JP2015191760A - Dispersant, dispersion composition, dispersion composition for batteries, and battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dispersant for a battery electrode, which is electrochemically stable against oxidation and reduction reactions in an electrode.SOLUTION: A dispersant comprises a triazine derivative expressed by the general formula (1). [Ris -X-Y; Xis an arylene group which may have a substituent group; Yis a sulfo group or a carboxyl group; Rand Rindependently H, an aryl group which may have a substituent group, a heterocyclic group which may have a substituent group, an organic pigment residue, a group expressed by -X-Y, or a group expressed by -X-Y-X; Xis an arylene group which may have a substituent group; Xis an aryl group which may have a substituent group, a heterocyclic group which may have a substituent group, or an organic pigment residue; Yis -CONH-, -NHCO-, -NHSO-, or -N=N-CH(-COCH)-CONH-, provided that both of Rand Rare never -X-Yat the same time.]

Description

  The present invention relates to a dispersant. More particularly, the present invention relates to a dispersant having electrochemical resistance. The present invention also relates to a dispersion composition using the dispersant and a battery.

  Various dispersants are used to uniformly disperse and stabilize fine particles such as organic pigments, carbon, and inorganic nanoparticles in a solvent. In particular, when a dispersant is used in the carbon material dispersion for battery electrodes, an oxidation-reduction reaction occurs at the electrode, and therefore, an electrochemically stable compound that hardly causes the reaction and decomposition associated therewith has been demanded.

  For example, Patent Documents 1 to 4 disclose organic dye derivatives or triazine derivatives useful as battery dispersants. However, the dispersants disclosed in these patent documents have a problem in that an oxidation reaction occurs when a high voltage is applied, and a reduction in discharge capacity retention rate due to repeated charge and discharge occurs.

International Publication No. WO2008 / 108360 Pamphlet JP 2009-26744 A JP 2010-061932 A JP 2011-162698 A

  In view of the above situation, it is an object of the present invention to provide an electrochemically stable dispersant as compared with conventional dispersants.

  As a result of intensive studies to solve the above problems, the present inventors have found that a compound in which the connecting site to the triazine ring is oxygen is very effective as an electrochemically stable dispersant, The present invention has been achieved.

  That is, the present invention relates to a dispersant comprising a triazine derivative represented by the following general formula (1).

[In General Formula (1), R ¹ represents a group represented by —X ¹ —Y ¹ . X ¹ represents an arylene group which may have a substituent, and Y ¹ represents a sulfo group or a carboxyl group.
R ² and R ³ are each independently represented by a hydrogen atom, an aryl group that may have a substituent, a heterocyclic group that may have a substituent, an organic dye residue, or —X ¹ —Y ^1. represents a that group or a group represented by -X ² -Y ² -X ^3,. X ² represents an arylene group which may have a substituent. X ³ represents an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or an organic dye residue. Y ² represents —CONH—, —NHCO—, —NHSO ₂ —, —N═N—CH (—COCH ₃ ) —CONH—. However, R ² and R ³ are not simultaneously -X ¹ -Y ¹ . ]

  The present invention further relates to the dispersant comprising an amine.

  The present invention also relates to a dispersion composition comprising the dispersant, a carbon material, and a solvent.

  The present invention further relates to the dispersion composition comprising a binder.

  The present invention also relates to a battery dispersion composition comprising the dispersion composition and an active material.

  The present invention also provides a battery comprising a positive electrode having a positive electrode mixture layer on a current collector, a negative electrode having a negative electrode mixture layer on the current collector, and an electrolyte, the positive electrode mixture layer Relates to a battery formed by using the battery dispersion composition.

  According to the present invention, an electrochemically stable dispersion composition can be obtained as compared with the case where a conventionally known dispersant is used. As a result, even when a high voltage is applied to the electrode, it is possible to provide a battery having excellent battery characteristics such as battery capacity and charge / discharge cycle characteristics without causing an oxidation reaction.

  Hereinafter, the present invention will be described in detail.

<Dispersant>
One embodiment of the present invention is a dispersant comprising a triazine derivative represented by the general formula (1). In General Formula (1), R ¹ represents a group represented by —X ¹ —Y ¹ . X ¹ represents an arylene group which may have a substituent, and Y ¹ represents a sulfo group or a carboxyl group.

The “substituents” of the arylene group which may have a substituent for X ¹ may be the same or different. Specific examples thereof include halogen groups such as fluorine, chlorine and bromine, nitro groups, alkyl groups, aryls. Group, cycloalkyl group, alkoxyl group, aryloxy group, alkylthio group, arylthio group and the like. Moreover, there may be a plurality of these substituents.

  Examples of the “arylene group” of the arylene group which may have a substituent include a phenylene group, a naphthylene group, and an anthrylene group.

X ¹ is preferably a phenylene group or naphthylene group having a small number of substituents, and more preferably a phenylene group or naphthylene group having no substituent.

R ² and R ³ are each independently represented by a hydrogen atom, an aryl group that may have a substituent, a heterocyclic group that may have a substituent, an organic dye residue, or —X ¹ —Y ^1. represents a that group or a group represented by -X ² -Y ² -X ^3,. X ² represents an arylene group which may have a substituent. X ³ represents an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or an organic dye residue. Y ² represents —CONH—, —NHCO—, —NHSO ₂ —, —N═N—CH (—COCH ₃ ) —CONH—. However, R ² and R ³ are not simultaneously -X ¹ -Y ¹ .

The “substituent” of the aryl group which may have a substituent of R ² and R ^{3 and} the heterocyclic group which may have a substituent has the same meaning as the substituent of X ¹ .

Examples of the “aryl group” of the aryl group which may have a substituent for R ² and R ³ include a phenyl group, a naphthyl group, and an anthryl group.

The “heterocyclic group” of the heterocyclic group which may have a substituent of R ² or R ³ is, for example, an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. Specifically, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, pyrrolyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, Xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group , Purinyl group, 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl Quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, Phenothiazinyl, isoxazolyl, furazanyl, phenoxazinyl, isochromanyl, chromanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, piperidyl, piperazinyl, indolinylyl, isoindolinyl Group, morpholinyl group, thioxanthryl group, benzofuryl group, benzothiazolyl group, benzoxazolyl group, benzoimidazolyl group, benzotriazolyl group Etc. The. In particular, a heterocyclic group containing at least either a nitrogen atom or an oxygen atom is preferable because of its excellent dispersibility, and among these, a carbazolyl group and a benzoimidazolyl group are more preferable.

Examples of the “organic dye” of the organic dye residue of R ² and R ³ include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, metal-free phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, Anthraquinone dyes such as flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, quinacridone dye, dioxazine dye, perinone dye, perylene dye, thioindigo dye, isoindoline dye, isoindolinone dye Quinophthalone dyes, selenium dyes, and the like. Of these, azo dyes, anthraquinone dyes, metal-free phthalocyanine dyes, quinacridone dyes, and dioxazine dyes are preferable because of their excellent dispersibility. More preferred are azo dyes, quinacridone dyes, and dioxazine dyes.

The arylene group which may have a substituent for X ² has the same meaning as the arylene group which may have a substituent for X ¹ .

The aryl group which may have a substituent for X ³ has the same meaning as the aryl group which may have a substituent for R ² and R ³ .

The “substituent” of the heterocyclic group which may have a substituent for X ³ has the same meaning as the substituent for X ¹ .

The “heterocyclic group” of the heterocyclic group which may have a substituent for X ³ has the same meaning as the heterocyclic group for R ² and R ³ .

The organic dye residue of X ³ is synonymous with the organic dye residues of R ² and R ³ .

Y ² —CONH—, —NHCO—, —NHSO ₂ —, —N═N—CH (—COCH ₃ ) —CONH— is the bonding position with X ² on the left side and the bonding position with X ³ on the right side. Represents.

The combination of R ² and R ³ includes a hydrogen atom, a heterocyclic group having no substituent, an organic dye residue, or a group represented by —X ² —Y ² —X ^3. Are preferably selected from those having no heterocyclic group or organic dye residue, and those in which the above heterocyclic group is a carbazolyl group or a benzoimidazolyl group, and the organic dye residue is an azo dye, quinacridone dye, dioxazine It is preferable that the dye is selected from those which are system dyes.

  Moreover, as a dispersing agent content, 0.5-20% is preferable with respect to the carbon material demonstrated later by mass%, 0.5-10% is more preferable, 0.5-5% is further more preferable.

  Another aspect of the present invention is a dispersant in which an amine is further contained in the triazine derivative represented by the general formula (1). This can be suitably used as a dispersant for a carbon material such as carbon black in battery applications.

  Here, as an amine that can be used in combination with the triazine derivative represented by the general formula (1), a linear or branched primary, secondary, tertiary, which has 1 to 40 carbon atoms and may contain a hydroxyl group or an ether bond. An alkylamine is mentioned.

Examples of the linear or branched primary alkylamine having 1 to 40 carbon atoms which may contain a hydroxyl group or an ether bond include propylamine, butylamine, isobutylamine, octylamine, 2-ethylhexylamine, laurylamine, stearylamine, Examples include oleylamine, 2-aminoethanol, 3-aminopropanol, 3-ethoxypropylamine, and 3-lauryloxypropylamine.
Examples of the linear or branched secondary alkylamine having 1 to 40 carbon atoms which may be substituted with a hydroxyl group include dibutylamine, diisobutylamine, N-methylhexylamine, dioctylamine, distearylamine, and 2-methylaminoethanol. Etc.
Examples of the linear or branched tertiary alkylamine having 1 to 40 carbon atoms which may be substituted with a hydroxyl group include triethylamine, tributylamine, N, N-dimethylbutylamine, N, N-diisopropylethylamine, dimethyloctylamine, Examples include octylamine, dimethyldecylamine, dimethyllaurylamine, dimethylmyristylamine, dimethylpalmitylamine, dimethylstearylamine, dilaurylmonomethylamine, triethanolamine, and 2- (dimethylamino) ethanol.

  Among these, a linear or branched primary, secondary or tertiary alkylamine having 1 to 40 carbon atoms is preferable, and a linear or branched primary, secondary or tertiary alkylamine having 5 to 20 carbon atoms is more preferable. A linear or branched primary, secondary or tertiary alkylamine having 8 to 20 carbon atoms is more preferable.

  The addition amount of the amine used in the present invention is not particularly limited, but is 0.1 mole equivalent or more and 3 mole equivalent or less with respect to 1 mole equivalent of the triazine derivative represented by the general formula (1). Preferably, 0.5 molar equivalent or more and 2 molar equivalent or less are more preferable.

<Carbon material>
The carbon material used in the present invention is not particularly limited, but when used as a carbon material for a battery, graphite, carbon black, carbon nanotube, carbon nanofiber, carbon fiber, fullerene, etc. alone, Or it is preferable to use 2 or more types together. When used as a carbon material, carbon black is preferably used from the viewpoint of conductivity, availability, and cost.

  As the carbon black used in the present invention, various types such as commercially available furnace black, channel black, thermal black, acetylene black, and ketjen black can be used alone or in combination of two or more. Ordinarily oxidized carbon black, hollow carbon and the like can also be used. The carbon black has a particle diameter of preferably 0.01 to 1 μm, more preferably 0.01 to 0.2 μm. As used herein, the particle size refers to the average primary particle size measured with an electron microscope, and the physical property values are generally used to represent the physical characteristics of carbon black.

  The carbon nanotube used in the present invention is a carbon material having a shape in which graphite is wound in a cylindrical shape. The diameter obtained by observation with an electron microscope is about several nm to 100 nm, and the length is about several nm to 1 mm. is there. In order to exhibit semiconductor characteristics, transparency of the coating film, etc., the diameter is preferably 50 nm or less, particularly preferably 20 nm or less. The length is preferably from 100 nm to 1 mm, particularly preferably from 500 nm to 1 mm. There are single-walled carbon nanotubes and multi-walled carbon nanotubes, but any structure may be used. In addition, fibers having a fiber diameter of about 100 nm to about 1 μm, which are classified as carbon nanofibers and obtained by observation with an electron microscope, can be used.

<Solvent>
The solvent used in the present invention is preferably an aprotic polar solvent. Particularly when used in battery applications, amide solvents are preferred, and in particular, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl- The use of amide aprotic solvents such as 2-pyrrolidone and hexamethylphosphoric triamide is preferred.

<Binder>
The binder to be used is not particularly limited, but ethylene, propylene, vinyl chloride, vinyl acetate, vinyl alcohol, maleic acid, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylonitrile, styrene, vinyl butyral, vinyl acetal, Polymer or copolymer containing vinylpyrrolidone as a structural unit, polyurethane resin, polyester resin, phenol resin, epoxy resin, phenoxy resin, urea resin, melamine resin, alkyd resin, acrylic resin, formaldehyde resin, silicon resin, fluorine resin And cellulose resins such as carboxymethyl cellulose, rubbers such as styrene-butadiene rubber and fluororubber, and conductive resins such as polyaniline and polyacetylene. Moreover, the modified body and copolymer of these resin may be sufficient. In particular, when used in battery applications, it is preferable to use a polymer compound containing a fluorine atom in the molecule, for example, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene, etc. from the viewpoint of resistance. These binders can be used alone or in combination.

<Active material>
The active material is a material that sends out or receives electrons and performs an oxidation or reduction reaction in the battery. Examples include a positive electrode active material used for a positive electrode and a negative electrode active material used for a negative electrode.

<Positive electrode active material>
The positive electrode active material to be used is not particularly limited as long as it functions as a battery active material. For example, when used in a lithium ion secondary battery, metal oxides capable of doping or intercalating lithium ions, metal compounds such as metal sulfides, conductive polymers, and the like can be used.

Specifically, lithium manganese composite oxide (for example, Li _x Mn ₂ O ₄ or Li _x MnO ₂ ), lithium nickel composite oxide (for example, Li _x NiO ₂ ), lithium cobalt composite oxide (Li _x Co ₂ ), lithium nickel cobalt composite oxide (e.g., _{Li x Ni 1-y Co y} O 2), lithium manganese cobalt composite oxides (e.g., _{Li x Mn y Co 1-y} O 2), lithium nickel manganese cobalt composite oxide (e.g., Li _x Ni _1/3 Co _1/3 Mn _1/3 O ₂ ), spinel-type lithium manganese nickel composite oxide (for example, Li _x Mn _{2 -y} Ni _y O ₄ ), etc., composite oxide powder of lithium and transition metal , lithium phosphorus oxide powder having an olivine structure (for example, _{Li x FePO 4, Li x Fe} 1-y Mn y PO 4, Li x CoPO 4), manganese oxide, iron oxide, Copper, nickel oxide, vanadium oxide (e.g. _{V 2 O 5, V 6 O} 13), a transition metal oxide powder such as titanium oxide, iron sulfate _{(Fe 2 (SO 4) 3} ), TiS 2, and FeS, etc. Transition metal sulfide powder and the like. In addition, conductive polymers such as polyaniline, polyacetylene, polypyrrole, and polythiophene can also be used. These positive electrode active materials can be used alone or in combination.

<Negative electrode active material>
There are no particular limitations on the negative electrode active material to be used, lithium ion doping or capable of intercalating Li metal or its alloy, tin alloy, silicon alloy negative _{electrode, Li X Fe 2 O 3,} Li X Fe 3 O 4 Metal oxides such as Li _x WO ₂ , conductive polymers such as polyacetylene and poly-p-phenylene, amorphous carbonaceous materials such as soft carbon and hard carbon, artificial graphite such as highly graphitized carbon materials, or Carbonaceous powders such as natural graphite, carbon black, mesophase carbon black, resin-fired carbon materials, gas-grown carbon fibers, carbon fibers and the like are used. These negative electrode active materials can be used alone or in combination.

<Dispersion composition>
As described above, the dispersion composition of the present invention can be used in the fields of printing inks, paints, plastics, toners, color filter resist inks, batteries and the like that require uniform and good film properties. In particular, since a coating film suitable for an electrode layer having a uniform and good coating film property and a low surface resistance can be provided, it can be suitably used in an application for forming a battery electrode.

  Dispersion is obtained by using a dispersing device such as a ball mill, a bead mill, a roll mill, or a high-speed impact mill together with a dispersant, a carbon material, a solvent, and optionally various additives such as a binder. Can do.

<Dispersion composition for battery>
The battery dispersion composition of the present invention is a battery composition in which a positive electrode active material is contained in a dispersion composition containing the dispersant, carbon material, solvent, and binder (hereinafter referred to as “positive electrode mixture paste”). It is preferable to use as.

  This positive electrode mixture paste can be produced by mixing the dispersant, a carbon material, a solvent, a binder, and an active material. The order of addition of each component is not limited. For example, a method in which all components are mixed at once, a method in which a carbon material is dispersed in a solvent in advance using a dispersant, and the remaining components are added thereto and mixed. In addition, after dissolving the dispersant in a solvent, a carbon material and a binder are added, the carbon material is dispersed and the binder is dissolved simultaneously, and the remaining components are added and mixed. Moreover, you may add the above-mentioned solvent further as needed.

  As an apparatus for producing the mixture paste, a disperser usually used for pigment dispersion or the like can be used. For example, mixers such as dispersers, homomixers, planetary mixers, homogenizers ("Clearmix" manufactured by M Technique, PRIMIX "Fillmix", etc.), paint conditioners (manufactured by Red Devil), ball mills, sand mills ( Media type dispersers such as “Dynomill” manufactured by Shinmaru Enterprises, Inc.), Attritor, Pearl Mill (“DCP Mill” manufactured by Eirich), Coball Mill, etc., Wet Jet Mill (“Genus PY” manufactured by Genus, Sugino Machine Co., Ltd.) Media-less dispersers such as “Starburst” manufactured by Nanomizer, “Nanomizer” manufactured by Nanomizer, etc., “Claire SS-5” manufactured by M Technique, and “MICROS” manufactured by Nara Machinery Co., other roll mills, etc. It is not limited to.

  Moreover, as the disperser, it is preferable to use a disperser that has been subjected to a metal contamination prevention treatment from the disperser. For example, when using a media-type disperser, a metal agitator and vessel are made of ceramic or resin dispersers, or the metal agitator and vessel surface are coated with tungsten carbide spray or resin coating. It is preferable to use a disperser that has been treated as described above. As the medium, glass beads, ceramic beads such as zirconia beads or alumina beads are preferably used. Moreover, also when using a roll mill, it is preferable to use a ceramic roll. Only one type of disperser may be used, or a plurality of types of devices may be used in combination.

<Battery>
Next, a battery using the composition of the present invention will be described. The composition of the present invention can be suitably used particularly for a lithium ion secondary battery. Hereinafter, a lithium ion secondary battery will be described, but a battery using the composition of the present invention is not limited to a lithium ion secondary battery.

  The lithium ion secondary battery includes a positive electrode having a positive electrode mixture layer on a current collector, a negative electrode having a negative electrode mixture layer on the current collector, and an electrolyte containing lithium.

  Regarding the electrode, the material and shape of the current collector to be used are not particularly limited, and as the material, metals and alloys such as aluminum, copper, nickel, titanium, and stainless steel are used. In particular, as the positive electrode material, aluminum is used as the negative electrode. The material is preferably copper. As the shape, a flat plate foil is generally used, but a roughened surface, a perforated foil shape, and a mesh shape can also be used.

  The electrode mixture layer can be formed by directly applying the electrode mixture paste on a current collector and drying it. The thickness of the electrode mixture layer is generally 1 μm or more and 500 μm or less, preferably 10 μm or more and 300 μm or less. There is no restriction | limiting in particular about the coating method, A well-known method can be used. Specific examples include a die coating method, a dip coating method, a roll coating method, a doctor coating method, a spray coating method, a gravure coating method, a screen printing method, and an electrostatic coating method. Moreover, you may perform the rolling process by a lithographic press, a calender roll, etc. after application | coating.

As an electrolytic solution constituting the lithium ion secondary battery, a solution in which an electrolyte containing lithium is dissolved in a non-aqueous solvent is used. As electrolytes, LiBF ₄ , LiClO ₄ , LiPF ₆ , LiAsF ₆ , LiSbF ₆ , LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, LiC ₄ F ₉ SO ₃ , Li (CF ₃ SO ₂ ) ₃ C , LiI, LiBr, LiCl, LiAlCl, LiHF ₂ , LiSCN, LiBPh _{4 and the} like, but are not limited thereto.

  The non-aqueous solvent is not particularly limited, but carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, γ-butyrolactone, γ-valerolactone, γ-octanoic lactone. Lactones such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,2-methoxyethane, 1,2-ethoxyethane, 1,2-dibutoxyethane, etc. Glymes, esters such as methyl formate, methyl acetate and methyl propionate, sulfoxides such as dimethyl sulfoxide and sulfolane, nitriles such as acetonitrile, and 1-methyl-2-pyrrolidone . These solvents may be used alone or in combination of two or more.

  Furthermore, the electrolyte solution may be a gelled polymer electrolyte held in a polymer matrix. Examples of the polymer matrix include, but are not limited to, an acrylate resin having a polyalkylene oxide segment, a polyphosphazene resin having a polyalkylene oxide segment, a polysiloxane having a polyalkylene oxide segment, and the like.

  The structure of the battery using the composition of the present invention is not particularly limited, but is usually composed of a positive electrode and a negative electrode, and a separator provided as necessary, such as a paper type, a cylindrical type, a button type, a laminated type, Various shapes can be formed according to the purpose of use.

  The dispersant of the present invention can be suitably used as a dispersant for carbon materials such as carbon black used for batteries, capacitors and capacitors, but it can be used as a coloring composition for various inks, paints, color filter resists and the like. It can also be used as a dispersant for pigments used in the above.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to a following example, unless the summary is exceeded. In addition, in order to clarify the difference between individual compositions, a dispersion composition comprising a dispersant, a carbon material, and a solvent is referred to as a “carbon material dispersion”, and a dispersion composition comprising a dispersant, a carbon material, a solvent, and a binder. A battery dispersion composition comprising “carbon material dispersion varnish”, a dispersant, a carbon material, a solvent, a binder, and an active material is referred to as “mixture paste”. Unless otherwise specified, N-methyl-2-pyrrolidone used as a solvent is abbreviated as “NMP”, and mass% is abbreviated as “%”.

<Dispersant>
The structures of the dispersants A to R made of the triazine derivative represented by the general formula (1) of the present invention are shown below. Moreover, the structure of the dispersing agents S-U mentioned as a comparative example is shown.

<Method for producing dispersant>
A dispersant comprising the triazine derivative represented by the general formula (1) of the present invention was produced by the method described in the following examples. The dispersant of the present invention uses a MALDI mass spectrometer autoflex III (hereinafter referred to as TOF-MS) manufactured by Bruker Daltonics, Inc., the molecular ion peak of the obtained mass spectrum, and the mass number obtained by calculation. Identified with the agreement. Moreover, the dispersing agent which consists of a triazine derivative of patent document 1 was manufactured as a comparative example.

[Example 1]
(Production of Dispersant A)
200 g of water was cooled to 5 to 10 ° C., and 0.045 mol of cyanuric chloride was added. While maintaining the temperature at 5 to 10 ° C., 0.045 mol of sodium 4-hydroxybenzenesulfonate was added. Further, a solution prepared by dissolving 0.045 mol of triethylamine in 100 g of water was dropped over 30 minutes while maintaining the temperature at 5 to 10 ° C. Thereafter, 200 g of water and 0.27 mol of caustic soda in terms of sodium hydroxide were added and heated at 60 ° C. for 3 hours. After cooling to room temperature, hydrochloric acid was added to adjust the pH to 3.0 or less, and filtration purification was performed. Dispersant A was obtained by drying the obtained residue at 80 ° C. for 24 hours. As a result of mass spectrometry by TOF-MS, the structure of the dispersant A was confirmed.

[Example 2]
(Production of Dispersant B)
Dispersant B was obtained in the same manner as in Example 1 except that 4-hydroxybenzoic acid was added instead of sodium 4-hydroxybenzenesulfonate in the manufacture of Dispersant A. As a result of mass spectrometry by TOF-MS, the structure of the dispersant B was confirmed.

[Example 3]
(Production of Dispersant C)
0.045 mol of cyanuric chloride was added to 200 g of water at room temperature. Subsequently, 0.090 mol of sodium 1-naphthol-4-sulfonate was added. Further, a solution prepared by dissolving 0.090 mol of triethylamine in 100 g of water was added dropwise over 30 minutes. Thereafter, 200 g of water and 0.27 mol of caustic soda in terms of sodium hydroxide were added and heated at 60 ° C. for 3 hours. After cooling to room temperature, hydrochloric acid was added to adjust the pH to 3.0 or less, and filtration purification was performed. Dispersant C was obtained by drying the obtained residue at 80 ° C. for 24 hours. As a result of mass spectrometry by TOF-MS, the structure of the dispersant C was confirmed.

[Example 4]
(Production of Dispersant D)
Dispersant D was obtained in the same manner as in Example 3 except that 4-hydroxy-3-methylbenzoic acid was added instead of sodium 1-naphthol-4-sulfonate in the manufacture of Dispersant C. . As a result of mass spectrometry by TOF-MS, the structure of the dispersant D was confirmed.

[Example 5]
(Production of Dispersant E)
200 g of water was cooled to 5 to 10 ° C., and 0.045 mol of cyanuric chloride was added. While maintaining the temperature at 5 to 10 ° C., 0.045 mol of sodium 4-hydroxybenzenesulfonate was added. Further, a solution prepared by dissolving 0.045 mol of triethylamine in 100 g of water was dropped over 30 minutes while maintaining the temperature at 5 to 10 ° C. Thereafter, the temperature was raised to room temperature, and 0.045 mol of 5-hydroxy-2-benzimidazolinone was added. Further, a solution in which 0.045 mol of triethylamine was dissolved in 100 g of water was dropped over 30 minutes. Thereafter, 200 g of water and 0.27 mol of caustic soda in terms of sodium hydroxide were added and heated at 90 ° C. for 3 hours. Then, it cooled to room temperature, added hydrochloric acid, adjusted pH to 3.0 or less, and filtered and refined. Dispersant E was obtained by drying the obtained residue at 80 ° C. for 24 hours. As a result of mass spectrometry by TOF-MS, the structure of the dispersant E was confirmed.

[Example 6]
(Production of Dispersant F)
Dispersant F was obtained in the same manner as in Example 5 except that 4-hydroxybenzoic acid was added instead of sodium 4-hydroxybenzenesulfonate in the manufacture of Dispersant E. As a result of mass spectrometry by TOF-MS, the structure of the dispersant F was confirmed.

[Example 7]
(Production of Dispersant G)
200 g of water was cooled to 5 to 10 ° C., and 0.045 mol of cyanuric chloride was added. While maintaining the temperature at 5 to 10 ° C., 0.045 mol of 3-hydroxybenzoic acid was added. Further, a solution prepared by dissolving 0.045 mol of triethylamine in 100 g of water was dropped over 30 minutes while maintaining the temperature at 5 to 10 ° C. Thereafter, the temperature was raised to room temperature, and 0.090 mol of 3-hydroxy-2′-methoxy-2-naphthanilide was added. Further, a solution prepared by dissolving 0.090 mol of triethylamine in 200 g of water was dropped over 30 minutes. Then, it heated at 90 degreeC and stirred for 4 hours. After cooling to room temperature, hydrochloric acid was added to adjust the pH to 3.0 or less, and filtration purification was performed. The obtained residue was dried at 80 ° C. for 24 hours to obtain Dispersant G. As a result of mass spectrometry by TOF-MS, the structure of the dispersant G was confirmed.

[Example 8]
(Production of Dispersant H)
200 g of water was cooled to 5 to 10 ° C., and 0.045 mol of cyanuric chloride was added. While maintaining the temperature at 5 to 10 ° C., 0.045 mol of 4-hydroxybenzoic acid was added. Further, a solution prepared by dissolving 0.045 mol of triethylamine in 100 g of water was dropped over 30 minutes while maintaining the temperature at 5 to 10 ° C. Thereafter, the temperature was raised to room temperature, and 0.045 mol of 4-hydroxyacetanilide was added. Further, a solution in which 0.045 mol of triethylamine was dissolved in 100 g of water was dropped over 30 minutes. Thereafter, caustic soda was added to adjust the pH to 12.5 to 13.0, and the mixture was stirred at 90 ° C. for 4 hours. After cooling to room temperature, hydrochloric acid was added to adjust the pH to 3.0 or less, and filtration purification was performed. The obtained residue was added to 100 g of water and cooled to 5 ° C., and 50 g of hydrochloric acid was added and stirred for 30 minutes while maintaining the temperature at 5 ° C. Further, a solution prepared by dissolving 0.045 mol of sodium nitrite in 20 g of water was added and stirred for 1 hour. Sulfamic acid was added to eliminate excess sodium nitrite, which was used as a diazonium salt aqueous solution. On the other hand, 0.045 mol of 5-acetoacetylaminobenzimidazolone was added to 600 g of water, 13.9 g of caustic soda and 43.7 g of soda ash were added and stirred for 30 minutes to obtain a coupler solution. This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. At this time, it was confirmed that the pH was 9.0 or more, and after stirring for 2 hours at room temperature, the pH was adjusted to 9.0 or more by adding soda ash, heated to 80 ° C. and stirred for 1 hour. . Then, it cooled to room temperature, added hydrochloric acid, adjusted pH to 3.0 or less, and filtered and refined. The obtained residue was dried at 80 ° C. for 24 hours to obtain Dispersant H. As a result of mass spectrometry by TOF-MS, the structure of the dispersant H was confirmed.

[Example 9]
(Production of Dispersant I)
In the preparation of Dispersant H, 4-hydroxybenzenesulfonic acid sodium is used instead of 4-hydroxybenzoic acid and 5- (3′-hydroxy-2′-naphthoylamino) benzimidazolone is used instead of 5-acetoacetylaminobenzimidazolone. A dispersant I was obtained in the same manner as in Example 8 except that was added. As a result of mass spectrometry by TOF-MS, the structure of the dispersant I was confirmed.

[Example 10]
(Production of Dispersant J)
Except that 2-hydroxybenzoic acid was added instead of 3-hydroxybenzoic acid and 1-naphthol was added instead of 3-hydroxy-2′-methoxy-2-naphthanilide in the production of Dispersant G, the same as Example 7 Dispersant J was obtained. As a result of mass spectrometry by TOF-MS, the structure of the dispersant J was confirmed.

[Example 11]
(Production of Dispersant K)
200 g of water was cooled to 5 to 10 ° C., and 0.045 mol of cyanuric chloride was added. While maintaining the temperature at 5 to 10 ° C., 0.045 mol of sodium 4-hydroxybenzenesulfonate was added. Further, a solution prepared by dissolving 0.045 mol of triethylamine in 100 g of water was dropped over 30 minutes while maintaining the temperature at 5 to 10 ° C. Thereafter, the temperature was raised to room temperature, and 0.045 mol of 4-hydroxyacetanilide was added. Further, a solution in which 0.045 mol of triethylamine was dissolved in 100 g of water was dropped over 30 minutes. Thereafter, caustic soda was added to adjust the pH to 12.5 to 13.0, and the mixture was stirred at 90 ° C. for 4 hours. After cooling to room temperature, hydrochloric acid was added to adjust the pH to 3.0 or less, and filtration purification was performed. On the other hand, 0.045 mol of sulfonyl chloride of quinacridone pigment produced by a known technique was added to 500 g of ice water (200 g of water, 300 g of ice). While maintaining the temperature at 10 ° C. or lower, the solution was neutralized with an aqueous sodium carbonate solution and adjusted to pH = 3.0. The previously prepared triazine compound residue was added to the quinacridone derivative slurry, and then the mixture was stirred at room temperature for 1 hour and further stirred at 70 ° C. for 2 hours. After cooling to room temperature, filtration and purification were performed, and the resulting residue was dried at 80 ° C. for 24 hours to obtain Dispersant K. As a result of mass spectrometry by TOF-MS, the structure of the dispersant K was confirmed.

[Example 12]
(Production of Dispersant L)
Dispersant L was produced in the same manner as in Example 11 except that 4-hydroxybenzoic acid was added in place of sodium 4-hydroxybenzenesulfonate and dioxazine pigment was added in place of quinacridone pigment. Got. As a result of mass spectrometry by TOF-MS, the structure of the dispersant L was confirmed.

[Example 13]
(Production of Dispersant M)
In the preparation of Dispersant G, sodium 4-hydroxybenzenesulfonate is used instead of 3-hydroxybenzoic acid, and 7-chloro-6-nitro-4-hydroxyquinazoline is used instead of 3-hydroxy-2′-methoxy-2-naphthanilide. A dispersant M was obtained in the same manner as in Example 7 except that was added. As a result of mass spectrometry by TOF-MS, the structure of the dispersant M was confirmed.

[Example 14]
(Production of Dispersant N)
The same method as in Example 7 except that 4-hydroxybenzoic acid was added instead of 3-hydroxybenzoic acid and salicylanilide was added instead of 3-hydroxy-2′-methoxy-2-naphthanilide in the production of Dispersant G Dispersant N was obtained. As a result of mass spectrometry by TOF-MS, the structure of the dispersant N was confirmed.

[Example 15]
(Production of Dispersant O)
In the production of Dispersant G, potassium 4-hydroxy-3-methoxybenzenesulfonate hemihydrate instead of 3-hydroxybenzoic acid is used instead of 3-hydroxy-2′-methoxy-2-naphthanilide. A dispersant O was obtained in the same manner as in Example 7 except that hydroxyanthraquinone was added. As a result of mass spectrometry by TOF-MS, the structure of the dispersant O was confirmed.

[Example 16]
(Production of Dispersant P)
The same as in Example 7 except that 4-hydroxybenzoic acid was added instead of 3-hydroxybenzoic acid and 4-phenoxyphenol was added instead of 3-hydroxy-2′-methoxy-2-naphthanilide in the production of Dispersant G. The dispersant P was obtained. As a result of mass spectrometry by TOF-MS, the structure of the dispersant P was confirmed.

[Example 17]
(Production of Dispersant Q)
Implemented except that 3-chloro-4-hydroxybenzoic acid was added in place of 3-hydroxybenzoic acid and 4-hydroxycarbazole was added in place of 3-hydroxy-2′-methoxy-2-naphthanilide in the production of Dispersant G Production was conducted in the same manner as in Example 7 to obtain Dispersant Q. As a result of mass spectrometry by TOF-MS, the structure of the dispersant Q was confirmed.

[Example 18]
(Production of Dispersant R)
200 g of water was cooled to 5 to 10 ° C., and 0.045 mol of cyanuric chloride was added. While maintaining the temperature at 5 to 10 ° C., 0.045 mol of 4-hydroxybenzoic acid was added. Further, a solution prepared by dissolving 0.045 mol of triethylamine in 100 g of water was dropped over 30 minutes while maintaining the temperature at 5 to 10 ° C. Thereafter, 200 g of water and 0.090 mol of 4-hydroxyacetanilide were added. Further, a solution prepared by dissolving 0.090 mol of triethylamine in 200 g of water was dropped over 30 minutes. Then, it heated at 90 degreeC and stirred for 4 hours. After cooling to room temperature, hydrochloric acid was added to adjust the pH to 3.0 or less, and filtration purification was performed. On the other hand, 0.045 mol of pyridine-3-carbonyl chloride hydrochloride was added to 500 g of ice water (water 200 g, ice 300 g). While maintaining the temperature at 10 ° C. or lower, the solution was neutralized with an aqueous sodium carbonate solution and adjusted to pH = 3.0. The previously prepared triazine compound residue was added to this aqueous solution, and then the mixture was stirred at room temperature for 1 hour and further stirred at 70 ° C. for 2 hours. After cooling to room temperature, filtration and purification were performed, and the resulting residue was dried at 80 ° C. for 24 hours to obtain Dispersant R. As a result of mass spectrometry by TOF-MS, the structure of the dispersant R was confirmed.

[Comparative Example 1]
(Production of Dispersant S)
200 g of water was cooled to 5 to 10 ° C., and 0.045 mol of cyanuric chloride was added. While maintaining the temperature at 5-10 ° C., 0.045 mol of 4-aminoacetanilide was added. Further, a solution prepared by dissolving 0.045 mol of triethylamine in 100 g of water was dropped over 30 minutes while maintaining the temperature at 5 to 10 ° C. Thereafter, the temperature was raised to room temperature, and 0.045 mol of 4-hydroxybenzenesulfonic acid was added. Further, a solution in which 0.045 mol of triethylamine was dissolved in 100 g of water was dropped over 30 minutes. Thereafter, 0.135 mol of a methanol solution of sodium methoxide was added in terms of sodium methoxide, and the mixture was stirred at 90 ° C. for 4 hours. After cooling to room temperature, hydrochloric acid was added to adjust the pH to 3.0 or less, and filtration purification was performed. On the other hand, 0.045 mol of sulfonyl chloride of quinacridone pigment produced by a known technique was added to 500 g of ice water (200 g of water, 300 g of ice). While maintaining the temperature at 10 ° C. or lower, the solution was neutralized with an aqueous sodium carbonate solution and adjusted to pH = 3.0. The previously prepared triazine compound residue was added to the quinacridone derivative slurry, and then the mixture was stirred at room temperature for 1 hour and further stirred at 70 ° C. for 2 hours. After cooling to room temperature, filtration purification was performed, and the resulting residue was dried at 80 ° C. for 24 hours to obtain Dispersant S. As a result of mass spectrometry by TOF-MS, the structure of the dispersant S was confirmed.

[Comparative Example 2]
(Production of Dispersant T)
200 g of water was cooled to 5 to 10 ° C., and 0.045 mol of cyanuric chloride was added. While maintaining the temperature at 5-10 ° C., 0.045 mol of 4-aminoacetanilide was added. Further, a solution prepared by dissolving 0.045 mol of triethylamine in 100 g of water was dropped over 30 minutes while maintaining the temperature at 5 to 10 ° C. Thereafter, the temperature was raised to room temperature, and 0.045 mol of 4-hydroxybenzenesulfonic acid was added. Further, a solution in which 0.045 mol of triethylamine was dissolved in 100 g of water was dropped over 30 minutes. Thereafter, 0.135 mol of a methanol solution of sodium methoxide was added in terms of sodium methoxide, and the mixture was stirred at 90 ° C. for 4 hours. After cooling to room temperature, hydrochloric acid was added to adjust the pH to 3.0 or less, and filtration purification was performed. On the other hand, 0.045 mol of sulfonyl chloride of 9-ethylcarbazole produced by a known technique was added to 500 g of ice water (200 g of water, 300 g of ice). While maintaining the temperature at 10 ° C. or lower, the solution was neutralized with an aqueous sodium carbonate solution and adjusted to pH = 3.0. To this carbazole derivative slurry, the previously prepared triazine compound residue was added, and then stirred at room temperature for 1 hour and further stirred at 70 ° C. for 2 hours. After cooling to room temperature, filtration and purification were performed, and the resulting residue was dried at 80 ° C. for 24 hours to obtain Dispersant T. As a result of mass spectrometry by TOF-MS, the structure of the dispersant T was confirmed.

[Comparative Example 3]
(Manufacture of dispersant U)
200 g of water was cooled to 5 to 10 ° C., and 0.045 mol of cyanuric chloride was added. While maintaining the temperature at 5-10 ° C, 0.045 mol of 5-aminosalicylic acid was added. Further, a solution prepared by dissolving 0.045 mol of triethylamine in 100 g of water was dropped over 30 minutes while maintaining the temperature at 5 to 10 ° C. Thereafter, the temperature was raised to room temperature, and 0.045 mol of 3-amino-9-ethylcarbazole was added. Further, a solution in which 0.045 mol of triethylamine was dissolved in 100 g of water was dropped over 30 minutes. Thereafter, caustic soda was added to adjust the pH to 12.5 to 13.0, and the mixture was stirred at 90 ° C. for 4 hours. After cooling to room temperature, hydrochloric acid was added to adjust the pH to 3.0 or less, and filtration purification was performed. The obtained residue was dried at 80 ° C. for 24 hours to obtain Dispersant U. As a result of mass spectrometry by TOF-MS, the structure of the dispersant U was confirmed.

<Method for producing dispersant containing amine>
Dispersants a to af shown in Table 1 were produced by the methods described in the following examples.

[Example 19]
(Production of Dispersant a)
0.040 mol of dispersant A obtained in Example 1 was added to 200 g of water. 0.040 mol of octylamine was added to this, and it stirred at 60 degreeC for 2 hours. After cooling to room temperature, filtration purification was performed. The obtained residue was dried at 80 ° C. for 48 hours to obtain Dispersant a.

[Example 20] to [Example 36]
(Production of Dispersant b to Dispersant r)
In the production of Dispersant a, Dispersant B was produced in the same manner as Example 19 except that Dispersant B to Dispersant R described in Example 20 to Example 36 of Table 1 were added instead of Dispersant A. Agents b to r were obtained.

[Example 37] to [Example 46]
(Production of Dispersant s to Dispersant ab)
A dispersant f was prepared in the same manner as in Example 24 except that amines described in Examples 37 to 46 in Table 1 were added instead of octylamine in the manufacture of the dispersant f. Obtained.

[Example 47]
(Manufacture of dispersant ac)
A dispersant ac was obtained in the same manner as in Example 24 except that the amount of octylamine added was changed from 0.040 mol to 0.004 mol in the manufacture of the dispersant f.

[Example 48]
(Manufacture of dispersant ad)
Manufacture was performed in the same manner as in Example 24 except that the amount of octylamine added was changed from 0.040 mol to 0.020 mol in the manufacture of Dispersant f to obtain Dispersant ad.

[Example 49]
(Production of dispersant ae)
Manufacture was performed in the same manner as in Example 24 except that the amount of octylamine added was changed from 0.040 mol to 0.080 mol in the manufacture of Dispersant f to obtain Dispersant ae.

[Example 50]
(Production of dispersant af)
A dispersant af was obtained in the same manner as in Example 24 except that the amount of octylamine added was changed from 0.040 mol to 0.120 mol in the manufacture of the dispersant f.

<Production and evaluation of carbon material dispersion>
Carbon material dispersions were produced by the methods described in the following examples and comparative examples, and the dispersibility was evaluated by measuring the dispersed particle size and viscosity.

  For the production of carbon material dispersions, Dispersant A to Dispersant R described in Examples 1 to 18, Dispersant S to Dispersant U described in Comparative Examples 1 to 3, and Examples 19 to Dispersant a to Dispersant af described in Example 50, N-methyl-2-pyrrolidone, and the following carbon materials were used.

# 30 (Mitsubishi Chemical Co., Ltd.): Furnace black, the average primary particle diameter determined by observation with an electron microscope is 30 nm, and the specific surface area determined by the S-BET formula from the nitrogen adsorption amount is 74 m ² / g.
Monarch 800 (manufactured by Cabot): Furnace black, average primary particle diameter determined by observation with an electron microscope of 17 nm, specific surface area determined by S-BET formula from nitrogen adsorption amount is 210 m ² / g, hereinafter referred to as “M800” Abbreviated.
Denka black granular product (manufactured by Denki Kagaku Kogyo Co., Ltd.): acetylene black, the average primary particle diameter determined by observation with an electron microscope is 35 nm, the specific surface area determined by the S-BET formula from the amount of nitrogen adsorption is 68 m ² / g or less Abbreviated as “granular product”.
EC-300J (manufactured by Akzo): Ketjen black, the average primary particle diameter determined by observation with an electron microscope is 40 nm, and the specific surface area determined by the S-BET formula from the amount of nitrogen adsorbed is 800 m ² / g.
Carbon nanotubes: multi-walled carbon nanotubes, fiber diameters of 10 to 20 nm and fiber lengths of 2 to 5 μm determined by observation with an electron microscope, hereinafter abbreviated as CNT.
VGCF (manufactured by Showa Denko KK): carbon nanofiber, fiber diameter 150 nm, fiber length 10-20 μm determined by observation with an electron microscope.

[Example 51 to Example 68]
In accordance with the composition shown in Table 2, N-methyl-2-pyrrolidone and each dispersant were charged into a glass bottle, mixed and dissolved, then each carbon material was added, and zirconia beads were used as media to disperse with a paint conditioner for 2 hours. A dispersion was obtained. In all cases, the dispersibility was good.

[Examples 69 to 105]
In accordance with the composition shown in Table 3, N-methyl-2-pyrrolidone and each dispersant were charged in a glass bottle, mixed and dissolved, then each carbon material was added, and dispersed with a paint conditioner for 2 hours using zirconia beads as a medium. A dispersion was obtained. In all cases, the dispersibility was good.

[Comparative Examples 4 to 11]
In accordance with the composition shown in Table 4, N-methyl-2-pyrrolidone and each dispersant were charged in a glass bottle, mixed and dissolved, then each carbon material was added, and dispersed using a zirconia bead as a medium with a paint conditioner for 2 hours. A dispersion was obtained. In all cases, the dispersibility was good.

<Production and evaluation of carbon material dispersion varnish>
Carbon material-dispersed varnishes were produced by the methods described in the following examples and comparative examples. Moreover, using the produced carbon material-dispersed varnish, cyclic voltammetry (hereinafter abbreviated as CV) was measured to evaluate electrochemical resistance.

  For the production of the carbon material-dispersed varnish, the carbon material dispersions described in Examples 51 to 105 and Comparative Examples 4 to 11, N-methyl-2-pyrrolidone, and the following binders were used.

  KF polymer W1100 (manufactured by Kureha): polyvinylidene fluoride (PVDF), hereinafter abbreviated as PVDF.

Moreover, the working electrode for CV measurement was produced as follows. The obtained carbon material-dispersed varnish was applied onto a 20 μm-thick aluminum foil serving as a current collector using a doctor blade, and then heated and dried at 120 ° C. under reduced pressure to obtain an electrode having a coating amount of 1.5 mg / cm ² . A sheet was produced. This was punched out to a diameter of 16 mm as a working electrode, a metallic lithium foil (thickness 0.15 mm) as a counter electrode, and a separator (thickness 20 μm, porosity 50%) made of a porous polypropylene film between the working electrode and the counter electrode Inserted and laminated, filled with electrolyte (non-aqueous electrolyte in which LiPF ₆ was dissolved at a concentration of 1M in a mixed solvent of ethylene carbonate and diethyl carbonate in a volume ratio of 1: 1) and filled with a bipolar metal cell (treasure) HS flat cell manufactured by Izumi Co., Ltd.) was assembled. The cell was assembled in a glove box substituted with argon gas.

  Evaluation of CV is performed using HOKUTO HSV-110, scanning from the OCV (open circuit voltage) to the plus side, and performing 10 cycles between 2.0V and 4.5V at a scanning speed of 0.1 mV / sec. It was. The evaluation was performed with ◯ when the oxidation peak was not observed and x when the oxidation peak was observed.

[Example 106 to Example 123]
According to the composition shown in Table 5, various carbon material dispersions prepared in Examples 51 to 68, a binder, and N-methyl-2-pyrrolidone were mixed with a disper to obtain various carbon material dispersion varnishes. All had good dispersibility. In addition, no oxidation peak was observed in either case.

[Examples 124 to 160]
According to the composition shown in Table 6, the various carbon material dispersions prepared in Examples 69 to 103, the binder, and N-methyl-2-pyrrolidone were mixed with a disper to obtain various carbon material dispersion varnishes. All had good dispersibility. In addition, no oxidation peak was observed in either case.

[Comparative Examples 12 to 19]
According to the composition shown in Table 7, the various carbon material dispersions prepared in Comparative Examples 4 to 11, the binder, and N-methyl-2-pyrrolidone were mixed with a disper to obtain various carbon material dispersion varnishes. In all cases, the dispersibility was good, but an oxidation peak was observed by CV evaluation.

<Production and evaluation of mixture paste>
A mixture paste was prepared by the method described in the following examples and comparative examples, applied onto a polyethylene terephthalate (PET) film using a doctor blade, and then dried to evaluate the surface resistance of each coating film.

  For the production of the mixture paste, the carbon material-dispersed varnish described in Examples 106 to 160 and Comparative Examples 12 to 19, N-methyl-2-pyrrolidone, and the following active materials were used.

HLC-22 (Honjo Chemical Co., Ltd.): Positive electrode active material, lithium cobaltate (LiCoO ₂ ), average primary particle size determined by observation with an electron microscope was 6.6 μm, determined from the amount of nitrogen adsorption by the S-BET equation Specific surface area is 0.62 m ² / g, hereinafter abbreviated as LCO.

[Example 161 to Example 215]
According to the composition shown in Table 8 and Table 9, various carbon material dispersion varnishes prepared in Examples 106 to 160, the active material, and N-methyl-2-pyrrolidone were mixed with a disper to obtain various mixture pastes. . In any case, there was no problem in the surface resistance value of the coating film, and even when the carbon material-dispersed varnish of the present invention was used, there was no particular problem in the preparation of the mixture paste.

[Comparative Examples 20 to 27]
According to the composition shown in Table 10, various carbon material-dispersed varnishes prepared in Comparative Examples 12 to 19, active materials, and N-methyl-2-pyrrolidone were mixed with a disper to obtain various mixture pastes. In any case, there was no problem in the surface resistance value of the coating film, and even when the carbon material-dispersed varnish of the present invention was used, there was no particular problem in the preparation of the mixture paste.

<Assembly and evaluation of lithium ion secondary battery positive electrode evaluation cell>
[Example 216 to Example 270]
The previously prepared mixture paste (Example 161 to Example 215) was applied onto a 20 μm thick aluminum foil serving as a current collector using a doctor blade, and then heat-dried at 120 ° C. under reduced pressure to obtain a roller. A positive electrode mixture layer having a coating amount of 20 mg / cm ² and a density of 3.0 g / cm ³ was produced by rolling with a press. This was punched out to a diameter of 16 mm as a working electrode, a metallic lithium foil (thickness 0.15 mm) as a counter electrode, and a separator (thickness 20 μm, porosity 50%) made of a porous polypropylene film between the working electrode and the counter electrode Inserted and laminated, filled with electrolyte (non-aqueous electrolyte in which LiPF ₆ was dissolved at a concentration of 1M in a mixed solvent of ethylene carbonate and diethyl carbonate in a volume ratio of 1: 1) and filled with a bipolar metal cell (treasure) HS flat cell manufactured by Izumi Co., Ltd.) was assembled. The cell was assembled in a glove box substituted with argon gas.

  The produced battery evaluation cell is fully charged at a constant current and constant voltage charge (upper limit voltage 4.5 V) at room temperature (25 ° C.) and at a charge rate of 0.2 C and 1.0 C, and at a constant current at the same rate as during charging. Charge / discharge for discharging to a discharge lower limit voltage of 3.0V is defined as one cycle (charge / discharge interval rest time 30 minutes). ) From Table 11 and Table 12, the battery using the electrode of the present invention showed good results in the battery capacity and the 200 cycle capacity retention rate for both discharge rates of 0.2C and 1.0C.

[Comparative Example 28 to Comparative Example 35]
Using the mixture paste prepared in Comparative Examples 20 to 27, battery evaluation cells were assembled in the same manner as in Examples 216 to 270, and charge / discharge cycle characteristics were evaluated. As a result, the decrease in the 200-cycle capacity retention rate was significant compared to Examples 216 to 270 in Tables 11 and 12 (Table 13).

Claims (6)

A dispersant comprising a triazine derivative represented by the following general formula (1).

[In General Formula (1), R ¹ represents a group represented by —X ¹ —Y ¹ . X ¹ represents an arylene group which may have a substituent, and Y ¹ represents a sulfo group or a carboxyl group.
R ² and R ³ are each independently represented by a hydrogen atom, an aryl group that may have a substituent, a heterocyclic group that may have a substituent, an organic dye residue, or —X ¹ —Y ^1. represents a that group or a group represented by -X ² -Y ² -X ^3,. X ² represents an arylene group which may have a substituent. X ³ represents an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or an organic dye residue. Y ² represents —CONH—, —NHCO—, —NHSO ₂ —, —N═N—CH (—COCH ₃ ) —CONH—. However, R ² and R ³ are not simultaneously -X ¹ -Y ¹ . ]   The dispersant according to claim 1, further comprising an amine.   A dispersion composition comprising the dispersant according to claim 1 or 2, a carbon material, and a solvent.   The dispersion composition according to claim 3, further comprising a binder.   A battery dispersion composition comprising the dispersion composition according to claim 3 or 4 and an active material.   6. A battery comprising a positive electrode having a positive electrode mixture layer on a current collector, a negative electrode having a negative electrode mixture layer on the current collector, and an electrolyte, wherein the positive electrode mixture layer is defined in claim 5. A battery formed by using the battery dispersion composition.