufficiently carbonized.

[Comparative example 2]
An organic-inorganic composite (C2) was obtained by the method described in Example 23 except that the heating temperature was 270°C. However, no signal from the carbon material could be confirmed by Raman analysis, and only fluorescence derived from low-molecular-weight compounds was confirmed. That is, it was found that hexahydroxytriphenylene was not sufficiently carbonized.

[Comparative example 3]
The silica spherical fine particles used in Example 9 were baked at 700°C for 2 hours in a nitrogen atmosphere, and particles were then coated with carbon in the gas phase using a quick carbon coater (manufactured by Sanyu Electronics, SC-701CT). . The presence of carbon was confirmed by Raman analysis. The results of ¹³ C-NMR and ²⁹ Si-NMR analysis of this particle are shown in FIGS. 12 and 13. In comparison with Example 9, the particles obtained in Comparative Example 3 have carbon on the surface, but are not sp2 carbon, and furthermore, there is no Si-O-C bond, and the particles are covalently bonded on the surface of the particle. It was found that this was not the case (of course, no bonding could be confirmed even with the raw silica spherical particles). Comparing the results of Comparative Example 3 with Examples, it was found that the present invention can provide a carbon material-containing material in which the surface of an inorganic substance is strongly coated with an sp2 carbon component by covalent bonding.

[Reference example 1]
An organic-inorganic composite (R1) was obtained by the method described in Example 9 except that the heating temperature was 520°C. However, the carbon component was insoluble in NMP (N-methylpyrrolidone), making subsequent treatment impossible.

[Examples 25 to 32]
1 g of phloroglucinol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was placed on a quartz boat (volume: 5 ml), and using a ring furnace (manufactured by Toyo Thermo System Co., Ltd., KTF045N1, furnace tube: quartz φ50 mm x 1 m) under nitrogen flow. It was heated at the temperature shown in Table 1 for 2 hours. Yield of the obtained carbon material, carbon, hydrogen, oxygen ratio by elemental analysis and compositional formula calculated from the ratio, solubility in NMP (N-methylpyrrolidone) (completely soluble: 〇, partially soluble: △ , insoluble: ×) are shown in Table 3.
Furthermore, the results of ¹³ C-NMR analysis of the obtained carbon material are shown in FIG.
From these results, compounds having two or more phenolic OH groups in the molecule show a high carbonization yield, and C-H It can be seen that carbonization progresses with the condensation reaction between C--H and C--OH.
The estimated unit structure of the carbon material obtained in Example 26 is shown in the following chemical formula (A), and the estimated unit structure of the carbon material obtained in Example 27 is shown in the following chemical formula (B). The estimated unit structure of the carbon material obtained in Example 31 is shown in the following chemical formula (C). Although the actual molecular weight is much larger, the average unit structure is estimated to be the following chemical formulas (A), (B), and (C).

From the above examples and the like, it was found that the present invention can provide a method for easily producing a carbon material whose structure is precisely controlled under mild conditions. Furthermore, it has been found that it is possible to provide a carbon material whose structure is precisely controlled. It has also been found that it is possible to provide a method for easily producing a carbon material-containing material that is soluble in a solvent or a carbon material-containing material whose structure is precisely controlled under mild conditions. Furthermore, it has been found that according to the present invention, it is possible to provide a carbon material-containing material whose structure is precisely controlled and in which a carbon material and an inorganic substance are bonded by covalent bonds. Furthermore, the present invention provides an organic-inorganic composite that can be industrially manufactured under mild conditions and is useful for industrially manufacturing carbon material-containing materials such as carbon-coated inorganic particles and hollow carbon fine particles. It turns out that it can be done.

The carbon material obtained by the production method of the present invention and the carbon material of the present invention have a more precisely controlled structure than conventional carbon materials, and can be used for various purposes.
The carbon material-containing material obtained by the production method of the present invention and the carbon material-containing material of the present invention are lightweight, and have excellent lubricity, excellent electrical conductivity, excellent thermal conductivity, and excellent antioxidant properties. It can be effectively used as a material in the industrial production of carbon-coated inorganic particles and hollow carbon particles useful as fillers and the like. Possible uses include solid lubricants, lubricating additives for lubricating oils, conductive aids for inorganic materials and organic materials such as resins, antistatic agents, strength agents, and friction reducers. , a thermal conductivity imparting agent, and the like. In addition, the organic-inorganic composite of the present invention is lightweight and has excellent lubricity, excellent electrical conductivity, excellent thermal conductivity, and excellent anti-oxidation properties, and is useful as a filler such as carbon-coated inorganic particles. It can be effectively used as a material for industrially manufacturing hollow carbon particles. Possible uses include solid lubricants, lubricating additives for lubricating oils, conductive aids for inorganic materials and organic materials such as resins, antistatic agents, strength agents, and friction reducers. , a thermal conductivity imparting agent, and the like.

10 carbon material 20 inorganic particle 30 carbon material bonding region 100 organic-inorganic composite 200 core-shell particle

Claims (16)

A method of manufacturing a carbon material-containing material, the method comprising:
Including a heating step (I) of heating a composition containing a compound (A) in which a condensation reaction occurs between the same molecules and/or different molecules when heated, and a particulate inorganic substance,
The heating temperature in the heating step (I) is 220°C to 500°C (excluding 500°C), and when the condensation reaction temperature of the compound (A) is T°C, (T-150) ℃ or more,
The compound (A) is a compound having two or more phenolic OH groups in the molecule,
The inorganic substance is at least one selected from the group consisting of inorganic oxide particles, inorganic nitrides, inorganic sulfides, inorganic carbides, and insoluble salts having a functional group on the surface,
The heating step (I) includes a condensation reaction between the two phenolic OH groups of the compound (A) between the same molecules and/or between different molecules.
A method for producing a carbon material-containing material. The method for producing a carbon material-containing material according to claim 1, further comprising, after the heating step (I), a carbon material removing step of removing at least a part of the carbon material generated by heating the compound (A). The method for producing a carbon material-containing material according to claim 2 , further comprising a heating step (II) of heating after the carbon material removing step. The method for producing a carbon material-containing material according to claim 1 , further comprising an inorganic substance removal step of removing the inorganic substance after the heating step (I). The method for producing a carbon material-containing material according to claim 4 , further comprising a heating step (II) of heating after the inorganic substance removal step. The method for producing a carbon material-containing material according to any one of claims 1 to 5 , wherein the compound (A) has a molecular weight of 500 or less. The method for producing a carbon material-containing material according to any one of claims 1 to 6 , wherein the condensation reaction temperature of the compound (A) is 450°C or less. The method for producing a carbon material-containing material according to claim 7 , wherein the condensation reaction temperature of the compound (A) is 400°C or less. The weight M500 at a temperature of 500°C relative to the initial weight M50 at a temperature of 50°C when TG-DTA analysis of the compound (A) was performed under a nitrogen gas atmosphere from 40°C under heating conditions of 10°C/min. The method for producing a carbon material-containing material according to any one of claims 1 to 8 , wherein the weight ratio (M500/M50) is 0.2 or more. The inorganic oxide particles are selected from the group consisting of silica particles, alumina particles, titania particles, magnesium oxide particles, polyacid particles, metal particles whose surfaces are at least partially oxidized, composite oxide particles, and solid solution oxide particles. The method for producing a carbon material-containing material according to any one of claims 1 to 9, wherein the carbon material is at least one selected from the group consisting of at least one selected carbon material. The method for producing a carbon material-containing material according to claim 10 , wherein the metal constituting the polyacid particles is at least one selected from the group consisting of molybdenum, vanadium, tungsten, niobium, titanium, and tantalum. The method for producing a carbon material-containing material according to any one of claims 1 to 11 , wherein the inorganic oxide has a decomposition temperature of 800°C or higher. An organic-inorganic composite containing a carbon material and particulate inorganic matter,
the carbon material is soluble in a solvent,
The content ratio of carbon atoms, hydrogen atoms, and oxygen atoms in the elemental analysis of the carbon material is such that when the content ratio of carbon atoms is 6.0 atom%, the content ratio of hydrogen atoms is 2.9 atom% to 4.5 atom%. , the content of oxygen atoms is 1.4 atom% to 2.0 atom%,
The inorganic substance is at least one selected from the group consisting of inorganic oxide particles, inorganic nitrides, inorganic sulfides, inorganic carbides, and insoluble salts having functional groups on the surface.
Organic-inorganic complex. The organic-inorganic composite according to claim 13 , wherein the solvent is N-methylpyrrolidone. The inorganic oxide particles are selected from the group consisting of silica particles, alumina particles, titania particles, magnesium oxide particles, polyacid particles, metal particles whose surfaces are at least partially oxidized, composite oxide particles, and solid solution oxide particles. The organic-inorganic composite according to claim 13 or 14 , which is at least one selected type. The organic-inorganic composite according to claim 15 , wherein the metal constituting the polyacid particles is at least one selected from the group consisting of molybdenum, vanadium, tungsten, niobium, titanium, and tantalum.

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