JP6563226B2 - Method for producing flaky carbon - Google Patents

Description

  The present invention relates to a method for producing flaky carbon. In particular, flaky carbon, flaky carbon composition for use in conductive materials, heat transfer materials, power storage devices such as transistors and capacitors, sensors, piezoelectric materials, antibacterial materials, filtration materials, resin additives, optical materials, Alternatively, the present invention relates to a method for producing a flaky carbon dispersion.

The graphene sheet is a two-dimensional single-layer sheet in which carbon atoms are arranged in a honeycomb lattice shape, and is also a structural unit such as graphite, fullerene, and carbon nanotube. The flaky carbon in which the graphene sheet is laminated to a thickness of about 10 nm or less (in the present invention, the concept including the graphene sheet) has its unique properties (for example, a Young's modulus of 1.0 in the case of a single-layer graphene sheet). TPa, carrier mobility 200,000 cm ² V ^-1 s ^-1 , electrical conductivity 30 · □ ^-1 , thermal conductivity 5000 Wm ^-1 K ^-1 etc.) It is attracting attention as a new material used for power storage devices such as transistors and capacitors, sensors, piezoelectric materials, antibacterial materials, filtration materials, resin additives, optical materials and the like.

As a method for producing flaky carbon,
(1) Mechanical exfoliation method using tape, etc. (2) Formation on metal foil by CVD (3) Heating of SiC substrate (4) Delamination by oxidation of graphite and reduction of graphene oxide obtained ing.

  Among these, the methods (1) to (3) have a problem in mass productivity and are difficult to isolate because flaky carbon is obtained on the substrate or attached to the tape. In particular, in the case of flaky carbon having a small thickness, it is almost impossible to isolate the flaky carbon by peeling off from these substrates or tapes. Moreover, even if it can be isolated, the flaky carbon obtained by these methods is very easily aggregated, and it is very difficult to isolate it in a dispersed state. It is also very difficult to peel off the agglomerated flaky carbon.

  On the other hand, the method (4) is a process in which graphite oxide generated by oxidizing graphite is delaminated by ultrasonic treatment or the like to obtain graphene oxide, which is then reduced to graphene. When this method is employed, if graphene oxide is reduced in the liquid, aggregation occurs and film formation cannot be performed. Moreover, it is difficult to peel the aggregated graphene on a sheet-by-sheet basis. In order to prevent agglomeration after reduction, the coexistence of a surfactant such as sodium dodecylbenzenesulfonate has been studied (Non-patent Document 1). However, since intense oxidation and reduction are performed, it is very difficult to obtain flaky carbon while maintaining the graphene structure, and there is also a problem in safety. Furthermore, even if this method is adopted, flaky carbon is precipitated, and dispersion stabilization in the liquid has not been achieved.

  Thus, although flaky carbon has excellent physical properties, it is very difficult to isolate it in a dispersed state, and a method for this is required.

Adv. Funct. Mater. 2010, 20, 2893-2902

  An object of the present invention is to provide a method that can be obtained in a state in which flaky carbon can be stably dispersed using an inexpensive material and a simple process. Another object of the present invention is to provide a flaky carbon, a flaky carbon composition and a flaky carbon dispersion obtained by using this method.

  As a result of intensive studies to achieve the above object, the present inventors have performed a high-pressure treatment on a carbonaceous material having a layered structure in the presence of a specific water-soluble compound, thereby reducing an inexpensive material and It has been found that the flaky carbon can be obtained in a state where it can be stably dispersed despite the use of a simple process. The inventors of the present invention have further studied based on the findings and have completed the present invention. That is, this invention includes the following structures.

Item 1. A method for producing flaky carbon,
A manufacturing method in which a carbonaceous material having a layered structure is pressurized at 30 MPa or more in the presence of a water-soluble compound having a hydrophobic group having a high affinity for carbon and a hydrophilic group.

  Item 2. A pressure of 30 MPa or more is applied to a carbonaceous material having a layered structure, a water-soluble compound having a high affinity with carbon, a water-soluble compound having a hydrophilic group, and a carbonaceous material dispersion containing a solvent. 2. The production method according to 1.

  Item 3. Item 3. The production method according to Item 2, wherein the solvent contains water, and the content of the water is 70% by weight or more in the solvent.

  Item 4. The hydrophobic group may have an alkyl group that may have a substituent, an alkenyl group that may have a substituent, a cycloalkyl group that may have a substituent, and a polyoxygen having 3 or more carbon atoms. Item 4. The production method according to any one of Items 1 to 3, which is at least one selected from the group consisting of alkylene groups.

  Item 5. The hydrophilic group is represented by the general formulas (1) to (4):

[In the formula, —OH is an alcoholic hydroxyl group or a phenolic hydroxyl group; R is a divalent organic group; X ¹ is a hydrogen atom, alkali metal, NH ₄ , or organic ammonium; X ² is a hydrogen atom, alkali metal, NH ₄ , an organic ammonium or alkyl group; the oxygen atom of the general formula (2) is an ether bond. ]
The manufacturing method in any one of claim | item 1 -4 which is at least 1 type shown by these.

  Item 6. Item 6. The production method according to Item 5, wherein the hydrophilic group represented by the general formula (2) is a polyoxyethylene group and / or a polyglyceryl group.

  Item 7. Item 7. The production method according to any one of Items 1 to 6, wherein the number of carbon atoms of components other than the hydrophilic group is 10 or more.

  Item 8. Item 8. The production method according to Item 1 to 7, wherein the constituent components other than the hydrophilic group are a polyoxypropylene group having a polymerization degree of 4 or more and / or a polyoxybutylene group having a polymerization degree of 3 or more.

  Item 9. Item 9. The production method according to any one of Items 1 to 8, wherein the water-soluble compound having a hydrophobic group having a high affinity for carbon and a hydrophilic group has an HLB value of 12 or more.

  Item 10. Item 10. The production method according to any one of Items 1 to 9, wherein the carbonaceous material having a layered structure is at least one selected from the group consisting of natural graphite, artificial graphite, expanded graphite, oxidized graphite, and earthy graphite.

  Item 11. Item 11. The method according to any one of Items 1 to 10, wherein an ultrasonic dispersion treatment of 100 W or more is further performed as a pretreatment for the pressure treatment.

Item 12. By the pressure treatment,
(I) causing two or more carbonaceous material dispersions to collide with each other; (ii) causing the carbonaceous material dispersion to collide with a metal or ceramic material; and (iii) isolating the carbonaceous material dispersion. Item 12. The production method according to any one of Items 2 to 11, wherein at least one treatment selected from the group consisting of passing through a space having an area of 1 cm ² or less is performed.

  Item 13. Item 13. The method according to any one of Items 1 to 12, wherein the carbonaceous material having a layered structure is contained at a concentration of 10% by weight or less.

  Item 14. Item 15. A flaky carbon obtained by the production method according to any one of items 1 to 13.

  Item 15. Item 15. The flaky carbon according to Item 14, wherein the thickness is 10 nm or less.

Item 16. A method for producing a flaky carbon dispersion,
A carbonaceous material having a layered structure, a hydrophobic group having a high affinity for carbon, a water-soluble compound having a hydrophilic group, and a carbonaceous material dispersion containing a solvent is subjected to a pressure treatment of 30 MPa or more. Production method.

  Item 17. Item 17. A flaky carbon dispersion obtained by the production method according to item 16.

Item 18. A flaky carbon dispersion comprising a flaky carbon, a water-soluble compound having a hydrophobic group having a high affinity for carbon, a hydrophilic group, and a solvent,
The hydrophobic group is an alkyl group having 6 or more carbon atoms which may have a substituent and / or a cycloalkyl group having 6 or more carbon atoms which may have a substituent,
The hydrophilic group is represented by the general formulas (1) to (4):

[In the formula, —OH is an alcoholic hydroxyl group or a phenolic hydroxyl group; R is a divalent organic group; X ¹ is a hydrogen atom, alkali metal, NH ₄ , or organic ammonium; X ² is a hydrogen atom, alkali metal, NH ₄ , an organic ammonium or alkyl group; the oxygen atom of the general formula (2) is an ether bond. ]
A flaky carbon dispersion that is at least one of the following:

  Item 19. The flaky carbon dispersion obtained by the production method according to Item 16, or the flaky carbon dispersion according to Claim 18, wherein the solvent is dried. The flaky carbon and carbon have high affinity. A method for producing a flaky carbon composition comprising a water-soluble compound having a hydrophobic group and a hydrophilic group.

  Item 20. Item 20. A flaky carbon composition obtained by the production method according to Item 19.

  Item 21. Item 21. The flaky carbon composition according to Item 20, wherein the content of the water-soluble compound having a hydrophobic group having a high affinity for carbon and a hydrophilic group is 1 part by weight or more with respect to 100 parts by weight of the flaky carbon. .

  Item 22. The flaky carbon composition obtained by the production method according to Item 19 is washed with water or an organic solvent to remove a water-soluble compound having a hydrophobic group having a high affinity for carbon and a hydrophilic group. A method for producing flaky carbon.

  Item 23. Item 23. A flaky carbon obtained by the production method of Item 22.

  According to the present invention, flaky carbon can be obtained in a state where it can be stably dispersed using an inexpensive material and a simple process.

  Further, according to the present invention, the flaky carbon is a flaky carbon-containing material of any aspect of the flaky carbon alone, the flaky carbon composition, and the flaky carbon dispersion, while suppressing aggregation. Can be obtained. That is, the versatility is high because the form to be used can be appropriately set according to the application. In particular, since the flaky carbon can be easily isolated and the flaky carbon can be uniformly mixed with other materials, application to a nanocomposite containing the flaky carbon is also expected.

It is a scanning electron microscope (TEM) photograph about the flaky carbon obtained in Example 1-1. It is a scanning electron microscope (TEM) photograph about the flaky carbon obtained in Example 1-1. It is a scanning electron microscope (SEM) photograph about the flaky carbon obtained in Example 2-1. It is a scanning electron microscope (TEM) photograph about the flaky carbon obtained in Example 2-1. It is a scanning electron microscope (TEM) photograph about the flaky carbon obtained in Example 2-1. It is a scanning electron microscope (SEM) photograph about the flaky carbon obtained in Example 2-2. It is a scanning electron microscope (SEM) photograph about the flaky carbon obtained in Example 4-1. It is a scanning electron microscope (SEM) photograph about the flaky carbon obtained in Example 4-2.

1. Method for producing flaky carbon dispersion In the method for producing flaky carbon of the present invention, a carbonaceous material having a layered structure is prepared under the coexistence of a water-soluble compound having a hydrophobic group having a high affinity for carbon and a hydrophilic group. Then, a pressure treatment of 30 MPa or more is performed.

  The method of coexisting a carbonaceous material having a layered structure, a hydrophobic group having high affinity with carbon, and a water-soluble compound having a hydrophilic group is not particularly limited, but a flaky carbon dispersion in which flaky carbon is stably dispersed. Is a carbonaceous material dispersion containing a carbonaceous material having a layered structure, a water-soluble compound having a hydrophobic group having a high affinity for carbon, a hydrophilic group, and a solvent. On the other hand, it is preferable to perform a pressure treatment of 30 MPa or more.

Carbonaceous material having a layered structure The carbonaceous material having a layered structure is not particularly limited, and examples thereof include natural graphite, artificial graphite, expanded graphite, earthy graphite, and graphite oxide. As the graphite oxide, for example, graphite oxidized with one or more oxidizing agents such as sulfuric acid, nitric acid, potassium permanganate, hydrogen peroxide and the like can be used. For example, when obtaining graphite oxide by the Hammers method, after immersing graphite in concentrated sulfuric acid, adding potassium permanganate to oxidize graphite, the reaction is quenched with dilute sulfuric acid and / or hydrogen peroxide, Thereafter, by washing with distilled water or the like, oxygen atoms are bonded to carbon atoms, and oxygen atoms are introduced between layers to obtain graphite oxide.

  In particular, when obtaining flaky carbon having a high purity that does not contain hetero atoms such as oxygen, graphite is preferably used as a raw material, and natural graphite and expanded graphite are more preferable. In addition, when using expanded graphite, it is preferable to employ | adopt expanded graphite with little oxidation of a graphene structure.

  In addition, graphite oxide may be used when importance is attached to manufacturing. By using graphite oxide, it is easy to insert solvent molecules between layers, it is easy to peel only in the layer direction, and the thinning efficiency and dispersibility are improved, so the processing time can be shortened. is there. However, when graphite oxide is used, reduction treatment is necessary later, and from the viewpoint of maintaining the graphene structure, conductivity and strength, other materials (natural graphite, artificial graphite, expanded graphite, earthy graphite) Is preferred.

  On the other hand, in order to further improve dispersibility, earth graphite can be employed. However, from the viewpoint of crystallinity and structure maintenance, other materials (natural graphite, artificial graphite, expanded graphite, graphite oxide) are preferable.

  In addition, artificial graphite may be used when importance is attached to the crystallinity, strength, structure maintenance, etc. of the flaky carbon obtained. However, since the treatment time tends to be longer, other materials (natural graphite, artificial graphite, expanded graphite, earth graphite, graphite oxide) are preferable for further efficiency.

  From the above, natural graphite or expanded graphite is particularly preferable in consideration of the balance of purity, ease of production, graphene structure maintenance, conductivity, strength, and the like.

  In the present invention, the content of the carbonaceous material having a layered structure in the system during the pressure treatment is not particularly limited, but is preferably 10% by weight or less, more preferably 0.0001 to 7% by weight, and more preferably 0.001 to 5%. More preferred is weight percent. In addition, the content of the carbonaceous material having a layered structure tends to make flaky carbon more efficient because thinning (delamination) is more likely to occur, and there is a tendency that the number of treatments can be reduced, There is a tendency that pressure treatment is easily performed while maintaining the viscosity appropriately. On the other hand, the higher the content of the carbonaceous material having a layered structure, the better the productivity. For this reason, it is preferable to appropriately set the content of the carbonaceous material having a layered structure from the viewpoint of the balance of flaking efficiency, viscosity, productivity, and the like. In the production method of the present invention, when a carbonaceous material dispersion is used, the content of the carbonaceous material having a layered structure in the dispersion is preferably within the above range.

A water-soluble compound having a hydrophobic group having a high affinity for carbon and a hydrophilic group Conventionally, when a flaky carbon is produced by a wet method, it is reduced to an aqueous dispersion containing an oxide of the flaky carbon and an aqueous solvent. However, with this method, it is difficult to maintain the graphene structure, and the obtained flaky carbon agglomerates violently, so it is difficult to obtain a flaky carbon water dispersion. There was also a problem in terms of safety. On the other hand, in the present invention, by using a water-soluble compound having an aromatic ring, the flaky carbon in a uniformly dispersed state (flaky carbon dispersion, etc.) without agglomerating the flaky carbon maintaining the graphene structure. Can be obtained. At this time, the water-soluble compound having an aromatic ring can also function as a dispersant for uniformly dispersing the flaky carbon.

  Such a water-soluble compound is not particularly limited, and various water-soluble compounds that can function as a carbonaceous material having a layered structure and a flaky carbon dispersant can be used.

  Among them, the hydrophobic group of the water-soluble compound having a hydrophobic group having a high affinity for carbon and a hydrophilic group is not particularly limited, but an alkyl group, an alkenyl group, a cycloalkyl group, and a carbon number of 3 or more. At least one selected from the group consisting of polyoxyalkylene groups is preferred.

  The alkyl group may be a chain alkyl group or a branched chain alkyl group, but a chain alkyl group is preferred from the viewpoint of affinity with carbon. Moreover, 6 or more are preferable from a viewpoint of affinity with carbon, as for carbon number of an alkyl group, 8-28 are more preferable, and 10-22 are more preferable. Such alkyl groups include hexyl, octyl, decyl, undecyl, dodecyl (or lauryl), tridecyl, tetradecyl (or myristyl), pentadecyl, hexadecyl (or cetyl), An octadecyl group, an icosyl group, etc. are mentioned.

  This alkyl group may or may not have a substituent. Examples of such a substituent include a cycloalkyl group, an aryl group, and an aralkyl group. Examples of cycloalkyl groups include those described below.

  The aryl group as a substituent of the alkyl group is preferably an aryl group having 6 to 10 carbon atoms. Specifically, a phenyl group or an alkylphenyl group (alkyl: an alkyl group having 1 to 6 carbon atoms; a tolyl group, 2 A methylphenyl group such as a methylphenyl group and a 3-methylphenyl group), a dimethylphenyl group such as a xylyl group), a naphthyl group and the like are preferable.

  The aralkyl group as the substituent of the alkyl group is preferably an aralkyl group having 7 to 14 carbon atoms having the above-described aryl group and an alkyl group having 1 to 6 carbon atoms, specifically, a benzyl group, a phenethyl group, or the like. preferable.

  In addition, as a substituent, it is not restrict | limited only to the above, You may have groups (fluorenyl group etc.) derived from a fluorene structure. In particular, when importance is attached to water solubility, a phenyl group or the like is preferable as a substituent, and when importance is attached to compatibility with a carbonaceous material having a layered structure and flaky carbon, a naphthyl group, a fluorenyl group or the like is preferable as a substituent.

  The alkenyl group preferably has 4 or more carbon atoms, more preferably 6 to 100, and still more preferably 8 to 30 from the viewpoint of affinity with carbon and water solubility. Examples of such alkenyl groups include oleyl groups and linoleyl groups.

  This alkenyl group may or may not have a substituent. Examples of such a substituent include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Examples of the aryl group and aralkyl group include those described above, and examples of the cycloalkyl group include those described below.

  The alkyl group as a substituent of the alkenyl group is preferably an alkyl group having 1 to 6 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, or the like is preferable.

  Examples of the cycloalkyl as the substituent of the alkenyl group include those described below, and examples of the aryl group and aralkyl group as the substituent of the alkenyl group include those exemplified above.

  In addition, as a substituent, it is not restrict | limited only to the above, You may have groups (fluorenyl group etc.) derived from a fluorene structure. In particular, when importance is attached to water solubility, a phenyl group or the like is preferable as a substituent, and when importance is attached to compatibility with a carbonaceous material having a layered structure and flaky carbon, a naphthyl group, a fluorenyl group or the like is preferable as a substituent.

  As the cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms (preferably 5 to 8, particularly 5 to 6) is preferable, and specifically, a cyclopentyl group, a cyclohexyl group, or the like is preferable.

  This cycloalkyl group may or may not have a substituent. Examples of such a substituent include an alkyl group, an aryl group, and an aralkyl group.

  As the alkyl group as a substituent of the cycloalkyl group, an alkyl group having 1 to 6 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, and the like are preferable.

  Examples of the aryl group and aralkyl group as the substituent of the cycloalkyl group include those exemplified above.

  Polyoxyalkylene groups such as polyoxyethylene groups are usually hydrophilic, but polyoxyalkylene groups having 3 or more carbon atoms such as polyoxypropylene groups and polyoxybutylene groups increase in hydrophobicity as the degree of polymerization increases. Can be used as a hydrophobic group. In particular, a polyoxypropylene group having a polymerization degree of 4 or more and a polyoxybutylene group having a polymerization degree of 3 or more are preferable, and a copolymer with polyoxyethylene is more preferable. For example, when polyoxyethylene-polyoxypropylene or polyoxyethylene-polyoxybutylene is used as the water-soluble compound, the polyoxypropylene group and the polyoxybutylene group can also function as a hydrophobic group.

  In addition, as a substituent, it is not restrict | limited only to the above, You may have groups (fluorenyl group etc.) derived from a fluorene structure. In particular, when importance is attached to water solubility, a phenyl group or the like is preferable as a substituent, and when importance is attached to compatibility with a carbonaceous material having a layered structure and flaky carbon, a naphthyl group, a fluorenyl group or the like is preferable as a substituent.

  Such hydrophobic groups include hexyl, octyl, decyl, undecyl, dodecyl (or lauryl), laurylphenyl, tridecyl, tetradecyl (or myristyl), pentadecyl, hexadecyl (or Cetyl group), octadecyl group, icosyl group, cyclopentyl group, cyclohexyl group, polyoxypropylene group having a polymerization degree of 4 or more, polyoxybutylene group having a polymerization degree of 3 or more, and the like are preferable.

  The hydrophilic group of the water-soluble compound having a hydrophobic group having a high affinity for carbon and a hydrophilic group is not particularly limited as long as it can increase the solubility of the water-soluble compound in water. From the viewpoints of water solubility of the water-soluble compound, thinning efficiency of the carbonaceous material having a layered structure, dispersibility of the obtained flaky carbon, etc., the general formulas (1) to (4):

[In the formula, —OH is an alcoholic hydroxyl group or a phenolic hydroxyl group; R is a divalent organic group; X ¹ is a hydrogen atom, alkali metal, NH ₄ , or organic ammonium; X ² is a hydrogen atom, alkali metal, NH ₄ , an organic ammonium or alkyl group; the oxygen atom of the general formula (2) is an ether bond. ]
At least one of the following is preferable.

  In the general formula (1), -OH can employ both alcoholic hydroxyl groups and phenolic hydroxyl groups. However, an alcoholic hydroxyl group is preferred from the viewpoints of water solubility of the water-soluble compound, thinning efficiency of the carbonaceous material having a layered structure, dispersibility of the obtained flaky carbon, and the like. In the case where —OH is a phenolic hydroxyl group, from the viewpoints of water solubility of the water-soluble compound, thinning efficiency of the carbonaceous material having a layered structure, dispersibility of the obtained flaky carbon, etc., the general formula (2) It is preferably substituted with a hydrophilic group represented by any one of (4).

  In the general formula (2), the divalent organic group represented by R is not particularly limited, but a divalent hydrocarbon group is preferable. Examples of the divalent hydrocarbon group include an aliphatic hydrocarbon group (an alkylene group (or alkylidene group), a cycloalkylene group, an alkylene (or alkylidene) -cycloalkylene group, a bi- or tricycloalkylene group, etc.), an aromatic hydrocarbon. Group (arylene group, alkylene (or alkylidene) -arylene group, etc.) and the like.

In the general formula (2), the alkylene group (or alkylidene group) represented by the group R is preferably an alkylene group, more preferably a C _1-8 alkylene group, still more preferably a C _1-4 alkylene group, and C _{2- A 4-} alkylene group is particularly preferred, and a C _2-3 alkylene group is most preferred. Specifically, methylene group, ethylene group, ethylidene group, trimethylene group, propylene group, propylidene group, tetramethylene group, ethylethylene group, butane-2-ylidene group, 1,2-dimethylethylene group, pentamethylene group, Examples include pentane-2,3-diyl group.

In the general formula (2), the cycloalkylene group represented by the group R is preferably a C _5-10 cycloalkylene group, and more preferably a C _5-8 cycloalkylene group. Specific examples include a cyclopentylene group, a cyclohexylene group, a methylcyclohexylene group, and a cycloheptylene group.

In the general formula (2), the alkylene (or alkylidene) -cycloalkylene group represented by the group R is preferably an alkylene-cycloalkylene group, more preferably a C _1-6 alkylene-C _5-10 cycloalkylene group, and C _1-4 alkylene-C _5-8 cycloalkylene groups are more preferred. Specific examples include a methylene-cyclohexylene group, an ethylene-cyclohexylene group, an ethylene-methylcyclohexylene group, and an ethylidene-cyclohexylene group.

  Specific examples of the bi- or tricycloalkylene group represented by the group R in the general formula (2) include a norbornane-diyl group.

In the general formula (2), the arylene group represented by the group R is preferably a C _6-10 arylene group. Specific examples include a phenylene group and a naphthalenediyl group.

In the general formula (2), the alkylene (or alkylidene) -arylene group represented by the group R is preferably an alkylene-arylene group, more preferably a C _1-6 alkylene-C _6-20 arylene group, and C _1-4 An alkylene-C _6-10 arylene group is more preferred, and a C _1-2 alkylene-phenylene group is particularly preferred. Specific examples include a methylene-phenylene group, an ethylene-phenylene group, an ethylene-methylphenylene group, and an ethylidenephenylene group.

Among these, a divalent aliphatic hydrocarbon group, particularly an alkylene group (for example, a C _1-4 alkylene group such as a methylene group or an ethylene group) is preferable.

  The alkylene (or alkylidene) -cycloalkylene group and the alkylene (alkylidene) -arylene group are -Ra-Rb- (wherein Ra and Rb are each bonded to a separate oxygen atom in the general formula (2)). An alkylene group or an alkylidene group, and Rb represents a cycloalkylene group or an arylene group).

Examples of the hydrophilic group represented by the general formula (2) is not particularly limited, for _{example, -OC 2 H 4 O -,} - OC 3 H 6 O -, - OCH 2 O- and the like are preferably used obtain. In particular, when having a structure in which three or more hydrophilic groups represented by the general formula (2) are polymerized, the more the carbon of R (for example, the number of carbons is 3 or more), the hydrophilicity decreases and the hydrophobicity increases, so the degree of polymerization increases. _-OC 2 _H 4 can retain hydrophilicity be O -, - _OCH 2 O- are preferred.

In the general formula (3), the alkali metal represented by X ¹ is not particularly limited, and examples thereof include sodium, potassium, and lithium.

In the general formula (3), the organic ammonium represented by X ^1, quaternary ammonium are preferred, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium or the like can be suitably used.

Examples of the hydrophilic group represented by the general formula (3) is not particularly limited, for _{^{example, -SO 3 - H +, -SO}} 3 - Na +, -SO 3 - K +, -SO 3 - Li + _{^{, -SO 3 - NH 4 +,}} -SO 3 - N (CH 3) 4 +, -SO 3 - N (C 2 H 5) 4 +, -SO 3 - N (C 3 H 7) 4 +, - _{^{SO 3 - N (C 4 H}} 9) 4 + , and the like.

In the general formula (4), examples of the alkali metal and organic ammonium represented by X ² include those exemplified above.

In general formula (4), the alkyl group represented by X ² may be a chain alkyl group or a branched chain alkyl group, but a chain alkyl group is preferred from the viewpoint of affinity with carbon. Moreover, as for carbon number of an alkyl group, 1-2 are preferable from a viewpoint of affinity with carbon.

The hydrophilic group represented by the general formula (4) is not particularly limited. For example, —COOH, —COONa, —COOK, —COOLi, —COONH ₄ , —COON (CH ₃ ) ₄ , —COON ( C ₂ H ₅ ) ₄ , —COON (C ₃ H ₇ ) ₄ ⁺ , —COON (C ₄ H ₉ ) ₄ ^{+ and the} like.

  Among these hydrophilic groups, from the viewpoint of water solubility of the water-soluble compound, stability independent of pH, thinning efficiency of the carbonaceous material having a layered structure, dispersibility of the obtained flake-like carbon, etc., the general formula ( The hydrophilic group represented by 2) and / or (4) is preferred. These hydrophilic groups may be used alone or a plurality of hydrophilic groups may be used. In addition, when using a plurality of hydrophilic groups, the same hydrophilic group may be used in plural, a plurality of hydrophilic groups represented by the same general formula may be used, or the hydrophilic groups represented by different general formulas may be used. Multiple types may be used.

  However, in the case of having a plurality of the same hydrophilic groups represented by the general formula (2), that is, having a polymerized structure, the hydrophilicity of the water-soluble compound increases as the degree of polymerization increases, but the number of carbons is 3 or more. In the case of, the hydrophobicity may increase as the degree of polymerization increases.

  In the water-soluble compound having a hydrophobic group having a high affinity for carbon and a hydrophilic group used in the present invention, the number of carbon atoms of the constituent parts other than the hydrophilic group (such as a brine group) is the water-soluble, layered structure of the water-soluble compound. 10 or more are preferable and 12-18 are more preferable from the viewpoints of the thinning efficiency of the carbonaceous material having the above and the dispersibility of the obtained flaky carbon.

  In the present invention, when a nonionic material (nonionic surfactant or the like) is used as a water-soluble compound having a hydrophobic group having a high affinity for carbon and a hydrophilic group, the HLB value is From the viewpoints of water solubility of the water-soluble compound, thinning efficiency of the carbonaceous material having a layered structure, dispersibility of the obtained flaky carbon, and the like, 12 or more are preferable, and 13 to 19 are more preferable. When the hydrophobic groups are the same (when the affinity with the carbonaceous material having a layered structure is about the same), the higher the HLB value, the better.

  The water-soluble compound having a hydrophobic group having a high affinity for carbon that satisfies the above conditions and a hydrophilic group is not particularly limited, and an aromatic water-soluble compound may be used, or a non-aromatic compound. Water-soluble compounds may be used, but non-aromatic water-soluble compounds are preferred. Examples of water-soluble compounds having a hydrophobic group having a high affinity for carbon and a hydrophilic group include polyoxyethylene lauryl ether, polyoxyethylene decyl ether, polyoxypropylene decyl ether, polyoxyethylene lauryl ether, and polyoxypropylene. Lauryl ether, polyoxyethylene myristyl ether, polyoxypropylene myristyl ether, polyoxyethylene cetyl ether, polyoxypropylene cetyl ether, polyoxyethylene octyl phenyl ether, polyoxypropylene octyl phenyl ether, polyoxyethylene undecyl phenyl ether, poly Oxypropylene undecyl phenyl ether, polyoxyethylene tridecyl phenyl ether, polyoxypropylene tridecyl phenyl Ether, polyoxyethylene pentadecyl phenyl ether, polyoxypropylene pentadecyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxypropylene polyglyceryl ether, sodium cholate, potassium cholate, sodium dodecyl sulfonate, potassium dodecyl sulfonate, Examples include dilauroyl glutamic acid ricin sodium, dilauroyl glutamic acid lysine potassium, decaglycerin lauric acid ester, n-decyl alcohol, and the like. In addition, when a water-soluble compound is a liquid, it can also be used as a solvent.

  Examples of water-soluble compounds having a hydrophobic group having a high affinity for carbon and a hydrophilic group include Emulgen 103, Emulgen 104P, Emulgen 105, Emulgen 106, Emulgen 108, Emulgen 109P, Emulgen 120, Emulgen 123P, Emulgen 130K, Emulgen 147, Emulgen 150, Emulgen 210P, Emulgen 220 (polyoxyethylene alkyl ethers manufactured by Kao Corporation), Triton X-100, Triton X-114, Triton X-305, Triton X-405 ( Polyoxyethylene octyl phenyl ethers manufactured by Dow Chemical Co., Ltd.) can be used.

  In the present invention, the content of the water-soluble compound in the system during the pressure treatment is not particularly limited, but is preferably 0.00001 to 99.9% by weight, more preferably 0.0001 to 50% by weight, and 0.001 to 30% by weight. Is more preferable, and 0.01 to 20% by weight is particularly preferable. On the other hand, in the present invention, the content of the water-soluble compound added before the treatment is preferably 10 to 100,000 parts by weight, and more preferably 20 to 10,000 parts by weight with respect to 100 parts by weight of the carbonaceous material having a layered structure. . In addition, the content of the water-soluble compound is relatively thin, the content of the carbonaceous material having a layered structure is relatively large, and the conductivity is easily improved, and the treatment is inexpensive. On the other hand, when the content of the water-soluble compound is thicker, flaking (interlaminar separation) is more likely to occur, and thus flaky carbon tends to be obtained more efficiently. However, as the viscosity increases, the flaking efficiency decreases. There is a possibility. For this reason, it is preferable to set content of the said water-soluble compound suitably from a viewpoint of balance, such as electroconductivity, cost, and the efficiency of thinning. In addition, in the manufacturing method of this invention, when using a carbonaceous material dispersion, it is preferable to make content of the said water-soluble compound in the said dispersion into the said range.

Solvent In the present invention, as described above, the carbonaceous material having a layered structure is subjected to specific treatment in the coexistence of the water-soluble compound. From the viewpoint of versatility of the fibrous carbon, it is preferable to perform a specific treatment on the carbonaceous material having a layered structure and the carbonaceous material dispersion containing the water-soluble compound.

  The carbonaceous material dispersion may be formed as a dispersion or may be formed as a coating on the substrate.

  At this time, as a solvent used for preparing a dispersion (dispersion or coating film), it is preferable to use water as a main solvent from the viewpoint of the exfoliation efficiency of a carbonaceous material having a layered structure.

  The content of water in the solvent to be used is not particularly limited, but it is 70% by weight or more (70 to 100% by weight) from the viewpoint of thinning efficiency of the carbonaceous material having a layered structure, solubility of the water-soluble compound, and the like. Is preferable, 80% by weight or more (80 to 100% by weight) is more preferable, and 90 to 100% by weight is further preferable.

  In the present invention, as a solvent, only water may be used, and an organic solvent is not necessarily used. In order to further improve the solubility of the water-soluble compound in water, methanol, An alcohol such as ethanol, 2-propanol, or t-butyl alcohol; a glycol such as ethylene glycol; a glycerin; or an organic solvent such as 2-methoxyethanol may be used.

  The content of the organic solvent in the solvent to be used is preferably 30% by weight or more (0 to 30% by weight) from the viewpoint of exfoliation efficiency of the carbonaceous material having a layered structure, solubility of the water-soluble compound, and the like. The weight percent or less (0 to 20 weight percent) is more preferred, and 0 to 10 weight percent is even more preferred.

  In the present invention, when a specific treatment is performed using a carbonaceous material dispersion using a solvent, the total amount of the solvent in the carbonaceous material dispersion is not particularly limited, but the carbonaceous material having a layered structure is thinned. From the viewpoint of efficiency, solubility of the water-soluble compound, etc., 40 to 99.9998% by weight is preferable, 63 to 99.998% by weight is more preferable, and 85 to 99.98% by weight is more preferable.

  In the present invention, when a specific treatment is performed using a carbonaceous material dispersion using a solvent, the carbonaceous material dispersion may be supplied with a carbonaceous material having a layered structure in a water-soluble compound dispersion. The water-soluble compound may be added to a carbonaceous material dispersion having a layered structure. Further, the carbonaceous material having a layered structure and the water-soluble compound may be simultaneously introduced into the solvent.

Other Components In the present invention, when a specific treatment is performed, the carbonaceous material having a layered structure may coexist with other components in addition to the water-soluble compound. That is, another component may be included in the carbonaceous material dispersion before the specific treatment. Thereby, these other components can be contained also in the flaky carbon dispersion and flaky carbon composition finally obtained. Examples of such other components include carbon fibers (particularly carbon nanofibers having a fiber diameter of 500 nm or less), activated carbon, carbon black (acetylene black, oil furnace black, etc .; ketjen black having particularly high conductivity and a large specific surface area). , Glassy carbon, carbon microcoil, fullerene, biomass-based carbon materials (bagasse, sorghum, wood waste, sawdust, bamboo, bark, rice straw, rice husk, coffee grounds, tea shells, okarasu, rice straw, pulp waste, etc. Or carbon fibers produced from lignin) may be used as long as the effects of the present invention are not impaired.

Treatment In the present invention, as described above, a specific pressure treatment is performed on the carbonaceous material having a layered structure in the presence of the water-soluble compound. In addition, when using a carbonaceous material dispersion, a specific pressurization process is performed with respect to a carbonaceous material dispersion.

  By applying pressure treatment, the carbonaceous material having a layered structure is atomized, and depending on the conditions, the graphene structure may not be maintained. However, the carbonaceous material having the layered structure can be thinned efficiently. And the processing time can be reduced. The pressure level at the time of performing such pressure treatment is not particularly limited as long as the carbonaceous material having a layered structure can be sufficiently thinned, but is 30 MPa or more, preferably 50 to 400 MPa. More preferably, it is 100 to 300 MPa. Such pressure treatment can be performed using a high-pressure dispersion device, a supercritical water preparation device, or the like. The high-pressure dispersion device can disperse by applying dynamic pressure, and the supercritical water preparation device can raise the pressure of the system by heating water.

By such pressurization, for example,
(I) causing two or more carbonaceous material dispersions to collide with each other;
(Ii) colliding the carbonaceous material dispersion with a metal or ceramic material (high hardness material such as silicon carbide or alumina);
(Iii) Processing such as passing the carbonaceous material dispersion through a space having a cross-sectional area of 1 cm ² or less can be performed.

  According to the above (i) and (ii), it is possible to make the pressurization condition stronger, the thinning of the carbonaceous material having a layered structure can be performed more efficiently, and the processing time is further reduced. be able to. According to the above (iii), the carbonaceous material having a layered structure can be more appropriately thinned while maintaining the graphene structure. This pressurizing operation may be performed once or more, preferably 10 times or more.

  The pressurization temperature is not particularly limited, and may be a temperature at which the carbonaceous material having a layered structure can be sufficiently thinned. In the cases (i) and (ii), 0 to 100 ° C., particularly 20 Can be -95 ° C. In the case of (iii) above, when the pressure is applied dynamically, it is preferably 0 to 100 ° C., and when the pressure is generated by the supercritical state of water, it is preferably 373 to 700 ° C., more preferably 380 to 450 ° C. preferable.

  In addition, when performing the said pressurization process, it is preferable to perform the ultrasonic dispersion process as a preliminary process (pretreatment), and to atomize the carbonaceous material which has a layered structure. Thereby, it can have effects, such as clogging prevention.

  Although there is no restriction | limiting in particular in the output at the time of performing an ultrasonic dispersion process, it shall be stronger than the ultrasonic dispersion process (about 40-50W) performed normally from a viewpoint of thinning of the carbonaceous material which has a layered structure. It is preferable. Specifically, the output of the ultrasonic dispersion process is 100 W or more, preferably 300 to 20000 W, more preferably 400 to 18000 W.

  The ultrasonic dispersion temperature is not particularly limited, and may be set to a temperature at which thinning of the carbonaceous material having a layered structure can be sufficiently performed, and may be 0 to 80 ° C., particularly 10 to 70 ° C. The ultrasonic dispersion time is not particularly limited, and may be a time that allows the carbonaceous material having a layered structure to be sufficiently thinned, and may be 1 to 600 minutes, particularly 3 to 120 minutes.

  Further, as a pre-treatment or post-treatment of these treatments, normal mechanical stirring, dispersion treatment with an emulsifying device, dispersion treatment with other dispersion devices such as dispersion treatment with a bead mill may be used in combination.

  In the present invention, when graphite oxide is used as the carbonaceous material having a layered structure, it is present as an oxide of flaky carbon in the dispersion subjected to the pressure treatment. For this reason, when graphite oxide is used as the carbonaceous material having a layered structure, it is preferable to perform a reduction treatment as a post-treatment. As the reduction treatment, various methods such as chemical reduction and electrochemical reduction can be adopted, but chemical reduction is preferable. Of these, chemical reduction with a reducing agent such as hydrazine and sodium borohydride is preferred. The amount of the reducing agent is preferably 1 to 1000 parts by weight, more preferably 10 to 500 parts by weight, and still more preferably 50 to 300 parts by weight with respect to 100 parts by weight of the flaky carbon oxide. Moreover, when it heats at the time of reduction | restoration, it will become easier to reduce | restore. The heating temperature is preferably 40 to 200 ° C, more preferably 50 to 150 ° C, and further preferably 60 to 120 ° C. The reduction time is preferably 10 minutes to 64 hours, more preferably 30 minutes to 48 hours, and even more preferably 1 to 24 hours. However, it is preferable that the graphene structure is not excessively destroyed.

2. Flaky carbon dispersion According to the production method of the present invention described above, desired flaky carbon is obtained. In particular, according to the production method of the present invention, a flaky carbon dispersion in which desired flaky carbon is dispersed can be obtained.

  The flaky carbon thus obtained is preferably thin because of its excellent physical properties. However, flaky carbon having a thickness of 10 nm or less, particularly 0.3 to 5 nm can be obtained. Although flaky carbon having a very large thickness may be obtained, the thickness of many flaky carbon is within the above range.

  The flaky carbon thus obtained is preferably thin because of its excellent physical properties. However, flaky carbon having a layered structure in which ten or fewer layers (that is, 1 to 10 layers) of graphene are laminated can be obtained. Although flaky carbon having a very large number of layers may be obtained, the number of flaky carbon layers is within the above range. Since such flaky carbon has a planar shape with many convex angles and concave angles, its size cannot be defined unconditionally. In this specification, the distance between the convex angles that are farthest in one piece of flaky carbon is defined as the size of the flaky carbon.

  As such flaky carbon, carbon having a size of 20 nm or more, preferably 30 nm or more, more preferably 50 nm or more can be obtained. Such a flaky carbon can provide sufficient conductivity. In addition, since it is known that the larger flaky carbon is better in various physical properties such as electrical properties, the upper limit of the size is not limited. The size of the flaky carbon is measured by observation with a microscope (such as a laser microscope).

  According to the production method of the present invention, the flaky carbon can be obtained as a flaky carbon dispersion. In the production method of the present invention, since the water-soluble compound is contained, the water-soluble compound is also contained in the flaky carbon dispersion. Since this water-soluble compound can be adsorbed on the surface of the flaky carbon and disperse the flaky carbon in a high concentration in the solvent, it functions as a dispersant in the flaky carbon dispersion. Moreover, the said water-soluble compound can use a commercial item, and has an advantage over the conventional product in both cost and dispersibility. Furthermore, this water-soluble compound can maintain sufficient conductivity even if it remains on the flaky carbon surface, and has an advantage that it can be easily removed from the flaky carbon. is there.

  In addition, in the conventional method of performing oxidation treatment and reduction treatment, the plastic substrate is hydrolyzed during the reduction treatment, and flaky carbon aggregates when subjected to the reduction treatment, so that it cannot exist as a dispersion. Therefore, it was impossible to form a flaky carbon dispersion on a plastic substrate. However, in the present invention, polyethylene terephthalate (PET) or the like is obtained by performing a specific treatment while containing the water-soluble compound. It is also possible to form a flaky carbon dispersion on the substrate without subjecting the plastic substrate to hydrolysis. In addition, as described above, it is easy to separate and purify flaky carbon from this flaky carbon dispersion, and it is also possible to uniformly mix flaky carbon with other materials, so nanocomposites containing flaky carbon, etc. Applicable to. Furthermore, the flaky carbon composition, which is a dried product of the flaky carbon dispersion, has excellent physical properties such as conductivity even if it contains the water-soluble compound, and also easily removes the remaining water-soluble compound. Therefore, it can be applied to various uses such as conductive materials, heat transfer materials, power storage devices such as transistors and capacitors, sensors, piezoelectric materials, antibacterial materials, filtration materials, resin additives, and optical materials.

3. Flaky carbon composition and flaky carbon In the present invention, the flaky carbon composition is a dried product of the flaky carbon dispersion, and contains the flaky carbon and the water-soluble compound. Although there is no restriction | limiting in particular as a shape of such a flaky carbon composition, A coating film, a sheet | seat, a lump, etc. can be mentioned.

  In order to obtain a dried product, in addition to drying the flaky carbon dispersion, a method of drying the flaky carbon dispersion on a substrate after spin coating or coating, the flaky carbon composition is recovered by ordinary solid-liquid separation. It can be implemented by a method or the like. As a method of performing this separation, for example, a method used for usual solid-liquid separation, for example, a method of filtering using a filter paper, a glass filter or the like; a method of filtering after centrifugation; a method of using a vacuum filter Can be illustrated. Next, it does not specifically limit as a drying method, For example, the method of drying for about 1 to 24 hours at about 50-200 degreeC using a warm air dryer etc. can be illustrated. Further, it may be dried by an evaporator, a vacuum drying furnace, a hot air drying furnace, etc., and pulverized for use. Further, when powdered instantaneously with a spray dryer or the like, there is an advantage that the composition in the powder is more integrated, and there is an advantage that the dispersion is easier when dispersed in the liquid thereafter. Furthermore, it is also possible to produce a powder that is easily disintegrated by freeze drying or the like.

  The flaky carbon composition thus obtained has not only sufficient conductivity but also excellent gas barrier properties. The composition of the flaky carbon composition to be obtained is not particularly limited. For example, the content of the water-soluble compound is 1 part by weight or more, preferably 5 to 100,000 parts by weight with respect to 100 parts by weight of the flaky carbon. Preferably it is 10-50000 weight part, More preferably, it can be 100-10000 weight part.

  In the present invention, the flaky carbon composition may have various physical properties such as electrical conductivity even if the water-soluble compound remains on the flaky carbon surface. Can be removed. Specifically, the water-soluble compound can be removed by washing the flaky carbon composition with water, an organic solvent, or the like. The washing treatment can be removed by washing with a dilute acid or dilute alkali in addition to water and an organic solvent. When the water-soluble compound is an organic ammonium salt, the organic ammonium salt is decomposed by heat treatment at 150 to 400 ° C., preferably 200 to 350 ° C., so that the water-soluble compound can also be removed by heat treatment. .

  The conventional dispersant is considered to be adsorbed by utilizing the hydrophobic interaction between the dispersant molecule and the flaky carbon, and since the molecular weight is relatively large, the adsorbing power is also considered to be large. On the other hand, the water-soluble compound used in the present invention is not chemically bonded to flaky carbon, and has a low molecular weight, so its adsorption power is weak compared to conventional products. Therefore, the water-soluble compound used in the present invention has an advantage that it is easier to remove from the flaky carbon composition than the conventional product.

  The cleaning for removing the water-soluble compound can be performed by bringing the flaky carbon composition and the cleaning liquid into contact with each other. As the cleaning liquid, water, various organic solvents, and the like can be used as long as they can dissolve the water-soluble compound. As the organic solvent, for example, alcohols such as methanol, ethanol and isopropyl alcohol (IPA) (particularly lower alcohols having 1 to 6 carbon atoms), acetone and the like can be used. These may be used alone or in combination of two or more.

  Among these, an organic solvent that evaporates from the flaky carbon composition in a short time after washing is preferable. Examples of the organic solvent include those having a boiling point at normal pressure of about 50 to 250 ° C., particularly about 60 to 200 ° C., such as methanol, ethanol, acetone, N-methylpyrrolidone, dimethylformamide and the like.

  Further, as described above, the washing for removing the water-soluble compound may be performed by bringing the flaky carbon composition into contact with a dilute acid or dilute alkali and then washing with water. The diluted acid is preferably 0.1 to 5% hydrochloric acid, and the diluted alkali is preferably 0.1 to 3% aqueous ammonia.

  The cleaning operation may be performed by bringing the cleaning liquid into contact with the flaky carbon composition. For example, it is preferable that the flaky carbon composition recovered from the flaky carbon dispersion is gently immersed in the cleaning liquid at room temperature. The immersion time is preferably within 30 minutes, and more preferably within 20 minutes in order to maintain the shape of the flaky carbon composition.

  The amount of the cleaning liquid used is not particularly limited as long as it is an effective amount for cleaning, and can be appropriately selected from a wide range. In general, the cleaning liquid is 100 to 100000 parts by weight with respect to 100 parts by weight of the flaky carbon composition. Good results are obtained when about 1 part, especially about 1000 to 5000 parts by weight is used.

  Thus, the flaky carbon can be isolated, and the flaky carbon obtained at this time has the characteristics as described above.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the examples.

Example 1-1
10 g of polyoxyethylene lauryl ether (manufactured by Kanto Chemical Co., Inc .; estimated HLB value 16.9; equivalent to Brigi 35) is added to 100 g of water, 0.01 g of expanded graphite (manufactured by Ito Graphite Co., Ltd.) is added, and 600 W Dispersion treatment was performed for 5 minutes while cooling with ice using a sonic dispersion device, and further, dispersion treatment (causing two or more carbonaceous material dispersions to collide with each other) at about 250 MPa using a high-pressure dispersion device was performed 50 times. It was.

  As a result, a dispersion of a carbonaceous material was obtained, and the dispersion state was maintained even after one month. In addition, the material was washed with ethanol to remove polyoxyethylene lauryl ether and analyzed by scanning electron microscope (SEM), transmission electron microscope (TEM), and Raman spectroscopy, and flaky carbon was obtained. It was. Most of the flaky carbon had 2 to 10 layers, and most of the thickness was 5 nm or less. The results are shown in FIGS.

Example 1-2
10 g of polyoxyethylene lauryl ether (manufactured by Kanto Chemical Co., Inc .; estimated HLB value 16.9; equivalent to Brigi 35) is added to 100 g of water, 0.01 g of expanded graphite (manufactured by Ito Graphite Co., Ltd.) is added, and 600 W Dispersion treatment was added for 5 minutes while cooling with ice using a sonic dispersion device, and further, dispersion treatment (colliding carbonaceous material dispersion with silicon carbide) was performed 50 times at about 250 MPa using a high pressure dispersion device. .

  As a result, a dispersion of a carbonaceous material was obtained, and the dispersion state was maintained even after one month. In addition, the material was washed with ethanol to remove polyoxyethylene lauryl ether and analyzed by scanning electron microscope (SEM), transmission electron microscope (TEM), and Raman spectroscopy, and flaky carbon was obtained. It was. Most of the flaky carbon had 2 to 10 layers, and most of the thickness was 5 nm or less.

Example 2-1
An experiment was conducted in the same manner as in Example 1-1 except that polyoxyethylene lauryl ether was changed to 5 g of Triton X-100 (polyoxyethylene alkylphenyl ether; estimated HLB value 13.5).

  As a result, a dispersion of a carbonaceous material was obtained, applied to conductive glass, and observed with a scanning electron microscope (SEM) and a transmission electron microscope (TEM), and flaky carbon was obtained. Most of the flaky carbon had 2 to 10 layers, and most of the thickness was 5 nm or less. The results are shown in FIGS.

Example 2-2
The experiment was performed in the same manner as in Example 1-2 except that polyoxyethylene lauryl ether was changed to 5 g of Triton X-100 (polyoxyethylene alkylphenyl ether; estimated HLB value 13.5).

  As a result, a dispersion of carbonaceous material was obtained, applied to conductive glass, and observed with a scanning electron microscope (SEM). As a result, flaky carbon was obtained. Most of the flaky carbon had 2 to 10 layers, and most of the thickness was 5 nm or less. The results are shown in FIG.

Example 3-1.
The experiment was performed in the same manner as in Example 1-1 except that polyoxyethylene lauryl ether was changed to 5 g of Triton X-405 (polyoxyethylene alkylphenyl ether; estimated HLB value 17.9).

  As a result, a dispersion of carbonaceous material was obtained, applied to conductive glass, and observed with a scanning electron microscope (SEM). As a result, flaky carbon was obtained. Most of the flaky carbon had 2 to 10 layers, and most of the thickness was 5 nm or less.

Example 3-2
The experiment was performed in the same manner as in Example 1-2 except that polyton ethylene X-405 (polyoxyethylene alkylphenyl ether; estimated HLB value 17.9) was 5 g.

  As a result, a dispersion of carbonaceous material was obtained, applied to conductive glass, and observed with a scanning electron microscope (SEM). As a result, flaky carbon was obtained. Most of the flaky carbon had 2 to 10 layers, and most of the thickness was 5 nm or less.

Example 4-1
The experiment was performed in the same manner as in Example 1-1 except that polyoxyethylene lauryl ether was changed to 5 g of sodium cholate.

  As a result, a dispersion of carbonaceous material was obtained, applied to conductive glass, and observed with a scanning electron microscope (SEM). As a result, flaky carbon was obtained. Most of the flaky carbon had 2 to 15 layers, and most of the thickness was 7 nm or less. The results are shown in FIG.

Example 4-2
The experiment was performed in the same manner as in Example 1-2 except that polyoxyethylene lauryl ether was changed to 5 g of sodium cholate.

  As a result, a dispersion of carbonaceous material was obtained, applied to conductive glass, and observed with a scanning electron microscope (SEM). As a result, flaky carbon was obtained. Most of the flaky carbon had 2 to 15 layers, and most of the thickness was 7 nm or less. The results are shown in FIG.

Example 5-1
The experiment was performed in the same manner as in Example 1-1 except that polyoxyethylene lauryl ether was changed to 5 g of sodium dodecyl sulfonate.

  As a result, a dispersion of carbonaceous material was obtained, applied to conductive glass, and observed with a scanning electron microscope (SEM). As a result, flaky carbon was obtained. Most of the flaky carbon had 2 to 20 layers, and most of the thickness was 10 nm or less.

Example 5-2
The experiment was performed in the same manner as in Example 1-2 except that polyoxyethylene lauryl ether was changed to 5 g of sodium dodecyl sulfonate.

  As a result, a dispersion of carbonaceous material was obtained, applied to conductive glass, and observed with a scanning electron microscope (SEM). As a result, flaky carbon was obtained. Most of the flaky carbon had 2 to 20 layers, and most of the thickness was 10 nm or less.

Example 6-1
The experiment was performed in the same manner as in Example 1-1 except that polyoxyethylene lauryl ether was changed to 5 g of lysine sodium dilauroylglutamate.

  As a result, a dispersion of carbonaceous material was obtained, applied to conductive glass, and observed with a scanning electron microscope (SEM). As a result, flaky carbon was obtained. Most of the flaky carbon had 2 to 20 layers, and most of the thickness was 10 nm or less.

Example 6-2
The experiment was performed in the same manner as in Example 1-2 except that polyoxyethylene lauryl ether was changed to 5 g of lysine sodium dilauroylglutamate.

  As a result, a dispersion of carbonaceous material was obtained, applied to conductive glass, and observed with a scanning electron microscope (SEM). As a result, flaky carbon was obtained. Most of the flaky carbon had 2 to 20 layers, and most of the thickness was 10 nm or less.

Example 7
10g of polyoxyethylene polyoxypropylene glycol (Wako Pure Chemical Industries, Ltd .: 160EO-30PO) is added to 100g of water, 0.01g of expanded graphite (Ito Graphite Co., Ltd.) is added, and 600W ultrasonic dispersion is added. Using an apparatus, a dispersion treatment was added for 5 minutes while cooling with ice, and further, a dispersion treatment (a collision between the carbonaceous material dispersion liquid and silicon carbide) was performed 50 times at about 250 MPa using a high-pressure dispersion apparatus.

  As a result, a dispersion of a carbonaceous material was obtained, and the dispersion state was maintained even after one month. Moreover, when the material was washed with ethanol to remove polyoxyethylene polyoxypropylene glycol and analyzed by a scanning electron microscope (SEM) and a transmission electron microscope (TEM), flaky carbon was obtained. Most of the flaky carbon had 2 to 10 layers, and most of the thickness was 5 nm or less.

Example 8
10 g of decaglycerin laurate (Sakamoto Yakuhin Kogyo Co., Ltd.) is added to 100 g of water, 0.01 g of expanded graphite (Ito Graphite Co., Ltd.) is added, and ice-cooled using a 600 W ultrasonic dispersion device. Then, a dispersion treatment was added for 5 minutes, and further, a dispersion treatment (a collision between the carbonaceous material dispersion and silicon carbide) was performed 50 times at about 250 MPa using a high-pressure dispersion apparatus.

  As a result, a dispersion of a carbonaceous material was obtained, and the dispersion state was maintained even after one month. Further, the material was washed with ethanol to remove decaglycerin laurate and analyzed by a scanning electron microscope (SEM) and a transmission electron microscope (TEM). As a result, flaky carbon was obtained. Most of the flaky carbon had 2 to 10 layers, and most of the thickness was 5 nm or less.

Example 9
10 g of polyoxypropylene polyglyceryl ether (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) is added to 100 g of water, 0.01 g of expanded graphite (manufactured by Ito Graphite Co., Ltd.) is added, and ice-cooled using a 600 W ultrasonic dispersion device. Then, a dispersion treatment was added for 5 minutes, and further, a dispersion treatment (a collision between the carbonaceous material dispersion and silicon carbide) was performed 50 times at about 250 MPa using a high-pressure dispersion apparatus.

  As a result, a dispersion of a carbonaceous material was obtained, and the dispersion state was maintained even after one month. Further, the material was washed with ethanol to remove polyoxypropylene polyglyceryl ether and analyzed by a scanning electron microscope (SEM) and a transmission electron microscope (TEM), and flaky carbon was obtained. Most of the flaky carbon had 2 to 10 layers, and most of the thickness was 5 nm or less.

Example 10
Add 0.01 g of expanded graphite (made by Ito Graphite Co., Ltd.) to 100 ml (83 g) of n-decyl alcohol, and apply a dispersion treatment for 5 minutes while cooling with ice using a 600 W ultrasonic dispersion device. Dispersion treatment (a collision between the carbonaceous material dispersion and silicon carbide) was performed 150 times at about 250 MPa using an apparatus.

  As a result, a dispersion of a carbonaceous material was obtained, and the dispersion state was maintained even after one month. Further, the material was washed with ethanol to remove n-decyl alcohol and analyzed by a scanning electron microscope (SEM) and a transmission electron microscope (TEM), and flaky carbon was obtained. Most of the flaky carbon had 2 to 10 layers, and most of the thickness was 5 nm or less.

  In this way, without using tape peeling, high-cost CVD, etc., and without destroying the aromatic ring structure of the carbon-based material using a strong oxidizing agent or performing its reduction process, it is extremely advanced It was possible to produce high-purity carbon that was thinly sliced by a method that can be easily mass-produced.

  The exfoliated carbon could be obtained in the form of a dispersion, and could also be isolated without a troublesome process such as peeling it from the substrate or tape.

Claims (15)

A method for producing flaky carbon,
A carbonaceous material having a layered structure, a hydrophobic group having a high affinity for carbon, a water-soluble compound having a hydrophilic group, and a carbonaceous material dispersion containing a solvent are subjected to a pressure treatment of 30 MPa or more, By the pressure treatment,
(I) causing two or more carbonaceous material dispersions to collide with each other; and (ii) causing the carbonaceous material dispersion to collide with a metal or ceramic material,
Performing at least one treatment selected from the group consisting of, manufacturing methods. It said solvent contains water, and the content of water is at least 70 wt% of the solvent, the production method according to claim 1. The hydrophobic group may have an alkyl group that may have a substituent, an alkenyl group that may have a substituent, a cycloalkyl group that may have a substituent, and a polyoxygen having 3 or more carbon atoms. The production method according to claim 1 or 2 , which is at least one selected from the group consisting of alkylene groups. The hydrophilic group is represented by the general formulas (1) to (4):
[In the formula, —OH is an alcoholic hydroxyl group or a phenolic hydroxyl group; R is a divalent organic group; X ¹ is a hydrogen atom, alkali metal, NH ₄ , or organic ammonium; X ² is a hydrogen atom, alkali metal, NH ₄ , an organic ammonium or alkyl group; the oxygen atom of the general formula (2) is an ether bond. ]
At least a kind, a manufacturing method according to any one of claims 1 to 3, in shown. The manufacturing method of Claim 4 whose hydrophilic group shown by the said General formula (2) is a polyoxyethylene group and / or a polyglyceryl group. The manufacturing method according to any one of claims 1 to 5 , wherein the number of carbon atoms of a constituent part other than the hydrophilic group is 10 or more. The components other than the hydrophilic group, the polymerization degree of 4 or more polyoxypropylene group and / or a degree of polymerization of 3 or more polyoxybutylene group, The process according to any one of claims 1-6. The manufacturing method according to any one of claims 1 to 7 , wherein the water-soluble compound having a hydrophobic group having a high affinity for carbon and a hydrophilic group has an HLB value of 12 or more. The production method according to any one of claims 1 to 8 , wherein the carbonaceous material having a layered structure is at least one selected from the group consisting of natural graphite, artificial graphite, expanded graphite, oxidized graphite, and earthy graphite. . The manufacturing method according to any one of claims 1 to 9 , wherein an ultrasonic dispersion treatment of 100 W or more is further performed as a pretreatment of the pressure treatment. The content of the carbonaceous material having a layered structure is performed at a concentration of 10 wt% or less, the production method according to any one of claims 1 to 10. A method for producing a flaky carbon dispersion,
A carbonaceous material having a layered structure, a hydrophobic group having a high affinity for carbon, a water-soluble compound having a hydrophilic group, and a carbonaceous material dispersion containing a solvent are subjected to a pressure treatment of 30 MPa or more, By the pressure treatment,
(I) causing two or more carbonaceous material dispersions to collide with each other; and (ii) causing the carbonaceous material dispersion to collide with a metal or ceramic material,
The manufacturing method which performs at least 1 sort (s) of processing chosen from the group which consists of. A flaky carbon dispersion comprising a flaky carbon, a water-soluble compound having a hydrophobic group having a high affinity for carbon, a hydrophilic group, and a solvent,
The hydrophobic group is an alkyl group having 6 or more carbon atoms which may have a substituent and / or a cycloalkyl group having 6 or more carbon atoms which may have a substituent,
The hydrophilic group is represented by the general formulas (1) to (4):
[In the formula, —OH is an alcoholic hydroxyl group or a phenolic hydroxyl group; R is a divalent organic group; X ¹ is a hydrogen atom, alkali metal, NH ₄ , or organic ammonium; X ² is a hydrogen atom, alkali metal, NH ₄ , an organic ammonium or alkyl group; the oxygen atom of the general formula (2) is an ether bond. ]
A flaky carbon dispersion, which is at least one of the following. A flaky carbon dispersion obtained by the production method according to claim 12 or a flaky carbon dispersion according to claim 13 , wherein the solvent is dried. A method for producing a flaky carbon composition comprising a water-soluble compound having a high hydrophobic group and a hydrophilic group. The flaky carbon composition obtained by the production method according to claim 14 is washed with water or an organic solvent to remove a water-soluble compound having a hydrophobic group having a high affinity for carbon and a hydrophilic group. A method for producing flaky carbon.