JP2019189469A - Carbon material complex and carbon material-metal complex - Google Patents

Abstract

To provide a method for obtaining a carbon material-metal complex in which carbon materials are combined together by sufficiently strong interaction.SOLUTION: The present invention provides a carbon material-metal complex of graphite oxide, a compound represented by a general formula (1), and a metal and/or metal compound (where Ris a direct bond or a divalent linking group. A is -NRRor -NRRR, and R, R, and Rare the same or different to represent a hydrogen atom or an organic group. Xand Xare the same or different to represent a hydrogen atom or a metal atom, or there is not any corresponding atom. If Xdoes not have any corresponding atom, -OXrepresents -O. If Xdoes not have any corresponding atom, -OXis -O).SELECTED DRAWING: None

Description

The present invention relates to a carbon material composite and a carbon material-metal composite. More specifically, thermoelectric conversion materials, pump parts, cutting tools, seal rings, bearings, ball mill balls and blades and other pulverized parts, surgical instruments, jigs, electrical equipment, device parts, building material products, etc. The present invention relates to a carbon material-metal composite that can be used and a carbon material composite suitable for obtaining the composite.

Composite ceramics are composites of ceramics combined with fibers, particles, and the like to improve properties such as hardness, and are used in various fields such as semiconductors, batteries, automobiles, information communication, and industrial equipment.

In addition, graphite oxide is obtained by oxidizing graphite having a layered structure in which carbon atoms bonded by sp ² bonds are arranged in a plane and imparting an oxygen-containing functional group. Due to its unique structure and physical properties, Research has been done. It is known that graphite oxide interacts with metal ions and can be used to form a carbon material-metal composite which is a kind of composite ceramics.

Incidentally, as an effective catalyst for methanol oxidation in a direct methanol fuel cell, self-assembled platinum nanoparticles on graphene grafted with sulfonic acid groups have been disclosed (see Non-Patent Document 1).

Lu J. et al. Scientific Reports 6 21530 (2016).

As described above, graphite oxide interacts with metal ions, and by introducing such a carbon material into ceramics, there is a possibility that more excellent hardness and wear resistance can be exhibited. However, the interaction between graphite oxide and ceramics is weak, particularly depending on the metal species, and there is a problem that, once combined, graphite oxide is peeled off.

This invention is made | formed in view of the said present condition, and it aims at providing the method for obtaining the carbon material-metal composite_body | complex in which the carbon material was compounded by the sufficiently strong interaction.

The present inventors have studied various methods for obtaining a carbon material-metal composite in which a carbon material is complexed with a sufficiently strong interaction, and has graphite oxide, an amine group, and a phosphoric acid (salt) group. A carbon material-metal composite of a specific compound and a metal and / or metal compound was formed. The present inventors have found that this carbon material-metal composite becomes a strong structure composited by a sufficiently strong interaction. The reason is that graphite oxide and the amine group of the above compound or the ammonium cation derived from the amine group strongly interact with each other and are derived from the phosphoric acid (salt) group or phosphoric acid (salt) group of the above compound complexed with graphite oxide. This is considered to be because the phosphate ions (salt) or the phosphate ions strongly interact with the metal and / or metal compound. As described above, the present inventors have a stronger action of compounding the carbon material by using the above-mentioned specific compound, and have excellent hardness, etc., and are strong ceramics that may be applicable to various applications. It was found that can be formed. Furthermore, the present inventors have also found a carbon material composite of graphite oxide and the above compound, which can suitably obtain the above carbon material-metal composite by combining with the above metal and / or metal compound. The inventors have conceived that the above problems can be solved brilliantly and have reached the present invention.

That is, the present invention is a carbon material composite of graphite oxide and a compound represented by the following general formula (1).

(In the formula, R ¹ represents a direct bond or a divalent linking group. A represents —NR ² R ³ or —N ⁺ R ² R ³ R ⁴ , R ² , R ³ , and R ^4. Are the same or different and each represents a hydrogen atom or an organic group, X ¹ and X ² are the same or different and each represents a hydrogen atom or a metal atom, or there is no corresponding atom, corresponding to X ¹ . If there exist no atoms, -OX ¹ is -O ^- if there is no corresponding atoms .X ² representing the, -OX ² is -O ^- represents a).

The present invention is also a carbon material-metal composite of graphite oxide, a compound represented by the following general formula (1), and a metal and / or a metal compound.

(In the formula, R ¹ represents a direct bond or a divalent linking group. A represents —NR ² R ³ or —N ⁺ R ² R ³ R ⁴ , R ² , R ³ , and R ^4. Are the same or different and each represents a hydrogen atom or an organic group, X ¹ and X ² are the same or different and each represents a hydrogen atom or a metal atom, or there is no corresponding atom, corresponding to X ¹ . If there exist no atoms, -OX ¹ is -O ^- if there is no corresponding atoms .X ² representing the, -OX ² is -O ^- represents a).
The carbon material-metal composite of the present invention is a composite of graphite oxide as a carbon material, a compound represented by the general formula (1), and a metal compound containing a metal and / or a metal (element). To tell.

The carbon material-metal composite of the present invention is a solid material in which graphite oxide is composited by a sufficiently strong interaction.

The present invention is described in detail below.
In addition, the form which combined two or more each preferable characteristic of this invention described separately in a paragraph below is also a preferable form of this invention.

<Carbon material composite>
The carbon material composite of the present invention is a carbon material composite of graphite oxide and a compound represented by the above general formula (1). The compound represented by the general formula (1) is a specific compound having an amine group and a phosphoric acid (salt) group, and the compound is compounded in, for example, water to obtain the carbon material composite of the present invention. In this case, it may have undergone dissociation of phosphoric acid (salt) groups or cationization of amine groups, which normally occurs depending on the pH of water, and such ionic compounds are also complexed with graphite oxide with sufficiently strong interaction. The effect of the present invention can be exhibited. By further complexing the carbon material composite of the present invention with a metal and / or metal compound, the carbon material-metal composite of the present invention described later can be suitably obtained.

(Graphite oxide)
The graphite oxide in the carbon material composite of the present invention is one in which oxygen is bonded by oxidizing a graphitic carbon material such as graphene, graphite (graphite) (the one in which oxygen is bonded to the carbon material), Oxygen is present as a substituent such as a carboxyl group, a carbonyl group, a hydroxyl group, and an epoxy group with respect to the graphitic carbon material.
The graphite oxide is preferably graphene oxide in which oxygen is bonded to carbon of graphene.
In general, graphene refers to a sheet composed of one layer in which carbon atoms bonded by sp ² bonds are arranged in a plane, and a stack of graphene sheets is referred to as graphite. In the present invention, graphene oxide Includes not only a sheet composed of only one carbon atom layer but also a sheet having a structure in which about 2 to 100 layers are laminated. The graphene oxide is preferably a sheet composed of only one carbon atom layer, or has a structure in which about 2 to 20 layers are laminated.
The graphite oxide may further have a functional group such as a sulfur-containing group and a nitrogen-containing group, but the content of carbon, hydrogen, and oxygen as constituent elements with respect to all constituent elements is 97 mol% or more. It is preferable that it is 99 mol% or more, and it is still more preferable that the graphite oxide contains only carbon, hydrogen, and oxygen as constituent elements.

The graphite oxide preferably has a ratio of carbon atoms to oxygen atoms (C / O) of 0.5 to 20. The ratio is more preferably 1 or more, and still more preferably 1.2 or more. The ratio is more preferably 10 or less, still more preferably 6 or less, still more preferably 4 or less, and particularly preferably 3 or less. When the ratio of the number of carbon atoms to the number of oxygen atoms is within the above range, the graphite oxide, the compound represented by the general formula (1), and the metal and / or metal compound can be combined more firmly.
The ratio of the number of carbon atoms to the number of oxygen atoms can be confirmed by the ratio of the total peak area of the O1s region and the total peak area of the C1s region obtained by XPS measurement.

As a method for producing graphite oxide, a method of synthesizing graphite oxide by generally reacting graphite with a strong oxidizing agent in an acid solvent is used, and a Hummers method using sulfuric acid and potassium permanganate as an oxidizing agent is used. it can. As other methods, Brodie method using nitric acid and potassium chlorate, Staudenmaier method using sulfuric acid, nitric acid and potassium chlorate as oxidizing agents, and the like can be used. A method of adding permanganate to a mixed solution containing graphite and sulfuric acid, which employs the oxidation method in the Hummers method, may be used. The graphite oxide thus obtained is usually purified by techniques such as filtration, decantation, centrifugation, liquid separation extraction, and water washing. Purification may be performed in air or in an inert gas atmosphere such as nitrogen, helium, or argon. Moreover, you may carry out on any of pressurization conditions, normal-pressure conditions, and pressure reduction conditions.

The content of graphite oxide in the carbon material composite of the present invention is preferably 0.01% by weight or more, more preferably 0.1% by weight or more in 100% by weight of the carbon material composite, More preferably, it is 2% by mass or more, and particularly preferably 0.4% by mass or more. Further, the content is preferably 99% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass or less, and particularly preferably 80% by mass or less.

(Compound represented by the general formula (1))
The compound in the carbon material composite of the present invention is represented by the following general formula (1) as described above.

(In the formula, R ¹ represents a direct bond or a divalent linking group. A represents —NR ² R ³ or —N ⁺ R ² R ³ R ⁴ , R ² , R ³ , and R ^4. Are the same or different and each represents a hydrogen atom or an organic group, X ¹ and X ² are the same or different and each represents a hydrogen atom or a metal atom, or there is no corresponding atom, corresponding to X ¹ . If there exist no atoms, -OX ¹ is -O ^- if there is no corresponding atoms .X ² representing the, -OX ² is -O ^- represents a).

R ¹ is not particularly limited as long as it represents a direct bond or a divalent linking group, but preferably represents a divalent linking group. The divalent linking group may be, for example, an alkylene group, an arylene group, a carbonyl group, an ester group, an ether group, or a combination of two or more of these groups, which may have a substituent. preferable. Examples of the substituent include an alkoxy group, an acyl group, and a halogen atom. The divalent linking group is more preferably an alkylene group or an arylene group. The alkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and specific examples include a methylene group, an ethylene group, and a propylene group. The arylene group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and specific examples thereof include a phenylene group and a naphthylene group.

The R ² and R ³ are not particularly limited as long as they represent a hydrogen atom or an organic group, but when the R ² and R ³ are the same or different and represent an organic group, the organic group has, for example, 1 to 1 carbon atoms. 30 hydrocarbon groups are preferred. The hydrocarbon group preferably has 20 or less carbon atoms, more preferably 10 or less, and still more preferably 5 or less.
R ² and R ³ particularly preferably represent, for example, a hydrogen atom.
If the A represents ^{-N + R 2 R 3 R 4} , preferred of the ^{R 4} are the same as those preferred above ^R 2, ^{R 3.}

When X ¹ and X ² are the same or different and represent a metal atom, the metal atom is not particularly limited, but is preferably an alkali metal, and more preferably Li, Na, or K, for example. More preferably, Na.
It said X ¹ and X ^2, for example, represent a hydrogen atom, or, it is particularly preferable that the corresponding atoms are not present.

The compound represented by the general formula (1) is particularly preferably, for example, ethanolamine phosphoric acid or propanolamine phosphoric acid.

The mass ratio of the compound represented by the general formula (1) is preferably 10% by mass or more with respect to 100% by mass of graphite oxide in the carbon material composite of the present invention. More preferably, it is 15 mass% or more, More preferably, it is 20 mass% or more, Most preferably, it is 200 mass% or more. Moreover, it is preferable that this mass ratio is 10,000 mass% or less. More preferably, it is 5000 mass% or less, More preferably, it is 2000 mass% or less.

The carbon material composite of the present invention may be composited using graphite oxide and one compound each represented by the above general formula (1), or may be composited using two or more kinds. It may be a thing. Moreover, other components other than the graphite oxide and the compound represented by the general formula (1) may be included.
The content ratio of the other components is preferably 10% by mass or less in 100% by mass of the carbon material composite of the present invention. More preferably, it is 2 mass% or less, More preferably, it is 0.4 mass% or less.

By combining the carbon material composite of the present invention with a metal and / or a metal compound, the carbon material-metal composite of the present invention described later can be suitably obtained.

(Preparation method of carbon material composite of the present invention)
The carbon material composite of the present invention can be produced by mixing graphite oxide and the compound represented by the general formula (1) using various mixing methods.

Various mixing methods can be used for mixing, and a mixer, blender, kneader, bead mill, ready mill, ball mill, ultrasonic treatment, and the like can be used. Among them, ultrasonic treatment is preferable. Prior to mixing, water, an organic solvent such as methanol, ethanol, propanol, isopropanol, butanol, hexanol, tetrahydrofuran, N-methylpyrrolidone, or a mixed solvent of water and an organic solvent may be added. Among these, it is preferable to add water. Further, an aqueous dispersion of graphite oxide may be mixed as graphite oxide. The excess of the compound represented by the general formula (1) may be washed away before or after the mixing or during the mixing using a solvent.

<Carbon material-metal composite>
The carbon material-metal composite of the present invention is a carbon material-metal composite of graphite oxide, a compound represented by the above general formula (1), and a metal and / or a metal compound.

In the carbon material-metal composite of the present invention, the metal and / or metal compound usually interacts directly with the compound represented by the general formula (1), in other words, the metal and / or metal compound is The compound represented by the general formula (1) interacts with the compound represented by the general formula (1) without intervening other components. In the present specification, the interaction is a force attracting so as to be complexed, and the force repelling between anion components does not correspond to the interaction.

The metal and / or metal compound preferably interacts with the phosphate (salt) group or phosphate ion of the compound represented by the general formula (1). For example, the metal and / or metal compound is represented by the general formula (1). Between the phosphate (salt) group or phosphate ion of the compound directly (between the metal and / or metal compound and the phosphate (salt) group or phosphate ion of the compound represented by the general formula (1)) It is preferred that they are interacting (without other components).

In this specification, the interaction can be rephrased as binding. In the present specification, the bond is not particularly limited, but for example, an ionic bond, a bond by intermolecular force (hydrogen bond, van der Waals force, etc.) is preferable, and an ionic bond is more preferable. In general, the metal and / or metal compound is directly bonded to the compound represented by the general formula (1). In other words, the metal and / or metal compound is represented by the general formula (1). And the compound represented by the general formula (1) are bonded without intervening other components. The metal and / or metal compound is preferably bonded to a phosphate (salt) group or a phosphate ion of the compound represented by the general formula (1), for example, represented by the general formula (1). Other than between the phosphate (salt) group or phosphate ion of the compound and directly (the metal and / or metal compound and the phosphate (salt) group or phosphate ion of the compound represented by the general formula (1)) It is preferable that it is couple | bonded (without going through this component).

The content of graphite oxide in the carbon material-metal complex of the present invention is preferably 0.01% by mass or more, and 0.05% by mass or more in 100% by mass of the carbon material-metal complex. More preferably, it is more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more. The content is preferably 50% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 1% by mass or less.

In addition, the preferable mass ratio of the compound represented by the general formula (1) with respect to graphite oxide in the carbon material-metal composite of the present invention is the above-described ratio with respect to graphite oxide in the carbon material composite of the present invention described above. It is the same as the preferable mass ratio of the compound represented by General formula (1).

(Metal and / or metal compound)
Examples of metals constituting the metal and / or metal compound in the carbon material-metal composite of the present invention include Li, Na, K, Rb, Be, Mg, Ca, Sr, Ba, Ra, Sc, Y, and lanthanoids. Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ru, Co, Ni, Pd, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl It is preferably at least one element selected from the group consisting of Sn, Pb, and Bi. Among these, metals that are polyvalent metal ions having two or more valences are more preferable. For example, Mg, Ca, Sr, Ba, Ra, Sc, Y, lanthanoid, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo W, Mn, Fe, Ru, Co, Ni, Pd, Cu, Zn, Cd, Hg, Al, Ga, In, Tl, Sn, Pb, Bi are more preferable.

Moreover, in the carbon material-metal composite of the present invention, it is also preferable that the metal constituting the metal and / or metal compound has a solubility in 100 g of water at 20 ° C. of 1 g or less when converted to a phosphate. Such a metal can be strongly bonded to the phosphate (salt) group or phosphate ion of the compound represented by the above general formula (1) without dissociating in water, and the effect of the present invention is further improved. It will be remarkable. Examples of the metal include Li, Mg, Ca, Sr, Ba, Ra, Ce, Cd, Al, Tl, Pb, and Bi.

From the viewpoint of cost reduction, the metal constituting the carbon material-metal composite of the present invention and / or the metal compound is a metal other than noble metals (Au, Ag, Pt, Pd, Rh, Ir, Ru, Os). It is preferable that For example, it is preferable to use a metal other than platinum (Pt, Ir, Os).

The metal and / or metal compound is preferably a metal compound. Examples of the metal compound include oxides, hydroxides, layered double hydroxides, clay compounds, alloys, zeolites, carboxylate compounds, carbonate compounds, hydrogen carbonate compounds, nitric acid compounds, boric acid compounds, silicic acid compounds, and the like. Examples thereof include sulfides; sulfuric acid compounds; phosphoric acid compounds; carbides; Among these, the metal compound is preferably at least one selected from the group consisting of oxides, hydroxides, sulfuric acid compounds, and phosphoric acid compounds.

Preferred examples of the oxide include calcium oxide, strontium oxide, barium oxide, radium oxide, cadmium oxide, lead oxide, cerium oxide, thallium oxide, bismuth oxide, magnesium oxide, lithium oxide, aluminum oxide, and titanium oxide. Aluminum is more preferred.

Examples of the hydroxide include calcium hydroxide, strontium hydroxide, barium hydroxide, radium hydroxide, cadmium hydroxide, lead hydroxide, cerium hydroxide, thallium hydroxide, bismuth hydroxide, magnesium hydroxide, lithium hydroxide Aluminum hydroxide is preferred.

As the sulfuric acid compound, calcium sulfate, strontium sulfate, barium sulfate, radium sulfate, cadmium sulfate, lead sulfate, cerium sulfate, thallium sulfate, bismuth sulfate, magnesium sulfate, lithium sulfate, and aluminum sulfate are preferable.
Examples of the phosphate compound include calcium phosphate, strontium phosphate, barium phosphate, radium phosphate, cadmium phosphate, lead phosphate, cerium phosphate, thallium phosphate, bismuth phosphate, magnesium phosphate, lithium phosphate, phosphorus Aluminum oxide is more preferred.

Examples of the shape of the metal and / or metal compound include fine powder, powder, granule, granule, scale, polyhedron, rod, and curved surface.

The metal and / or metal compound preferably has an average particle size of 10 nm to 1000 μm. The average particle diameter is preferably 20 nm or more, more preferably 50 nm or more, and further preferably 100 nm or more. The average particle size is more preferably 500 μm or less.
The average particle size is determined by LA-920 (Horiba, Ltd.), a laser diffraction / scattering particle size distribution measuring device obtained by dispersing a suitable amount of metal and / or metal compound in a 0.2 mass% sodium hexametaphosphate aqueous solution. It is measured using.

In the carbon material-metal composite of the present invention, it is briefly described below which part of the metal and / or metal compound interacts (bonds) with the compound represented by the general formula (1). Explained. Basically, metal atoms (elements) on the surface of the metal and / or metal compound interact. For example, in the case of a metal compound, the metal atoms constituting the metal compound interact on the surface of the metal compound. ing. Further, the surface metal atoms themselves may interact, but the hydroxyl group (M-OH) bonded to the metal atom M may interact, and the carbon material-metal composite of the present invention is compounded in water. If to give the body, the pH of the metal type (electronegativity) and water, a hydroxyl group is dissociated proton MO ^- or group, the MOH ₂ ⁺ group in which a hydroxyl group has received the protons may interact . The surface metal atom may have a valence (valence) of zero or a positive valence.

The mass ratio of the metal and / or metal compound is preferably 10% by mass or more with respect to 100% by mass of graphite oxide in the carbon material-metal composite of the present invention. More preferably, it is 50 mass% or more, More preferably, it is 100 mass% or more, Most preferably, it is 1000 mass% or more. Moreover, it is preferable that this mass ratio is 100000 mass% or less. More preferably, it is 50000 mass% or less, More preferably, it is 20000 mass% or less.

The carbon material-metal composite of the present invention may be composited using graphite oxide, a compound represented by the above general formula (1), and each of the above metals and / or metal compounds. Two or more types may be combined. Further, graphite oxide, a compound represented by the above general formula (1), the above metal and / or other components other than the metal compound may be included.
The content of the other components is preferably 5% by mass or less in 100% by mass of the carbon material-metal composite of the present invention. More preferably, it is 1 mass% or less, More preferably, it is 0.2 mass% or less.

The carbon material-metal composite of the present invention can exhibit excellent hardness due to the introduction of the carbon material, and can be applied to various applications. Among them, thermoelectric conversion materials, pump parts, cutting It is preferably used as a tool, a seal ring, a bearing, a pulverized part such as a ball / blade of a ball mill, a surgical instrument, a jig, an electric device, a device part, or a building material product. In addition, when used as a thermoelectric conversion material, for example, it can be suitably used for one or both of an n-type thermoelectric conversion material and a p-type thermoelectric conversion material. In general, depending on the type of metal compound (for example, oxide) used for the composite, it is determined whether it is an n-type thermoelectric conversion material or a p-type thermoelectric conversion material.
The thermoelectric conversion material is a material generally used for a thermoelectric conversion layer in a thermoelectric conversion element that converts heat into electric power, and may be the carbon material-metal composite itself of the present invention. These resins, various additives, and the like may be further included as necessary.

(Method for Preparing Carbon Material-Metal Composite of the Present Invention)
The carbon material-metal composite of the present invention is prepared by mixing graphite oxide, the compound represented by the general formula (1), and the metal and / or metal compound using various mixing methods. Can do. The order of mixing is not particularly limited, and graphite oxide, the compound represented by the general formula (1), and the metal and / or metal compound may be mixed at the same time. Mixing in advance may be followed by mixing the remaining one component. When two components are mixed in advance and the remaining one component is then mixed, for example, graphite oxide and the compound represented by the general formula (1) are mixed in advance to prepare the carbon material composite of the present invention. The carbon material composite of the present invention and the metal and / or metal compound are preferably mixed, but graphite oxide and the metal and / or metal compound are mixed in advance, and then the general formula (1) ) May be mixed. The compound represented by the general formula (1) and the metal and / or metal compound alone do not interact with each other, and the compound represented by the general formula (1) interacts with itself. Graphite oxide and the compound represented by general formula (1) interact strongly, and when graphite oxide is added, graphite oxide and the amine group or ammonium cation of the compound represented by general formula (1) interact strongly. In addition, the phosphate (salt) group or phosphate ion of the above compound complexed with graphite oxide faces outward, and the phosphate (salt) group or phosphate ion and the metal and / or metal compound interact strongly. .

For mixing, various mixing methods similar to the above-described method for preparing the carbon material composite of the present invention can be used, and mixers, blenders, kneaders, bead mills, ready mills, ball mills, ultrasonic treatments and the like can be used. Of these, ultrasonic treatment is preferable. Prior to mixing, water, an organic solvent such as methanol, ethanol, propanol, isopropanol, butanol, hexanol, tetrahydrofuran, N-methylpyrrolidone, or a mixed solvent of water and an organic solvent may be added. Among these, it is preferable to add water. Further, an aqueous dispersion of graphite oxide may be mixed as graphite oxide. The excess of the compound represented by the general formula (1) may be washed away before or after the mixing or during the mixing using a solvent.

The carbon material-metal composite of the present invention may be obtained directly by the above mixing, or may be obtained by further reducing after the above mixing. Reduction is preferably performed by heating, light irradiation, or reduction using a reducing agent. By reducing after the above mixing, a stronger carbon material-metal composite of the present invention can be obtained.

The carbon material-metal composite of the present invention may be obtained by further sintering after the above mixing. Depending on the atmosphere during sintering, reduction may also proceed. In the carbon material-metal composite of the present invention obtained directly by the above mixing, since the carbon material and the metal and / or metal compound are well composited, a mixture of graphite oxide and the metal and / or metal compound is simply prepared. It is considered that a stronger interaction is expressed by sintering than by sintering. Therefore, the carbon material-metal composite of the present invention obtained by further sintering after the above mixing becomes stronger and the hardness, durability and the like are further improved.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.

(Example 1)
To 30 ml of 0.01% graphite oxide (GO) aqueous dispersion (containing 3 mg of GO), 300 mg of ethanolamine phosphoric acid (EAP) was added. At this time, it was a uniform dispersion without aggregation.
Next, 300 mg of alumina was added and sonicated for several minutes. The dispersion was allowed to stand for 1 minute, and the state of aggregation was observed. Precipitation of aggregates in which GO was adsorbed on alumina was observed, and very good aggregation ability was confirmed (the supernatant was colorless and transparent).

(Example 2)
An experiment was performed in the same manner as in Example 1 except that the amount of EAP to be added was changed to 30 mg, and the sedimentation property was compared. As a result, precipitation of aggregates in which GO was adsorbed on alumina was observed, and very good aggregation ability was confirmed (the supernatant was colorless and transparent).

(Example 3)
An experiment was performed in the same manner as in Example 1 except that the amount of EAP to be added was 3 mg, and the sedimentation property was compared. As a result, precipitation of aggregates in which GO was adsorbed on alumina was observed, and good aggregation ability was confirmed (the supernatant was thin brown transparent).

Example 4
An experiment was conducted in the same manner as in Example 2 except that the alumina to be added was changed to barium sulfate, and the sedimentation properties were compared. As a result, precipitation of aggregates in which GO was adsorbed on barium sulfate was observed, and very good aggregation ability was confirmed (the supernatant was colorless and transparent).

(Comparative Example 1)
The experiment was performed in the same manner as in Example 1 except that EAP was not added, and the sedimentation property was compared. As a result, GO and alumina remained separated, and only precipitation of alumina was observed, and the supernatant had a brown color derived from GO, and there was almost no aggregation ability.

(Comparative Example 2)
An experiment was performed in the same manner as in Example 1 except that GO was not added, and the sedimentation property was compared. As a result, there was no interaction between the EAP aqueous solution and alumina, and only precipitation of alumina was observed, and EAP alone had no aggregation ability.
(Comparative Example 3)
An experiment was performed in the same manner as in Example 1 except that EAP to be added was taurine, and the sedimentation property was compared. As a result, precipitation of aggregates in which GO was adsorbed on alumina was observed, and very good aggregation ability was confirmed (the supernatant was colorless and transparent). However, the density of precipitation (the degree of precipitation tightening) was weaker than in Example 1.

From the results of Examples 1 to 4 and Comparative Examples 1 and 2, by adding EAP having an amine group and a phosphoric acid (salt) group, GO strongly interacts with alumina and barium sulfate, I found out that Furthermore, from the results of Example 1 and Comparative Example 3, the phosphoric acid group (derived from EAP) interacts more strongly with alumina than the sulfonic acid group (derived from taurine). This is because aluminum sulfonate (sulfate) is a water-soluble salt, but aluminum phosphate is an insoluble salt. The ceramic is considered to be excellent in hardness since GO is introduced.

The composite is a composite of GO, a compound represented by the general formula (1), and a metal and / or a metal compound, and the metal and / or the metal compound is represented by the general formula (1). The interaction with the compound can be analyzed by a general chemical technique, but for example, the phenomenon observed in the examples, that is, the compound represented by the general formula (1) The EAP, GO, and the three components of alumina or barium sulfate corresponding to the metal compound were mixed to cause aggregation and precipitation, so that a composite composed of these three components was formed, and In this complex, it is clear that the phosphate groups or phosphate ions derived from phosphate groups of EAP interact (bond) with alumina or barium sulfate.

Claims (3)

A carbon material composite of graphite oxide and a compound represented by the following general formula (1).

(In the formula, R ¹ represents a direct bond or a divalent linking group. A represents —NR ² R ³ or —N ⁺ R ² R ³ R ⁴ , R ² , R ³ , and R ^4. Are the same or different and each represents a hydrogen atom or an organic group, X ¹ and X ² are the same or different and each represents a hydrogen atom or a metal atom, or there is no corresponding atom, corresponding to X ¹ . If there exist no atoms, -OX ¹ is -O ^- if there is no corresponding atoms .X ² representing the, -OX ² is -O ^- represents a). A carbon material-metal composite of graphite oxide, a compound represented by the following general formula (1), and a metal and / or a metal compound.

(In the formula, R ¹ represents a direct bond or a divalent linking group. A represents —NR ² R ³ or —N ⁺ R ² R ³ R ⁴ , R ² , R ³ , and R ^4. Are the same or different and each represents a hydrogen atom or an organic group, X ¹ and X ² are the same or different and each represents a hydrogen atom or a metal atom, or there is no corresponding atom, corresponding to X ¹ . If there exist no atoms, -OX ¹ is -O ^- if there is no corresponding atoms .X ² representing the, -OX ² is -O ^- represents a). 3. The carbon material-metal according to claim 2, wherein the metal and / or the metal constituting the metal compound has a solubility in 100 g of water at 20 ° C. of 1 g or less when converted to a phosphate. Complex.