JP2012148970A - Dispersant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition having high dispersibility and dispersion stability to carbon powder and ceramic powder.SOLUTION: The composition contains a compound of formula (1) and carbon powder or ceramic powder. In the formula, Rdenotes a 1-23C hydrocarbon group; Rdenotes hydrogen, or a 1-3C hydrocarbon group which may have a carboxylic acid group or a sulfonic acid group; Y denotes a carboxyl group, a sulfonic acid group, a sulfate group, a phosphate group, or a salt thereof; Z denotes -NR'- (R' is hydrogen or a 1-10C hydrocarbon group), -O-, or -S-; j and k are one of 0, 1 and 2, and j and k are not simultaneously 0; n is an integer of 2 to 20; X denotes a hydrocarbon chain which may have a substituent and has a molecular weight of ≤1,000,000.

Description

  The present invention relates to a composition containing a specific compound and carbon powder or ceramic powder.

In recent years, utilization of carbon powders or ceramic powders such as carbon nanotubes (hereinafter referred to as CNT) and barium titanate has been attempted in various applications.
For example, CNTs have characteristics such as electronics (transistor elements, wiring, etc.), energy (electrode materials for fuel cells, solar power generation devices, gas storage, etc.), electron emission (flat panel devices, etc.), chemistry (adsorbents, catalysts, Sensors, etc.), composite materials (conductive plastics, reinforced materials, flame retardant nanocomposites, etc.) are expected to be applied in various fields.
However, it is very difficult to disperse the CNT, and various dispersion methods have been tried so far.

Patent Documents 1 and 2 propose a method of dispersing CNTs using an anionic surfactant such as sodium dodecyl sulfate or sodium dodecylbenzenesulfonate.
However, in this case, since all the dispersants are metal salts, the fields that can be used as CNT dispersants are limited, such as difficulty in use in the field of electronic materials.

In addition, barium titanate is used in multilayer ceramic capacitor applications. Specifically, a multilayer ceramic capacitor is a multilayered composite layer in which a ceramic dielectric layer is sandwiched between electrodes. Barium titanate having a high dielectric constant is the base in this multilayer ceramic capacitor. Used for dielectric layers. As a method for facilitating the formation of the dielectric layer, a method of coating a composition containing barium titanate and then firing it to obtain a dielectric layer is performed.
In order to increase the size and capacity of multilayer ceramic capacitors, it is necessary to reduce the thickness of electrode-dielectric composite layers and increase the number of layers. Currently, dielectric layers are formed with a thickness of 1 μm or less. What is laminated about several tens to several thousand layers is manufactured.
In order to form this dielectric layer by the above-described coating method, it is necessary to atomize barium titanate and to stably disperse the barium titanate particles in the medium in the coating liquid.
Moreover, since it is calculated | required to give smoothness to the coating film surface, it is also required that the coating liquid containing a barium titanate has sufficient fluidity | liquidity. Furthermore, a polar organic solvent is generally used for the coating liquid, and the dispersant for dispersing barium titanate needs to be usable in a polar organic solvent.

  As described above, various proposals have been made as dispersants for dispersing powders of inorganic materials that are difficult to disperse, such as CNT and barium titanate.

  Patent Document 3 discloses a technique of using a condensed hydroxycarboxylic acid having an acid value of 10 to 100 or a salt thereof obtained by condensing hydroxycarboxylic acid as a dispersant for dispersing an inorganic pigment.

  Patent Document 4 proposes a technique of using an esterified product of polyhydroxycarboxylic acid having a degree of condensation of 2 or more and a polyhydric alcohol as a method for dispersing ceramic powder in an organic medium.

JP 2003-238126 A Japanese Patent Laid-Open No. 2005-95806 Japanese Patent Publication No.54-34009 Japanese Patent Laid-Open No. 06-15157

However, conventional dispersants have a problem that dispersibility and dispersion stability are not sufficient.
An object of the present invention is to provide a composition having high dispersibility and dispersion stability with respect to carbon powder and ceramic powder.
Furthermore, the present invention is a composition having high dispersibility and dispersion stability with respect to carbon powder or ceramic powder, which can be sufficiently used for applications in the field of electronic materials in which the dispersant does not preferably contain a metal salt. It is intended to provide.

（上記一般式（１）において、Ｒ^１は、炭素数１〜２３の炭化水素基を示し、Ｒ^２は、水素又は、カルボン酸基或いはスルホン酸基を有してもよい炭素数１〜３の炭化水素基を示す。Ｙは、カルボキシル基、スルホン酸基、硫酸エステル基、リン酸エステル基、又はそれらの塩を示す。Ｚは、−ＮＲ’−（Ｒ’は、水素又は炭素数１〜１０の炭化水素基）、−Ｏ−、又は−Ｓ−を示す。ｊ、ｋは０、１、２のいずれかであり、且つｊ、ｋは同時に０ではなく、ｎは２〜２０の整数を示す。Ｘは、置換基を有していてもよい分子量１００万以下の炭化水素鎖を示す。）
［２］ 前記一般式（１）中のＸの炭素数が、１〜４０である［１］に記載の組成物。
［３］ 前記一般式（１）で示される化合物が、下記一般式（２）で示される化合物である［１］又は［２］に記載の組成物。

（上記一般式（２）において、Ｒ^１は炭素数１〜２３の炭化水素基を示し、Ｒ^２は水素又は、カルボン酸基或いはスルホン酸基を有してもよい炭素数１〜３の炭化水素基を示す。Ｙは、カルボキシル基、スルホン酸基、硫酸エステル基、リン酸エステル基、又はそれらの塩を示す。Ｚは、−ＮＲ’−（Ｒ’は、水素又は炭素数１〜１０の炭化水素基）、−Ｏ−、又は−Ｓ−を示す。Ｘ’は、カルボキシル基又はその塩、−ＮＨＲ’基（Ｒ’は、水素又は炭素数１〜１０の炭化水素基）、−ＯＨ基、−ＳＨ基のうち少なくともいずれか一つを有する炭素数が１〜２０の炭化水素鎖を示す。ｊ、ｋは０、１、２のいずれかであり、且つｊ、ｋは同時に０ではない。）
［４］ 炭素粉末を含み、該炭素粉末が、カーボンナノチューブ、カーボンナノコイル、カーボンナノホーン、カーボンナノファイバー、フラーレンからなる群から選択される１種以上からなることを特徴とする［１］〜［３］のいずれか一つに記載の組成物。
［５］ セラミック粉末を含み、該セラミック粉末が、下記の群から選択される１種以上からなることを特徴とする［１］〜［３］のいずれか一つに記載の組成物。
（酸化チタン、チタン酸バリウム、チタン酸バリウムカルシウム、チタン酸ストロンチウム、チタン酸鉛、ジルコン酸バリウム、チタン酸バリウムを主成分に酸化物（例えば、Ｍｎ、Ｃｒ、Ｓｉ、Ｃａ、Ｂａ、Ｍｇ、Ｖ、Ｗ、Ｔａ、Ｎｂおよび１種類以上の希土類元素の酸化物）を副成分に含むセラミック粉末、チタン酸バリウム（ＢａＴｉＯ_３）のＢａ原子又はＴｉ原子がＳｎ、Ｐｂ、Ｚｒ原子のいずれかで置換されたペロブスカイト型酸化物強誘電体のセラミック粉末、ＺｎＯ、フェライト、ＰＺＴ、ＢａＯ、Ａｌ_２Ｏ_３、Ｂｉ_２Ｏ_３、Ｒ（希土類元素）_２Ｏ_３、ＴｉＯ_２、Ｎｄ_２Ｏ_３、２ＭｇＯ・ＳｉＯ_２、ＺｒＯ_２、ＺｒＯ_２・ＳｉＯ_２、３Ａｌ_２Ｏ_３・２ＳｉＯ_２、ＭｇＯ・ＳｉＯ_２、２ＭｇＯ・２Ａｌ_２Ｏ_３・５ＳｉＯ_２の酸化物の粉末、Ｎｉ−Ｃｕ−Ｚｎフェライト、Ｎｉ−Ｚｎフェライト、Ｃｕ−Ｚｎフェライトのフェライト磁性粉末、Ｙ_１Ｂａ_２Ｃｕ_３Ｏ_７、Ｂｉ_２Ｓｒ_２Ｃａ_２Ｃｕ_３Ｏ_１０の超電導セラミック粉末、酸化チタンナノチューブ、ＡｌＮ、Ｓｉ_３Ｎ_４、ＳｉＣ）
［６］ ［１］〜［５］のいずれか一つに記載の組成物を含む電子材料。
［７］ ［１］〜［５］のいずれか一つに記載の組成物を含む印刷材料。
［８］ ［４］に記載の組成物を含む導電性電子材料。
［９］ ［５］に記載の組成物を含む誘電性電子材料。 As a result of intensive studies to solve the above problems, the present inventor used a specific compound, that is, a specific compound having a plurality of hydrophobic groups and hydrophilic groups in the molecule, and carbon powder or ceramic powder. The present inventors have found that the above problems can be solved by using a composition, and have completed the present invention. That is, the present invention is as follows.
[1] A composition comprising a compound represented by the following general formula (1) and carbon powder or ceramic powder.

In (the above general formula (1), ^{R 1} is a hydrocarbon group of 1 to 23 carbon atoms, ^{R 2} is hydrogen or a carboxylic acid group or carbon atoms 1-3 have a sulfonic acid group Y represents a carboxyl group, a sulfonic acid group, a sulfuric ester group, a phosphoric ester group, or a salt thereof. Z represents —NR ′ — (R ′ represents hydrogen or carbon number 1). -10 hydrocarbon group), -O-, or -S-, j and k are either 0, 1 or 2 and j and k are not 0 at the same time, and n is 2 to 20 X represents an optionally substituted hydrocarbon chain having a molecular weight of 1,000,000 or less.
[2] The composition according to [1], wherein the carbon number of X in the general formula (1) is 1 to 40.
[3] The composition according to [1] or [2], wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(In the above general formula (2), R ¹ represents a hydrocarbon group having 1 to 23 carbon atoms, R ² represents hydrogen, a carbon atom having 1 to 3 carbon atoms which may have a carboxylic acid group or a sulfonic acid group. Y represents a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, or a salt thereof, Z represents —NR ′ — (R ′ represents hydrogen or a carbon number of 1 to 10; X ′ represents a carboxyl group or a salt thereof, —NHR ′ group (R ′ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms), — A hydrocarbon chain having 1 to 20 carbon atoms and having at least one of an OH group and an —SH group, j and k are 0, 1 and 2, and j and k are simultaneously 0. is not.)
[4] Carbon powder is included, and the carbon powder is composed of one or more selected from the group consisting of carbon nanotubes, carbon nanocoils, carbon nanohorns, carbon nanofibers, and fullerenes. 3] The composition according to any one of 3).
[5] The composition according to any one of [1] to [3], comprising ceramic powder, wherein the ceramic powder is composed of one or more selected from the following group.
(Oxides based on titanium oxide, barium titanate, barium calcium titanate, strontium titanate, lead titanate, barium zirconate, barium titanate (for example, Mn, Cr, Si, Ca, Ba, Mg, V , W, Ta, Nb, and oxides of one or more rare earth elements), Ba atoms or Ti atoms of barium titanate (BaTiO ₃ ) are replaced with any of Sn, Pb, Zr atoms Perovskite oxide ferroelectric ceramic powder, ZnO, ferrite, PZT, BaO, Al ₂ O ₃ , Bi ₂ O ₃ , R (rare earth element) ₂ O ₃ , TiO ₂ , Nd ₂ O ₃ , 2MgO. _{SiO 2, ZrO 2, ZrO 2} · SiO 2, 3Al 2 O 3 · 2SiO 2, MgO · SiO 2, 2MgO · 2Al O powder ₃ · 5SiO oxide _2, Ni-Cu-Zn ferrite, Ni-Zn ferrite, ferrite magnetic powder Cu-Zn _{ferrite, Y 1 Ba 2 Cu 3 O} 7, Bi 2 Sr 2 Ca 2 Cu 3 O ₁₀ superconducting ceramic powder, titanium oxide nanotubes, AlN, Si ₃ N ₄ , SiC)
[6] An electronic material comprising the composition according to any one of [1] to [5].
[7] A printing material comprising the composition according to any one of [1] to [5].
[8] A conductive electronic material comprising the composition according to [4].
[9] A dielectric electronic material comprising the composition according to [5].

The composition of the present invention exhibits the effect that the carbon powder or ceramic powder is stably dispersed in the dispersion medium and does not separate or aggregate even after long-term storage without impairing the properties of the carbon powder or ceramic powder itself.
In addition, the composition of the present invention has an effect that it can be sufficiently used for applications in the field of electronic materials where it is not preferable that the dispersant contains a metal salt.

Hereinafter, the present invention will be described in detail.
The composition of the present invention is a composition containing a compound represented by a specific general formula (1) (or (2)) and carbon powder or ceramic powder.

[Compound shown in general formula (1)]
The compound represented by the following general formula (1) will be described.

In the general formula (1), R ¹ is a hydrocarbon group having 1 to 23 carbon atoms. Preferably, it is a hydrocarbon group having 7 to 17 carbon atoms.
In general formula (1), R ² or, a carboxylic acid group or a hydrocarbon group having carbon atoms of 1 to 3 have a sulfonic acid group.
Specific examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxy (iso) propyl group, a dihydroxy (iso) propyl group, a carboxymethyl group, and a carboxyethyl group. , Carboxypropyl group, sulfoethyl group and the like.
R ² is preferably hydrogen.

  In general formula (1), Y is a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, or a salt thereof. Preferably, it is a carboxyl group or a salt thereof.

  Y can form salts with various basic substances. Specific examples of metals that can form salts are given below.

Examples of the alkali metal include sodium, potassium, and lithium. Examples of the alkaline earth metal include calcium and magnesium. Examples of metals other than those described above include salts of aluminum, zinc, iron, cobalt, titanium, zirconium, silver, and the like.
Moreover, although it does not specifically limit as a basic substance containing the above-mentioned metal, The following are mentioned.

  Examples of the organic amine salt include salts of ammonia, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, and the like.

Examples of basic amino acid salts include arginine and lysine salts.
Other examples include ammonium salts and polyvalent metal salts.
Moreover, in General formula (1), Y may contain the 1 type, or 2 or more types of salt arbitrarily chosen from said salt.

  In the general formula (1), Z is —NR′— (R ′ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms), —O—, or —S—.

  In the general formula (1), j and k are either 0, 1 or 2, and j and k are not 0 at the same time, and n represents an integer of 2 to 20.

Next, X in the general formula (1) will be described.
X is a hydrocarbon chain having a molecular weight of 1 million or less which may have a substituent. X may be a straight chain, a branched chain, a cyclic chain, or an aromatic hydrocarbon chain. X may have a substituent, and particularly preferably has a carboxyl group. The number of carbon atoms in X is preferably 1 to 40, and the molecular weight is preferably 28 to 2000.

In addition, when X contains a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, or the like, salts may be formed with various basic substances. Examples of the metal capable of forming a salt and the basic substance containing the metal include those described above. Moreover, there are n parts in parentheses in the general formula (1), which may be the same or different.
The compound represented by the general formula (1) is a gemini-type surfactant compound having two or more hydrophilic groups Y and two or more hydrophobic groups R ¹ CO.

  The compound represented by the following general formula (2) is an example in the case of n = 2 in the compound represented by the general formula (1). A composition using the compound is particularly preferable because excellent dispersibility and dispersion stability are observed.

In the general formula (2), X ′ is a carboxyl group or a salt thereof, —NHR ′ group (R ′ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms), —OH group, or —SH group. The C1-C20 hydrocarbon chain which has any one is shown. R ¹ , R ² , Y, Z, j, and k are the same as those in the general formula (1).
In addition, when using the compound represented by the general formula (1) or (2) in the non-aqueous composition of the present invention that does not contain water, in the general formula (1) or (2), Y is From the viewpoint of solubility, it is preferable to use a compound that is a carboxyl group, a sulfonic acid group, a sulfate ester group, or a phosphate ester group. For example, in the non-aqueous composition of the present invention, it is preferable to use an unneutralized product obtained without neutralization after the reaction in the production method described later.
Further, when the composition of the present invention is used for an electronic material application, in the compound of the general formula (1) or (2), a metal such as an unneutralized compound, an organic amine salt, a basic amino acid salt, or an ammonium salt It is preferable to be in a salt state not containing. That is, in the compound of the general formula (1) or (2), Y is more preferably a carboxyl group, an organic amine salt, a basic amino acid salt, or an ammonium salt. When X or X ′ has a carboxyl group or a salt thereof, the form is more preferably a carboxyl group, or an organic amine salt, a basic amino acid salt, or an ammonium salt. For example, as such a compound, “Perisea (registered trademark) L-30” (manufactured by Asahi Kasei Chemicals Corporation) may be mentioned as a commercial product.

[Method for producing compound represented by general formula (1)]
As a method for producing the compound represented by the general formula (1), an N-acyl acidic amino acid anhydride represented by the following general formula (3) and m functional groups selected from a hydroxyl group, an amino group, and a thiol group are used. There is a method in which a compound represented by the general formula (1) is obtained by reacting a compound having a molecular weight of 1 million or less (hereinafter referred to as m-valent compound) having m (m is n or more).

The N-acyl acidic amino acid anhydride represented by the general formula (3) is an anhydride in which an acidic amino acid is N-acylated. The N-acyl acidic amino acid anhydride may be any of D-form, L-form, and racemate which are optical isomers.
In particular, an L-acidic amino acid which is an L-form is preferable because of its excellent biodegradability.

Acidic amino acids are those having more carboxyl groups than amino groups in the molecule. For example, monoaminodicarboxylic acid having 2 and 1 carboxyl groups and amino groups, respectively, can be mentioned.
The hydrogen of the amino group may be substituted with a hydrocarbon group having 1 to 3 carbon atoms.
Specific examples of the acidic amino acid include glutamic acid and aspartic acid.

  The m-valent compound is a compound having a molecular weight of 1,000,000 or less having m functional groups selected from a hydroxyl group, an amino group, and a thiol group (m ≧ n and an integer of 2 to 20). Here, the m-valent compound can form a bond derived from m functional groups. That is, a hydroxyl group can create an ester bond, an amino group can create an acid amide bond, and a thiol group can create a thioester bond. Further, this compound may have a substituent other than the above-described functional group.

  Specific examples of such m-valent compounds include the following. Specific examples of the compound having two or more hydroxyl groups in the molecule include the following.

  Examples of the divalent hydroxyl compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, pentanediol, , 6-hexanediol, cyclohexanediol, dimethylolcyclohexane, neopentyl glycol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, isoprene glycol, 3-methyl-1,5- Pentanediol, sorbite, catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, dimer diol, dimethylolpropionic acid, dimethylolbutanoic acid, tartaric acid, dihydroxytartaric acid, mevalon , 3,4-dihydroxy cinnamic acid, 3,4-dihydroxy-hydro cinnamic acid, hydroxy benzoic acid, dihydroxy stearic acid, dihydroxyphenylalanine and the like.

  Examples of the trivalent hydroxyl compound include glycerin, trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, and 2-methyl-2. , 3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptane Triol, 2,4-dimethyl-2,3,4-pentanetriol, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylolethane, trimethylolpropane, diethanolamine, triethanolamine and triol Examples thereof include hydroxystearic acid.

  Examples of tetravalent hydroxyl compounds include pentaerythritol, erythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, , 3,4,5-hexanetetrol, diglycerin, sorbitan and the like.

  Examples of pentavalent hydroxyl compounds include adonitol, arabitol, xylitol, and triglycerin.

  Examples of the hexavalent hydroxyl compound include dipentaerythritol, sorbitol, mannitol, iditol, inositol, dulcitol, talose, and allose.

  Or the dehydration condensate of above-mentioned 2-6 valent hydroxyl compounds, polyglycerol, etc. are mentioned.

  Examples of the m-valent polyhydroxyl compound include saccharides. Specific examples are given below.

Examples of tetrose include erythrose, sreose and erythrulose.
Examples of pentose include ribose, arabinose, xylose, lyxose, xylulose and ribulose.
Examples of monosaccharides include hexose such as allose, altrose, glucose, mannose, guylose, idose, galactose, talose, fructose, sorbose, psicose and tagatose.
Examples of the oligosaccharide include maltose, isomaltose, cellobiose, gentiobiose, melibiose, lactose, tulanose, trehalose, saccharose, mannitolose, cellotriose, gentianose, raffinose, meretitol, cellotetorose, and stachyose.

  Other sugars include residues such as heptose, deoxy sugar, amino sugar, thio sugar, seleno sugar, aldone sugar, uronic acid, sugar acid, ketoaldonic acid, anhydro sugar, unsaturated sugar, sugar ester, sugar ether and glycoside. Alternatively, polysaccharides such as starch, glycogen, cellulose, chitin, and chitosan, or those obtained by hydrolyzing the above saccharides may be used.

  Specific examples of the compound having two or more amino groups in the molecule include the following.

  Aliphatic diamines include N, N′-dimethylhydrazine, ethylenediamine, N, N′-dimethylethylenediamine, diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminoheptane, diaminooctane, diaminononane, diaminodecane, diaminododecane , Diaminoadipic acid, diaminopropanoic acid, diaminobutanoic acid and the like.

  Aliphatic triamines include diethylenetriamine, triaminohexane, triaminododecane, 1,8-diamino-4-aminomethyl-octane, 2,6-diaminocapric acid-2-aminoethyl ester, 1,3,6- Examples include triaminohexane, 1,6,11-triaminoundecane, and di (aminoethyl) amine.

  Examples of the alicyclic polyamines include diaminocyclobutane, diaminocyclohexane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, and triaminocyclohexane.

  Examples of aromatic polyamines include diaminobenzene, diaminotoluene, diaminobenzoic acid, diaminoanthraquinone, diaminobenzenesulfonic acid, diaminobenzoic acid and the like.

  Examples of the araliphatic polyamines include diaminoxylene, di (aminomethyl) benzene, di (aminomethyl) pyridine, and di (aminomethyl) naphthalene. Moreover, the polyamines which substituted the hydroxyl group to the above-mentioned amine derivatives like diaminohydroxypropane etc. are mentioned.

  Examples of amino acids include serine, threonine, cysteine, cystine, cystine disulfoxide, cystathionine, methionine, arginine, lysine, tyrosine, histidine, tryptophan, and oxyproline. These amino acids may be proteins, peptides, etc., or hydrolyzed ones thereof.

  Specific examples of the compound having two or more thiol groups in the molecule include dithiol compounds such as dithioethylene glycol, dithioerythritol and dithiothreitol. Here, the m-valent compound may have two or more functional groups selected from a hydroxyl group, an amino group, and a thiol group. Examples are given below.

Examples of the compound having an amino group and a hydroxyl group in the molecule include aminoethanol, aminopropanol, aminobutanol, aminopentanol, aminohexanol, aminopropanediol, aminoethylethanolamine, aminoethylaminoethanol, aminocresol, aminonaphthol, Examples include aminonaphtholsulfonic acid, aminohydroxybenzoic acid, aminohydroxybutanoic acid, aminophenol, aminophenethyl alcohol, and glucosamine.
Examples of the compound having a thiol group and a hydroxyl group in the molecule include mercaptoethanol, mercaptophenol, mercaptopropanediol, and glucothiose.
Examples of the compound having a thiol group and an amino group in the molecule include aminothiophenol and aminotriazole thiol.

The m-valent compound may be any of the optical isomers D-form, L-form, and racemate, and may be each isomer.
Further, among m-valent compounds, those having 1 to 40 carbon atoms are preferable, and those having 1 to 20 carbon atoms are more preferable.
In addition, since naturally occurring compounds are more biodegradable, the m-valent compounds are preferably amino acids, peptides, saccharides and the like.
When reacting the N-acyl acidic amino acid anhydride and the m-valent compound, a solvent may be used. Examples of the solvent used in the reaction include water, a mixed solvent of water and an organic solvent, or an inert solvent such as tetrahydrofuran, benzene, toluene, xylene, carbon tetrachloride, chloroform, and acetone. The reaction temperature is preferably −5 ° C. to 200 ° C. and mixed and reacted at a temperature equal to or higher than the melting point of the above compound.

  As another method for producing the compound represented by the general formula (1), not an N-acyl acidic amino acid anhydride but an N-acyl acidic amino acid mono-lower ester (for example, methyl ester, ethyl ester) and the above m-valent Examples thereof include a method of reacting a compound to obtain the compound represented by the general formula (1).

  For example, N-acyl acidic amino acid mono-lower ester and m-valent compound are dissolved in a suitable solvent such as dimethylformamide, a catalyst such as potassium carbonate is added, and the reaction is heated at -5 to 250 ° C. under reduced pressure. Then, the compound represented by the general formula (1) is obtained by removing the reaction solvent. The compound represented by the general formula (1) can also be obtained by heating and melting without solvent without using a solvent, adding a catalyst such as sodium hydroxide, and carrying out a transesterification reaction at room temperature to 250 ° C. .

[Carbon powder, ceramic powder]
The carbon powder or ceramic powder used in the present invention is not particularly limited depending on the production method and surface modification. Moreover, what is pulverized using a ball-type kneading apparatus such as a ball mill, a vibration mill, a sand mill, or a roll mill, or one that has been cut short by chemical or physical treatment can be used.
The carbon powder or ceramic powder used in the present invention is specifically as follows.
Carbon powders include carbon nanotubes (single-walled carbon nanotubes, multi-walled carbon nanotubes), carbon nanocoils, carbon nanofibers, fullerenes, isotropic graphite, anisotropic graphite, graphite (artificial graphite, natural graphite, mesocarbon microbeads) ), Hard carbon, and the like.
Examples of the ceramic powder include the following. The ceramic powder is composed of one or more of the following.
Titanium oxide, various titanate porcelain powders (for example, barium titanate, barium calcium titanate, strontium titanate, lead titanate), zirconate porcelain powders (for example, dielectric ceramic raw material powders such as barium zirconate) ) And the like, and barium titanate as a main component, and oxides (for example, oxides of Mn, Cr, Si, Ca, Ba, Mg, V, W, Ta, Nb and one or more rare earth elements) are added. Ceramic powder, etc. included in the component, and ceramic powder of perovskite oxide ferroelectrics in which Ba atoms and Ti atoms of barium titanate (BaTiO ₃ ) are substituted with other atoms (for example, Sn, Pb, Zr, etc.) Other ceramic powders include ZnO, ferrite, PZT, BaO, Al ₂ O ₃ , Bi ₂ O ₃ , R (rare earth element) ₂ O _3. , TiO ₂ , Nd ₂ O ₃ , 2MgO · SiO ₂ , ZrO ₂ , ZrO ₂ · SiO ₂ , 3Al ₂ O ₃ · 2SiO ₂ , MgO · SiO ₂ , 2MgO · 2Al ₂ O ₃ · 5SiO ₂ Powder, ferrite magnetic powder such as Ni—Cu—Zn ferrite, Ni—Zn ferrite, Cu—Zn ferrite, superconducting ceramic powder such as Y ₁ Ba ₂ Cu ₃ O ₇ , Bi ₂ Sr ₂ Ca ₂ Cu ₃ O ₁₀ , Titanium oxide nanotubes, AlN, Si ₃ N ₄ , SiC, Y ₂ O ₃ , TiC / TiN, spinel, silica, MgO, CaO, sillimanite, apatite and other calcium phosphate ceramics, aluminum titanate, boron carbide, beryllia, CaO · SiO _3, boron _{nitride, LaB 6, Li 2 O ·} Al 2 O 3 · It includes SiO _2, lithium niobate, lithium tantalate, molybdenum silicide, lead lanthanum zirconate titanate, sialon, titanium boride, titanium carbide, titanium nitride, tungsten carbide, zirconium boride, magnesium carbonate, barium carbonate, and the like It is done.

<Carbon nanotube>
The carbon nanotube is not particularly limited as long as it is a carbon nanotube. Examples of the carbon nanotube include a single-walled carbon nanotube, a multi-layered carbon nanotube in which several layers are concentrically overlapped, and these are coiled. Things can be used.
Further, carbon nanohorns having a shape in which one side of the carbon nanotube is closed, a cup-shaped nanocarbon material having a hole in the head thereof, and the like can also be used.
In the case of a composition containing carbon nanotube powder, the composition of the present invention includes a compound containing no metal salt represented by the general formula (1) or (2) as a dispersant. As an application to the field of electronic materials where it is not preferable to contain, there is an advantage that it can be used sufficiently.

<Barium titanate>
In the case of a composition containing barium titanate powder, a coating liquid containing the compound represented by the general formula (1) or (2) as a dispersant is used, so that the barium titanate particles are contained in the medium in the coating liquid. Can be dispersed stably.
The coating liquid has high fluidity, and the compound represented by the general formula (1) or (2) can be used in a polar organic solvent.
From the above, the composition of the present invention is very effective as a coating liquid for forming a dielectric layer of a multilayer ceramic capacitor.

[Composition of the present invention]
In the present invention, the mass ratio of the compound represented by the general formula (1) or (2) and the carbon powder or ceramic powder is such that the general formula (1) or (2) is 0.01% to the powder. It is preferably 500%.
In addition, the compound represented by the general formula (1) or (2) may be used separately from the carbon powder or ceramic powder, or directly treated on the surface of the carbon powder or ceramic powder, or using other compounds. It may be used by chemically bonding to the surface. This utilization method can be used for other powders (pigments, metals, resins, etc., as long as the powder is not particularly limited).
The composition of the present invention is optimal for use in paints, electronic materials, coated paper, resin materials, industrial abrasives, and the like. In particular, application to electronic materials is preferable.
As applications to electronic materials, in particular, dielectric materials such as multilayer capacitors obtained by firing the composition of the present invention after being molded by a method such as extrusion, insulating materials for multilayer wiring boards for electronic circuits, electrodes for various batteries Suitable for applications such as conductive materials such as conductive paste, conductive film, piezoelectric materials such as sensors and piezoelectric elements, magnetic materials such as transformer cores and coils of electronic components, and heat conductive materials such as semiconductor packages .
As the use of the resin material, the composition of the present invention is suitable for the antistatic or reinforcement use of resins such as a transport tray and an automobile fuel tube.
The composition of the present invention stably disperses without impairing the properties such as conductivity of the carbon powder or ceramic powder, and does not separate or aggregate even during long-term storage.
In addition, since the present composition can be produced even with a small amount of the compound represented by the general formula (1) or (2), it is possible to lower the firing temperature when used for electrical materials.
Furthermore, since the dispersibility is good, it is possible to coat smoothly and thinly.

Moreover, various substances can be added to the composition of the present invention as needed.
For example, dispersion medium, conductive polymer, polymer compound, basic compound, surfactant, silane coupling agent, organopolysiloxane, colloidal silica, plasticizer, dispersant, coating surface conditioner, fluidity conditioner, ultraviolet light Absorbers, antioxidants, storage stabilizers, adhesion aids, thickeners, conductive materials, binder resins, plasticizers, polymer dispersants, antifoaming agents, auxiliaries, leveling agents, liquid coating formation Elements, solid film forming elements, desiccants, curing agents, emulsifiers, thickeners, anti-skinning agents, insecticides, pigments, subcomponent powders, and the like can be blended.
In the present invention, two or more additive components can be used in combination.

The dispersion medium is not particularly limited as long as it dissolves or disperses the compound represented by the general formula (1), carbon powder or ceramic powder, and various additive substances.
Specifically, alcohols such as water, methanol, ethanol, isopropyl alcohol, propyl alcohol, butanol and butyl alcohol; ketones such as acetone, methyl ethyl ketone, ethyl isobutyl ketone, methyl isobutyl ketone and cyclohexanone; ethylene glycol, diethylene glycol, Ethylene glycols such as ethylene glycol, ethylene glycol methyl ether, ethylene glycol mono-n-propyl ether; propylene glycols such as propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycol propyl ether; polyethylene Glycol, dipropylene glycol, tripropylene glycol Polyoxyethylene or polyoxypropylene addition polymers such as coal and polypropylene glycol; Ethers such as polyethylene glycol monomethyl ether, tetrahydrofuran, dioxane and methyl cellosolve; Ether alcohols such as ethoxyethanol and methoxyethoxyethanol; N, N Amides such as dimethylformamide and N, N-dimethylacetamide; amines such as triethylamine and trimethanolamine; pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone; dimethylsulfoxide, γ-butyrolactone, methyl lactate, Hydroxyesters such as ethyl lactate, methyl β-methoxyisobutyrate, methyl α-hydroxyisobutyrate; methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl Glycol ether solvents such as Rosolve; alkylene glycols such as 1,2,6-hexanetriol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ether acetates such as ether acetate and dipropylene glycol monomethyl ether acetate; acetates such as ethyl acetate, butyl acetate, isobutyl acetate and propyl acetate; lactates such as lactate methyl ester, lactate ethyl ester and lactate propyl ester; ethylene Cyclic esters such as carbonate, propylene carbonate, γ-butyrolactone; aniline, N-methyl Anilines such as ruaniline; aromatic hydrocarbons such as benzene, toluene and xylene; chlorine-containing hydrocarbons such as methylene chloride, chloroform and chlorobenzene; m-cresol, acetonitrile, cyclohexane, glycerin, 2-pyrrolidone, terpineol, dihydroter Pinyl acetate, isobornyl acetate, isobornyl propinate, isobornyl butyrate, isobornyl isobutyrate.

The polymer compound is not particularly limited as long as it can be dissolved or dispersed (emulsion formation) in the solvent used in the present invention.
Specifically, polyvinyl alcohols such as polyvinyl alcohol, polyvinyl formal, and polyvinyl butyral; polyacrylamides such as polyacrylamide, poly (Nt-butylacrylamide), polyacrylamide methylpropanesulfonic acid; polyvinylpyrrolidones , Polystyrene sulfonic acid and its soda salts, cellulose, alkyd resin, melamine resin, urea resin, phenol resin, epoxy resin, polybutadiene resin, acrylic resin, urethane resin, vinyl ester resin, urea resin, polyimide resin, maleic acid resin, polycarbonate Resin, vinyl acetate resin, chlorinated polyethylene resin, chlorinated polypropylene resin, styrene resin, acrylic / styrene copolymer resin, vinyl acetate / acrylic copolymer resin, poly Ester resins, styrene / maleic acid copolymer resin, fluorine resin, cellulose, polyacrylonitrile, pitch and their copolymers are used. In addition, these polymer compounds may be a mixture of two or more kinds in any ratio.
In the case of finally obtaining a carbon nanotube-containing carbon material, cellulose, polyacrylonitrile, pitch, and copolymers thereof are preferable in terms of easiness of firing.

Although it does not specifically limit as a basic compound, For example, ammonia, an aliphatic amine, cyclic saturated amines, cyclic unsaturated amines, ammonium salts, an inorganic base, etc. are used preferably.
As cyclic saturated amines, piperidine, pyrrolidine, morpholine, piperazine, derivatives having these skeletons, and ammonium hydroxide compounds thereof are preferably used.
As the cyclic unsaturated amines, pyridine, α-picoline, β-picoline, γ-picoline, quinoline, isoquinoline, pyrroline, derivatives having these skeletons, and ammonium hydroxide compounds thereof are preferably used.
As the inorganic base, hydroxide salts such as sodium hydroxide, potassium hydroxide and lithium hydroxide are preferably used.

  The surfactant is not particularly limited. For example, alkyl sulfonic acid, alkyl benzene sulfonic acid, alkyl carboxylic acid, alkyl naphthalene sulfonic acid, α-olefin sulfonic acid, dialkyl sulfosuccinic acid, α-sulfonated fatty acid, N-methyl-N-oleyl taurine, petroleum sulfonic acid, alkyl sulfuric acid, sulfated oil, polyoxyethylene alkyl ether sulfuric acid, polyoxyethylene styrenated phenyl ether sulfuric acid, alkyl phosphoric acid, polyoxyethylene alkyl ether phosphoric acid, polyoxy Anionic surfactants such as ethylene alkylphenyl ether phosphoric acid, naphthalenesulfonic acid formaldehyde condensates and their salts; primary to tertiary aliphatic amines, quaternary ammonium, tetraalkylammonium, trial Killbenzylammoniumalkylpyridinium, 2-alkyl-1-alkyl-1-hydroxyethylimidazolinium, N, N-dialkylmorpholinium, polyethylene polyamine fatty acid amide, urea condensate of polyethylene polyamine fatty acid amide, polyethylene polyamine fatty acid amide Cationic surfactants such as quaternary ammonium of urea condensates and their salts; N, N-dimethyl-N-alkyl-N-carboxymethylammonium betaine, N, N, N-trialkyl-N-sulfoalkylene Betaines such as ammonium betaine, N, N-dialkyl-N, N-bispolyoxyethylene ammonium sulfate betaine, 2-alkyl-1-carboxymethyl-1-hydroxyethylimidazolinium betaine; N Amphoteric surfactants such as aminocarboxylic acids such as N-dialkylaminoalkylenecarboxylates; polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene-polyoxypropylene glycol, Polyoxyethylene-polyoxypropylene alkyl ether, polyhydric alcohol fatty acid partial ester, polyoxyethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, polyoxyethylenated castor oil, fatty acid diethanolamide, poly Nonionic surfactants such as oxyethylene alkylamine, triethanolamine fatty acid partial ester, trialkylamine oxide; and Fluoroalkyl carboxylic acids, perfluoroalkyl carboxylic acids, perfluoroalkyl benzene sulfonic acids, fluorine-based surfactants such as perfluoroalkyl polyoxyethylene ethanol is used. Here, the alkyl group preferably has 1 to 24 carbon atoms, and more preferably 3 to 18 carbon atoms.

The silane coupling agent is not particularly limited, but methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane Alkoxysilanes such as hexyltriethoxysilane, octyltriethoxysilane, tetraethoxysilane and tetramethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane , Γ-mercaptopropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycid Shi propyl methyl dimethoxy silane, .gamma.-chloropropyl trimethoxy silane, and the like.
Examples of those having an epoxy group include γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropylmethyldimethoxysilane, and γ-glycidyloxypropyltriethoxysilane.
Examples of those having an amino group include γ-aminopropyltriethoxysilane, β-aminoethyltrimethoxysilane, and γ-aminopropoxypropyltrimethoxysilane.
Examples of those having a thiol group include γ-mercaptopropyltrimethoxysilane and β-mercaptoethylmethyldimethoxysilane.
Examples of those having a hydroxyl group include β-hydroxyethoxyethyltriethoxysilane and γ-hydroxypropyltrimethoxysilane.
Examples of those having an epoxycyclohexyl group include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

  Examples of the organopolysiloxane include polysiloxane, methyl hydrogen polysiloxane, and modified polysiloxane.

Although it does not specifically limit as colloidal silica, What is disperse | distributed to the mixed solvent of water, an organic solvent, or water and an organic solvent is used preferably.
Examples of the organic solvent include, but are not limited to, alcohols such as methanol, ethanol, isopropyl alcohol, propyl alcohol, butanol, and pentanol; ketones such as acetone, methyl ethyl ketone, ethyl isobutyl ketone, and methyl isobutyl ketone; ethylene glycol, Ethylene glycols such as ethylene glycol methyl ether and ethylene glycol mono-n-propyl ether; propylene glycols such as propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether and propylene glycol propyl ether are preferably used. .
Further, as the colloidal silica, those having a particle diameter of 1 nm to 300 nm, preferably 1 nm to 150 nm, more preferably from the viewpoint of avoiding the problem that the hardness is insufficient and the solution stability of the colloidal silica itself is lowered. Those having a range of 1 nm to 50 nm are preferably used.

  The conductive substance is not particularly limited, and examples thereof include carbon-based substances such as carbon fiber, conductive carbon black, and graphite, metal oxides such as tin oxide and zinc oxide, and metals such as silver, nickel, and copper.

  Although it does not specifically limit as binder resin, Acrylic resin, polyvinyl butyral resin, butyral resin, vinyl-type non-curable resin such as polyvinyl alcohol, phenol resin, alkyd resin, rosin ester, ethyl cellulose, ethyl hydroxyethyl cellulose and derivatives thereof The various cellulose derivatives are mentioned.

  The plasticizer is not particularly limited, but phthalic acid esters such as benzyl butyl phthalate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, dipropyl phthalate, dicyclohexyl phthalate, dioctyl adipate, adipine Examples include adipic acid esters such as diisononyl acid, sebacic acid esters such as dibutyl sebacate and dioctyl sebacate, tricresyl phosphate, and n-hydroxymethylphthalimide.

Examples of the polymer dispersant include styrene-acrylic acid copolymers, styrene-maleic acid copolymers, polycarboxylic acids and salts thereof.
Examples of the auxiliary component powder include powders of compounds such as oxides and carbonates containing any one element of Mg, Ba, Ca, Si, Mn, Al, V, Dy, Y, Ho, and Yb. As for the powder of such a compound, 1 type may be used and 2 or more types may be used together.

[Method for producing composition of the present invention]
When mixing these components, there is no particular limitation as long as they can be mixed, but ultrasonic, homomixer, homogenizer, spiral mixer, planetary mixer, disperser, hybrid mixer, ball mill, sand grinder, roller mill, high-speed rotary mill, classification Built-in high-speed rotary mill, ball mill, medium agitating mill, airflow mill, compaction shear mill, colloid mill, roll mill, bead mill, sand mill, media mill, paint conditioner, attritor, pearl mill, coball mill, basket mill, wet jet A stirring device, a kneading device, and a dispersing device such as a mill and a media type disperser (glass beads, zirconia beads, alumina beads, magnetic beads, stainless beads) are used.

  Hereinafter, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to only these examples.

  The compound represented by the general formula (1) was produced by the method described below.

[Production Example 1]
9.1 g (0.05 mol) of L-lysine hydrochloride was mixed with 57 g of water. This liquid was stirred while adjusting the pH range to 10 to 11 with a 25% aqueous sodium hydroxide solution and maintaining the reaction temperature at 5 ° C. Under stirring, 31.1 g (0.1 mol) of N-lauroyl-L-glutamic anhydride was added over 2 hours to carry out the reaction. Thereafter, stirring was continued for another 30 minutes, and tertiary butanol was added to a concentration of 20% by mass in the liquid, 75% sulfuric acid was added dropwise to adjust the pH value of the liquid to 2, and the liquid temperature was adjusted to 65. Adjusted to ° C. After completion of the sulfuric acid addition, stirring was stopped, and the mixture was allowed to stand at 65 ° C. for 20 minutes to separate into an organic layer and an aqueous layer, and the organic layer was separated therefrom. Tertiary butanol and water were added to the separated organic layer, the temperature was raised to 65 ° C., and the mixture was stirred for 20 minutes. After the stirring was stopped, the mixture was allowed to stand to separate into an organic layer and an aqueous layer. After repeating the same water washing operation described above for the obtained organic layer, the solvent was removed from the obtained organic layer, and the resulting solution was made into an aqueous solution having a solid content of 30% by mass and pH 6.5 (25 ° C.) with sodium hydroxide. After neutralization and preparation, this was dried to obtain a compound represented by the following formula (4).

In the reaction of N-lauroyl-L-glutamic anhydride and L-lysine hydrochloride, four types of compounds are produced as shown by the following formula (4) depending on the way of binding.

(In Formula 4, R is a hydrocarbon group having 11 carbon atoms, and M is each independently H or Na)

[Production Example 2]
The same procedure as in Production Example 1 was performed except that 31.1 g of N-lauroyl-L-glutamic acid anhydride was changed to 31.1 g of N-cocoyl-L-glutamic acid anhydride in Production Example 1.

[Production Example 3]
In the manufacture example 1, it implemented on the same conditions as the method of the manufacture example 1 except having implemented the neutralization process with ammonia aqueous solution.

[Production Example 4]
In the manufacture example 1, it implemented on the same conditions as the method of manufacture example 1 except not having implemented the neutralization process, and the unneutralized body was obtained.

[Evaluation test method]
(Solution state)
After the preparation of the composition, the solution state after 24 hours was visually observed.
○: Uniformly dispersed or dissolved.
X: Unevenly dispersed.
(Dispersion granularity)
The average particle diameter (D50 value) was measured using a dynamic light scattering particle size distribution meter ("Microtrack UPA" manufactured by Nikkiso Co., Ltd.). Water or methyl ethyl ketone (hereinafter referred to as MEK) was used as a dilution solvent. The storage stability was evaluated by measuring the dispersion particle size after storing the dispersion at 40 ° C. for 10 days.
(Liquidity)
Judgment was made based on whether the composition was liquid or gel (purine).
○: Liquid ×: Gel (Dispersibility evaluation method)
Viscosity was measured under conditions of 25 ° C. and a shear rate of 10 sec ⁻¹ (using Brookfield DV-II). Those having a lower viscosity have better dispersibility than those having a higher viscosity.
(Antistatic property)
A table-type precision testing machine equipped with a 90-degree peel test jig with the release film cut into a 4 cm x 10 cm test piece and the side opposite the coating surface (film side) facing down It fixed to the base of Shimadzu Corporation autograph AGS-X) using the double-sided tape. Next, after slightly peeling one end of the ceramic sheet from the release film, it peeled 90 degrees at a rate of 1 cm / second, and the electrostatic charge was placed 3 cm away from the maximum charge amount on the peeling surface side of the ceramic sheet. It measured with the sensor (Keyence SK-200). The smaller the peel charge amount, the better the antistatic property.

[Example 1]
Carbon nanotube dispersant composition 1 was prepared by mixing 0.1 part by mass of the compound of Production Example 1, 0.1 part by mass of carbon nanotubes, and 99.8 parts by mass of N, N-dimethylacetamide at room temperature. The results are shown in Table 1.

[Example 2]
Carbon nanotube dispersant composition 2 was prepared by mixing 0.1 part by mass of the compound of Production Example 3, 0.1 part by mass of carbon nanotubes, and 99.8 parts by mass of N-methylpyrrolidone at room temperature. The results are shown in Table 1.

[Example 3]
Carbon nanotube dispersant composition 3 was prepared by mixing 0.1 part by mass of the compound of Production Example 4, 0.1 part by mass of carbon nanotubes, and 99.8 parts by mass of N-methylpyrrolidone at room temperature. The results are shown in Table 1.

[Comparative Example 1]
Carbon nanotube dispersant composition 4 was prepared by mixing 0.1 parts by mass of carbon nanotubes and 99.8 parts by mass of N-methylpyrrolidone at room temperature. The results are shown in Table 1.

[Example 4]
Carbon nanotubes (diameter 10 nm, length 10 μm) 1.0 g, 1 g of the compound of Production Example 3 above, and MEK 27.9 g were charged into a 70 cc glass bottle, and dispersed for 1 hour using a paint shaker with zirconia beads as a medium. Dispersant composition 5 was obtained. This dispersion was diluted with MEK, and the dispersion particle size was measured. The results are shown in Table 2.

[Example 5]
Carbon nanotubes (diameter 10 nm, length 10 μm) 1.0 g, 0.1 g of the compound of Production Example 4 above and 27.85 g of toluene are charged into a 70 cc glass bottle and dispersed for 1 hour using a paint shaker with zirconia beads as media. The carbon nanotube dispersion liquid of the present invention was obtained. This dispersion was diluted with MEK, and the dispersion particle size was measured. The results are shown in Table 2.

[Comparative Example 2]
Carbon nanotubes (diameter 10 nm, length 10 μm) 1.0 g and MEK 29.0 g were charged into a 70 cc glass bottle and dispersed using a paint shaker for 1 hour using zirconia beads as a medium to obtain a carbon nanotube dispersion. This dispersion was diluted with MEK, and the dispersion particle size was measured. The results are shown in Table 2.

[Example 6]
(Preparation of carbon nanotube aggregate dispersion)
Weigh 10 mg of carbon nanotubes and 100 mg of an aqueous solution (30% by weight) of the compound of Production Example 3 in a 50 mL container, add 9.93 mL of distilled water, and disperse under ultrasonic cooling with an ultrasonic homogenizer output of 25 W for 20 minutes. A carbon nanotube assembly liquid was prepared. Aggregates could not be visually confirmed in the prepared liquid, and the carbon nanotube aggregates were well dispersed.

(Transparent conductive film containing carbon nanotube aggregates)
After adding 300 μL of methanol / water (weight ratio 1/1) as a wetting agent to 300 μL of the carbon nanotube aggregate dispersion obtained above, a polyethylene terephthalate (PET) film (manufactured by Toray Industries, Inc. (Lumirror® U36) ), Light transmittance 90.7%, 15 cm × 10 cm) using a bar coater (No. 8, coating thickness 12 μm), air-dried, rinsed with distilled water, and 2 in a 60 ° C. dryer. The carbon nanotube aggregate was fixed by drying for a minute. The obtained coated film has a surface resistance value of 1.2 × 10 ³ Ω / □, a light transmittance of 85% (transparent conductive film 85% / PET film 90.7% = 0.94), and high conductivity. Showed transparency and transparency.

[Example 7]
40 parts by mass of barium titanate having an average primary particle diameter of 20 nm, 6 parts by mass of the compound of Production Example 2, and 54 parts by mass of propyl acetate were ground with zirconia beads having a diameter of 0.3 mm using a paint shaker, A barium titanate dispersion composition 1 was obtained. The results are shown in Table 3.

[Example 8]
40 parts by mass of barium titanate having an average primary particle diameter of 20 nm, 0.1 part by mass of the compound of Production Example 3, and 59.9 parts by mass of propyl acetate are coated with zirconia beads having a diameter of 0.3 mm using a paint shaker. The meat was kneaded to obtain a barium titanate dispersion composition 2. The results are shown in Table 3.

[Example 9]
40 parts by mass of barium titanate having an average primary particle diameter of 20 nm, 1 part by mass of the compound of Production Example 4 and 59 parts by mass of propyl acetate were ground with zirconia beads having a diameter of 0.3 mm using a paint shaker, A barium titanate dispersion composition 3 was obtained. The results are shown in Table 3.

[Example 10]
A Henschel mixer was charged with 40 parts by mass of barium titanate having an average primary particle size of 20 nm, and then 1 part by mass of the compound of Production Example 4 dissolved in 50 parts of ethanol was added dropwise and mixed well. Thereafter, the interior of the Henschel mixer was heated and decompressed to remove ethanol. It was taken out from the Henschel mixer and pulverized to obtain barium titanate treated with 1 part by mass of the compound of Production Example 4.
59 parts by mass of propyl acetate was added to the surface-treated barium titanate, and kneaded with zirconia beads having a diameter of 0.3 mm using a paint shaker to obtain a barium titanate dispersion composition 4. The results are shown in Table 3.

[Comparative Example 3]
40 parts by mass of barium titanate having an average primary particle diameter of 20 nm, 6 parts by mass of a polycarboxylic acid dispersant (G700, manufactured by Kyoeisha Chemical Co., Ltd.), and 54 parts by mass of propyl acetate are Φ (diameter) 0 with a paint shaker. The mixture was kneaded with 3 mm zirconia beads to obtain a barium titanate dispersion composition 4. The results are shown in Table 3.

[Example 11]
20 g of barium titanate (average particle size calculated from BET specific surface area of 50 nm) and 0.4 g of the compound of Production Example 4 are placed in a 100 mL container together with 50 g of zirconia beads having a diameter of 1 mm, and toluene / ethanol = 48/52 (volume) The mixture was adjusted so that the solid content concentration of barium titanate was 50%, and dispersion treatment was performed for 96 hours in a table-top ball mill. Next, 1.6 g of butyral resin, 0.32 g of dioctyl phthalate as a plasticizer, 0.16 g of 1-ethyl-3-hydroxymethylpyridinium ethyl sulfate, and a mixed solvent of toluene / ethanol = 48/52 (volume ratio) were added. Then, the solid content concentration of barium titanate was adjusted to 35% and mixed for 2 hours with a desktop ball mill to obtain a barium titanate dispersion composition 5. Using this, a ceramic sheet was formed and evaluated. The results are shown in Table 4.

[Comparative Example 4]
A barium titanate dispersion composition 6 was obtained in the same manner as in Example 10 except that the compound of Production Example 4 was not used. The ceramic sheet had a high viscosity and could not be formed. The results are shown in Table 4.

[Example 12]
A resin obtained by mixing and pelletizing 2 kg of a polystyrene-based carbon nanotube masterbatch (manufactured by Hyperion Catalysis International Inc .: PS / 20 BN) containing 20% by weight of carbon nanotubes and the compound of Production Example 1 and 18 kg of polystyrene. A composition (carbon nanotube content: 2% by weight) was obtained. This resin composition is charged into a batten felt injection molding machine PLUS250 (Toshiba Machine Co., Ltd.), heated at 310 ° C., and injected into a 60 ° C. mold at an injection filling rate of 1.3 cc / sec. A test plate of 80 mm × 50 mm × 3 mm was obtained.
About the obtained test plate, the surface resistance value was measured using the surface resistance measuring device (Hiresta-UP and Loresta-GP by Mitsubishi Chemical Corporation). The surface resistance value of the obtained test plate was 10 ¹ to 10 ² Ω / cm ² .

[Comparative Example 5]
2 kg of a polystyrene-based carbon nanotube masterbatch (Hyperion Catalysis International Inc .: PS / 20 BN) containing 20% by weight of carbon nanotubes and 18 kg of polystyrene were mixed and pelletized to obtain a resin composition (carbon nanotube content : 2% by weight). This resin composition is charged into a batten felt injection molding machine PLUS250 (Toshiba Machine Co., Ltd.), heated at 310 ° C., and injected into a 60 ° C. mold at an injection filling rate of 1.3 cc / sec. A test plate of 80 mm × 50 mm × 3 mm was obtained.
About the obtained test plate, the surface resistance value was measured using the surface resistance measuring device (Hiresta-UP and Loresta-GP by Mitsubishi Chemical Corporation). The surface resistance value of the obtained test plate was 10 ² to 10 ³ Ω / cm ² .

  Without impairing the properties of the carbon powder or the ceramic powder itself, the carbon powder or the ceramic powder can be dispersed or solubilized in the dispersion medium, and a composition that does not separate or aggregate even during long-term storage can be provided. Moreover, the composition which can fully be used can be provided also for the use to the electronic material field | area where it is not preferable that a dispersing agent contains a metal salt.

Claims (9)

The composition containing the compound shown by following General formula (1), and carbon powder or ceramic powder.

In (the above general formula (1), ^{R 1} is a hydrocarbon group of 1 to 23 carbon atoms, ^{R 2} is hydrogen or a carboxylic acid group or carbon atoms 1-3 have a sulfonic acid group Y represents a carboxyl group, a sulfonic acid group, a sulfuric ester group, a phosphoric ester group, or a salt thereof. Z represents —NR ′ — (R ′ represents hydrogen or carbon number 1). -10 hydrocarbon group), -O-, or -S-, j and k are either 0, 1 or 2 and j and k are not 0 at the same time, and n is 2 to 20 X represents an optionally substituted hydrocarbon chain having a molecular weight of 1,000,000 or less.   The composition according to claim 1, wherein the carbon number of X in the general formula (1) is 1 to 40. The composition according to claim 1 or 2, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(In the above general formula (2), R ¹ represents a hydrocarbon group having 1 to 23 carbon atoms, R ² represents hydrogen, a carbon atom having 1 to 3 carbon atoms which may have a carboxylic acid group or a sulfonic acid group. Y represents a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, or a salt thereof, Z represents —NR ′ — (R ′ represents hydrogen or a carbon number of 1 to 10; X ′ represents a carboxyl group or a salt thereof, —NHR ′ group (R ′ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms), — A hydrocarbon chain having 1 to 20 carbon atoms and having at least one of an OH group and an —SH group, j and k are 0, 1 and 2, and j and k are simultaneously 0. is not.)   The carbon powder comprises carbon powder, and the carbon powder is composed of at least one selected from the group consisting of carbon nanotubes, carbon nanocoils, carbon nanohorns, carbon nanofibers, and fullerenes. The composition according to one item. The composition according to any one of claims 1 to 3, wherein the composition comprises ceramic powder, and the ceramic powder comprises at least one selected from the following group.
(Oxides based on titanium oxide, barium titanate, barium calcium titanate, strontium titanate, lead titanate, barium zirconate, barium titanate (for example, Mn, Cr, Si, Ca, Ba, Mg, V , W, Ta, Nb, and oxides of one or more rare earth elements), Ba atoms or Ti atoms of barium titanate (BaTiO ₃ ) are replaced with any of Sn, Pb, Zr atoms Perovskite oxide ferroelectric ceramic powder, ZnO, ferrite, PZT, BaO, Al ₂ O ₃ , Bi ₂ O ₃ , R (rare earth element) ₂ O ₃ , TiO ₂ , Nd ₂ O ₃ , 2MgO. _{SiO 2, ZrO 2, ZrO 2} · SiO 2, 3Al 2 O 3 · 2SiO 2, MgO · SiO 2, 2MgO · 2Al O powder ₃ · 5SiO oxide _2, Ni-Cu-Zn ferrite, Ni-Zn ferrite, ferrite magnetic powder Cu-Zn _{ferrite, Y 1 Ba 2 Cu 3 O} 7, Bi 2 Sr 2 Ca 2 Cu 3 O ₁₀ superconducting ceramic powder, titanium oxide nanotubes, AlN, Si ₃ N ₄ , SiC)   The electronic material containing the composition as described in any one of Claims 1-5.   Printing material containing the composition as described in any one of Claims 1-5.   A conductive electronic material comprising the composition according to claim 4.   A dielectric electronic material comprising the composition according to claim 5.