JP2014050780A - Dispersant for nano-carbon - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dispersant capable of uniformly and easily dispersing nano-carbon at a high concentration in a dispersion medium.SOLUTION: A dispersant for nano-carbon is used which contains a nonionic surfactant represented by a general formula (1) or (2). (1) Z-{(AO)n-X}p (2) Z-{(AO)n-H}p (in the formulas: Zis 1-32C amine having p atoms of active hydrogen, or a reaction residue obtained by removing active hydrogen atoms from ammonia; Zis 1-12C amine having p atoms of active hydrogen, or a reaction residue obtained by removing active hydrogen atoms from ammonia; AO is a 2-4C oxyalkylene group; n is an integer of 1-100; X is a methyl group or an acetyl group; H is a hydrogen atom; and p is an integer of 1-5.)

Description

  The present invention relates to a dispersant for nanocarbon. More specifically, the present invention relates to a dispersant suitable for uniformly dispersing nano-sized carbon particles such as fullerene and carbon nanotubes uniformly and easily in a dispersion medium.

  Nanocarbons such as fullerenes and carbon nanotubes (hereinafter abbreviated as CNT) have specific properties such as electrical conductivity, thermal conductivity, and mechanical strength, and are expected to be applied to various applications. Yes.

  In order to fully exhibit the characteristics of nanocarbon and facilitate application to various uses, it is required to form a dispersion in which nanocarbon is uniformly dispersed in a dispersion medium (such as water or an organic solvent). However, nanocarbon has a strong tendency to agglomerate because its size is nano-size, and dispersion in a simple dispersion medium is often difficult.

In order to disperse nanocarbon, various dispersing agents for nanocarbon have been proposed. For example, a nanocarbon dispersant containing at least one compound represented by the following formula (1), R—X— (Y) n Formula (1) {wherein R is a carbon number m of 13 to 21 X represents an oxygen atom, a nitrogen atom, CO, COO, CON, or a direct bond, and Y represents a polyalkylene oxide group [C ₂ H ₃ (C _a H _{2a + 1} ) · O] _b —H (wherein a is an integer of 0 to 2 and b is 1 to 100), n is a case where X is an oxygen atom, CO, COO or a direct bond 1 and 2 when X is a nitrogen atom or CON. } (Patent Document 1) and the like are known.

JP 2010-247099 A

  However, the conventional dispersants are not sufficiently dispersible, and there may be a problem that it takes time for dispersion or the concentration cannot be increased. That is, an object of the present invention is to provide a dispersant that can uniformly disperse nanocarbon in a dispersion medium uniformly and at a high concentration.

  The feature of the dispersant for nanocarbon of the present invention is that it contains a nonionic surfactant represented by the general formula (1) or (2).

^{Z 1 - {(AO) n} -X} p (1)

^{Z 2 - {(AO) n} -H} p (2)

(In the formula, Z ¹ represents a reaction residue obtained by removing an active hydrogen atom from an amine or ammonia having 1 to 32 carbon atoms having p active hydrogen atoms, and Z ² represents 1 to 1 carbon atoms having p active hydrogen atoms. A reactive residue obtained by removing an active hydrogen atom from 12 amines or ammonia, AO is an oxyalkylene group having 2 to 4 carbon atoms, n is an integer of 1 to 100, X is a methyl group or an acetyl group, H is a hydrogen atom, p Is an integer from 1 to 5.)

  The feature of the nanocarbon dispersion liquid of the present invention is that it contains nanocarbon, a dispersion medium, and the above dispersant.

A feature of the method for producing a nanocarbon dispersion of the present invention is that a mixing step (1) in which a dispersion medium and the above-mentioned dispersant are mixed to prepare a dispersant mixture.
A pre-dispersing step (2) for preparing a pre-dispersion by mixing the dispersant mixture and nano-carbon; and a dispersion for preparing a nano-carbon dispersion by dispersing the pre-dispersion with a wet disperser or an ultrasonic disperser The gist includes the step (3).

  The dispersion liquid for nanocarbon of the present invention can be easily dispersed uniformly and at a high concentration in a dispersion medium.

  Since the nanocarbon dispersion liquid of the present invention contains the above-mentioned dispersant, it can contain nanocarbon in a uniform and high concentration.

  Since the method for producing a nanocarbon dispersion of the present invention uses the above-mentioned dispersant, a uniform and high concentration nanocarbon dispersion can be easily prepared.

<Nonionic surfactant represented by general formula (1)>
The amine having 1 to 32 carbon atoms having p active atoms (p is an integer of 1 to 5) that can constitute Z ¹ (a1) is preferably an amine having an aliphatic hydrocarbon group, An amine having a linear aliphatic hydrocarbon group is preferred, and an amine having a linear saturated aliphatic hydrocarbon group is particularly preferred. Examples of such amines include the following amines.

  (1) P = 1: 1 C2-C32 amine having 1 active hydrogen atom (a11); dimethylamine, diethylamine, dibutylamine, dihexylamine, diisopropylamine, diphenylamine, dioctylamine, dilaurylamine, lauryl Stearylamine, phenylstearylamine, 2-ethylhexyl oleylamine, octylbehenylamine, dicetylamine and the like.

  (2) p = 2: C1-C32 amine having two active hydrogen atoms (a12); methylamine, ethylamine, propylamine, isopropylamine, butylamine, pentylamine, hexylamine, octylamine, 2- Ethylhexylamine, nonylamine, decylamine, dodecylamine, palmitylamine, stearylamine, behenylamine, allylamine, 3-hexenylamine, 4-dodecenylamine, oleylamine, phenylamine, 4-ethylphenylamine, 4-stearylphenylamine, dimethylamino Ethylamine and 3-octadecyl-5-octylphenylamine.

  (3) p = 3: C3-C32 amine having three active hydrogen atoms (a13): N-methylethylenediamine, N-cyclohexyl-1,3-propanediamine, N-ethylethylenediamine (ethylaminoethylamine) ), N-methylpropylenediamine (methylaminopromylamine), hexylaminohexylamine, decylaminoethylamine, ethylaminobehenylamine, phenylaminostearylamine, cetylaminocetylamine and the like.

  (4) p = 4: C2-C32 amine having 4 active hydrogen atoms (a14): ethylenediamine, 1,2-diaminopropane, diaminobutane, diaminopentane, trimethylenediamine, hexamethylenediamine, octa Methylene diamine, dodecamethylene diamine, diphenyl ether diamine, 1,2-diamino-3-octadecyl-5-octylbenzene and the like.

  (5) p = 5: C4-C32 amine having 5 active hydrogen atoms (a15): diethylenetriamine, bis (3-aminopropyl) amine, bis (hexamethylene) triamine and 1,2,3- Triamino-4-octadecyl-6-octylbenzene and the like.

Two or more of these amines may be used in combination.
2-24 are preferable, as for carbon number of amine (a1), More preferably, it is 4-22, Most preferably, it is 8-18. Within this range, the adsorptivity of the nonionic surfactant to the nanocarbon is further improved, and the dispersibility is further improved.

  Of these amines, (a12), (a13) and (a14) are preferable, (a12) and (a14) are more preferable, and (a12) is particularly preferable.

  Examples of the oxyalkylene group (AO) having 2 to 4 carbon atoms include an oxyethylene group, an oxypropylene group, and an oxybutylene group. Of these, an oxyethylene group and an oxypropylene group are preferable, and an oxyethylene group is more preferable. Two or more of these may be used in combination. When two or more kinds of AO are used in combination, the bonding mode (block bond, random bond, combination thereof) is not particularly limited. Depending on the type of the dispersion medium, the type and amount of AO (number of n) and the bonding mode can be appropriately selected to constitute a dispersant. For example, water or a dispersion medium containing water or a hydrophilic organic solvent In this case, it is desirable that it is composed only of a relatively hydrophilic AO, for example, an oxyethylene group, or its content is increased. Conversely, in the case of a dispersion medium that does not contain water or a hydrophobic organic solvent, it may be composed of a relatively hydrophobic AO, for example, only an oxypropylene group, or the content ratio of an oxypropylene group or an oxybutylene group may be increased. desirable.

  n is an integer of 1 to 100, and is preferably an integer of 5 to 80, more preferably an integer of 8 to 50, and particularly preferably an integer of 10 to 35 from the viewpoint of nanocarbon dispersion stability. In addition, when p is 2 or more, the addition reaction may not proceed evenly depending on the structure of the amine (a1), the steric hindrance, the type of AO, etc., so p in the same molecule represented by the general formula (1) N may be different from each other.

  In the case where p is 2 or more in the methyl group or acetyl group (X), p pieces of X may be different from each other. Among these, X is preferably a methyl group from the viewpoints of solubility in a hydrophobic dispersion medium and thermal stability.

  Examples of the nonionic surfactant represented by the general formula (1) include those obtained by methylating or acetylating the following alkylene oxide adducts (b11) to (b15) of amines. In the following examples, the type of amine is described, and then the type of added alkylene oxide and the number of added moles thereof are described to represent the alkylene oxide adduct. (EO) represents ethylene oxide, (PO) represents propylene oxide, and (BO) represents butylene oxide, and the number after each alkylene oxide represents the number of added moles of each alkylene oxide. When alkylene oxide is described, it indicates that both are added in combination, and the addition mode (random addition or block addition, in the case of block, indicates that blocks are added in the order of description in parentheses) ).

  (B11): Dimethylamine (EO) 1, Diethylamine (EO) 5, Dimethylamine (PO) 10, Diisopropylamine (EO) 20, Diisopropylamine (PO) 5, Dibutylamine (PO) 80, Diphenylamine (EO) 60 , Diisopropylamine (EO) 1 (PO) 1 (block), dioctylamine (EO) 10, dilaurylamine (PO) 22, distearylamine (EO) 35, phenylstearylamine (EO) 5 (PO) 10 ( Random), octylbehenylamine (EO) 30, and the like.

  (B12): Ethylamine (EO) 10 (PO) 10 (block), propylamine (EO) 10, octylamine (EO) 5, octylamine (EO) 20, octylamine (BO) 10, octylamine (EO) 5 (PO) 5 (random), dodecylamine (EO) 14, dodecylamine (EO) 24, dodecylamine (EO) 70, 2-ethylhexylamine (EO) 10, 2-ethylhexylamine (PO) 40, phenylamine (PO) 20, phenylamine (EO) 40, stearylamine (EO) 20, stearylamine (PO) 40, allylamine (EO) 2, behenylamine (PO) 26, oleylamine (PO) 15, oleylamine (EO) 10 (PO) 5 (block), dimethylaminoethylamine (EO) 60, etc.

  (B13): ethylaminoethylamine (EO) 7, ethylaminoethylamine (EO) 30, ethylaminoethylamine (EO) 80, ethylaminoethylamine (EO) 20 (PO) 80 (random), ethylaminoethylamine (EO) 100 (PO) 35 (random), ethylaminobehenylamine (PO) 20, phenylaminostearylamine (EO) 105, phenylaminostearylamine (PO) 5 (EO) 20 (block), and the like.

  (B14): ethylenediamine (EO) 40, ethylenediamine (PO) 20, ethylenediamine (BO) 12, triethylenediamine (EO) 5 (PO) 10 (block), triethylenediamine (PO) 5, hexamethylenediamine (EO) 15 , Hexamethylene diamine EO 140, hexamethylene diamine (BO) 10, dodecamethylene diamine (EO) 40, dodecamethylene diamine (PO) 10 (EO) 10 (random), diphenyl ether diamine (EO) 40, diphenyl ether diamine (EO) 100 , Diphenyl ether diamine (PO) 5, diphenyl ether diamine (BO) 20 and the like.

  (B15): Diethylenetriamine (EO) 10, diethylenetriamine (EO) 50, diethylenetriamine (EO) 175, diethylenetriamine (PO) 250, diethylenetriamine (EO) 50 (PO) 50 (random), and the like.

<Nonionic surfactant represented by general formula (2)>
The number p (P is an integer of from 1 to 5) amine having 1 to 12 carbon atoms having active hydrogen atoms which can constitute the Z ² (a2), an amine having an aliphatic hydrocarbon group is preferable, further An amine having a linear aliphatic hydrocarbon group is preferred, and an amine having a linear saturated aliphatic hydrocarbon group is particularly preferred. As such an amine, an amine having 1 to 12 carbon atoms among those exemplified above as the amine (a1) can be applied. (1) p = 1: 1: C2-C12 amine having active hydrogen atoms (a21), (2) p = 2: C1-C12 amine having 2 active hydrogen atoms (A22), (3) p = 3: C3-C12 amine having 3 active hydrogen atoms (a23), (4) p = 4: C2-C12 having 4 active hydrogen atoms Amine (a24), (5) p = 5: amine having 4 to 12 carbon atoms (a25) having 5 active hydrogen atoms.

Two or more of these amines may be used in combination.
2-12 are preferable, as for carbon number of amine (a2), More preferably, it is 4-12, Most preferably, it is 6-12. Within this range, the adsorptivity of the nonionic surfactant to the nanocarbon is further improved, and the dispersibility is further improved.

  Of these amines, (a22), (a23) and (a24) are preferable, (a22) and (a24) are more preferable, and (a22) is particularly preferable.

  In the general formula (2), AO, n and p are the same as those in the general formula (1), and the preferred ranges are also the same.

  As the nonionic surfactant represented by the general formula (2), among the alkylene oxide adducts (b11) to (b15) of amines exemplified above, those having 1 to 12 carbon atoms of the amine {(b21 ) To (b25)}.

  The nonionic surfactant represented by the general formula (1) or (2) can be produced by a known method. For example, the nonionic surfactant represented by the general formula (1) is first subjected to an addition reaction of an alkylene oxide having 2 to 4 carbon atoms with an amine (a1) or ammonia to obtain an alkylene oxide adduct, It can be obtained by methylating or acetylating the hydroxyl terminal. Further, the nonionic surfactant represented by the general formula (2) can be obtained by addition reaction of an alkylene oxide having 2 to 4 carbon atoms with the amine (a2) or ammonia.

  In any nonionic surfactant, the addition reaction of alkylene oxide is common, and a known method can be applied. For example, a raw material (amine or ammonia) is put into a pressurized reaction vessel and the presence of a catalyst is present. Alternatively, a method in which an alkylene oxide adduct is obtained by dropping an alkylene oxide having 2 to 4 carbon atoms and adding it in the absence can be applied. The reaction temperature during the alkylene oxide addition reaction is preferably 70 to 200 ° C. Moreover, when using a reaction catalyst, as a reaction catalyst, an alkali catalyst (sodium hydroxide, potassium hydroxide, etc.), an ammonium salt catalyst [a quaternary ammonium salt of a lower alkyl (1 to 4 carbon atoms)] and Lewis Examples include acid catalysts (such as boron trifluoride and tin tetrachloride). In this case, the amount of the catalyst used is preferably 0.01 to 5% by weight, more preferably 0.1 to 0.5% by weight, based on the weight of the amine or ammonia. When a reaction catalyst is used, the catalyst may be left as it is after completion of the reaction, or a method of adsorbing, filtering and removing using an adsorbent or the like, or neutralizing with an acid or alkali to inactivate the catalyst. It can also be processed by a method, a method of decomposing under reduced pressure by thermal decomposition, or the like.

  In order to obtain the nonionic surfactant represented by the general formula (1), a known method can be applied to the methylation reaction or acetylation reaction of the alkylene oxide adduct of amine. For example, for the methylation reaction, an alkylene oxide adduct is charged into a pressurized reaction vessel, and a methyl halide is obtained by reacting a monohalogenated methyl (eg, methyl chloride) under strong alkali (eg, potassium hydroxide) conditions. (Williamson synthesis method) or a method of reacting an alkylene oxide adduct with dimethyl sulfate can be applied. As for acetylation, a method in which an alkylene oxide adduct is charged into a pressure reaction vessel and acetic anhydride is reacted, a method in which acetic chloride is reacted, or the like can be applied.

  The nanocarbon dispersant of the present invention may be composed of only the nonionic surfactant represented by the general formula (1) or (2), and the nanocarbon dispersant of the nonionic surfactant represented by the general formula (1) Mixture of at least two kinds, at least two kinds of nonionic surfactants represented by the general formula (2), or at least one kind of nonionic surfactants represented by the general formula (1) and the general formula ( You may comprise from the mixing of at least 1 sort (s) of the nonionic surfactant shown by 2).

  In addition to the nonionic surfactant represented by the general formula (1) or (2), the nanocarbon dispersant of the present invention may have the general formula (1) or Other surfactants other than the nonionic surfactant represented by (2) can be contained, and various additives {wetting agents, antifoaming agents, fillers (organic, inorganic, etc.) as long as the dispersibility is not impaired. ), A thickener and / or a viscoelasticity modifier, etc.}.

  As other surfactants, the following anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants other than the nonionic surfactants represented by the general formula (1) or (2) Surfactants and other surfactants are included.

(1) Anionic surfactant (1-1) Sulfonic acid surfactant Alkylbenzene sulfonate, alkyl naphthalene sulfonate, condensed naphthalene sulfonate, alkyl sulfonate, dialkyl sulfosuccinate ester salt, alkanoyl methyl tau Ride etc.

(1-2) Carboxylic acid surfactant Fatty acid soap, polyoxyalkylene alkyl ether carboxylate, alkyl hydroxy ether carboxylate, polyacrylate, acrylic acid-alkyl methacrylate copolymer salt, acrylic acid-styrene -Maleic acid copolymer salt, acrylic acid-acrylic acid polyalkylene glycol ester copolymer salt, and the like.

(1-3) Phosphate-based surfactant Alkyl phosphate ester salt, polyoxyalkylene alkyl ether phosphate ester salt, dithiophosphate ester salt, polyphosphate, and the like.

(1-4) Sulfate ester surfactants Alkyl sulfate esters, polyoxyalkylene alkyl ether sulfates, sulfated oils, sulfated fatty acid esters, sulfated olefins and the like.

(2) Cationic surfactant (2-1) Amine salt type surfactant Monoalkylamine salt, dialkylamine salt, trialkylamine salt, fatty acid ester amine salt (Soramine A etc.), fatty acid amidoamine salt (Sapamine A etc.) ), Urea condensed amine salts (Arcobell A, etc.) and the like.

(2-2) Imidazoline-type surfactant 2-heptadecenyl-1-hydroxyethylimidazoline and the like.

(2-3) Quaternary ammonium salt type surfactant Alkyltrimethylammonium salt, alkylbenzyldimethylammonium salt, fatty acid amide type quaternary ammonium salt, pyridinium salt and the like.

(3) Amphoteric surfactant Amino acid type, betaine type and the like.

(4) Nonionic surfactants other than the nonionic surfactant represented by the general formula (1) or (2) (4-1) Polyethylene glycol polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, Polyoxyalkylene fatty acid ester, polyoxyalkylene polyhydric alcohol fatty acid ester, polyoxyalkylene fatty acid amide, polyoxyalkylene glycol and the like.

(4-2) Polyhydric alcohol type Glycerin fatty acid ester, pentaerythritol fatty acid ester, sorbitol / sorbitan fatty acid ester, sucrose fatty acid ester, alkyl polyglycoside and the like.

(5) Other surfactants Carboxymethyl cellulose, carboxymethyl ethyl cellulose, hexaethyl cellulose, polyvinyl alcohol and the like.

These other surfactants may contain 2 or more types.
In the case where these other surfactants are contained, anionic surfactants (1), cationic surfactants (2) and amphoteric surfactants (3) from the viewpoint of not inhibiting the electrical properties of the nanocarbon. More preferably, anionic surfactant (1) and cationic surfactant (2), particularly preferably anionic surfactant (1), most preferably sulfonic acid surfactant (1-1). And a carboxylic acid surfactant (1-2).

  When other surfactant is contained, the content (% by weight) is preferably 10 to 500 based on the weight of the nonionic surfactant represented by the general formula (1) or (2), Preferably it is 20-300, Most preferably, it is 50-200.

  As various additives {wetting agents, antifoaming agents, fillers (organic, inorganic), thickeners and / or viscoelasticity adjusting agents, etc.}, those generally used can be appropriately selected.

  When various additives are contained, the content (% by weight) of the wetting agent is preferably 1 to 100 based on the weight of the nonionic surfactant represented by the general formula (1) or (2). Preferably it is 5-50, Most preferably, it is 10-30. Moreover, 0.01-100 are preferable, as for content (weight%) of an antifoamer, More preferably, it is 0.1-50, Most preferably, it is 1-30. Moreover, 10-100 are preferable, as for content (weight%) of a filler, More preferably, it is 15-80, Most preferably, it is 20-60. Moreover, 0.1-100 are preferable, as for content (weight%) of a thickener and / or a viscoelasticity regulator, More preferably, it is 0.5-50, Most preferably, it is 1-20.

  The nanocarbon dispersant of the present invention is composed of a mixture of a nonionic surfactant represented by the general formula (1) and / or a nonionic surfactant represented by the general formula (2). In the case of a mixture of the surfactant and other surfactants and various additives, the nanocarbon dispersant of the present invention is not limited in the production method as long as these components can be mixed uniformly.

The nanocarbon dispersant of the present invention can be applied to the dispersion of various particles, but is suitable for the dispersion of nanocarbon.
The nanocarbon is not particularly limited as long as it is nano-sized carbon particles, and includes carbon materials such as fullerene, CNT, nanohorn, and nanofiber. These nanocarbons are readily available from the market.

  Of these nanocarbons, they are optimal for CNT dispersion. CNTs are most suitable for those produced by any production method (known production methods include arc discharge, CVD, laser ablation, etc.). CNTs are composed of single-walled carbon nanotubes (hereinafter abbreviated as SWCNT), double-walled double-walled carbon nanotubes (hereinafter abbreviated as DWCNT), and multi-walled carbon nanotubes having a structure of two or more layers (in terms of the number of layers). The dispersant of the present invention is applicable to any of SWCNT, DWCNT, and MWCNT. Among these, it is particularly suitable for dispersion of MWCNT. The CNT usually has a size (shape) of several to several tens of nm in diameter and 1 to 500 μm in length, and the dispersant of the present invention can be applied to any size within the above range.

  The nanocarbon dispersion liquid of the present invention contains nanocarbon, a dispersion medium, and the above dispersant.

  As the dispersion medium, water, an organic solvent, or the like can be used. Depending on the intended application, these can be selected in a timely manner, and may be a mixture of water and an organic solvent or a mixture of two or more organic solvents. Of these dispersion media, water is preferable in terms of safety and environment.

  Examples of the organic solvent include alcohol (alcohol having 1 to 10 carbon atoms; methanol, ethanol, isopropanol, ethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, n-hexanol, decyl alcohol, and the like), ketone (3 carbon atoms). ~ 6 ketones, etc .; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (4-10 carbon esters, etc .; ethyl acetate, butyl acetate, butyl cellosolve acetate, octyl acetate, etc.), ethers (4-10 carbon atoms) Ether, etc .; diethyl ether, ethylene glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran, butyl hexyl ether, etc.), aromatic hydrocarbon (aromatic carbon having 6 to 9 carbon atoms) Hydrogen, etc .; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, etc.), alicyclic hydrocarbons (C5-C10 alicyclic hydrocarbons, etc .; cyclopentane, cyclohexane, tetramethylcyclohexane, etc.), aliphatic hydrocarbons (C5-C10 aliphatic hydrocarbons, etc .; pentane, hexane, peptane, octane, nonane, decane, etc.), other solvents (petroleum ether, petroleum naphtha, etc.), lubricating oils, vegetable oils and mineral oils.

  Although content (weight%) of said dispersing agent in the nanocarbon dispersion liquid of this invention is not specifically limited, Based on the weight of nanocarbon, 20-500 are preferable, More preferably, it is 50-400, Most preferably 100-300. Within this range, the dispersibility becomes better.

  Further, the content (% by weight) of the dispersion medium is not particularly limited, but is preferably 200 to 100,000, more preferably 400 to 20,000, and particularly preferably 500 to 10,000 based on the weight of the nanocarbon. It is.

  The nanocarbon dispersion liquid of the present invention may contain a dispersant other than the above-described dispersant for nanocarbon for the purpose of further improving dispersibility and dispersion stability. Other dispersants include the other surfactants described above. Furthermore, in the nanocarbon dispersion liquid of the present invention, various additives {wetting agents, antifoaming agents, fillers (organic, inorganic), thickeners and / or viscoelasticity adjusting agents, etc.} within a range that does not impair dispersibility} Can be contained.

  When other dispersants are contained, the content (% by weight) is preferably 10 to 200, more preferably 15 to 150, and particularly preferably 20 to 100 based on the weight of the nanocarbon.

When a wetting agent is contained, the content (% by weight) is preferably 10 to 100, more preferably 15 to 50, and particularly preferably 20 to 30 based on the weight of the nanocarbon.
In the case of containing an antifoaming agent, the content (% by weight) is preferably 0.005 to 3, more preferably 0.01 to 2, particularly preferably 0. 0 based on the total weight of the nanocarbon dispersion. It is 05-1.
When the filler is contained, the content (% by weight) is preferably 10 to 500, more preferably 15 to 300, and particularly preferably 20 to 200, based on the weight of the nanocarbon.
When a thickener and / or a viscoelasticity modifier is contained, the content (% by weight) is preferably 0.1 to 5, more preferably 0.5 to, based on the total weight of the nanocarbon dispersion. 3, particularly preferably 1-3.

  The nanocarbon dispersion liquid of the present invention is not limited to any production method as long as it contains nanocarbon, a dispersion medium and the above-mentioned dispersant, but it is preferably produced by the following method.

A mixing step (1) of preparing a dispersant mixture by mixing the dispersion medium and the above-mentioned dispersant for nanocarbon;
A pre-dispersing step (2) for preparing a pre-dispersion by mixing the dispersant mixture and nano-carbon; and a dispersion for preparing a nano-carbon dispersion by dispersing the pre-dispersion with a wet disperser or an ultrasonic disperser A production method comprising step (3).

  When other dispersants other than the above-mentioned nanocarbon dispersant are used, other dispersants may be added in any step, but are added and mixed in the mixing step (1) or the preliminary dispersion step (2). It is preferable. Various additives {wetting agents, antifoaming agents, foaming agents, preservatives, colorants, fillers (organic, inorganic), resins, thickeners and / or viscoelasticity modifiers, etc.} The agent may be added in any step, but is preferably added and mixed after the dispersion step (3).

  In the mixing step (1) and the preliminary dispersion step (2), the mixing method is not limited as long as uniform mixing is possible. In the dispersion step (3), there is no limitation on the dispersion method as long as uniform dispersion is possible.

  Dispersers that can be used in the dispersion step (3) include, for example, high shear dispersers (homogenizers, homomixers, ultramixers, etc.), wet media type dispersers (bead mills, sand mills, etc.), high-pressure homogenizers, ultrasonic homogenizers, and the like. Can be mentioned. Two or more kinds of these dispersers may be used. Among these dispersers, wet media type dispersers and ultrasonic homogenizers are preferable from the viewpoint of easy dispersion and prevention of contamination.

  In the dispersion step (3), when the temperature of the dispersion liquid rises, it is desirable to carry out the cooling appropriately, from the viewpoint of preventing water evaporation and preventing nanocarbon aggregation. The dispersion temperature (° C.) is preferably 5 to 50, more preferably 10 to 40, and particularly preferably 15 to 35.

  The nanocarbon dispersion liquid of the present invention can be applied to various applications, for example, applied to electrodes utilizing conductivity, and kneaded into various resins, plastics, urethane foam, etc. for the purpose of improving strength and heat resistance. And can be applied by addition to a lubricating oil for the purpose of improving lubrication and wear resistance.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. Unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.

<Production Example 1>
Into a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a dropping cylinder, 73 parts (1 mol) of diethylamine and 0.07 part of potassium hydroxide were added, sealed after nitrogen substitution, and reduced pressure (-0.097 MPa). ), The contents were heated to 130 ° C. while stirring. While stirring the contents, 220 parts (5 mol) of ethylene oxide (EO) was added dropwise over 5 hours while adjusting the pressure to be 0.5 MPa or less, and further stirred (ripened) at 130 ° C. for 2 hours. . Next, after cooling to 90 ° C., 3 parts of an adsorption treatment agent (KYOWARD 600, Kyowa Chemical Industry Co., Ltd., “KYOWARD” is a registered trademark of the company) are added, and stirred at 90 ° C. for 1 hour for hydroxylation. After adsorption treatment of potassium, the adsorption treatment agent was removed by filtration to obtain diethylamine (EO) 5 mol adduct (b21-1).

  Next, 293 parts of diethylamine (EO) 5-mole adduct (b21-1) were put into the same pressure-resistant reaction vessel, 15 parts of potassium hydroxide was added, the mixture was purged with nitrogen, sealed, stirred and mixed at 80 ° C. for 30 minutes, The temperature was raised to 0 ° C. and dehydrated under reduced pressure for 3 hours. After dehydration, the mixture was cooled, 51 parts of methyl chloride was added over 4 hours while maintaining the temperature at 70 ° C. with stirring, the mixture was stirred (aged) for 2 hours, and then degassed at 120 ° C. for 1 hour under reduced pressure. After returning the reaction vessel to normal pressure (atmospheric pressure), 100 parts of water was added while stirring, and after stirring at 80 ° C., the aqueous layer was removed, and the remaining oil layer was neutralized by adding phosphoric acid. , 3 parts of an adsorption treatment agent (KYOWARD 600) was added, and the neutralization salt was adsorbed by stirring at 90 ° C. for 1 hour, and then the adsorption treatment agent was removed by filtration to give a 5 mol adduct of diethylamine (EO). Terminal methylation product (b11-1) was obtained.

<Production Example 2>
"Diethylamine 73 parts (1 mole)", "Potassium hydroxide 0.07 parts", "Ethylene oxide (EO) 220 parts (5 moles)" and "Adsorption treatment agent (Kyoward 600) 3 parts" “Butylamine 12.9 parts (0.1 mole)”, “Potassium hydroxide 0.01 parts”, “Propylene oxide (PO) 464 parts (8 moles)” and “Adsorption treatment agent (KYOWARD 600) 5 parts” Except having changed, it carried out similarly to manufacture example 1, and obtained the dibutylamine (PO) 80 mol adduct (b21-2).

  Next, “diethylamine (EO) 5 molar adduct (b21-1) 293 parts”, “potassium hydroxide 15 parts”, “methyl chloride 51 parts” and “adsorption treatment agent (Kyoward 600) 3 parts” Dibutylamine (PO) 80 molar adduct (b21-2) 477 parts ”,“ potassium hydroxide 24 parts ”,“ methyl chloride 5.1 parts ”and“ adsorption treatment agent (KYOWARD 600) 5 parts ” Except that, terminal methylated product (b11-2) of 80 mol dibutylamine (PO) adduct was obtained in the same manner as in Production Example 1.

<Production Example 3>
“Diethylamine 73 parts (1 mole)”, “Ethylene oxide (EO) 220 parts (5 moles)” and “Adsorption treatment agent (KYOWARD 600) 3 parts” were replaced with “Ethylamine 45 parts (1 mole)”, “Ethylene After changing to 440 parts (10 moles) of oxide (EO), 580 parts (10 moles) of propylene oxide (PO) and 11 parts of adsorption treatment agent (KYOWARD 600) and reacting (EO) , (PO) was reacted in the same manner as in Production Example 1 to obtain an ethylamine (EO) 10 mol (PO) 10 mol block adduct (b22-1).

  Next, 1065 parts of ethylamine (EO) 10 mol (PO) 10 mol block adduct (b22-1) was charged into the same pressure resistant reaction vessel used in Production Example 1, and the temperature was raised to 120 ° C. after nitrogen substitution. 102 parts of acetic anhydride was added dropwise and stirred for 2 hours. Then, it cooled to 90 degreeC and neutralized the unreacted acetic acid with potassium hydroxide. Next, 11 parts of an adsorption treatment agent (KYOWARD 600) is added at the same temperature, and the mixture is stirred for 1 hour to perform adsorption treatment. Then, the adsorption treatment agent is removed by filtration, and 10 mol block of ethylamine (EO) 10 (PO) is added A terminal acetylated product (b12-1) was obtained.

<Production Example 4>
"Diethylamine 73 parts (1 mole)", "Potassium hydroxide 0.07 parts", "Ethylene oxide (EO) 220 parts (5 moles)" and "Adsorption treatment agent (Kyoward 600) 3 parts" Other than changing to "129 parts (1 mole) of amine", "0.1 parts of potassium hydroxide", "880 parts (20 moles) of ethylene oxide (EO)" and "10 parts of adsorption treatment agent (Kyoward 600)" In the same manner as in Production Example 1, an octylamine (EO) 20 mol adduct (b22-2) was obtained.

  Next, “293 parts of diethylamine (EO) 5 mol adduct (b21-1)”, “15 parts of potassium hydroxide”, “51 parts of methyl chloride”, “100 parts of water” and “adsorption treatment agent (KYOWARD 600) ) 3 parts "," octylamine (EO) 20 mol adduct (b22-2) 1009 parts "," potassium hydroxide 51 parts "," methyl chloride 101 parts "," 500 parts water "and" adsorption treatment ". Except for changing to “10 parts of agent (Kyoward 600)”, a terminal methylated product (b12-2) of octylamine (EO) 20 mol adduct was obtained in the same manner as in Production Example 1.

<Production Example 5>
"Diethylamine 73 parts (1 mole)", "Potassium hydroxide 0.07 parts", "Ethylene oxide (EO) 220 parts (5 moles)" and "Adsorption treatment agent (Kyoward 600) 3 parts""Amine 93 parts (0.5 mole)", "Potassium hydroxide 0.1 parts", "Ethylene oxide (EO) 616 parts (14 moles)" and "Adsorption treatment agent (Kyoward 600) 7 parts" Except this, it carried out similarly to manufacture example 1, and obtained the laurylamine (EO) 28 mol adduct (b22-3).

  Next, “diethylamine (EO) 5 mol adduct (b21-1) 293 parts”, “potassium hydroxide 15 parts”, “100 parts water” and “adsorption treatment agent (Kyoward 600) 3 parts” Other than changing to 708 parts of laurylamine (EO) 28-mol adduct (b22-3), 35 parts of potassium hydroxide, 500 parts of water, and 7 parts of adsorption treatment agent (Kyoward 600) In the same manner as in Production Example 1, a terminal methylated product (b12-3) of 28-mol adduct of laurylamine (EO) was obtained.

<Production Example 6>
"Diethylamine 73 parts (1 mole)", "Potassium hydroxide 0.07 parts", "Ethylene oxide (EO) 220 parts (5 moles)" and "Adsorption treatment agent (Kyoward 600) 3 parts""Amine 135 parts (0.5 mol)", "Potassium hydroxide 0.2 parts", "Ethylene oxide (EO) 880 parts (20 mol)" and "Adsorption treatment agent (Kyoward 600) 10 parts" Except for this, in the same manner as in Production Example 1, a stearylamine (EO) 40 mol adduct (b22-4) was obtained.

  Next, “diethylamine (EO) 5 mol adduct (b21-1) 293 parts”, “potassium hydroxide 15 parts”, “100 parts water” and “adsorption treatment agent (Kyoward 600) 3 parts” Other than changing to stearylamine (EO) 40 mol adduct (b22-4) 1015 parts "," potassium hydroxide 51 parts "," 500 parts water "and" adsorption treatment agent (Kyoward 600) 11 parts " In the same manner as in Production Example 1, a terminal methylated product (b12-4) of 40 mol adduct of stearylamine (EO) was obtained.

<Production Example 7>
"Diethylamine 73 parts (1 mole)", "Potassium hydroxide 0.07 parts", "Ethylene oxide (EO) 220 parts (5 moles)" and "Adsorption treatment agent (Kyoward 600) 3 parts""67 parts (0.25 mol)", "potassium hydroxide 0.07 parts", "propylene oxide (PO) 870 parts (15 mol)" and "adsorption treatment agent (KYOWARD 600) 9 parts" Otherwise, in the same manner as in Production Example 1, an oleylamine (PO) 60 mol adduct (b22-5) was obtained.

  Next, “ethylamine (EO) 10 mol (PO) 10 mol adduct (b22-1) 1065 parts”, “acetic anhydride 102 parts” and “adsorption treatment agent (Kyoward 600) 11 parts” were converted into “oleylamine (PO). ) Oleylamine (PO) in the same manner as in Production Example 3, except that the content was changed to 937 parts of 60 mol adduct (b22-5), 26 parts of acetic anhydride, and 10 parts of adsorption treatment agent (Kyoward 600). ) A terminal acetylated product (b12-5) of 60 mol adduct was obtained.

<Production Example 8>
"Diethylamine 73 parts (1 mole)", "Potassium hydroxide 0.07 parts", "Ethylene oxide (EO) 220 parts (5 moles)" and "Adsorption treatment agent (Kyoward 600) 3 parts" A mixture of 9 parts (0.1 mol) of aminoethylamine, 0.01 part of potassium hydroxide, 440 parts (10 mol) of ethylene oxide (EO) and 203 parts (3.5 mol) of propylene oxide (PO) And 35 parts random adduct (b23-1) of ethylaminoethylamine (EO) 100 (PO) in the same manner as in Production Example 1 except that the adsorption agent was changed to 7 parts of adsorption treatment agent (KYOWARD 600). It was.

  Next, “ethylamine (EO) 10 mol (PO) 10 mol adduct (b22-1) 1065 parts”, “acetic anhydride 102 parts” and “adsorption treatment agent (Kyoward 600) 11 parts” were converted into “ethylaminoethylamine”. (EO) 100 mol (PO) 35 mol random adduct (b23-1) 652 parts "," 16 parts of acetic anhydride "and" 7 parts of adsorption treatment agent (KYOWARD 600) "Production Example 3 In the same manner as above, a terminal acetylated product (b13-1) of 35 mol random adduct of ethylaminoethylamine (EO) 100 (PO) was obtained.

<Production Example 9>
"Diethylamine 73 parts (1 mole)", "Potassium hydroxide 0.07 parts", "Ethylene oxide (EO) 220 parts (5 moles)" and "Adsorption treatment agent (Kyoward 600) 3 parts" 60 parts (1 mole) "," potassium hydroxide 0.06 parts "," butylene oxide (BO) 864 parts (12 moles) "and" adsorption treatment agent (Kyoward 600) 9 parts ", In the same manner as in Production Example 1, an ethylenediamine (BO) 12-mol adduct (b24-1) was obtained.

  Next, “ethylamine (EO) 10 mol (PO) 10 mol adduct (b22-1) 1065 parts” and “acetic anhydride 102 parts” are converted to “ethylenediamine (BO) 12 mol adduct (b24-1) 924 parts”. And except having changed into "204 parts of acetic anhydride", it carried out similarly to manufacture example 3, and obtained the terminal acetylation thing (b14-1) of ethylenediamine (BO) 12 mol adduct.

<Production Example 10>
"Diethylamine 73 parts (1 mole)", "Potassium hydroxide 0.07 parts", "Ethylene oxide (EO) 220 parts (5 moles)" and "Adsorption treatment agent (Kyoward 600) 3 parts""Diamine 20 parts (0.1 mol)", "Potassium hydroxide 0.02 parts", "Ethylene oxide (EO) 440 parts (10 mol)" and "Adsorption treatment agent (Kyoward 600) 5 parts" Except this, it carried out similarly to manufacture example 1, and obtained diphenyl ether diamine (EO) 100 mol adduct (b24-2).

  Next, “diethylamine (EO) 5 molar adduct (b21-1) 293 parts”, “potassium hydroxide 15 parts”, “methyl chloride 51 parts” and “adsorption treatment agent (Kyoward 600) 3 parts” Other than changing to 460 parts of diphenyl ether diamine (EO) 100 mol adduct (b24-2), 23 parts of potassium hydroxide, 21 parts of methyl chloride, and 5 parts of adsorption treatment agent (Kyoward 600) In the same manner as in Production Example 1, a terminal methylated product (b14-2) of a 100 mol diphenyl ether diamine (EO) adduct was obtained.

<Production Example 11>
"Diethylamine 73 parts (1 mole)", "Potassium hydroxide 0.07 parts", "Ethylene oxide (EO) 220 parts (5 moles)" and "Adsorption treatment agent (Kyoward 600) 3 parts""10 parts (0.1 mol)", "potassium hydroxide 0.01 parts", "propylene oxide (PO) 1450 parts (25 mol)" and "adsorption treatment agent (KYOWARD 600) 15 parts" In the same manner as in Production Example 1, except that diethylenetriamine (PO) 250 mol adduct (b25-1) was obtained.

  Next, “293 parts of diethylamine (EO) 5 mol adduct (b21-1)”, “15 parts of potassium hydroxide”, “51 parts of methyl chloride”, “100 parts of water” and “adsorption treatment agent (KYOWARD 600) ) 3 parts "," diethylenetriamine (PO) 250 molar adduct (b25-1) 1460 parts "," potassium hydroxide 73 parts "," methyl chloride 26 parts "," 500 parts water "and" adsorption treatment agent ". A terminal methylated product (b15-1) of diethylenetriamine (PO) 250 mol adduct was obtained in the same manner as in Production Example 3, except that the change was made to “(KYOWARD 600) 15 parts”.

<Production Example 12>
“Diethylamine 73 parts (1 mole)”, “Potassium hydroxide 0.07 parts” and “Ethylene oxide (EO) 220 parts (5 moles)” were replaced with “Laurylamine 18.5 parts (0.1 moles)”, 70 mol laurylamine (EO) adduct (b22-6) in the same manner as in Production Example 1, except that it was changed to “0.02 part potassium hydroxide” and 308 parts (7 mol) ethylene oxide (EO). )

  Next, “diethylamine (EO) 5 mol adduct (b21-1) 293 parts”, “potassium hydroxide 15 parts” and “methyl chloride 51 parts” were converted into “laurylamine (EO) 70 mol adduct (b22-6). ) 327 parts "," potassium hydroxide 16 parts ", and" methyl chloride 10.1 parts ", in the same manner as in Production Example 3, but the terminal methylated product of laurylamine (EO) 70 mol adduct (b12 -6) was obtained.

<Examples 1-34, Comparative Examples 1-5>
“Nonionic surfactant represented by general formula (1) or (2)” and “other surfactant” shown in Tables 1 to 3 are uniformly stirred and mixed in the amounts (parts) used in the same table. Then, dispersants 1 to 34 of the present invention were prepared. The dispersants shown in Table 4 were used as comparative dispersants H1 to H5.
And after mixing each dispersing agent and the usage-amount (part) water shown to Tables 1-4 uniformly, and preparing the dispersing agent liquid mixture 1-34 and the dispersing agent occlusion liquid H1-H5 for a comparison, each The dispersion liquid mixture and the amount (parts) of nanocarbon (CNT “NC-7000” manufactured by Nanocyl) shown in Tables 1 to 4 were uniformly mixed to prepare preliminary dispersions, respectively. Each preliminary dispersion was dispersed with a bead mill (diameter 2 mm zirconia beads, volume filling rate 80%, AMR1 manufactured by Ashizawa Finetech Co., Ltd., peripheral speed 11.4 m / s, 35 ° C.). The nanocarbon dispersion liquids 1 to 34 of the present invention and the comparative nanocarbon dispersion liquids H1 to H5 were obtained. Table 5 shows the results of evaluating the dispersion state, viscosity, and dispersion stability of each nanocarbon dispersion.

In Tables 1 to 3, the symbols described in the column of the nonionic surfactant represented by the general formula (1) or (2) are the symbols of the nonionic surfactant prepared in the production example. The symbols described in the surfactant column are as follows. In Table 4, the symbols described in the comparative dispersant column are also the same.
In addition, although there are those whose active ingredient (purity) is not 100% in the following, the numerical values shown in Tables 1 to 4 are shown in terms of 100% active ingredient (purity) and are effective unless otherwise specified. Almost everything except the ingredients is water.

(C-1) Na dodecylbenzenesulfonate: “Neopelex G-25” (active ingredient: 25%. “Neopelex” manufactured by Kao Corporation is a registered trademark of the company)
(C-2) Condensed naphthalenesulfonic acid ammonium salt: “Roma PWA-40K” (active ingredient: 40%, manufactured by San Nopco)
(C-3) Dialkylsulfosuccinic acid Na: “Sanmorin OT-70” (active ingredient: 70%, containing 16% propylene glycol. “Sanmorin” manufactured by Sanyo Chemical Industries, Ltd. is a registered trademark of the company)
(C-4) Polycarboxylic acid ammonium salt: “SN Dispersant 5468” (active ingredient: 40%, manufactured by San Nopco Corporation)
(C-5) Polyoxyalkyl ether carboxylic acid Na: “Viewlight LCA-25N” (active ingredient: 28%. “Viewlight” manufactured by Sanyo Chemical Industries, Ltd. is a registered trademark of the company)
(C-6) Carboxymethylcellulose: “Sunrose F150LC” (active ingredient: 100%, manufactured by Nippon Paper Chemicals Co., Ltd.)

<Evaluation method of dispersion>
(1) Dispersion state The dispersion liquid was allowed to stand at 25 ° C. for 1 day, and the dispersion state was visually confirmed according to the following criteria.
○: Uniformly dispersed and no aggregation Δ: Uniformly dispersed but partially aggregated ×: Not dispersed or severely aggregated

(2) Viscosity After adjusting the temperature of the dispersion to 25 ° C., it was measured with an E-type viscometer (RE80 type, manufactured by Toki Sangyo Co., Ltd.). The lower the viscosity, the better the dispersibility.

(3) Dispersion stability The dispersion is placed in a test tube with a 200 mm high stopper (diameter 15 mm) up to a height of 100 mm, and the height of the water separated into the surface layer after standing for 1 month at 40 ° C. in a sealed state. The ratio (length%) was determined and used as dispersion stability. The smaller the value, the better the dispersion stability.

  As is clear from Table 5, the nanocarbon dispersion using the dispersant of the present invention was superior in dispersibility, viscosity and dispersion stability to the nanocarbon dispersion using the comparative dispersant.

The nanocarbon dispersant of the present invention can uniformly and easily disperse nanocarbon at a high concentration, and the resulting nanocarbon dispersion can be used for various electrical and electronic related applications such as electrodes, strength and heat resistance. It can be used for applications such as improved resin properties, lubricants, and the like.

Claims (5)

A nanocarbon dispersant comprising a nonionic surfactant represented by the general formula (1) or (2).

^{Z 1 - {(AO) n} -X} p (1)

^{Z 2 - {(AO) n} -H} p (2)

(In the formula, Z ¹ represents a reaction residue obtained by removing an active hydrogen atom from an amine or ammonia having 1 to 32 carbon atoms having p active hydrogen atoms, and Z ² represents 1 to 1 carbon atoms having p active hydrogen atoms. A reactive residue obtained by removing an active hydrogen atom from 12 amines or ammonia, AO is an oxyalkylene group having 2 to 4 carbon atoms, n is an integer of 1 to 100, X is a methyl group or an acetyl group, H is a hydrogen atom, p Is an integer from 1 to 5.) The dispersant according to claim 1 or 2, wherein the nanocarbon is a carbon nanotube. A nanocarbon dispersion liquid comprising nanocarbon, a dispersion medium, and the dispersant according to claim 1. The nanocarbon dispersion liquid according to claim 3, wherein the content of the dispersant is 20 to 500 wt% and the content of the dispersion medium is 200 to 100,000 wt% based on the weight of the nanocarbon. A mixing step (1) for preparing a dispersant mixture by mixing the dispersion medium and the dispersant described in claim 1 or 2;
A pre-dispersing step (2) for preparing a pre-dispersion by mixing the dispersant mixture and nano-carbon; and a dispersion for preparing a nano-carbon dispersion by dispersing the pre-dispersion with a wet disperser or an ultrasonic disperser The manufacturing method of the nanocarbon dispersion liquid characterized by including a process (3).