JP2019008973A - Conductive wiring sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive wiring sheet having excellent conductivity, which has excellent conductivity, durability, surface texture, and adhesion to a base material of the conductive layer. A conductive wiring sheet having a sheet-shaped base material and a conductive layer arranged on the sheet-shaped base material, wherein the conductive layer is a binder resin (A) and a conductive carbon material (B). A wiring sheet comprising the above, wherein the density of the conductive layer is 1.2 to 2.0 g / cm3, and the thickness of the conductive layer is 500 μm or less. [Selection diagram] None

Description

  The present invention relates to a conductive wiring sheet having a conductive layer on a sheet-like substrate.

  In recent years, there has been a remarkable development in electronics, and conductive materials used in various electronic devices are also required to be smaller, lighter, lower in cost, and longer in various usage environments. It is coming. For example, when manufacturing a base wiring of an electronic device or a wiring for connecting an electronic device, a conductive composition having good conductivity is required, but a conductive composition using a metal filler such as silver or copper is generally used. And the big problem in terms of cost has not been solved yet. On the other hand, various studies have been made on conductive compositions using conductive carbon that does not use metals, but because of insufficient conductivity, it has been limited to use in semiconductive applications such as antistatic applications. It was.

As conductive carbon materials, various conductive materials having low volume resistivity such as graphite and carbon nanotubes have been studied. These conductive carbon materials have a high volume resistivity of less than 10 ⁻² Ω · cm, but many carbon materials with excellent electrical conductivity have a large specific surface area and are uniform in resins and solvents. It may be difficult to mix and disperse, and contact between the carbon material in the coating film or molded product obtained from the conductive composition containing conductive carbon material, resin, solvent, etc. is insufficient, Since the conductive network is insufficient, the volume resistivity is also a big problem (Patent Documents 1 to 3).
Therefore, Patent Documents 4 to 16 disclose conductive compositions in which graphite and carbon black are used in combination and dispersed in a binder in order to develop a conductive network between carbon materials in a coating film. Patent Documents 17 and 18 also disclose a conductive composition using a combination of carbon fibers and carbon nanotubes. Although improvement in conductivity was seen, the dispersibility of the conductive carbon material to the resin or solvent has not been solved, and the volume resistivity of the coating film often remains on the order of 10 ⁻² Ω · cm, Further improvement in conductivity has been desired.

  Therefore, in order to improve dispersibility, Patent Document 19 discloses a change in the dispersion method, Patent Documents 20 and 21 use an organic solvent-based composition dispersant, and Patent Documents 22 and 23 describe an aqueous dispersion in an aqueous composition. The use of agents is disclosed. However, although the dispersibility has been improved, there has been a problem that the conductivity is lowered by adding a dispersant which is an insulating material or damaging the conductive carbon material by miniaturization.

Japanese Patent Laid-Open No. 3-7740 JP 2001-60413 A Japanese Patent Laid-Open No. 2002-20515 JP 54-36343 A JP 62-88260 A JP-A-62-88261 JP-A-62-199663 JP-A 63-125580 JP-A 64-56777 JP-A-1-101373 JP-A-1-184901 JP-A-2-284968 Japanese Patent Laid-Open No. 5-65366 JP 7-33883 A Japanese Patent Laid-Open No. 7-41609 JP 7-53813 A JP-A-6-122785 JP 2004-221071 A JP-A-2-204317 Japanese Patent Laid-Open No. 2001-254013 JP 2013-119777 A JP 2004-10705 A JP2015-128006A

  An object of the present invention is to provide a conductive wiring sheet that is excellent in conductivity, and that is excellent in conductivity, durability, surface properties, and adhesion to a substrate of a conductive layer.

The present invention is a conductive wiring sheet having a sheet-like base material and a conductive layer disposed on the sheet-like base material, wherein the conductive layer is a binder resin (A) and a conductive carbon material (B). The wiring sheet having the density and thickness of a specific conductive layer, which can improve the conductivity, durability, surface properties, and adhesion to the substrate of the conductive layer.

That is, the present invention is a conductive wiring sheet having a sheet-like base material and a conductive layer disposed on the sheet-like base material,
The conductive layer includes a binder resin (A) and a conductive carbon material (B),
The wiring sheet is characterized in that the density of the conductive layer is 1.2 to 2.0 g / cm ³ and the thickness of the conductive layer is 500 μm or less.

The present invention also relates to the above wiring sheet, wherein the conductive layer has a volume resistivity of less than 1 × 10 ⁻² Ω · cm.

  The present invention also relates to the above-described wiring sheet, wherein the content of the conductive carbon material (B) in the conductive layer is 50 to 90% by mass.

  The present invention also relates to the above wiring sheet, wherein the conductive carbon material (B) contains flaky graphite.

  The present invention also relates to the above wiring sheet, wherein the conductive layer further contains a dispersant (C).

  In the conductive layer containing the binder resin (A) and the conductive carbon material (B), the contact density and the binding property between the carbon materials in the conductive layer are good due to the specific density, and thus excellent conductivity. A network can be formed and a wiring sheet excellent in conductivity can be provided.

The conductive wiring sheet can be obtained by various methods.

For example, on the surface of a substrate such as a PET (polyethylene terephthalate) film,
(1) A conductive composition containing a binder resin (A) and a conductive carbon material (B),
(2) a conductive composition containing a binder resin (A), a conductive carbon material (B), and a solvent;
(3) a conductive composition containing a binder resin (A), a conductive carbon material (B), and a dispersant (C);
(4) A conductive composition containing a binder resin (A), a conductive carbon material (B), a dispersant (C), and a solvent,
The conductive layer can be obtained by coating to form a conductive layer.

  In either case, the fact that the dispersion state of the conductive carbon material affects the performance of the conductive wiring sheet was described in detail in the section of the background art.

<Conductive composition>
The conductive composition contains a binder resin (A), a conductive carbon material (B), and, if necessary, a solvent.

  Moreover, although the appropriate viscosity of an electroconductive composition is based on the coating method of an electroconductive composition, generally it is preferable to set it as 10 mPa * s or more and 30,000 mPa * s or less.

First, the binder resin (A) will be described.
The binder resin is selected from the group consisting of polyurethane, polyamide, acrylonitrile, acrylic, butadiene, polyvinyl butyral, polyolefin, polyester, polystyrene, EVA, polyvinylidene fluoride, silicon resin, and the like. One or more can be included. However, it is not necessarily limited to these resins. Binder resin may be used individually by 1 type and may be used together 2 or more types.
The binder resin can also be a curable resin that undergoes a curing (crosslinking) reaction after the binder resin is applied to the substrate.
As the binder resin, a self-curing resin can be selected or combined with a curing agent to be described later, and the conductive composition can be printed (coated) on the substrate and then cured (crosslinked). .

As the binder resin, a polyurethane resin is preferable from the viewpoints of volume resistivity, adhesion to a substrate, and durability. After printing or coating the conductive composition on the substrate, the resin component softens when (hot) pressing, and the planar pattern shape of the conductive film during printing and coating is almost maintained. On the other hand, when flowing in the thickness direction, the voids are reduced and the contact between the conductive carbon materials (B) can be increased, so that a decrease in volume resistivity of the obtained conductive film can be expected. Accordingly, the binder resin is preferably one that softens and flows moderately during (hot) pressing.

<Polyurethane resin>
The method for synthesizing the polyurethane resin is not particularly limited. For example, the polyol compound (a) and the diisocyanate (b) are reacted, or the polyol compound (a), the diisocyanate (b), and a diol compound (c) having a carboxyl group. To obtain a urethane prepolymer (d) having an isocyanate group, further reacting the urethane prepolymer (d) with a polyamino compound (e), or reacting as necessary in the above three cases. Examples thereof include those obtained by reacting a terminator.

  As the polyol compound (a), various polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene glycols, or a mixture thereof, which are generally known as polyol components constituting a polyurethane resin, can be used.

Examples of polyether polyols include polymers or copolymers such as ethylene oxide, propylene oxide, and tetrahydrofuran.
Polyester polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1, Saturated and unsaturated low-molecular diols such as 5-pentanediol, hexanediol, octanediol, 1,4-butylenediol, diethylene glycol, triethylene glycol, dipropylene glycol, dimer diol, and n-butyl glycidyl ether, 2 -Alkyl glycidyl ethers of ethylhexyl glycidyl ethers, monocarboxylic acid glycidyl esters such as versatic acid glycidyl ester, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid Polyester polyols obtained by dehydration condensation of dicarboxylic acids such as fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, or the like, Examples include polyester polyols obtained by ring-opening polymerization of a cyclic ester compound.
As the polycarbonate polyol, 1) a reaction product of diol or bisphenol and a carbonic acid ester, and 2) a reaction product of diol or bisphenol with phosgene in the presence of an alkali can be used. Examples of the carbonate ester include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate. Examples of the diol include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3. '-Dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9 Nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl, 2,2 , 8, Examples thereof include bisphenol A, bisphenol F, and bisphenols obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to bisphenols. .

The number average molecular weight (Mn) of the polyol compound is appropriately determined in consideration of the solubility of the polyurethane resin when the conductive composition is produced, the durability of the formed conductive film, the adhesive strength to the substrate, and the like. However, usually the range of 580-8000 is preferable, More preferably, it is 1000-5000.
The above polyol compounds may be used alone or in combination of two or more. Furthermore, as long as the performance of the polyurethane resin is not lost, a part of the polyol compound can be replaced with low molecular diols, for example, various low molecular diols used in the production of the polyol compound.

As the diisocyanate compound (b), aromatic diisocyanate, aliphatic diisocyanate, alicyclic isocyanate, or a mixture thereof can be used, and isophorone diisocyanate is particularly preferable. Aromatic diisocyanates include 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-benzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1 , 3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate and the like.

Examples of the aliphatic diisocyanate include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate.
Examples of the alicyclic diisocyanate include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, norbornane diisocyanate methyl, bis (4-isocyanatocyclohexyl) methane, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate and the like. It is done.

Examples of the diol compound (c) having a carboxyl group include dimethylol alkanoic acid such as dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid and dimethylolpentanoic acid, dihydroxysuccinic acid, and dihydroxybenzoic acid. In particular, dimethylolpropionic acid and dimethylolbutanoic acid are preferable from the viewpoint of reactivity and solubility.
The conditions for obtaining the urethane prepolymer (d) having an isocyanate group by reacting the polyol compound (a), the diisocyanate (b), and the diol compound (c) having a carboxyl group are as follows: Although there is no particular limitation, the equivalent ratio of isocyanate group / hydroxyl group is preferably in the range of 1.05 / 1 to 3/1. More preferably, it is 1.2 / 1 to 2/1. The reaction is usually carried out at a temperature between normal temperature and 150 ° C., and is preferably carried out between 60 ° C. and 120 ° C. from the viewpoints of production time and side reaction control.

The polyamino compound (e) functions as a chain extender, and includes ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4′-diamine, norbornanediamine, 2 -(2-Aminoethylamino) ethanol, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxypropylethylenediamine and other amines having a hydroxyl group may also be used. it can. Of these, isophoronediamine is preferably used.

When synthesizing a polyurethane resin by reacting the urethane prepolymer (d) having an isocyanate group with the polyamino compound (e), a reaction terminator can be used in combination to adjust the molecular weight of the resulting polyurethane resin. As the reaction terminator, dialkylamines such as di-n-butylamine, dialkanolamines such as diethanolamine, and alcohols such as ethanol and isopropyl alcohol can be used.

The conditions for reacting the urethane prepolymer (d) having an isocyanate group with the polyamino compound (e) and, if necessary, the reaction terminator are not particularly limited, but are free isocyanates having both ends of the urethane prepolymer. When the group is 1 equivalent, the total equivalent of the amino group in the polyamino compound (e) and the reaction terminator is preferably in the range of 0.5 to 1.3. More preferably, it is in the range of 0.8 to 0.995.
The weight average molecular weight of the polyurethane resin is preferably in the range of 5,000 to 200,000.

When synthesizing a polyurethane resin, one or two kinds selected from ester solvents, ketone solvents, glycol ether solvents, aliphatic solvents, aromatic solvents, alcohol solvents, carbonate solvents, water, etc. The above can be used in combination.
Examples of ester solvents include ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, and ethyl lactate.
Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone benzene, diisobutyl ketone, diacetone alcohol, isophorone, and cyclohexanenone.
Examples of glycol ether solvents include ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, and acetates of these monoethers, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Examples include glycol monomethyl ether, propylene glycol monoethyl ether, and acetates of these monoethers.
Examples of the aliphatic solvent include n-heptane, n-hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane.
Examples of the aromatic solvent include toluene and xylene.
Examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and cyclohexanol.
Examples of the carbonate solvent include dimethyl carbonate, ethyl methyl carbonate, di-n-butyl carbonate and the like.

<Polyamide resin>
As the binder resin, a polyamide resin is preferable from the viewpoint of volume resistivity and adhesion to a substrate. The volume resistivity is good because the resin component in the (heat) press tends to flow.
The polyamide resin used in the present invention is a general term for polymers having an amide bond obtained by various reactions such as polycondensation of dibasic acid and diamine, polycondensation of aminocarboxylic acid, or ring-opening polymerization of lactam. In addition to various modified polyamides, products made from partially hydrogenated reactants, products obtained by partially copolymerizing other monomers, or other substances such as various additives were mixed. It is a broad concept including things.

The polyamide resin used in the present invention is not particularly limited as long as the above conditions are satisfied, but a dimer acid-modified polyamide resin obtained by condensation polymerization of dibasic acid mainly composed of dimer acid and polyamines is preferable. . As dimer acid in producing dimer acid-modified polyamide resin, dimer acid obtained by polymerizing natural monobasic unsaturated fatty acid contained in tall oil fatty acid, soybean oil fatty acid, etc. is widely used industrially. May be various dicarboxylic acids such as saturated aliphatic, unsaturated aliphatic, alicyclic, or aromatic.
Examples of commercially available dimer acids include Halidimer 200 and 300 (manufactured by Harima Chemicals), Versadim 228 and 216, Empor 1018, 1019, 1061, and 1062 (manufactured by Cognis). Furthermore, hydrogenated dimer acid can also be used, and examples of commercially available hydrogenated dimer acid include Prepol 1009 (manufactured by Croda Japan Co., Ltd.) and Empol 1008 (manufactured by Cognis).
In addition to the dimer acid, various dicarboxylic acids can be used as the dibasic acid in order to obtain a polyamide resin having appropriate flexibility. Specific examples of dicarboxylic acids include oxalic acid, malonic acid, (anhydrous) succinic acid, (anhydrous) maleic acid, glutaric acid, adipic acid, vimelic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid Acid, phthalic acid, naphthalenedicarboxylic acid, 1,3- or 1,4-cyclohexanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid and the like are used.

Furthermore, what has a phenolic hydroxyl group as a dibasic acid can also be used. By using a dibasic acid having a phenolic hydroxyl group, the phenolic hydroxyl group can be introduced into the side chain of the polyamide resin, and can be used for reaction with a curing agent.
As a dibasic acid having a phenolic hydroxyl group,
2-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, hydroxyisophthalic acid such as 5-hydroxyisophthalic acid,
2,5-dihydroxyisophthalic acid, 2,4-dihydroxyisophthalic acid, dihydroxyisophthalic acid such as 4,6-dihydroxyisophthalic acid,
Dihydroxyterephthalic acid such as 2-hydroxyterephthalic acid, 2,3-dihydroxyterephthalic acid, 2,6-dihydroxyterephthalic acid,
4-hydroxyphthalic acid, hydroxyphthalic acid such as 3-hydroxyphthalic acid,
Examples include 3,4-dihydroxyphthalic acid, 3,5-dihydroxyphthalic acid, 4,5-dihydroxyphthalic acid, and dihydroxyphthalic acid such as 3,6-dihydroxyphthalic acid.
Furthermore, these acid anhydrides and ester derivatives such as polybasic acid methyl esters are also included.
Of these, 5-hydroxyisophthalic acid is preferred from the viewpoints of copolymerizability and availability.

Furthermore, various monocarboxylic acids are used as necessary in order to obtain a polyamide resin having appropriate fluidity when heated. Specific examples of the monocarboxylic acid include propionic acid, acetic acid, caprylic acid (octanoic acid), stearic acid, and oleic acid.
Examples of the polyamines as reactants when producing the dimer acid-modified polyamide resin include various diamines such as aliphatic, alicyclic, and aromatic, triamine, and polyamine.
Specific examples of the diamine include ethylene diamine, propane diamine, butane diamine, triethylene diamine, tetraethylene diamine, hexamethylene diamine, p- or m-xylene diamine, 4,4′-methylene bis (cyclohexylamine), and 2,2-bis. -(4-cyclohexylamine), polyglycoldiamine, isophoronediamine, 1,2-, 1,3- or 1,4-cyclohexanediamine, 1,4-bis- (2'-aminoethyl) benzene, N-ethyl Examples include aminopiperazine and piperazine.
Examples of the triamine include diethylenetriamine, and examples of the polyamine include triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. Further, dimer diamine obtained by converting a dimerized aliphatic nitrile group and reducing it with hydrogen can also be used.

Examples of the polyamine compound include compounds obtained by converting a carboxyl group of a polybasic acid compound having a cyclic or non-cyclic hydrocarbon group having 20 to 48 carbon atoms into an amino group. Examples thereof include “Priamine 1071”, “Priamine 1073”, “Priamine 1074”, and “Puriamine 1075” manufactured by Japan Co., Ltd., “Versamin 551” manufactured by Cognis Japan Co., Ltd., and the like.
Alkanolamine may be used in combination with diamine. Examples of the alkanolamine include ethanolamine, propanolamine, diethanolamine, butanolamine, 2-amino-2-methyl-1-propanol, 2- (2-aminoethoxy) ethanol and the like.
Further, polyether diamine having oxygen in the skeleton can be used. This polyether has the general formula H ₂ N—R ₁ — (RO) _n —R ₂ —NH ₂ (wherein n is 2 to 100 and R ₁ and R ₂ have 1 to 14 carbon atoms) An alkylene group or an alicyclic hydrocarbon group, and R is an alkylene group or alicyclic hydrocarbon group having 1 to 10 carbon atoms. It may be expressed by: Examples of the ether diamine include polyoxypropylene diamine, and commercially available products include Jeffamines (manufactured by Sun Techno Chemical Co., Ltd.). Mention may also be made of bis- (3-aminopropyl) -polytetrahydrofuran.
The polyamines and dimer acid or various dicarboxylic acids are heat-condensed by a conventional method, and various polyamide resins including a dimer acid-modified polyamide resin are produced by an amidation process accompanied by dehydration. In general, the reaction temperature is about 100 to 300 ° C., and the reaction time is about 1 to 8 hours.

The binder resin has at least one structure selected from polyether, polyester, polycarbonate, or polybutadiene having a functional group capable of reacting with an isocyanate group from the viewpoint of volume resistivity, adhesion to a substrate, and durability. It is also preferable to contain a vinyl polymer (A1) having a side chain. The volume resistivity is good because the resin component in the (heat) press tends to flow.

(Polymer (A1))
Polymer (A1) is a polyether having a functional group capable of reacting with an isocyanate group in the main chain of a vinyl copolymer obtained by polymerizing a monomer having an ethylenically unsaturated double bond, A polyether, polyester, polycarbonate, or polybutadiene graft vinyl polymer into which at least one structure selected from polyester, polycarbonate, or polybutadiene is introduced as a side chain.

Examples of the functional group capable of reacting with an isocyanate group include a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an N-methylol group, and an N-alkoxymethyl group. A hydroxyl group is preferable in terms of reactivity.
The side chain introduction method is not particularly limited. For example, a copolymer (f) of an unsaturated dibasic acid and another monomer having an ethylenically unsaturated double bond is synthesized, It is selected from polyether, polyester, polycarbonate, or polybutadiene having a carboxylic acid or carboxylic anhydride portion of the copolymer (f), a functional group capable of reacting with a carboxyl group, and a functional group capable of reacting with an isocyanate group. It can introduce | transduce by carrying out a condensation reaction of the functional group which can react with the carboxyl group of at least 1 sort (s) (g).
In addition, when used in applications requiring higher toughness and durability, in order to obtain a higher crosslinking density, a functional group capable of reacting with isocyanate may be directly introduced into the vinyl polymer main chain. desirable. In that case, the polymer (A1) comprises an unsaturated dibasic acid (f1), a monomer (f2) other than (f1) having a functional group capable of reacting with isocyanate and an ethylenically unsaturated double bond, and ethylene. Copolymer (f) of monomer (f3) other than (f1) and (f2) having a functional unsaturated double bond, a functional group capable of reacting with a carboxyl group, and a functional group capable of reacting with an isocyanate group Can be obtained by a condensation reaction with at least one selected from the group consisting of polyether, polyester, polycarbonate, and polybutadiene.
Examples of the unsaturated dibasic acid (f1) that can be used for the synthesis of the copolymer (f) include maleic acid, maleic anhydride, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, crotonic acid, diphenylmethane-di -Γ-ketocrotonic acid and the like.
Unsaturated dibasic acid (f1) can be used 1 type or in mixture of 2 or more types according to required performance. Further, the proportion of the unsaturated dibasic acid (f1) in the monomer as the raw material of the copolymer (f) is preferably 0.01 to 30% by weight, more preferably 0.05 to 10% by weight. is there.
As a monomer (f2) other than (f1) having a functional group capable of reacting with isocyanate and an ethylenically unsaturated double bond, a (meth) acrylic monomer having a functional group capable of reacting with an isocyanate group, A vinyl monomer etc. can be used. Among these, a (meth) acrylic monomer is preferable in terms of reactivity.
Examples of the functional group capable of reacting with an isocyanate group include a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an N-methylol group, and an N-alkoxymethyl group. A hydroxyl group is preferable in terms of reactivity.

As the (meth) acrylic monomer having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Examples include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and polytetramethylene glycol mono (meth) acrylate.
Examples of (meth) acrylic monomers having an amino group include methylaminoethyl (meth) acrylate, ethylaminoethyl (meth) acrylate, butylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate. N, N-dialkylamino such as monoalkylaminoalkyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylamino (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate Examples include alkyl (meth) acrylate.
Examples of the (meth) acrylic monomer having a carboxyl group include acrylic acid and methacrylic acid.
Examples of the (meth) acrylic monomer having an epoxy group include glycidyl (meth) acrylate.
Examples of the (meth) acrylic monomer having an N-methylol group include N-methylol (meth) acrylamide.
Examples of the (meth) acrylic monomer having an N-alkoxymethyl group include N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-butoxymethyl ( (Meth) acrylamide and other (meth) acrylamides having N-monoalkoxymethyl groups, N, N-dimethylol (meth) acrylamide, N, N-di (methoxymethyl) (meth) acrylamide, N, N-di (ethoxymethyl) ) (Meth) acrylamide, N, N-di (propoxymethyl) (meth) acrylamide, (meth) acrylamide having an N, N-dialkoxymethyl group such as N, N-di (butoxymethyl) (meth) acrylamide Is mentioned.

Examples of the vinyl monomer include hydroxystyrene and vinyl alcohol.
Monomers (f2) other than (f1) having a functional group capable of reacting with isocyanate and an ethylenically unsaturated double bond may be used alone or in combination of two or more according to the required performance. it can. Further, the proportion of the monomer (f2) in the monomer that is a raw material of the copolymer (f) is preferably 0.01 to 50% by weight, more preferably 0.1 to 20% by weight, and particularly preferably. Is 0.1 to 10% by weight.

Monomers (f3) other than (f1) and (f2) having an ethylenically unsaturated double bond include (meth) acrylic monomers, aromatic vinyl monomers, olefinic hydrocarbon monomers Vinyl ether monomers can be used.
Examples of (meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and stearyl (meth) acrylate. Examples include alkyl (meth) acrylate and benzyl (meth) acrylate.
Examples of the aromatic vinyl monomer include styrene, methyl styrene, and ethyl styrene.
Examples of the olefinic hydrocarbon monomer include ethylene, propylene, butadiene, isobutylene, isoprene, 1,4-pentadiene and the like.
Examples of vinyl ether monomers include vinyl methyl ether.
Monomers other than (f1) and (f2) having an ethylenically unsaturated double bond can be used alone or in combination of two or more according to the required performance.

The copolymer (f) can be obtained by a known method, for example, solution polymerization. Solvents include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol methyl ether, diethylene glycol methyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc. Ethers, hydrocarbons such as hexane, heptane and octane, aromatics such as benzene, toluene, xylene and cumene, and esters such as ethyl acetate and butyl acetate can be used. Two or more solvents may be mixed and used.
The monomer concentration during synthesis is preferably 0 to 80% by weight.
Polymerization initiators include peroxides or azo compounds such as benzoyl peroxide, azoisobutylvaleronitrile, azobisisobutyronitrile, di-t-butyl peroxide, t-butyl perbenzoate, t-butyl peroctoate, Cumene hydroxy peroxide and the like can be used, and the polymerization temperature is preferably 50 to 200 ° C, particularly preferably 70 to 140 ° C.

The polystyrene equivalent weight average molecular weight of the copolymer (f) is preferably 5,000 to 500,000, more preferably 10,000 to 100,000.

Examples of the compound (g) include, for example, polyethers, polyesters, which have at least one functional group capable of reacting with a carboxyl group and at least one functional group capable of reacting with an isocyanate group at a linear end or a branched end. Polycarbonate or polybutadiene can be used. Among these, polyester is suitable for obtaining sufficient coating strength after hot pressing.
Examples of the functional group capable of reacting with the carboxyl group of the compound (g) include a hydroxyl group, an epoxy group, an amino group, and an isocyanate group, and a hydroxyl group is preferable in terms of reactivity. In addition, examples of the functional group capable of reacting with the isocyanate group of the compound (g) include a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an N-methylol group, and an N-alkoxymethyl group. Hydroxyl groups are preferred. The functional group capable of reacting with the carboxyl group of the compound (g) and the functional group capable of reacting with the isocyanate group may be the same functional group or different functional groups.

Examples of polyesters include terminal hydroxyl group-containing ester compounds obtained by esterifying at least one dicarboxylic acid and at least one polyol such as a polyhydric alcohol, a polyhydric phenol, or an alkoxy modified product thereof, and a terminal. And an ester compound in which the hydroxyl group is modified to an amino group, a carboxyl group, an epoxy group, an N-methylol group, or an N-alkoxymethyl group.
Examples of dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalic acid, p-oxybenzoic acid, p- (hydroxy) benzoic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, adipic acid And dicarboxylic acids such as azelaic acid, sebacic acid, and dodecanedicarboxylic acid.
Examples of polyhydric alcohols include 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 2-methyl-1,4-butanediol, 1,2-dimethyl- 1,4-butanediol, 2-ethyl-1,4-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,2 , 4-trimethyl-1,3-pentanediol, 3-ethyl-1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,6-hexanediol, 3-methyl-1,6-hexane Diol, 1,7-heptanediol, 2-methyl-1,7-heptanediol, 3-methyl-1,7-heptanediol, 4-methyl-1,7-heptanediol, 1, -Octanediol, 2-methyl-1,8-octanediol, 2-ethyl-1,8-octanediol, 3-methyl-1,8-octanediol, 4-methyl-1,8-octanediol, 1, 9-nonanediol, ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, cyclohexane dimethanol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, trimethylolpropane, 1,1,1-trimethylolpropane ethylene Examples include glycol, glycerin, erythritol, xylitol, sorbitol, and mannitol.
Examples of the polyhydric phenol include catechol, resorcin, hydroquinone, hexyl resorcin, trihydroxybenzene, dimethylolphenol and the like.
As polyester (polyester polyol) which has two or more hydroxyl groups of a commercial item, for example, Kuraray Polyol P-510, P-1010, P-1510, P-2010, P-3010, P-3010, manufactured by Kuraray Co., Ltd. P-5010, P-6010, P-2011, P-2013, P-520, P-1020, P-2020, P-1012, P-2012, P-530, P-1030, P-2030, PMHC- 2050, PMHC-2050R, PMHC-2070, PMHC-2090, PMSA-1000, PMSA-2000, PMSA-3000, PMSA-4000, F-2010, F-3010, N-2010, PNOA-1010, PNOA-2014, O-2010, Desmofe made by Sumitomo Bayer Urethane Co., Ltd. 650MPA, 651MPA / X, 670, 670BA, 680X, 680MPA, 800, 800MPA, 850, 1100, 1140, 1145, 1150, 1155, 1200, 1300X, 1652, 1700, 1800, RD181, RD181X, C200, Toyobo Co., Ltd. Byron 200, 560, 600, GK130, GK860, GK870, 290, GK590, GK780, GK790, and the like are available.
Examples of polyethers include polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and terminal hydroxyl groups to amino groups, carboxyl groups, epoxy groups, N-methylol groups or N-alkoxymethyl groups. Examples include modified ether compounds. Examples of the polyether (polyether polyol) having two or more commercially available hydroxyl groups include Desmophen 250U, 550U, 1600U, 1900U, 1915U, 1920D manufactured by Sumitomo Bayer Urethane Co., Ltd.

Examples of the polycarbonate include polycarbonate diols represented by the following general formula, and carbonate compounds in which the terminal hydroxyl group is modified with an amino group, carboxyl group, epoxy group, N-methylol group or N-alkoxymethyl group. .
H- (O-R-OCO-) nR-OH
(R: alkylene chain, diethylene glycol, etc.)
Examples of the commercially available polycarbonate having two or more hydroxyl groups include Kuraray Co., Ltd. Kuraray Polyol PNOC-1000, PNOC-2000, PMHC-2050, PMHC-2050R, PMHC-2070, PMHC-2070R, PMHC-2090R, C -2090 and the like.
Examples of polybutadiene include α, ω-polybutadiene glycol, α, β-polybutadiene glycol, and butadiene having a terminal hydroxyl group modified with an amino group, a carboxyl group, an epoxy group, an N-methylol group, or an N-alkoxymethyl group. Compounds.
Examples of the polybutadiene having two or more commercially available hydroxyl groups include NISSO-PBG-1000, G-2000, G-3000, GI-1000, GI-2000, GI-3000, GQ-1000, manufactured by Nippon Soda Co., Ltd. GQ-2000 etc. are mentioned.
Examples of the polybutadiene having two or more commercially available epoxy groups include NISSO-PBBF-1000, EPB-13, and EPB-1054 manufactured by Nippon Soda Co., Ltd.

The weight average molecular weight in terms of polystyrene of the compound (g) is preferably 500 to from the viewpoints of solubility in a solvent, compatibility with the copolymer (f), reactivity with the copolymer (f), and adhesion. 25,000, more preferably 1,000 to 10,000.

The polymer (A1) is obtained by subjecting the carboxylic acid or carboxylic anhydride portion of the copolymer (f) and the functional group capable of reacting with the carboxyl group of the compound (g) to a known method, for example, the compound (g). When the functional group capable of reacting with a carboxyl group is a hydroxyl group or an epoxy group, it can be obtained by esterification, when it is an amino group, it is amidated, and when it is an isocyanate group, it can be obtained by imidization. As the solvent, the solvent at the time of synthesizing the copolymer (f) can be used as it is, and other solvents can be added or desolvated depending on the conditions at the time of synthesis and the conditions at the time of coating. It doesn't matter.
As a reaction catalyst, tertiary amines, such as a triethylamine, a triethanolamine, ethylenediamine, etc. are used, for example, and 50-300 degreeC of reaction temperature is preferable.
The reaction ratio between the copolymer (f) and the compound (g) is such that the functional group capable of reacting with the carboxyl group of the compound (g) is 1 mol of the carboxylic acid or carboxylic anhydride of the copolymer (f). , 0.01 to 10 mol, preferably 0.1 to 5 mol, more preferably 0.5 to 2 mol.
The copolymer (f) and the compound (g) do not need to be used one by one, and a plurality of types may be used depending on the purpose and the required physical properties.
Moreover, the polystyrene equivalent weight average molecular weight of a polymer (A1) becomes like this. Preferably it is 5,000-500,000, More preferably, it is 10,000-100,000.

(Polyisocyanate compound (D))
When the binder resin is a vinyl polymer (A1) having a functional group capable of reacting with an isocyanate group and having at least one structure selected from polyether, polyester, polycarbonate, or polybutadiene in the side chain, Furthermore, it is preferable to contain a polyisocyanate compound (D) having two or more isocyanate groups.
The polyisocyanate compound having two or more isocyanate groups is used for crosslinking the polymer (A1) and the polymer (A1) and obtaining sufficient coating strength after hot pressing.
As the polyisocyanate compound, when used outdoors, it is preferable to use only an alicyclic or aliphatic compound in order to prevent the coating film from deteriorating with time.
Examples of the alicyclic polyisocyanate compound include isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, and the like.
Examples of the aliphatic polyisocyanate compound include trimethylhexamethylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.
Examples of the aromatic polyisocyanate compound include diphenylmethane diisocyanate, toluylene diisocyanate, naphthylene-1,5-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl. An isocyanate etc. are mentioned.
As the polyisocyanate compound, a bi-terminal isocyanate adduct of the above-mentioned compound and glycols or diamines, a biuret modified product, or an isocyanurate modified product may be used.
In particular, when the polyisocyanate compound contains an isocyanurate-modified product, particularly an isocyanurate ring-containing triisocyanate, it is preferable because sufficient coating strength can be obtained after hot pressing. Specific examples of the isocyanurate ring-containing triisocyanate include isocyanurate-modified isophorone diisocyanate (for example, Desmodur Z4470 manufactured by Sumitomo Bayer Urethane Co., Ltd.), isocyanurate-modified hexamethylene diisocyanate (for example, Sumidur manufactured by Sumitomo Bayer Urethane Co., Ltd.) N3300), isocyanurate-modified toluylene diisocyanate (for example, Sumidur FL-2, FL-3, FL-4, HLBA manufactured by Sumitomo Bayer Urethane Co., Ltd.).

The isocyanate group of the polyisocyanate compound is, for example, methanol, ethanol, n-pentanol, ethylene chlorohydrin, isopropyl alcohol, phenol, p-nitrophenol, m-cresol, acetylacetone, ethyl acetoacetate, or ε-caprolactam. You may use the block modified body which made it react with blocking agents, such as, and was made into a block.
Further, as the polyisocyanate compound, at least one (h) selected from polyether, polyester, polycarbonate, or polybutadiene having two or more functional groups capable of reacting with an isocyanate group and a diisocyanate compound having an isocyanate group at both ends (i ) May be used, and a both-terminal isocyanate prepolymer may be used. When the polyisocyanate compound contains the above-mentioned both-end isocyanate prepolymer, flexibility can be obtained with a small amount, and the adhesion to the substrate becomes good.
As the compound (h), the same compound as the compound (g) can be used. Examples of the compound (i) include toluylene diisocyanate, naphthylene-1,5-diisocyanate, o-toluylene diisocyanate, diphenylmethane diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, Examples include m-xylene diisocyanate, p-xylene diisocyanate, lysine diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, and the like.
Both terminal isocyanate prepolymers are compound (h) and compound (i) in such a ratio that the isocyanate group of compound (i) is larger than 1 mol with respect to 1 mol of the functional group capable of reacting with the isocyanate group of compound (h). It is obtained by mixing i) and reacting by heating and stirring. The polystyrene-equivalent weight average molecular weight of the prepolymer is preferably 500 to 50,000, more preferably 1,000 to 50,000, and particularly preferably 1,000 to 50,000 from the viewpoints of coating film strength, solubility, and compatibility. 10,000. .
In the polyisocyanate compound (D), the total number of isocyanate groups is preferably 0.1 times to 5.0 times, more preferably 0 with respect to the total number of functional groups of the polymer (A1), depending on the required performance. 1 type, or 2 or more types can be mixed and used by the ratio which becomes 0.5 times-3.0 times, Most preferably 0.8-2.0 times.

  Next, the conductive carbon material (B) will be described.

  The conductive carbon material (B) in the present invention is not particularly limited as long as it is a conductive carbon material, but graphite, carbon black, conductive carbon fiber (carbon nanotube, carbon nanofiber, carbon Fiber), fullerene, etc. can be used alone or in combination of two or more. From the viewpoint of conductivity, the use of graphite is preferred.

  For example, artificial graphite or natural graphite can be used as the graphite. Artificial graphite is made by artificially aligning irregularly arranged fine graphite crystals by heat treatment of amorphous carbon, and is generally manufactured using petroleum coke or coal-based pitch coke as the main raw material. The As natural graphite, scaly graphite, massive graphite, earthy graphite and the like can be used. It is also possible to use expanded graphite obtained by chemical treatment of flake graphite (also referred to as expandable graphite), expanded graphite obtained by heat treatment, and then expanded by refinement or pressing. I can do it. Among these graphites, when used in the conductive layer of the wiring sheet, flaky graphite such as flaky graphite, expanded graphite and exfoliated graphite is preferable from the viewpoint of conductivity.

These graphite surfaces are subjected to surface treatment such as epoxy treatment, urethane treatment, silane coupling treatment, and oxidation treatment in order to increase the affinity with the binder resin as long as the characteristics of the wiring sheet of the present invention are not impaired. May be.

The average particle size of the graphite used is preferably 0.5 to 500 μm, particularly preferably 2 to 100 μm.

  The average particle diameter as used in the present invention is a particle diameter (D50) that is 50% when the volume ratio of the particles is accumulated from a fine particle diameter in the volume particle size distribution. For example, a dynamic light scattering type particle size distribution meter ("Microtrack UPA" manufactured by Nikkiso Co., Ltd.).

  Examples of commercially available graphite include CMX, UP-5, UP-10, UP-20, UP-35N, CSSP, CSPE, CSP, CP, CB-150, and CB manufactured by Nippon Graphite Industries Co., Ltd. -100, ACP, ACP-1000, ACB-50, ACB-100, ACB-150, SP-10, SP-20, J-SP, SP-270, HOP, GR-60, LEP, F # 1, F # 2, F # 3, CX-3000, FBF, BF, CBR, SSC-3000, SSC-600, SSC-3, SSC, CX-600, CPF-8, CPF-3, CPB- manufactured by Chuetsu Graphite 6S, CPB, 96E, 96L, 96L-3, 90L-3, CPC, S-87, K-3, CF-80, CF-48, CF-32, CP-150, CP-100, CP, H -80, HF-48, HF-32, SC-120, SC-80, SC-60, SC-32, EC1500, EC1000, EC500, EC300, EC100, EC50, manufactured by Ito Graphite Industries, Ltd. 10099M, PB-99, etc. are mentioned. Examples of spherical natural graphite include CGC-20, CGC-50, CGB-20, and CGB-50 manufactured by Nippon Graphite Industries Co., Ltd. As the earth-like graphite, Blue P, AP, AOP, P # 1 manufactured by Nippon Graphite Industry Co., Ltd., APR, S-3, AP-6, 300F manufactured by Chuetsu Graphite Co., Ltd. may be mentioned. As artificial graphite, PAG-60, PAG-80, PAG-120, PAG-5, HAG-10W, HAG-150 manufactured by Nippon Graphite Industries Co., Ltd., RA-3000, RA-15, RA- manufactured by Chuetsu Graphite Co., Ltd. 44, GX-600, G-6S, G-3, G-150, G-100, G-48, G-30, G-50, SGP-100, SGP-50, SGP-25 manufactured by SEC Carbon Corporation , SGP-15, SGP-5, SGP-1, SGO-100, SGO-50, SGO-25, SGO-15, SGO-5, SGO-1, SGX-100, SGX-50, SGX-25, SGX -15, SGX-5, and SGX-1.

  Carbon black is a furnace black produced by continuously pyrolyzing a gas or liquid raw material in a reactor, especially ketjen black using ethylene heavy oil as a raw material. Channel black that has been rapidly cooled and precipitated, thermal black obtained by periodically repeating combustion and thermal decomposition using gas as a raw material, and particularly various types such as acetylene black using acetylene gas as a raw material, or 2 More than one type can be used in combination. Ordinarily oxidized carbon black, hollow carbon and the like can also be used.

  The oxidation treatment of carbon is performed by treating carbon at a high temperature in the air or by secondary treatment with nitric acid, nitrogen dioxide, ozone, etc., for example, such as phenol group, quinone group, carboxyl group, carbonyl group. This is a treatment for directly introducing (covalently bonding) an oxygen-containing polar functional group to the carbon surface, and is generally performed to improve the dispersibility of carbon. However, since it is common for the conductivity of carbon to fall, so that the introduction amount of a functional group increases, it is preferable to use the carbon which has not been oxidized.

As the specific surface area of the carbon black used increases, the number of contact points between the carbon black particles increases, which is advantageous in reducing the internal resistance of the electrode. Specifically, the specific surface area (BET) determined from the amount of nitrogen adsorbed is 20 m ² / g or more and 1500 m ² / g or less, preferably 50 m ² / g or more and 1500 m ² / g or less, more preferably 100 m ^2. / G or more,
It is desirable to use a thing of 1500 m < ² > / g or less. If carbon black having a specific surface area of less than 20 m ² / g is used, it may be difficult to obtain sufficient conductivity, and carbon black of more than 1500 m ² / g may be difficult to obtain from commercially available materials. is there.

  Further, the particle size of the carbon black to be used is preferably 0.005 to 1 μm, particularly preferably 0.01 to 0.2 μm in terms of primary particle size. However, the primary particle diameter here is an average of the particle diameters measured with an electron microscope or the like.

  Examples of commercially available carbon black include Toka Black # 4300, # 4400, # 4500, # 5500 manufactured by Tokai Carbon Co., Printex L manufactured by Degussa, Raven7000, 5750, 5250, 5000ULTRAIII manufactured by Colombian, 5000ULTRA, Conductex SC ULTRA, Conductex 975 ULTRA, PUERBLACK100, 115, 205, Mitsubishi Chemical Corporation # 2350, # 2400B, # 2600B, # 30050B, # 3030B, # 3230B, # 3350B, # 3400B, # 5400B, manufactured by Cabot MONARCH 1400, 1300, 900, Vulcan XC-72R, BlackPearls 2000, Ensaco 250G manufactured by TIMCAL, Ens furnace black such as aco260G, Ensaco350G, SuperP-Li, etc.), Ketjen black such as EC-300J, EC-600JD made by Lion, Denka black HS, Denka Black HS-100, FX-35 made by Denki Kagaku Kogyo Co., Ltd. Although acetylene black is mentioned, it is not limited to these, You may use combining 2 or more types.

  As the conductive carbon fibers, those obtained by firing from petroleum-derived raw materials are preferable, but those obtained by firing from plant-derived raw materials can also be used. Carbon nanotubes include single-walled carbon nanotubes that form a tube having a single graphene sheet and a diameter in the nanometer range, and multi-walled carbon nanotubes in which the graphene sheet is multilayered. Therefore, the diameter of the multi-walled carbon nanotube shows a large value of 30 nm as compared with 0.7 to 2.0 nm of a typical single-walled carbon nanotube.

Examples of commercially available conductive carbon fibers and carbon nanotubes include gas phase method carbon fibers such as VGCF manufactured by Showa Denko KK, EC1.0, EC1.5, EC2.0, EC1.5-P manufactured by Meijo Nanocarbon. Single-walled carbon nanotubes, FloTube 9000, FloTube 9100, FloTube 9110, FloTube 9200 made by CNano, NC7000 made by Nanocyl, 100T made by Kano, and the like.

Next, the dispersant (C) will be described. In the wiring sheet of the present invention, by using a dispersant in the conductive layer, a conductive layer excellent in dispersibility of the conductive carbon material (B) can be provided without inhibiting the conductivity. As a result, the conductivity, surface properties and adhesion of the conductive layer can be improved. Although it does not specifically limit as a dispersing agent which can be used, It is preferable to use the organic solvent dispersing agent and aqueous dispersing agent suitable for the solvent contained in an electroconductive composition, and 2 or more types may be used for it.

Examples of the organic solvent dispersant include a pigment derivative (I-1) having a basic functional group and a resin (I-2) having a basic functional group. Moreover, the pigment derivative (II-1) which has an acidic functional group, and resin (II-2) which has an acidic functional group are mentioned. Among the pigment derivatives having a basic functional group, preferred examples include an organic dye derivative (I-1) having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a base. And various derivatives such as a triazine derivative having a functional functional group. Further, among pigment derivatives having an acidic functional group, preferred forms include an organic dye derivative having an acidic functional group, an anthraquinone derivative having an acidic functional group, an acridone derivative having an acidic functional group, a triazine derivative having an acidic functional group, etc. And various derivatives thereof.

<Pigment derivative (I-1) having basic functional group>
The pigment derivative having a basic functional group comprises an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a triazine derivative having a basic functional group. One or more derivatives selected from the group may be contained.

  In particular, it is preferable to use a triazine derivative represented by the following formula (1) or an organic dye derivative represented by the following formula (6).

In the above formula (1),
X ¹ _{is, -NH -, - O -,} - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH-, or ^-X 2 ^-Y 1 ^{-X 3} - is and,
X ² _{is, -NH -, - O -,} - CONH -, - SO 2 NH -, - CH 2 NH -, - NHCO-, or -NHSO ₂ - and is,
Each X ³ is independently —NH— or —O—;
Y ¹ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
P is a substituent represented by any of the following formulas (2), (3), or (4),
Q is —O—R ² , —NH—R ² , a halogen group, —X ¹ —R ¹ , or a substituent represented by any of the following formulas (2), (3), or (4). ,
R ² is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group,
R ¹ is an organic dye residue, a substituted or unsubstituted heterocyclic residue, a substituted or unsubstituted aromatic ring residue, or a group represented by the following formula (5),
n ¹ is an integer of 1 to 4.

In the above formulas (2) to (4),
X ⁴ represents a direct bond, —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ NHCO.
_{NHCH 2 -, - CH 2 -} , or ^-X 5 ^-Y 2 ^{-X 6} - a and,
X ⁵ is —NH— or —O—.
X ⁶ represents a direct bond, —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ NHCO.
NHCH ₂ -, or -CH ₂ -,
Y ² is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
v is an integer from 1 to 10,
R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or R ³ and R ⁴ together. A substituted or unsubstituted heterocyclic residue containing additional nitrogen, oxygen or sulfur atoms,
R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group,
R ⁹ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group.

In the above formula (5),
T ^is a -X 8 ^{-R 10,} or ^{W 1,}
U ^is, -X 9 ^{-R 11,} or a ^{W 2,}
W ¹ and W ² are each independently —O—R ²⁰ , —NH—R ²⁰ , a halogen group, or a substituent represented by any one of the above formulas (2), (3), or (4). And
R ²⁰ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group,
X ⁷ is —NH— or —O—.
X ^8, and ^{X 9} are each independently, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH-, or a _-CH 2 NHCOCH ₂ NH-,
Y ³ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
R ¹⁰ and R ¹¹ are each independently an organic dye residue, a substituted or unsubstituted heterocyclic residue, or a substituted or unsubstituted aromatic ring residue.

Specific examples of organic dye residues represented by R ^{1 in the} above formula (1) and R ¹⁰ and R ¹¹ in the above formula (5) include diketopyrrolopyrrole dyes; azo, disazo, polyazo and the like Azo dyes; phthalocyanine dyes; anthraquinone dyes such as diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyrantrone, violanthrone; quinacridone dyes; dioxazine dyes; perinone dyes; Examples include a rylene dye, a thioindigo dye, an isoindoline dye, an isoindolinone dye, a quinophthalone dye, a slen dye, and a metal complex dye. In particular, from the viewpoint of enhancing the effect of suppressing the short circuit of the battery due to metal, it is preferable to use an organic dye residue that is not a metal complex dye.

Specific examples of the heterocyclic residue and aromatic ring residue represented by R ^{1 in the} above formula (1) and R ¹⁰ and R ¹¹ in the above formula (5) include thiophene, furan, pyridine, pyrazine, Examples include triazine, pyrazole, pyrrole, imidazole, isoindoline, isoindolinone, benzimidazolone, benzthiazole, benztriazole, indole, quinoline, carbazole, acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene, anthraquinone, and acridone. It is done. These heterocyclic residues and aromatic ring residues are alkyl groups (methyl group, ethyl group, butyl group, etc.), amino groups, alkylamino groups (dimethylamino group, diethylamino group, dibutylamino group, etc.), Nitro group, hydroxyl group, alkoxy group (methoxy group, ethoxy group, butoxy group, etc.), halogen (chlorine, bromine, fluorine, etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group) , May be substituted with an alkoxy group or halogen, etc.), and may be substituted with a phenylamino group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) May be substituted).

R ³ and R ⁴ in the above formulas (2) and (3) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, Alternatively, R ³ and R ⁴ are a heterocyclic residue which may have a substituent containing a further nitrogen, oxygen or sulfur atom together with R ³ and R ⁴ .

Y ¹ , Y ² and Y ³ in formulas (1) to (5) each independently represent a substituted or unsubstituted alkylene group, alkenylene group or arylene group having 20 or less carbon atoms, preferably substituted Alternatively, an unsubstituted phenylene group, a biphenylene group, a naphthylene group, or an alkylene group that may have a side chain having 10 or less carbon atoms is exemplified.

In equation (6),
Z is at least one selected from the group represented by the following formulas (7), (8), and (9), n ² is an integer of 1 to 4, and R ¹² is an organic dye residue. A group, a substituted or unsubstituted heterocyclic residue, or a substituted or unsubstituted aromatic residue.

In the above formulas (7) to (9),
X ¹⁰ represents a direct _{bond, -SO 2 -, - CO -} , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 -, - CH 2 -, or ^-X 11 ^-Y 4 ^{-X 12} - a and,
X ¹¹ is —NH— or —O—.
X ¹² represents a direct _{bond, -SO 2 -, - CO -} , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 -, or -CH ₂ -,
Y ⁴ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
v ¹ is an integer from ¹ to 10,
R ¹³ and R ¹⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted phenyl group, or R ³ and R ^4. Substituted or unsubstituted heterocyclic residues containing additional nitrogen, oxygen or sulfur atoms,
R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group,
R ¹⁹ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group.

Specific examples of the organic dye residue represented by R ¹² in formula (6) include diketopyrrolopyrrole dyes; azo dyes such as azo, disazo, and polyazo; phthalocyanine dyes; diaminodianthraquinone, anthrapyrimidine, Anthraquinone dyes such as flavantron, anthanthrone, indanthrone, pyranthrone and violanthrone; quinacridone dyes; dioxazine dyes; perinone dyes; perylene dyes; thioindigo dyes; Examples thereof include dyes; quinophthalone dyes; selenium dyes; and metal complex dyes. In particular, in order to enhance the effect of suppressing the short circuit of the battery due to metal, it is preferable to use an organic dye residue that is not a metal complex dye.

Examples of the heterocyclic residue and aromatic ring residue represented by R ¹² in the formula (6) include thiophene, furan, pyridine, pyrazole, pyrrole, imidazole, isoindoline, isoindolinone, and benzimidazolone. Benzthiazole, benztriazole, indole, quinoline, carbazole, acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene, anthraquinone, and acridone. These heterocyclic residues and aromatic ring residues are alkyl groups (such as methyl, ethyl, and butyl groups), amino groups, alkylamino groups (such as dimethylamino groups, diethylamino groups, and dibutylamino groups), Nitro group, hydroxyl group, alkoxy group (methoxy group, ethoxy group, butoxy group, etc.), halogen (chlorine, bromine, fluorine, etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group) , May be substituted with an alkoxy group, halogen, etc.), and may be substituted with a phenylamino group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) May be substituted).

R ¹³ and R ¹⁴ in formulas (7) and (8) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted phenyl group. Or a substituted or unsubstituted heterocyclic residue containing R ¹³ and R ¹⁴ together with an additional nitrogen, oxygen or sulfur atom.

Specific examples of the amine component used to form the substituents represented by the above formulas (2) to (4) and the above formulas (6) to (8) include the following.
Dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N- tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, Dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, , N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutyl Aminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoe Ruamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2 , 6-Lupetidine, 3,5-Lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonicopetinate, ethyl isonicopetinate, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N- Aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N- Butyl piperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like.

  The method for synthesizing an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, or a triazine derivative having a basic functional group is not particularly limited. A well-known method can be applied. For example, JP 54-62227, JP 56-118462, JP 56-166266, JP 60-88185, JP 63-305173, JP 3 A method described in JP-A No. 2676 or JP-A No. 11-199796 can be applied. The disclosure by the above publication is incorporated into a part of this specification by reference.

For example, various derivatives having a basic functional group react with an amine component after introducing a substituent represented by the following formulas (10) to (13) into an organic dye, anthraquinone, or acridone. Can be synthesized.
Formula (10):
-SO ₂ Cl
Formula (11):
-COCl
Formula (12):
-CH ₂ NHCOCH ₂ Cl
Formula (13):
—CH ₂ Cl

  Examples of the amine component include N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine, or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5. -Triazin-2-ylamino] aniline and the like can be used.

  For example, when introducing the substituent represented by the above formula (10), an organic dye, anthraquinone, or acridone is dissolved in chlorosulfonic acid and reacted with a chlorinating agent such as thionyl chloride. At that time, the number of substituents represented by the above formula (10) to be introduced into the organic dye, anthraquinone, or acridone can be controlled by adjusting conditions such as reaction temperature and reaction time.

  In addition, when the substituent represented by the above formula (11) is introduced, an organic dye having a carboxyl group, anthraquinone, or acridone is first synthesized by a known method, and then thionyl chloride in an aromatic solvent such as benzene. And the like, and the like.

  During the reaction of the substituents represented by the above formulas (10) to (13) and the amine component, a part of the substituents represented by the formulas (10) to (13) are hydrolyzed, and chlorine is substituted with hydroxyl groups. There are things to do. In that case, the substituent represented by the formula (10) is a sulfonic acid group, and the substituent represented by the formula (11) is a carboxylic acid group. Each acid group may remain as a free acid. Or you may form the salt with 1-3 said metal or said amine, respectively.

  When the organic dye is an azo dye, a substituent represented by formulas (7) to (9) or the following formula (14) is previously introduced into the diazo component or coupling component, and then the coupling reaction is performed. An azo dye derivative can also be produced by carrying out the process.

In equation (14),
X ¹³ represents —NH—, —O—, —CONH—, —SO ₂ NH—, —CH ₂ NH—, —CH _2.
NHCOCH ₂ NH—, or —X ¹⁴ —Y ⁵ —X ¹⁵ —,
X ¹⁴ _{is, -NH -, - O -,} - CONH -, - SO 2 NH -, - CH 2 NH -, - NHCO-, or -NHSO ₂ - and is,
Each X ¹⁵ is independently —NH— or —O—;
Y ⁵ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
P ¹ is a substituent represented by any of the above formulas (2), (3), or (4),
Q ² is —O—R ²⁴ , —NH—R ²⁴ , a halogen group, —X ¹ —R ²⁵ , or a substituent represented by any one of the above formulas (2), (3), or (4). Yes,
R ²⁴ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group,
R ²⁵ is an organic dye residue, a substituted or unsubstituted heterocyclic residue, a substituted or unsubstituted aromatic ring residue, or a group represented by the above formula (5).

  The triazine derivative having a basic functional group, for example, uses cyanuric chloride as a starting material, and at least one chlorine of cyanuric chloride has a substituent represented by the above formulas (7) to (9) or formula (14). It is obtained by reacting the amine component to be formed (for example, N, N-dimethylaminopropylamine, N-methylpiperazine or the like) and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

  As one of the effects of various derivatives having the above basic functional group, it is considered that the added derivative exerts a dispersion effect by acting (for example, adsorbing) on the surface of the carbon material. In the case of a carbon material, since the particle surface has high hydrophobicity, it is considered that the adsorption effect of various derivatives having a basic functional group is further improved, and a dispersion effect is also exhibited.

  That is, completely or partially dissolve an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, or a triazine derivative having a basic functional group in an organic solvent. By adding and mixing a conductive carbon material in the solution, the action of these derivatives on the carbon material (for example, adsorption) proceeds, and the basic function possessed by the derivative that acts on the surface of the carbon material (for example, adsorption) It is considered that the polarity of the group promotes the wetting of the surface of the carbon material with respect to the solvent and facilitates the aggregation of the carbon material.

  In preferable embodiment of this invention, the various derivative | guide_body which has a basic functional group is used together with resin (I-2) which has a basic functional group mentioned later. In another preferred embodiment of the present invention, various derivatives having a basic functional group are used in combination with an acidic compound. The acidic compound may be a resin (II-2) having an acidic functional group described later, or an inorganic acid described later or an organic acid having a molecular weight of 300 or less.

  As in the above embodiment, the dispersion stability of the carbon material can be further improved by appropriately combining a resin having a basic functional group or an acidic compound in addition to various derivatives having a basic functional group. In addition, since the adhesion between the carbon material and the binder resin (A) as a binder component is improved through the resin having the acidic functional group or the resin having the basic functional group, The adhesion with the conductive layer may also be improved.

  In particular, when a resin (I-2) having a basic functional group, which will be described later, is used in combination, the basic functional group acts on the surface of the carbon-based catalyst material (for example, adsorbs) like the derivative having the basic functional group. Thus, wetting of the carbon material surface to the solvent is promoted, and it is considered that the dispersion stability of the carbon material is further increased by repulsion due to steric hindrance of the resin.

  Moreover, when resin (II-2) which has an acidic functional group mentioned later as an acidic compound is used together, interaction (for example, acid-base interaction) of an acidic functional group and the basic functional group which the said derivative has, It is considered that the adhesion between the carbon material and the resin component is improved and the dispersion stability of the carbon material is further increased.

  Further, when an inorganic acid or an organic acid having a molecular weight of 300 or less is used in combination as an acidic compound, the interaction between the acidic compound and the basic functional group of the derivative (for example, formation of an ion pair by neutralization (salt formation) ), And polarization or dissociation of ion pairs (salts)), the electrostatic repulsion on the surface of the carbon material is promoted, and it is considered that the dispersion stability of the carbon material is further increased. Such an embodiment is described in further detail below.

<Acid compound: inorganic acid, organic acid having a molecular weight of 300 or less>
One or more derivatives selected from the group consisting of organic dye derivatives having basic functional groups, anthraquinone derivatives having basic functional groups, acridone derivatives having basic functional groups, and triazine derivatives having basic functional groups When used as a dispersant, it is preferable to add an acidic compound as a dispersion aid in order to obtain good dispersion and dispersion stability of the carbon material. The acidic compound used at this time is not particularly limited, and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and organic acids such as carboxylic acids, phosphoric acids and sulfonic acids can be used. Among them, it is preferable to use an acidic compound that decomposes or volatilizes in the drying step when preparing the conductive layer, and it is preferable to use an organic acid having a molecular weight of 300 or less, preferably 200 or less. Further, it is preferable to use an acid having low reactivity with the carbon material, and organic acids, particularly carboxylic acids are particularly preferable. Specifically, for example, formic acid, acetic acid, fluoroacetic acid, propionic acid, butyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, acrylic acid, methacrylic acid, crotonic acid, malein Examples include acids, fumaric acid, itaconic acid, and citraconic acid.

  These inorganic acids and organic acids having a molecular weight of 300 or less are organic dye derivatives having basic functional groups, anthraquinone derivatives having basic functional groups, acridone derivatives having basic functional groups, or triazine derivatives having basic functional groups. For example, formation of ion pairs by neutralization (salt formation) and polarization or dissociation of ion pairs (salts). As a result, the solubility of the derivatives having these basic functional groups is improved, and an electrical interaction is induced on the surface of the carbon material on which the derivatives having these basic functional groups act (for example, adsorbed). It seems that deagglomeration is promoted. Here, the interaction is, for example, electrostatic repulsion between cations derived from a derivative having a basic functional group adsorbed on the surface of the carbon material, or electrostatic repulsion by an electric double layer formed by dissociated acid anions. Is assumed.

  As described above, in one embodiment of the present invention, a functional group is directly introduced on the surface of a carbon material by using the derivative having a basic functional group and preferably an inorganic acid or an organic acid having a molecular weight of 300 or less ( Good dispersion can be obtained without using a covalent bond and without using a dispersion resin. As a result, a conductive layer in which the carbon material is favorably dispersed can be obtained without reducing the conductivity of the carbon material.

<Resin having basic functional group (I-2)>
In order to obtain good dispersion and dispersion stability of the carbon material, the conductive layer of the present invention may contain a resin having a basic functional group. Preferred basic functional groups are primary, secondary, and tertiary amino groups or amide groups. The resin having a basic functional group is selected from the group consisting of three types of resins described below from the viewpoint of dispersion stability, that is, a polymer (G1), a polymer (G2), and a vinylamide resin. It is preferable to use more than one resin.

  The resin having the basic functional group functions as a binder for binding the carbon materials to each other or binding the carbon material to the electrode membrane assembly. The resin having such a basic functional group is selected from the group consisting of various derivatives (II-1) having an acidic functional group described later, that is, organic dye derivatives having an acidic functional group and triazine derivatives having an acidic functional group. By using together with one or more kinds of compounds (x ″), the dispersion stability of the carbon material and the adhesion between the substrate of the wiring sheet and the conductive layer can be improved.

  In the above-described embodiment, an acidic functional group of a derivative having an acidic functional group acting (for example, adsorbing) on the carbon material surface interacts with a basic functional group of a resin having a basic functional group (for example, acid-base). Interact). Or the derivative | guide_body which has an acidic functional group, and resin which has a basic functional group interact (for example, acid-base interaction), On the other hand, it adsorb | sucks to the carbon material surface. As a result, in the above-described embodiment, the adsorption of the resin having the basic functional group to the surface of the carbon material is promoted, the adhesion between the carbon material and the resin component is improved, and the repulsion due to the steric hindrance of the resin. It is considered that the dispersion stability of the carbon material can be improved. Hereinafter, as specific examples of the resin having a basic functional group, three types of resins that can be suitably used in the present invention, the polymer (G1), the polymer (G2), and the vinylamide resin will be described.

<Resin having basic functional group (G1)>
Resin (G1) having a basic functional group that can be used in the present invention comprises a hydroxyl group of vinyl polymer (A1) having two hydroxyl groups in one terminal region, and an isocyanate group of diisocyanate (B1). Synthesis by reacting the isocyanate group of the urethane prepolymer (C1) having isocyanate groups at both ends obtained by reaction with the primary and / or secondary amino groups of polyamine (D1) and monoamine (E1). Is done.

  The vinyl polymer site grafted to the side chain derived from the vinyl polymer (A) has excellent affinity with a wide range of carbon materials and solvents, functions as a solvent affinity site, and the urea binding site of the main chain is acidic. It has an excellent ability to interact with an organic dye derivative having a functional group or a triazine derivative having an acidic functional group, and functions as an adsorbing group on the surface of a carbon material that is biased to an acid via the derivative. Furthermore, an amino group can be introduced into the main chain in order to further improve the adsorptivity.

  Hereinafter, each component of the polymer (G1) having a basic functional group will be described.

<Vinyl polymer having two hydroxyl groups in one end region (A1)>
The vinyl polymer (A1) having two hydroxyl groups in one end region (hereinafter sometimes abbreviated as vinyl polymer (A1)) has two hydroxyl groups and one thiol group in the molecule. It can be obtained by radical polymerization of the ethylenically unsaturated monomer (a12) in the presence of the compound (a11). The vinyl polymer part of the vinyl polymer (A1) is a part having a high affinity for the carbon material and is represented by the following formula (15).

In the above formula (15),
R ⁵⁰¹ is a residue obtained by removing a hydroxyl group and a thiol group from the compound (a11),
R ⁵⁰² is a residue obtained by removing the double bond site and R ⁵⁰³ from the ethylenically unsaturated monomer (a12),
R ⁵⁰³ is a hydrogen atom or a methyl group,
n ⁵⁰¹ is an integer of 2 or more, preferably an integer of 3 to 200.
Here, R ⁵⁰¹ is a terminal region in the vinyl polymer (A1).

<Compound (a11) having two hydroxyl groups and one thiol group in the molecule>
As the compound (a11) having two hydroxyl groups and one thiol group in the molecule (hereinafter sometimes referred to as compound (a11)), two hydroxyl groups and one thiol group in the molecule Is not particularly limited, for example, 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propane Diol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and 2-mercaptoethyl-2-ethyl-1,3-pro Njioru, and the like.

  A compound (a11), an ethylenically unsaturated monomer (a12), and optionally a polymerization initiator are mixed in accordance with the molecular weight of the vinyl polymer (A1) having two hydroxyl groups in one target end region. Then, the vinyl polymer (A1) can be obtained by heating. It is preferable to perform bulk polymerization or solution polymerization using 0.5 to 30 parts by weight of the compound (a11) with respect to 100 parts by weight of the ethylenically unsaturated monomer (a12). The amount of the compound (a11) used relative to 100 parts by weight of the ethylenically unsaturated monomer (a12) is more preferably 1 to 20 parts by weight, still more preferably 2 to 15 parts by weight, particularly preferably 2 to 10 parts by weight. It is. The reaction temperature is 40 to 150 ° C, preferably 50 to 110 ° C. When the amount of the compound (a11) used is less than 0.5 parts by weight, the molecular weight of the vinyl polymer portion is too high, and the absolute amount increases as an affinity portion for the carbon material and the solvent. The effect itself may decrease. On the other hand, if the amount used exceeds 30% by weight, the molecular weight of the vinyl polymer part is too low, and the effect of steric repulsion is lost as an affinity site for the carbon material and the solvent, and the aggregation of the carbon material is suppressed. May be difficult.

<Polymerization initiator>
In the polymerization, 0.001 to 5 parts by weight of a polymerization initiator can be arbitrarily used with respect to 100 parts by weight of the ethylenically unsaturated monomer (a12). As the polymerization initiator, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), and 2,2′-azobis [2- (2-imidazolin-2-yl) ) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more.

<Polymerization solvent>
In the case of solution polymerization, ethyl acetate, n-butyl acetate, isobutyl acetate, N-methyl-2-pyrrolidone, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, diethylene glycol diethyl ether, etc. are used as a polymerization solvent. However, it is not particularly limited to these. These polymerization solvents may be used as a mixture of two or more, but are preferably solvents used for end use.

<Ethylenically unsaturated monomer (a12)>
Examples of the ethylenically unsaturated monomer (a12) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl. (Meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, and isobornyl (meth) ) Alkyl (meth) acrylates such as acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxydiethylene glycol (meth) Aromatic (meth) acrylates such as acrylate; heterocyclic (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate and oxetane (meth) acrylate; methoxypolypropylene glycol (meth) acrylate, and ethoxypolyethylene glycol (meta ) Alkoxy polyalkylene glycol (meth) acrylates such as acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone ( N-substituted (meth) acrylamides such as meth) acrylamide and acryloylmorpholine; N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) a Amino group-containing (meth) acrylates such as Relate; and include (meth) nitriles such as acrylonitrile.

  Moreover, as monomers that can be used in combination with the acrylic monomers, styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether And fatty acid vinyls such as vinyl acetate and vinyl propionate.

  Moreover, a carboxyl group-containing ethylenically unsaturated monomer can be used in combination. As the carboxyl group-containing ethylenically unsaturated monomer, one or more kinds can be selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like.

<Polymerization conditions and others>
In the present invention, among the ethylenically unsaturated monomers (a12) exemplified above, methyl methacrylate can be preferably used from the viewpoint of dispersibility and resistance. From the viewpoint of affinity with the carbon material and the solvent, it is more preferable to use methyl methacrylate and butyl methacrylate or t-butyl methacrylate in combination. When methyl methacrylate is used as the ethylenically unsaturated monomer (a2) and butyl methacrylate is not used, the proportion of methyl methacrylate is 30 in the total 100% by weight of the ethylenically unsaturated monomer (a12). It is preferably ˜100% by weight, and more preferably 50˜100% by weight. In addition, when methyl methacrylate and butyl methacrylate or t-butyl methacrylate are used in combination as the ethylenically unsaturated monomer (a12), the total of both is 30 to 100 weight of the ethylenically unsaturated monomer (a12). %, Preferably 50 to 100% by weight. When methyl methacrylate is used as the ethylenically unsaturated monomer (a12), further, when methyl methacrylate and butyl methacrylate or t-butyl methacrylate are used in combination, the dispersibility becomes better. While the copolymerization site of methyl methacrylate and butyl methacrylate or t-butyl methacrylate retains basic physical properties such as dispersibility, it has good affinity with binder resins and dispersion solvents and is highly versatile.

  The weight average molecular weight (Mw) in terms of polystyrene by GPC of the vinyl polymer (A1) having two hydroxyl groups in one terminal region is preferably 500 to 30,000, and 1,000 to 15,000. Is more preferable, and 1,000 to 8,000 is particularly preferable. When the weight average molecular weight is less than 500, the effect of steric repulsion by the solvent affinity part is reduced, and it becomes difficult to prevent the carbon material from agglomerating, and the dispersion stability may be insufficient. On the other hand, if it exceeds 30,000, the absolute amount of the solvent-affinity part increases and the dispersibility effect itself may be lowered. Furthermore, the viscosity of the conductive composition may increase.

  When the weight average molecular weight of the resin having the basic functional group is 500 to 30,000, it is advantageous to suppress an increase in the viscosity of the conductive composition by preventing aggregation of the carbon material.

  The glass transition temperature (Tg) of the vinyl polymer (A1) having two hydroxyl groups in one end region is preferably 50 to 200 ° C., more preferably 50 to 120 ° C., from the viewpoint that the resistance of the coating film is improved. .

  As the Tg of the vinyl polymer (A1) having two hydroxyl groups in one terminal region, a value calculated by the following Fox formula was used. In addition, although the skeleton derived from the compound (a11) having two hydroxyl groups and one thiol group in the molecule is also present in the vinyl polymer (A1), it is excluded in the following calculation for calculating the glass transition temperature. .

      1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wn / Tgn

  In the above formula, W1 to Wn indicate the weight fraction of each monomer used, and Tg1 to Tgn are the glass transition temperatures of the respective homopolymers obtained from each monomer (units are absolute temperatures). "K").

The Tg of the main homopolymer used for the calculation is exemplified below.
Methyl methacrylate: 105 ° C (378K)
Butyl methacrylate: 20 ° C (293K)
t-butyl methacrylate: 107 ° C. (380 K)
Lauryl methacrylate: -65 ° C (208K)
2-ethylhexyl methacrylate: -10 ° C (263K)
Cyclohexyl methacrylate: 66 ° C (339K)
Butyl acrylate: -45 ° C (228K)
Ethyl acrylate: -20 ° C (253K)
Benzyl methacrylate: 54 ° C (327K)
Styrene: 100 ° C (373K)

<Diisocyanate (B1)>
As the diisocyanate (B1) which is a constituent element of the polymer (G1) having a basic functional group, conventionally known ones can be used. For example, aromatic diisocyanate (b11), aliphatic diisocyanate (b12) ), Araliphatic diisocyanate (b13), alicyclic diisocyanate (b14), and the like.

  Examples of the aromatic diisocyanate (b11) include xylylene diisocyanate, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and 2,4-tolylene diisocyanate. Examples include isocyanate, 2,6-tolylene diisocyanate, 4,4′-toluidine diisocyanate, naphthylene diisocyanate, and 1,3-bis (isocyanatomethyl) benzene.

  Examples of the aliphatic diisocyanate (b12) include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, Examples include dodecamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.

  As the araliphatic diisocyanate (b13), ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4- Examples include diethylbenzene, 1,4-tetramethylxylylene diisocyanate, and 1,3-tetramethylxylylene diisocyanate.

  Examples of the alicyclic diisocyanate (b14) include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate. , Methyl-2,4-cyclohexane diisocyanate, and methyl-2,6-cyclohexane diisocyanate.

  As mentioned above, listed diisocyanate (B1) is not necessarily limited to these, It can also be used in combination of 2 or more types.

  As the diisocyanate (B) used in the present invention, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (also known as isophorone diisocyanate, IPDI) is preferable because it is hardly yellow-modified.

<Polyamine (D1)>
The polyamine (D1), which is a component of the resin (G1) having a basic functional group, is a compound having at least two primary and / or secondary amino groups, and reacts with an isocyanate group to generate a urea bond. Used for. A diamine (d11) is mentioned as such an amine.

  As the diamine (d11) having two primary amino groups, known ones can be used. Specifically, ethylenediamine, propylenediamine [alias: 1,2-diaminopropane or 1,2-propanediamine], Trimethylenediamine [alias: 1,3-diaminopropane or 1,3-propanediamine], tetramethylenediamine [alias: 1,4-diaminobutane], 2-methyl-1,3-propanediamine, pentamethylenediamine [ Alias: 1,5-diaminopentane], hexamethylenediamine [alias: 1,6-diaminohexane], 2,2-dimethyl-1,3-propanediamine, 2,2,4-trimethylhexamethylenediamine, and tri Aliphatic diamines such as range amines; isophorone diamine and dicyclohexylmethane Alicyclic diamines such as 4,4'-diamine; and can include phenylenediamine, and an aromatic diamine such as xylylenediamine.

  Moreover, as diamine (d11) which has two secondary amino groups, a well-known thing can be used, Specifically, N, N- dimethylethylenediamine, N, N- diethylethylenediamine, and N, N Examples include '-di-tert-butylethylenediamine.

  Moreover, as diamine (d11) which has a primary and secondary amino group, a well-known thing can be used, Specifically, N-methylethylenediamine [alias: methylaminoethylamine], N-ethylethylenediamine [alias] : Ethylaminoethylamine], N-methyl-1,3-propanediamine [alias: N-methyl-1,3-diaminopropane or methylaminopropylamine], N, 2-methyl-1,3-propanediamine, N -Isopropylethylenediamine [alias: isopropylaminoethylamine], N-isopropyl-1,3-diaminopropane [alias: N-isopropyl-1,3-propanediamine or isopropylaminopropylamine], and N-lauryl-1,3- Propanediamine [alias: N-lauryl-1,3-dia It can be exemplified Nopuropan or lauryl amino propylamine], and the like.

  A polyamine is a compound having at least two primary and / or secondary amino groups, and the primary and / or secondary amine reacts with an isocyanate group to form a urea group, and this urea group serves as an adsorption site for the carbon material. However, when the polyamine (D1) is a compound having two primary and / or secondary amino groups at both ends and further having a secondary and / or tertiary amino group at both ends, Since the adsorptivity with respect to a carbon material improves, it is especially preferable.

  As such polyamine (D1), polyamines having two primary and / or secondary amino groups at both ends as shown below, and having secondary and / or tertiary amino groups at both ends (see below) d12).

  As polyamine (d12), methyliminobispropylamine [also known as N, N-bis (3-aminopropyl) methylamine], lauryliminobispropylamine [also known as N, N-bis (3-aminopropyl) laurylamine] , Iminobispropylamine [also known as N, N-bis (3-aminopropyl) amine], N, N′-bisaminopropyl-1,3-propylenediamine, and N, N′-bisaminopropyl-1,4 -Butylene diamine etc. can be mentioned, The methyliminobispropylamine and lauryliminobispropylamine which have two primary amino groups and one tertiary amino group are preferable since reaction with diisocyanate is easy to control.

  An iminobispropylamine having two primary amino groups and one secondary amino group is preferable because of its good adsorptivity to the carbon material.

  As the polyamine (D1), a polymer (d13) having two or more primary and / or secondary amino groups can also be used.

  Examples of the polymer (d13) having a primary and / or secondary amino group include an ethylenically unsaturated monomer having a primary amino group and an ethylenically unsaturated monomer having a secondary amino group, such as vinylamine and allylamine. Homopolymers (so-called polyvinylamine and polyallylamine), copolymers thereof with other ethylenically unsaturated monomers, ring-opening polymers of ethyleneimine, and polycondensates of ethylene chloride and ethylenediamine Or a ring-opening polymer of oxazolidone-2 (so-called polyethyleneimine). The content of primary and / or secondary amino groups in the polymer is preferably 10 to 100% by weight, more preferably 20 to 100% by weight, in terms of monomer units, based on the polymer. If the content is 10% by weight or more, it is effective for preventing aggregation of the carbon material and suppressing an increase in the viscosity of the conductive composition.

  Examples of the ethylenically unsaturated monomer copolymerizable with an ethylenically unsaturated monomer having a primary amino group and an ethylenically unsaturated monomer having a secondary amino group include (meth) acrylic acid, croton Unsaturated carboxylic acids such as acid, itaconic acid, maleic acid and fumaric acid; aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, chloromethylstyrene, indene and vinyltoluene; methyl (meth) (Meth) acrylic acid alkyl esters such as acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; (Meth) acrylic acid alkyl aryl ester; glycidyl (meth) acrylate (Meth) acrylic acid substituted alkyl ester having a functional group such as 2-hydroxyethyl (meth) acrylate; tertiary amino group such as dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylate (meth) Acrylic acid-substituted alkyl ester; (meth) acrylamide, dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, n-butyl (meth) acrylamide, tert-butyl (meth) acrylamide, tert-octyl (meth) acrylamide, etc. Alkyl (meth) acrylamides; substituted alkyl (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide; 1,3-butadiene, and isoprene Diene compounds such as one-end methacryloylated polymethyl methacrylate oligomer, one-end methacryloylated polystyrene oligomer, and one-end methacryloylated polyethylene glycol and other polymerizable oligomers (macromonomer); and vinyl cyanide.

  The polymer having a primary and / or secondary amino group has a polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography), preferably 300 to 75,000, 300 to 20, 000 is more preferable, and 500 to 5,000 is particularly preferable. When the weight average molecular weight is 300 to 75,000, it is effective to suppress an increase in viscosity of the conductive composition by preventing aggregation of the carbon material.

<Monoamine (E1)>
As the amine compound that is a constituent element of the resin (G1) having a basic functional group, in addition to the polyamine (D1), a monoamine (E1) can also be used. The monoamine (E1) is a monoamine compound having one primary amino group or secondary amino group in the molecule, and the monoamine (E1) has a high molecular weight in the reaction between the diisocyanate (B1) and the polyamine (D1). It is used as a reaction terminator in order to suppress excessive conversion. The monoamine (E1) may have a polar functional group other than the primary amino group or the secondary amino group in the molecule. Examples of such polar functional groups include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a cyano group, and a nitroxyl group.

  As the monoamine (E1), conventionally known ones can be used. Specific examples include aminomethane, aminoethane, 1-aminopropane, 2-aminopropane, 1-aminobutane, 2-aminobutane, 1-aminopentane, 2- Aminopentane, 3-aminopentane, isoamylamine, N-ethylisoamylamine, 1-aminohexane, 1-aminoheptane, 2-aminoheptane, 2-octylamine, 1-aminononane, 1-aminodecane, 1-aminododecane, 1-aminotridecane, 1-aminohexadecane, stearylamine, aminocyclopropane, aminocyclobutane, aminocyclopentane, aminocyclohexane, aminocyclododecane, 1-amino-2-ethylhexane, 1-amino-2-methylpropane, 2-amino-2-me Rupropane, 3-amino-1-propene, 3-aminomethylheptane, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 2-ethylhexyloxypropylamine, 3-decyloxypropylamine , 3-lauryloxypropylamine, 3-myristoxypropylamine, 2-aminomethyltetrahydrofuran, dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n- Propylamine, di-n-butylamine, disec-butylamine, N-ethyl-1,2-dimethylpropylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupe Gin, 3,5-lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonipecotate, ethyl isonipecotate, 2-piperidineethanol, 4-piperidineethanol, 4-piperidinebuty Rick acid hydrochloride, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, 3-pyrrolidinol, indoline, aniline, N-butylaniline, o-aminotoluene, m-aminotoluene, p-aminotoluene, o-benzylaniline, p -Benzylaniline, 1-anilinonaphthalene, 1-aminoanthraquinone, 2-aminoanthraquinone, 1-aminoanthracene, 2-aminoanthracene, 5-aminoisoquinoline, o-aminodiphenyl, 4-aminodiphenyl ether, β- Minoethylbenzene, 2-aminobenzophenone, 4-aminobenzophenone, o-aminoacetophenone, m-aminoacetophenone, p-aminoacetophenone, benzylamine, N-methylbenzylamine, 3-benzylaminopropionic acid ethyl ether, 4- Examples include benzylpiperidine, α-phenylethylamine, phenesylamine, p-methoxyphenesylamine, furfurylamine, p-aminoazobenzene, m-aminophenol, p-aminophenol, allylamine, and diphenylamine.

  Among them, a monoamine compound having only a secondary amino group as an aliphatic amine having no rigidity is preferable because of its good dispersibility.

  Examples of aliphatic monoamine compounds having only secondary amino groups include dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n-propylamine, and di-n-butylamine. , Disec-butylamine, N-ethyl-1,2-dimethylpropylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, Examples include 3-piperidinemethanol, 2-piperidineethanol, 4-piperidineethanol, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, and 3-pyrrolidinol.

  In addition, since the tertiary amino group does not have an active hydrogen that reacts with an isocyanate group, a diamine having a primary or secondary amino group and a tertiary amino group can be used as a monoamine (E1). A tertiary amino group having an effect of improving the adsorption ability to the carbon material can be introduced into the polymer terminal of the dispersant of the present invention.

  Examples of the diamine having a primary or secondary amino group and a tertiary amino group include N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dimethyl-1,3-propanediamine, and N, N. Diamine having a primary amino group and a tertiary amino group such as 1,2,2-tetramethyl-1,3-propanediamine; and a secondary amino group such as N, N, N′-trimethylethylenediamine and a tertiary amino group And diamines having a group.

  These monoamine (E1) compounds may be used alone or in combination. In addition, the active hydrogen of the urea bond after the primary amino group and the isocyanate group react with each other has low reactivity, and under the polymerization conditions of the dispersant, it does not further react with the isocyanate group and the molecular weight does not increase.

<Urethane prepolymer (C1)>
The urethane prepolymer (C1), which is a constituent element of the polymer (G1) having a basic functional group, is composed of a hydroxyl group of a vinyl polymer (A1) having two hydroxyl groups at one end region and an isocyanate of a diisocyanate (B1). It is obtained by reacting with a group.

  For example, when the number of moles of the vinyl polymer (A1) is α and the number of moles of the diisocyanate (B1) is β, when α / β = α / (α + 1), a urethane having an isocyanate group at both ends in theory. A prepolymer is obtained. When α is a positive integer, the molecular weight increases as α increases. The actual structure control will be described later in detail.

<Synthetic catalyst (F1)>
A known catalyst (F1) can be used during the synthesis of the urethane prepolymer (C1). For example, a tertiary amine compound and an organometallic compound can be mentioned.

  Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, and diazabicycloundecene (DBU).

  Examples of organometallic compounds include tin compounds and non-tin compounds.

  Examples of the tin compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyl Mention may be made of tin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate and tin 2-ethylhexanoate.

  Examples of the non-tin compound include titanium-based compounds such as dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, lead oleate; lead-based compounds such as lead 2-ethylhexanoate, lead benzoate, and lead naphthenate. Iron systems such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt systems such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc systems such as zinc naphthenate and zinc 2-ethylhexanoate; In addition, zirconium-based compounds such as zirconium naphthenate can be mentioned.

  Among the above catalysts, dibutyltin dilaurate (DBTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene.

  Catalysts such as the tertiary amine compounds and organometallic compounds can be used alone or in combination depending on the case.

  The organometallic compound catalyst used in the synthesis of the urethane prepolymer (E) significantly accelerates the reaction even in the further reaction with the amine described later.

<Synthetic solvent>
A known solvent is preferably used for the synthesis of the urethane prepolymer (C1). The use of a solvent serves to facilitate reaction control.

  Examples of the solvent used for this purpose include ethyl acetate, n-butyl acetate, isobutyl acetate, N-methyl-2-pyrrolidone, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, diethylene glycol. Monoethyl ether acetate, diethylene glycol diethyl ether and the like are used, but are not particularly limited thereto.

  In particular, ethyl acetate, toluene, methyl ethyl ketone, diethylene glycol diethyl ether, or a mixed solvent thereof is preferable from the viewpoint of amine solubility such as the solubility of the urethane prepolymer (C1) and the boiling point of the solvent.

  Further, the concentration in the urethane prepolymer reaction system when using a solvent is preferably 30 to 95% by weight from the viewpoint of reaction control in terms of the solid content concentration of the urethane prepolymer, and from the viewpoint of viscosity control. More preferably, it is 40 to 90% by weight. If it is less than 30% by weight, the reaction becomes slow and unreacted substances may remain. If it exceeds 95% by weight, the reaction may partially proceed abruptly, and it is difficult to control the molecular weight or the like, which is not preferable.

<Synthesis conditions>
There are various methods for the urethanization reaction in which the urethane prepolymer (C1) is prepared by reacting the hydroxyl group of the vinyl polymer (A1) having two hydroxyl groups in one terminal region with the isocyanate group of the diisocyanate (B1). Can be applied. Typical methods are 1) when the reaction is carried out in the whole amount, 2) vinyl polymer (A) having two hydroxyl groups at one end region, and if necessary, a solvent is charged into the flask, and diisocyanate (B1). After dripping, it is divided roughly into the method of adding a catalyst as needed. When the reaction is precisely controlled, the method 2) is preferable. The reaction temperature for obtaining the urethane prepolymer (C1) is preferably 120 ° C. or lower. More preferably, it is 50-110 degreeC. When the temperature is higher than 110 ° C., it becomes difficult to control the reaction rate, and a urethane prepolymer having a predetermined molecular weight and structure cannot be obtained. The urethanization reaction is preferably performed in the presence of a catalyst at 50 to 110 ° C. for 1 to 20 hours.

  The compounding ratio of the vinyl polymer (A1) having two hydroxyl groups in one end region and the diisocyanate (B1) is the integer α as the molar ratio of the vinyl polymer (A1) having two hydroxyl groups in one end region. When the molar ratio of diisocyanate (B1) is α + 1, a urethane prepolymer (C1) having isocyanate groups at both ends can be synthesized theoretically. Since the minimum α is 1, the blending molar ratio (α + 1) / α of the diisocyanate (B1) to the vinyl polymer (A1) is 2 or less. When the diisocyanate is further increased, all of the isocyanate groups in the mixture of urethane prepolymer (C1) and excess diisocyanate (B) react with primary and / or secondary amino groups of polyamine (D1) and monoamine (E1). If designed to do so, it is possible to incorporate excess diisocyanate (B1) into the dispersant molecule. When synthesizing a normal urethane prepolymer (C1), an excess polyisocyanate is often blended in anticipation of chain extension by the polyamine in the next step in order not to leave a polyol. However, there is a high possibility that the constituent units of the polymer derived from excess diisocyanate (B1) and the impurities derived from the hydrolyzate of excess diisocyanate (B1) will adversely affect the dispersibility and stability over time of the carbon material.

  Therefore, the blending molar ratio of the diisocyanate (B1) to the vinyl polymer (A1) having two hydroxyl groups in one terminal region is 1.01 to 3.00 from the viewpoint of the productivity of the urethane prepolymer (C1). Preferably, 1.30 to 2.30 is more preferable, and 1.50 to 2.00 is most preferable. When the said compounding molar ratio is too small, a dispersing agent will become high molecular weight and there exists a problem practically. Further, as described above, when the above-mentioned blending molar ratio is larger than 2.00, diisocyanate (B1) having no vinyl polymer part derived from vinyl polymer (A1) and urethane part derived therefrom increase, and the dispersibility is adversely affected. .

<Method for producing resin (G1) having basic functional group, synthesis conditions, etc.>
The polymer (G1) having a basic functional group radically polymerizes an ethylenically unsaturated monomer (a12) in the presence of a compound (a11) having two hydroxyl groups and one thiol group in the molecule. A first step of producing a vinyl polymer (A1) having two hydroxyl groups in one end region, and the hydroxyl group and diisocyanate of the vinyl polymer (A1) having two hydroxyl groups in the one end region The second step of producing a urethane prepolymer (C1) having an isocyanate group at both ends formed by reacting with the isocyanate group of (B1), and the isocyanate group of the urethane prepolymer (C1) having an isocyanate group at both ends And a third step of reacting polyamine (D1) and monoamine (E2) with primary and / or secondary amino groups It can be produced by.

In the polymer (G1) having a basic functional group, the urethane prepolymer (C1), the polyamine (D1), and the monoamine (E1), a urethane urea resin, or a polyurethane urea having a primary or secondary amino group at the terminal The urea reaction to get
1) A method in which a urethane prepolymer (C1) solution is charged into a flask and polyamine (D1) and monoamine (E1) are dropped.
2) A method in which a solution comprising a polyamine (D1) and a monoamine (E1) and, if necessary, a solvent is charged into a flask, and a urethane prepolymer (C1) solution is dropped.
It is divided roughly into.

  Synthesis may be carried out by appropriately selecting a method that can carry out the reaction stably, but the method of 1), which is easier to operate, is preferred if there is no problem in the reaction. The temperature of the urea reaction is preferably 100 ° C. or less. More preferably, it is 70 degrees C or less. Even at 70 ° C., the reaction rate is high, and when it cannot be controlled, 50 ° C. or less is more preferable. When the temperature is higher than 100 ° C., it is difficult to control the reaction rate, and it is difficult to obtain a urethane urea resin having a predetermined molecular weight and structure.

  Moreover, the compounding ratio with a urethane prepolymer (C1) and a polyamine (D1), and also monoamine (E1) as needed is not specifically limited, It selects arbitrarily by a use and required performance.

  The end point of the reaction is judged by measuring the isocyanate percentage by titration and disappearance of the isocyanate peak by IR measurement.

  The polymer (G1) having a basic functional group preferably has a weight average molecular weight (Mw) of 1,000 to 100,000, more preferably 1,500 to 50,000, particularly preferably 1,500. ~ 20,000. When the weight average molecular weight is less than 1,000, the dispersibility may be lowered. When the weight average molecular weight is more than 100,000, the interaction between the resins becomes strong and the composition may be thickened. Moreover, it is preferable that the amine value of the obtained polymer is 1-100 mgKOH / g, More preferably, it is 2-50 mgKOH / g, More preferably, it is 3-30 mgKOH / g. If the amine value is less than 1 mgKOH / g, the functional group adsorbing to the carbon material is insufficient, and thus it may be difficult to contribute to the dispersion of the carbon material. Aggregation may occur, resulting in insufficient viscosity reduction effect and a defect in the coating film.

<Resin having basic functional group (G2)>
The polymer (G2) having a basic functional group that can be used in the present invention is a (meth) acryloyl group of the polymer (A2) having one or two (meth) acryloyl groups in one end region; A primary and / or two polymer (C2) having an amino group obtained by reacting with a primary and / or secondary amino group of a polyamine (B2) containing one or more primary and / or secondary amino groups. It is synthesized by reacting a primary amino group with an isocyanate group of polyisocyanate (D2) containing two or more isocyanate groups.

  That is, an amino group and a urea formed by reacting a solvent-affinity site derived from the polymer (A2), a primary and / or secondary amino group of the polyamine (C2), and an isocyanate group of the polyisocyanate (D2). It has a structure having an adsorptive site to a carbon material having a binding site. The adsorption site to the carbon material having the amino group and urea binding site is excellent in the ability to interact with an organic dye derivative having an acidic functional group or a triazine derivative having an acidic functional group. It has excellent adsorptivity on the surface of the biased carbon material and can stabilize dispersion.

  In the present specification, when expressed as “(meth) acryloyl”, “(meth) acrylic acid”, “(meth) acrylate”, and “(meth) acryloyloxy”, unless otherwise specified, “Acryloyl and / or methacryloyl”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, and “acryloyloxy and / or methacryloyloxy” respectively.

<Polymer (A2) having one or two (meth) acryloyl groups in one end region>
The weight average molecular weight of the polymer (A) in the present invention is preferably from 500 to 30,000, whereby it is excellent in steric repulsion effect, and high dispersibility and storage stability can be obtained. The weight average molecular weight of the polymer (A) is more preferably 2,000 to 20,000, and most preferably 5,000 to 10,000. If it is less than 500, the steric repulsion effect by the solvent affinity block is reduced, which may not be preferable. Moreover, when exceeding 30,000, the viscosity of a dispersion becomes high and may be unpreferable.

  The polymer (A) in the present invention is preferably polyester (A21) or vinyl polymer (A22). These have good affinity for the solvent and can easily adjust the molecular weight. Moreover, the (meth) acryloyl group of one terminal area | region has a preferable acryloyl group which reaction reacts at comparatively low temperature from a viewpoint of reaction control with a primary and / or secondary amino group.

<Polyester (A21)>
The polyester (A21) can be produced by a known method. For example, the polyester (A21) can be easily obtained by ring-opening polymerization of a lactone and / or lactide using a monoalcohol having a (meth) acryloyl group as an initiator.

<Monoalcohol having (meth) acryloyl group>
The monoalcohol having a (meth) acryloyl group used as an initiator for ring-opening polymerization is not particularly limited, and 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2 One or more selected from the group consisting of 4-hydroxybutyl acrylate and 2-hydroxyethyl acrylate are used from the viewpoint of the reactivity of the hydroxyl group, including -hydroxy-3- (meth) acryloyloxypropyl methacrylate It is preferable to do this.

<Lactone and lactide>
The lactone is not particularly limited, and specific examples include β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, and alkyl-substituted ε-caprolactone. However, from the viewpoint of ring-opening polymerizability, it is preferable to use one or more selected from the group consisting of δ-valerolactone, ε-caprolactone, and alkyl-substituted ε-caprolactone.

  Lactones can be used without being limited to the above examples, and may be used alone or in combination of two or more.

  As a lactide, what is shown by following formula (16) is preferable (a glycolide is included).

In equation (16),
R ¹ and R ² are each independently a hydrogen atom or a saturated or unsaturated linear or branched alkyl group having 1 to 20 carbon atoms,
R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, or a saturated or unsaturated linear or branched lower alkyl group having 1 to 9 carbon atoms.

  Particularly preferred lactides are lactide (3,6-dimethyl-1,4-dioxane-2,5-dione) and glycolide (1,4-dioxane-2,5-dione).

  The lactone and lactide may be used alone or in combination of two or more. For lactone and lactide, it is preferable to use lactone from the viewpoint of solvent affinity.

  The number of moles of lactone and / or lactide polymerized with respect to 1 mole of initiator is preferably in the range of 3 to 60 moles, more preferably 10 to 40 moles, and most preferably 15 to 30 moles. If it is less than 3 mol, the molecular weight will be small and it will not function sufficiently as a solvent affinity site. When it exceeds 60 mol, the molecular weight becomes too large, and when used as a dispersant for a carbon material, the viscosity of the composition becomes high and problems are likely to occur.

<Ring-opening polymerization catalyst>
As the ring-opening polymerization catalyst, known catalysts can be used without limitation. For example, tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, tetrabutylammonium Quaternary ammonium salts such as iodo, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, and benzyltrimethylammonium iodide;
Tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodide, tetrabutylphosphonium iodide, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethylphosphonium iodide, tetraphenylphosphonium chloride, Quaternary phosphonium salts such as tetraphenylphosphonium bromide and tetraphenylphosphonium iodide; phosphorus compounds such as triphenylphosphine; organic carboxylates such as potassium acetate, sodium acetate, potassium benzoate and sodium benzoate; sodium alcoholate; And alkali metal alcoholates such as potassium alcoholates; Tertiary amines such as ruamine and triphenylamine; organotin compounds such as dibutyltin dilaurate, dibutyltin oxide, and dioctyltin oxide; aluminum alkyl acetoacetate / diisopropylate, aluminum bisethylacetoacetate / monoacetylacetonate Organic aluminum compounds such as aluminum trisacetylacetonate; organic titanate compounds such as tetra-n-butyl titanate, dimer, tetraisobutyl titanate, tetrastearyl titanate, and diisopropoxy bis (triethanolaminate) titanium; and And zinc compounds such as zinc chloride.

  The amount of the ring-opening polymerization catalyst used is 0.1 ppm to 3000 ppm, preferably 1 ppm to 1000 ppm with respect to 100% by weight of the lactone and / or lactide. When the amount of the catalyst exceeds 3000 ppm, the resin may be intensely colored. On the contrary, if the amount of the catalyst used is less than 0.1 ppm, the rate of ring-opening polymerization of lactone and / or lactide becomes extremely slow, which is not preferable.

<Synthesis conditions>
The lactone and / or lactide ring-opening polymerization temperature is 100 ° C to 220 ° C, preferably 110 ° C to 210 ° C. If the reaction temperature is less than 100 ° C., the reaction rate may be extremely slow. On the other hand, if the polymerization temperature exceeds 220 ° C., side reactions other than the addition reaction of lactone and / or lactide, for example, depolymerization of lactone adducts to lactone monomers, formation of cyclic lactone dimers and trimers may occur. is there.

<Radical polymerization inhibitor>
When a compound having a (meth) acryloyl group is polymerized, it is preferable to add a radical polymerization inhibitor and perform the reaction under a dry air flow. As the radical polymerization inhibitor, known ones can be used without limitation, and examples thereof include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, 2,4-dimethyl-6-t-butylphenol, and phenothiazine. Is preferred. These may be used alone or in combination within a range of 0.01% to 6% by weight, preferably 0.05% to 1.0% by weight, based on 100% by weight of the alcohol having a (meth) acryloyl group. .

  Polyester (A21) is a polyester having a hydroxyl group at one end obtained by ring-opening polymerization of a lactone using a monoalcohol having no (meth) acryloyl group as an initiator, a group capable of reacting with a hydroxyl group, and ( It can also be obtained by reacting a compound having a (meth) acryloyl group.

<Compound having a group capable of reacting with a hydroxyl group and a (meth) acryloyl group>
The compound having a group capable of reacting with a hydroxyl group and a (meth) acryloyl group is preferably a compound having an isocyanate group and a (meth) acryloyl group, and examples thereof include 2- (meth) acryloyloxyethyl isocyanate.

  In the preparation of the polyester (A21), a lactone is first subjected to ring-opening polymerization using a monoalcohol having no (meth) acryloyl group as an initiator to prepare a polyester having a hydroxyl group at one end, and then the polyester. And a compound having one dibasic acid anhydride group are reacted to prepare a polyester having a carboxyl group at one end. Subsequently, the polyester having the carboxyl group is reacted with a compound having an epoxy group and a (meth) acryloyl group, or a group capable of reacting with a hydroxyl group obtained by ring opening of the epoxy group and the (meth) acryloyl group. It can be carried out by reacting a compound having In this case, a polyester (A21) having two (meth) acryloyl groups in one end region is obtained.

<Monoalcohol without (meth) acryloyl group>
The monoalcohol having no (meth) acryloyl group may be any compound as long as it is a compound having one hydroxyl group.

  For example, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, tert-butanol, 1-pentanol, isopentanol, 1-hexanol, cyclohexanol, 4-methyl-2-pentanol, 1- Heptanol, 1-octanol, isooctanol, 2-ethylhexanol, 1-nonanol, isononanol, 1-decanol, 1-dodecanol, 1-myristyl alcohol, cetyl alcohol, 1-stearyl alcohol, isostearyl alcohol, 2-octyldecanol , Aliphatic monoalcohols such as 2-octyldodecanol, 2-hexyldecanol, behenyl alcohol, and oleyl alcohol; benzyl alcohol, phenoxyethyl alcohol, and para Aromatic ring-containing monoalcohols such as milphenoxyethyl alcohol; and ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, propylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Cole monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene Glycol monohexyl ether, dipropylene glycol mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monohexyl ether, triethylene Glico Mono-2-ethylhexyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monohexyl ether, tripropylene glycol mono-2-ethylhexyl ether, Tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol monohexyl ether, tetraethylene glycol mono-2-ethylhexyl ether, tetrapropylene glycol monomethyl ether, tetra Propylene rubber Examples include alkylene glycol monoalkyl ethers such as coal monoethyl ether, tetrapropylene glycol monopropyl ether, tetrapropylene glycol monobutyl ether, tetrapropylene glycol monohexyl ether, tetrapropylene glycol mono-2-ethylhexyl ether, and tetradiethylene glycol monomethyl ether. It is done.

<Compound having one dibasic acid anhydride group>
The compound having one dibasic acid anhydride group may be any compound as long as it has one dibasic acid anhydride group.

  For example, succinic anhydride, glutaric anhydride, cyclohexane-1,2-dicarboxylic anhydride, cyclohexene 1-2-dicarboxylic anhydride, dicyclo [2,2,2] -oct-5-ene-2, 3-dicarboxylic anhydride, phthalic anhydride, naphthalene-1,2-dicarboxylic anhydride, naphthalene-2,3-dicarboxylic anhydride, anthracene-1,2-dicarboxylic anhydride, and anthracene-2, 3-dicarboxylic anhydride etc. are mentioned. Moreover, the said dibasic acid anhydride which has substituents, such as a linear alkyl group, a branched alkyl group, a cyclic alkyl group, a heterocyclic ring, an aromatic ring, and a halogen, is also mentioned.

<Compound having epoxy group and (meth) acryloyl group>
Examples of the compound having an epoxy group and a (meth) acryloyl group include glycidyl acrylate, methyl glycidyl acrylate, 3,2-glycidoxyethyl acrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxybutyl acrylate, and 4, Examples include 5-epoxypentyl acrylate.

  The polyester (A21) is a polyester having a carboxyl group at one end obtained by ring-opening polymerization of a lactone using a monocarboxylic acid having no (meth) acryloyl group as an initiator. A compound having a (meth) acryloyl group is reacted, and further, a group capable of reacting with a hydroxyl group which can be reacted with a hydroxyl group obtained by ring opening of an epoxy group and a compound having a (meth) acryloyl group are reacted. Can also be obtained. In this case, a polyester (A21) having two (meth) acryloyl groups in one end region is obtained.

<Monocarboxylic acid not having (meth) acryloyl group>
The monocarboxylic acid having no (meth) acryloyl group may be any compound as long as it is a compound having a carboxyl group and having no (meth) acryloyl group.

  Examples include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and isostearic acid.

<Vinyl polymer (A22)>
A vinyl polymer (A22) having one or two (meth) acryloyl groups in one end region is converted into a vinyl polymer (a23) having one or two hydroxyl groups in one end region and a hydroxyl group. It can be obtained by reacting a group capable of reacting with the compound (a24) having a (meth) acryloyl group.

  The vinyl polymer (a23) having one or two hydroxyl groups in one end region (hereinafter sometimes abbreviated as vinyl polymer (a23)) has one or two hydroxyl groups in the molecule. And the compound (s) having 1 thiol group can be obtained by radical polymerization of the ethylenically unsaturated monomer (a21). Since the thiol group of the compound (s) having one or two hydroxyl groups and one thiol group in the molecule acts as a chain transfer agent, the vinyl polymer (a23) is synthesized through the S atom. The molecular weight of the vinyl polymer (a23) can be easily adjusted to the above range depending on the amount of the compound (s) used relative to the ethylenically unsaturated monomer (a21). The affinity of can also be adjusted suitably.

<Compound (s) having one or two hydroxyl groups and one thiol group in the molecule>
Examples of the compound (s) having one or two hydroxyl groups and one thiol group in the molecule include one hydroxyl group in the molecule such as 1-mercaptoethanol and 2-mercaptoethanol. Compound (s1) having one thiol group; and 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin) ), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2 Propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and 2-mercaptoethyl-2-ethyl-1, Examples thereof include a compound (s2) having two hydroxyl groups and one thiol group in the molecule such as 3-propanediol.

  In the present invention, the compound (s2) having two hydroxyl groups and one thiol group in the molecule is preferable, and 3-mercapto-1,2-propanediol (thioglycerin) is more preferable. .

  By using the compound (s2) having two hydroxyl groups and one thiol group in the molecule, the finally obtained dispersant has an adsorption site on a carbon material having a plurality of amino groups, a plurality of An ideal structure having a solvent-affinity site is obtained.

<Ethylenically unsaturated monomer (a21)>
Examples of the ethylenically unsaturated monomer (a21) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), Tertiary butyl (meth) acrylate, isoamyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) Linear or branched acrylates such as acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate Kill (meth) acrylates; cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Cyclic alkyl (meth) acrylates such as dicyclopentenyloxyethyl (meth) acrylate and isobornyl (meth) acrylate; trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate , And fluoroalkyl (meth) acrylates such as tetrafluoropropyl (meth) acrylate; (meth) acryloxy-modified polydimethylsiloxane (silicone macromer ); Tetrahydrofurfuryl (meth) acrylate and (meth) acrylates having a heterocyclic ring such as 3-methyl-3-oxetanyl (meth) acrylate; benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene (Meth) acrylates having an aromatic ring such as glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, and nonylphenoxypolyethylene glycol (meth) acrylate; 2-methoxy Ethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, diethylene glycol Monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, di (Poly) alkylene glycol monoalkyl ethers (meta) such as propylene glycol monomethyl ether (meth) acrylate, tripropylene glycol mono (meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, and polyethylene glycol monostearyl ether (meth) acrylate ) Acrylates; acrylic acid, acrylic acid dimer, methacrylic acid, a Unsaturated carboxylic acids such as conic acid, maleic acid, fumaric acid, and crotonic acid; caprolactone adducts of the above carboxylic acid (addition moles 1 to 5); (Meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth) acrylate, β-carboxyethyl (meta) ) Acrylate, and (meth) acrylates having a carboxyl group such as ω-carboxypolycaprolactone (meth) acrylate; styrenes such as styrene and α-methylstyrene; vinyl acetate, vinyl propionate, vinyl (meth) acrylate And (meth) acryl Vinyls such as allyl acid; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; amides having no amino group such as (meth) acrylamide and N-vinylformamide; In addition, acrylonitrile having no amino group can be used. These can be used alone or in admixture of two or more.

  In the present invention, among the ethylenically unsaturated monomers (a21) exemplified above, it is preferable to use an ethylenically unsaturated monomer (a22) represented by the following formula (17). The amount of the ethylenically unsaturated monomer (a22) represented by the following formula (17) is preferably 20% by weight to 100% by weight with respect to the whole ethylenically unsaturated monomer (a21), and is preferably 20 to 20%. 70% by weight is more preferred. When the monomer represented by the formula (17) is used, the solvent affinity is improved and the dispersibility is improved. If it is less than 20% by weight, the effect of improving the solvent affinity is insufficient.

In Formula (17), R ⁵ is a linear or branched alkyl group having 1 to 4 carbon atoms.

<Use amount of compound (s)>
Using the compound (s) as a chain transfer agent, the ethylenically unsaturated monomer (a21) and, optionally, a polymerization initiator are mixed and heated in accordance with the molecular weight of the target vinyl polymer (a23). Thus, the vinyl polymer (a23) can be obtained. The compound (s) is preferably subjected to bulk polymerization or solution polymerization using 0.8 to 30 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer (a21), more preferably 1.5. -15 parts by weight, more preferably 2-9 parts by weight, particularly preferably 5-9 parts by weight. If it is less than 1 part by weight, the molecular weight becomes large and the viscosity of the dispersion becomes high, which is not preferable. If it exceeds 30 parts by weight, the molecular weight is decreased, and the steric repulsion effect due to the solvent affinity block is decreased, which may be undesirable.

  The reaction temperature is 40 to 150 ° C, preferably 50 to 110 ° C. When the temperature is lower than 40 ° C., the polymerization does not proceed sufficiently. When the temperature exceeds 150 ° C., it becomes difficult to control the molecular weight such as an increase in the molecular weight.

<Radical polymerization initiator>
In the radical polymerization, 0.001 to 5 parts by weight of a polymerization initiator can be arbitrarily used with respect to 100 parts by weight of the ethylenically unsaturated monomer (a21).

As a polymerization initiator, for example,
2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2,2′-azobis (2, 4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate), 4,4′-azobis ( Azo compounds such as 4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), and 2,2′-azobis [2- (2-imidazolin-2-yl) propane] And organic peroxides; and benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydi -Bonate, di (2-ethoxyethyl) peroxydicarbonate, t-butylperoxyneodecanoate, t-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, And organic peroxides such as diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more.

<Compound (a24) having a group capable of reacting with a hydroxyl group and a (meth) acryloyl group>
As the compound (a24) having a group capable of reacting with a hydroxyl group and a (meth) acryloyl group, a compound having an isocyanate group and a (meth) acryloyl group is preferable, and examples thereof include 2- (meth) acryloyloxyethyl isocyanate. It is done.

<Polymerization solvent>
Polyester (A21) and vinyl polymer (A22) can be synthesized using no solvent or, if necessary, a solvent.

  In the case of solution polymerization, as a polymerization solvent, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol mono Ethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, N-methylpyrrolidone and the like are used, but are not particularly limited thereto. Two or more kinds of these polymerization solvents may be mixed and used. After completion of the reaction, the solvent used in the polymerization reaction can be removed by an operation such as distillation, or can be used as it is as a solvent for the next step, or can be used as a part of a product.

<Polyamine (B2)>
The polyamine (B2) is a compound having one or more primary and / or secondary amino groups, and the primary and / or secondary amine is a polymer (A2) having a (meth) acryloyl group in one terminal region. Addition reaction with a (meth) acryloyl group produces a polymer (C2) having an amino group. Furthermore, some or all of the primary and / or secondary amines of the polymer (C2) having an amino group are reacted with the isocyanate group of the polyisocyanate (D2) to form a urea group. That is, an amino group and a urea bond existing in one end region serve as an adsorption site for the carbon material. A diamine (b21) is mentioned as such a polyamine (B2). In addition, when the polyamine (B2) is a compound having two primary and / or secondary amino groups at both ends and further having a secondary and / or tertiary amino group at both ends, This is particularly preferable because the adsorptivity to the carbon material is improved.

  As the diamine (b21) having two primary amino groups, known ones can be used. Specifically, ethylenediamine, propylenediamine [alias: 1,2-diaminopropane or 1,2-propanediamine] can be used. ], Trimethylenediamine [alias: 1,3-diaminopropane or 1,3-propanediamine], tetramethylenediamine [alias: 1,4-diaminobutane], 2-methyl-1,3-propanediamine, pentamethylene Diamine [alias: 1,5-diaminopentane], hexamethylenediamine [alias: 1,6-diaminohexane], 2,2-dimethyl-1,3-propanediamine, 2,2,4-trimethylhexamethylenediamine, And aliphatic diamines such as tolylenediamine; isophoronediamine and dicyclohexylmeta Alicyclic diamines such as 4,4'-diamine; and can include phenylenediamine, and an aromatic diamine such as xylylenediamine.

  Moreover, as diamine (b21) which has two secondary amino groups, a well-known thing can be used, Specifically, N, N- dimethylethylenediamine, N, N- diethylethylenediamine, and N, N'-di-tert-butylethylenediamine and the like can be mentioned.

  Moreover, as diamine (b21) which has a primary and secondary amino group, a well-known thing can be used, Specifically, N-methylethylenediamine [alias: methylaminoethylamine], N-ethylethylenediamine [alias] : Ethylaminoethylamine], N-methyl-1,3-propanediamine [alias: N-methyl-1,3-diaminopropane or methylaminopropylamine], N, 2-methyl-1,3-propanediamine, N -Isopropylethylenediamine [alias: isopropylaminoethylamine], N-isopropyl-1,3-diaminopropane [alias: N-isopropyl-1,3-propanediamine or isopropylaminopropylamine], and N-lauryl-1,3- Propanediamine [alias: N-lauryl-1,3-dia It can be exemplified Nopuropan or lauryl amino propylamine], and the like.

  As the diamine (b21) having primary and tertiary amino groups, known diamines can be used. Specifically, N, N-dimethylethylenediamine [also known as dimethylaminoethylamine], N, N— Examples include diethylethylenediamine [alias: diethylaminoethylamine], N, N-dimethyl-1,3-propanediamine [alias: N, N-dimethyl-1,3-diaminopropane or dimethylaminopropylamine], and the like.

  As the polyamine (b22) having two primary and / or secondary amino groups at both ends and further having a secondary and / or tertiary amino group at both ends, a known one may be used. Specifically, methyliminobispropylamine [also known as N, N-bis (3-aminopropyl) methylamine], lauryliminobispropylamine [also known as N, N-bis (3-aminopropyl) laurylamine] , Iminobispropylamine [also known as N, N-bis (3-aminopropyl) amine], N, N′-bisaminopropyl-1,3-propylenediamine, and N, N′-bisaminopropyl-1, 4-butylenediamine and the like, methyliminobispropylamine having two primary amino groups and one tertiary amino group, and lauryliminobis Ropiruamin is preferably easily control of the reaction of a diisocyanate.

  An iminobispropylamine having two primary amino groups and one secondary amino group is preferable because of its good adsorptivity to the carbon material.

  As the polyamine (B2), a polymer (b23) having two or more primary and / or secondary amino groups can also be used.

  Examples of the polymer (b23) having a primary and / or secondary amino group include an ethylenically unsaturated monomer having a primary amino group and an ethylenically unsaturated monomer having a secondary amino group, such as vinylamine and allylamine. Homopolymers (so-called polyvinylamine and polyallylamine), copolymers thereof with other ethylenically unsaturated monomers, ring-opening polymers of ethyleneimine, and polycondensates of ethylene chloride and ethylenediamine Or a ring-opening polymer of oxazolidone-2 (so-called polyethyleneimine). The content of primary and / or secondary amino groups in the polymer is preferably 10 to 100% by weight, more preferably 20 to 100% by weight, in terms of monomer units, based on the polymer. If the content is 10% by weight or more, it is effective to prevent the carbon material from agglomerating and to suppress an increase in viscosity.

  Examples of the ethylenically unsaturated monomer copolymerizable with an ethylenically unsaturated monomer having a primary amino group and an ethylenically unsaturated monomer having a secondary amino group include (meth) acrylic acid, croton Unsaturated carboxylic acids such as acid, itaconic acid, maleic acid and fumaric acid; aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, chloromethylstyrene, indene and vinyltoluene; methyl (meth) (Meth) acrylic acid alkyl esters such as acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; (Meth) acrylic acid alkyl aryl ester; glycidyl (meth) acrylate (Meth) acrylic acid substituted alkyl ester having a functional group such as 2-hydroxyethyl (meth) acrylate; tertiary amino group such as dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylate (meth) Acrylic acid-substituted alkyl ester; (meth) acrylamide, dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, n-butyl (meth) acrylamide, tert-butyl (meth) acrylamide, tert-octyl (meth) acrylamide, etc. Alkyl (meth) acrylamides; substituted alkyl (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide; 1,3-butadiene, and isoprene Diene compounds such as one-end methacryloylated polymethyl methacrylate oligomer, one-end methacryloylated polystyrene oligomer, and one-end methacryloylated polyethylene glycol and other polymerizable oligomers (macromonomer); and vinyl cyanide.

  The polymer having a primary and / or secondary amino group has a polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography), preferably 300 to 75,000, 300 to 20, 000 is more preferable, and 500 to 5,000 is particularly preferable. When the weight average molecular weight is 300 to 75,000, it is effective to suppress an increase in viscosity of the conductive composition by preventing aggregation of the carbon material.

<Monoamine>
As the amine compound constituting the dispersant, in addition to the polyamine (B2), a monoamine can also be used. The monoamine is a monoamine compound having one primary amino group or one secondary amino group in the molecule, and the monoamine suppresses excessively high molecular weight in the reaction between the polymer (A2) and the polyamine (B). Therefore, it is used as a reaction terminator. The monoamine may have a polar functional group other than the primary amino group or the secondary amino group in the molecule. Examples of such polar functional groups include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a cyano group, and a nitroxyl group.

  As the monoamine, conventionally known monoamines can be used. Specifically, aminomethane, aminoethane, 1-aminopropane, 2-aminopropane, 1-aminobutane, 2-aminobutane, 1-aminopentane, 2-aminopentane, 3-aminopentane, isoamylamine, N-ethylisoamylamine, 1-aminohexane, 1-aminoheptane, 2-aminoheptane, 2-octylamine, 1-aminononane, 1-aminodecane, 1-aminododecane, 1-amino Tridecane, 1-aminohexadecane, stearylamine, aminocyclopropane, aminocyclobutane, aminocyclopentane, aminocyclohexane, aminocyclododecane, 1-amino-2-ethylhexane, 1-amino-2-methylpropane, 2-amino -2-methylpro , 3-amino-1-propene, 3-aminomethylheptane, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 2-ethylhexyloxypropylamine, 3-decyloxypropylamine , 3-lauryloxypropylamine, 3-myristoxypropylamine, 2-aminomethyltetrahydrofuran, dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n- Propylamine, di-n-butylamine, disec-butylamine, N-ethyl-1,2-dimethylpropylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine , , 5-Lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonipecotate, ethyl isonipecotate, 2-piperidineethanol, 4-piperidineethanol, 4-piperidinebutyric acid hydrochloride Salt, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, 3-pyrrolidinol, indoline, aniline, N-butylaniline, o-aminotoluene, m-aminotoluene, p-aminotoluene, o-benzylaniline, p-benzylaniline 1-anilinonaphthalene, 1-aminoanthraquinone, 2-aminoanthraquinone, 1-aminoanthracene, 2-aminoanthracene, 5-aminoisoquinoline, o-aminodiphenyl, 4-aminodiphenyl ether, β-aminoethyl Rubenzene, 2-aminobenzophenone, 4-aminobenzophenone, o-aminoacetophenone, m-aminoacetophenone, p-aminoacetophenone, benzylamine, N-methylbenzylamine, 3-benzylaminopropionic acid ethyl ether, 4-benzyl Examples include piperidine, α-phenylethylamine, phenesylamine, p-methoxyphenesylamine, furfurylamine, p-aminoazobenzene, m-aminophenol, p-aminophenol, allylamine, and diphenylamine.

<Polymer having amino group (C2)>
In the polymer (C2) having an amino group, as shown in the following formula (18), the primary or secondary amino group of the polyamine (B2) has one or two (meth) acryloyl groups in one end region. It can be obtained by addition reaction to the (meth) acryloyl group of the polymer (A2) having This reaction is generally called the Michael addition reaction. By adjusting the blending of the polymer (A2) and the polyamine (B2), a structure having a primary or secondary amino group capable of reacting with an isocyanate group can be obtained.

In the formula (18), X ¹ is a portion of the polymer (A2) excluding the (meth) acryloyloxy group, and Y ¹ is a polyamine (B2) excluding the primary and secondary amino groups. R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is a hydrogen atom or an alkyl group.

  For example, as shown in the following formula (19), a molecule of a diamine (B2) having two primary amino groups for one molecule of a polymer (A2) having one (meth) acryloyl group in one end region When one is reacted, theoretically, one molecule of the polymer (C2) having one primary amino group and one secondary amino group is obtained.

In the formula (19), X ¹ is a part of the polymer (A2) excluding the (meth) acryloyloxy group, and Y ² is a part of the polyamine (B2) excluding the primary amino group. R ⁶ is a hydrogen atom or a methyl group.

  Further, for example, as shown in the following formula (20), one primary amino group and one secondary amino group 1 per molecule of the polymer (A2) having two (meth) acryloyl groups in one end region. When two molecules of the diamine (B2) having 1 molecule are reacted, one molecule of the polymer (C2) having 4 secondary amino groups is theoretically obtained.

In the formula (20), X ² is a portion of the polymer (A2) excluding the (meth) acryloyloxy group, and Y ² is a polyamine (B2) excluding the primary and secondary amino groups. R ⁶ is a hydrogen atom or a methyl group, and R ⁸ is an alkyl group.

  Furthermore, for example, as shown in the following formula (21), the diamine (B) having two primary amino groups for n molecules of the polymer (A2) having two (meth) acryloyl groups in one terminal region. In theory, one molecule of the polymer (C2) having two primary amino groups and 2n secondary amino groups is obtained. (N is a positive integer.)

In the formula (21), X ² is a part of the polymer (A2) excluding the (meth) acryloyloxy group, and Y ² is a part of the polyamine (B2) excluding the primary amino group. R ⁶ is a hydrogen atom or a methyl group, and n is a positive integer.

  Further, for example, as shown in the following formula (22), a diamine having two secondary amino groups (B2) with respect to n molecules of the polymer (A2) having two (meth) acryloyl groups in one terminal region. ) Molecule (n + 1) molecules are reacted, theoretically, one polymer (C2) molecule having two secondary amino groups and 2n tertiary amino groups is obtained. (N is a positive integer.)

In the formula (22), X ² is a part of the polymer (A2) excluding the (meth) acryloyloxy group, and Y ² is a part of the polyamine (B2) excluding the secondary amino group. R ⁶ is a hydrogen atom or a methyl group, R ⁸ is an alkyl group, and n is a positive integer.

  Theoretically, in the above four examples, the primary amino group is assumed to react preferentially because it is more reactive than the secondary amino group, but in actuality, depending on the reaction conditions, etc. In some cases, a secondary amino group may react first, even if is left. Therefore, in some cases, a polymer (C2) having a structure different from that expected may be obtained. However, since the above addition reaction proceeds almost stoichiometrically, a polymer (C2) having a target structure is obtained mostly, and there is a problem in the subsequent reaction and the function as a final dispersant. There is no.

<Synthesis conditions>
A polymer (A2) having one or two (meth) acryloyl groups in one terminal region, a polyamine (B2) having one or more primary and / or secondary amino groups, and a polymer having an amino group. The Michael reaction for obtaining the coalescence (C2) is: 1) a method in which the reaction is carried out by charging the whole amount, 2) a solution comprising polyamine (B2) and a solvent as necessary is charged into the flask, and the polymer (A2) solution is added dropwise. Broadly divided into methods. The synthesis may be carried out by appropriately selecting a method that allows the reaction to be carried out stably. However, if there is no problem in the reaction, it is preferable to apply the method 2) described above, which makes reaction control (molecular design control) easier.

  The temperature of the Michael reaction is preferably 70 ° C. or less. More preferably, it is 60 degrees C or less. Even at 60 ° C., the reaction rate is high, and when it cannot be controlled, 50 ° C. or less is more preferable. When the temperature is higher than 70 ° C., it is difficult to control the reaction rate, and it tends to be difficult to obtain a polymer (C2) having a predetermined molecular weight and structure.

  The blending ratio of the polymer (A2) having one or two (meth) acryloyl groups in one terminal region, the polyamine (B2) having one or more primary and / or secondary amino groups is particularly limited. It is not arbitrarily selected according to the application and required performance. The end point of the reaction is judged by measuring the amine% due to titration.

<Dispersant having amino group and urea bond>
The polymer (G2) having a basic functional group is a dispersant having an amino group and a urea bond, the primary or secondary amino group of the polymer (C2) having an amino group, and two or more isocyanate groups It is obtained by reacting the isocyanate group of the polyisocyanate (D2) having The primary or secondary amino group of the polymer (C2) having an amino group is partially or entirely formed as a urea bond by adjusting the amount of the polyisocyanate to be reacted, and the remainder is an amino group in the dispersant. Exists as.

  In addition, when the polymer (C2) having an amino group has a tertiary amino group in addition to the primary or secondary amino group, the tertiary amino group does not react with the isocyanate group, and the carbon material is adsorbed as it is. It remains in the dispersant as a group.

For example, when one molecule of diisocyanate (D2) is reacted with two molecules of polymer (C2) having one primary amino group and two secondary amino groups as shown in the following formula (23) Theoretically, a primary amino group reacts with an isocyanate group to form a urea bond, and a dispersant having 4 secondary amino groups and 2 urea bonds is obtained. When W ¹ and W ² in the following formula (23) have a tertiary amino group derived from the polyamine (B2) and / or the polymer (C2), the dispersant also has a tertiary amino group.

In the formula (23), X ¹ is a portion excluding the (meth) acryloyloxy group in the polymer (A2) which is a precursor of the polymer (C2), and W ¹ and W ² are Of the polyamine (B2) which is a precursor of the union (C2), it is a portion excluding the primary and secondary amino groups, R ⁶ is a hydrogen atom or a methyl group, and Z ¹ is a polyisocyanate (D2 ) Is a portion excluding the isocyanate group.

Further, for example, when one molecule of diisocyanate (D2) is reacted with two molecules of polymer (C2) having one secondary amino group as in the following formula (24), The secondary amino group reacts with the isocyanate group to form a urea bond, and a dispersant having a urea bond is obtained. When W ³ in the following formula (24) has a tertiary amino group derived from the polyamine (B2) and / or the polymer (C2), the dispersant also has a tertiary amino group. The dispersant does not have an amino group having active hydrogen.

In the formula (24), X ¹ is a portion excluding the (meth) acryloyloxy group in the polymer (A2) which is a precursor of the polymer (C2), and W ³ is the polymer (C2). In the polyamine (B2) which is a precursor of the above, it is a portion excluding the primary amino group, R ⁶ is a hydrogen atom or a methyl group, and Z ¹ is an isocyanate group in the polyisocyanate (D2). Excluded part.

Further, for example, as shown in the following formula (25), the product of the above formula (23) is a polymer (C + 1) molecule (m + 1) molecules having two primary amino groups and 2n secondary amino groups. On the other hand, when m molecules of diisocyanate (D2) are reacted, theoretically, the primary amino group and the isocyanate group react to form a urea bond, and two primary amino groups and secondary amino groups (2 nm + 2n) And a dispersant having 2 m urea bonds is obtained. Y ² in formula (25) is, if having a tertiary amino group derived from a polyamine (B2) and / or polymer (C2), the dispersant also has a tertiary amino group. (N and m are positive integers.)

In the formula (25), X ² is a portion excluding the (meth) acryloyloxy group in the polymer (A2) which is a precursor of the polymer (C2), and Y ² is the polymer (C2). In the polyamine (B2) which is a precursor of the polymer, the primary amino group is removed, W ⁴ is the part of the polymer (C2) excluding the site having an amino group, and R ⁶ is hydrogen atom or a methyl group, Z ^1, of the polyisocyanate (D2), a portion excluding the isocyanate group, n and m are positive integers.

  Further, for example, as shown in the following formula (26), two molecules of a polyamine (B2) having one primary amino group and one molecule of a polymer (A2) having two (meth) acryloyl groups are reacted. And (m + 1) molecules (m + 1) of the polymer (C2) having two secondary amino groups in each of the terminal regions when viewed from the portion derived from the polymer (A2). When m molecules of diisocyanate (D2) are reacted, theoretically, the secondary amino group and the isocyanate group react to form a urea bond, and a secondary amino group is formed in both terminal regions as viewed from the polyurea chain. A dispersant having two groups, one group each, is obtained. (M is a positive integer.)

In the formula (26), X ² is a portion excluding the (meth) acryloyloxy group in the polymer (A2) which is a precursor of the polymer (C2), and Y ³ is the polyamine (B2). among them, a portion excluding the primary amino group, W ^5, of the polymer (C2), a portion excluding the portion having an amino group, R ⁶ is a hydrogen atom, or a methyl group, Z ¹ is a portion of the polyisocyanate (D2) excluding the isocyanate group, and m is a positive integer.

  Theoretically, in the above four examples, the primary amino group is assumed to react preferentially because it is more reactive than the secondary amino group, but in actuality, depending on the reaction conditions, etc. In some cases, a secondary amino group may react first, even if is left. Therefore, in some cases, a dispersant having a structure different from that expected may be obtained. However, since the reaction proceeds almost stoichiometrically, the polymer (C2) having a target structure is obtained mostly, and there is no problem in the function as a dispersant.

  As described above, by changing the reaction ratio between the polymer (C2) having an amino group and the polyisocyanate (D2), the molecular weight of the dispersant, the amino group (primary, secondary, and / or tertiary) and urea are changed. The amount of binding can be adjusted.

<Polyisocyanate (D2)>
As the polyisocyanate (D2), conventionally known ones can be used, but diisocyanates are preferred from the low viscosity effect of the dispersion. For example, aromatic diisocyanate (d21), aliphatic diisocyanate ( d22), aromatic-aliphatic diisocyanate (d23), alicyclic diisocyanate (d24), dimer of these diisocyanates (uretodione), reaction product of trimer of these diisocyanates (isocyanurate) and monoalcohol And reaction products of these diisocyanates and diols (urethane prepolymers of both terminal isocyanates) and the like.

  Aromatic diisocyanates (d21) include xylylene diisocyanate, 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl. Ether diisocyanate, dianisidine diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, naphthylene diisocyanate, and 1,3-bis (isocyanate) And methyl) benzene.

  Examples of the aliphatic diisocyanate (d22) include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter sometimes abbreviated as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, and 2,3-butylene. Examples include diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.

  Examples of the aromatic-aliphatic diisocyanate (d23) include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1, Examples include 4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, and 1,3-tetramethylxylylene diisocyanate.

  Examples of the alicyclic diisocyanate (d24) include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (hereinafter sometimes abbreviated as IPDI), 1,3-cyclopentane diisocyanate, 1,3- Examples include cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, and methyl-2,6-cyclohexane diisocyanate.

  As mentioned above, enumerated diisocyanate (D2) is not necessarily limited to these, It can also be used in combination of 2 or more types.

  As the diisocyanate (D2) used in the present invention, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (also known as isophorone diisocyanate, IPDI) is preferable because it is hardly yellow-modified.

  Further, for the purpose of increasing the molecular weight of the dispersant, a polyisocyanate (d25) having 3 or more isocyanate groups in one molecule may be used. An aromatic polyisocyanate, an aliphatic polyisocyanate, Aromatic-aliphatic polyisocyanate, alicyclic polyisocyanate and the like can be mentioned.

  As polyisocyanate (d25) having three or more isocyanate groups in one molecule, specifically, isocyanurate of the above diisocyanate and diisocyanate trimer such as biuret of the above diisocyanate, polyol adduct of the above diisocyanate, Examples thereof include copolymers of two or more of the above diisocyanates, aromatic triisocyanates, and polymeric aromatic isocyanate oligomers.

  Examples of the polyisocyanate (d25) having three or more isocyanate groups per molecule include, for example, isocyanurate of tolylene diisocyanate (hereinafter sometimes abbreviated as TDI), isophorone diisocyanate (hereinafter abbreviated as IPDI). Isocyanurate of 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), isocyanurate of hexamethylene diisocyanate (hereinafter abbreviated as HDI). , HDI biuret, HDI trimethylolpropane (hereinafter sometimes abbreviated as TMP) adduct, TDI TMP adduct, and TDI / HDI copolymer modified diisocyanate; 2,4,6- Triisocyanate Totor 1,3,5-triisocyanatobenzene, and aromatic triisocyanates such as 4,4 ′, 4 ″ -triphenylmethane triisocyanate; and polymethylene polyphenyl polyisocyanate (also known as MDI oligomer) ) And the like.

<Synthesis conditions>
The reaction between the polymer (C2) having an amino group and the polyisocyanate (D2) is 1) when the reaction is carried out by adding the whole amount, and 2) the polymer (C2) solution is charged into the flask, and the polyisocyanate (D2) is dropped. In order to make the reaction precise, 2) is preferable. The temperature of the urea reaction is preferably 70 ° C. or lower. More preferably, it is 60 degrees C or less. Even at 60 ° C., the reaction rate is high, and when it cannot be controlled, 50 ° C. or less is more preferable. When the temperature is higher than 70 ° C., it is difficult to control the reaction rate, and it tends to be difficult to obtain a dispersant having a predetermined molecular weight and structure.

  The compounding ratio of the polyisocyanate (D2) to the polymer (C2) having an amino group is such that the equivalent of amino groups (primary and secondary amino groups) having active hydrogen of the polymer (C2) is [C2], polyisocyanate. When the isocyanate group equivalent of (D2) is [D2], [D2] / [C2] is 0.25 to 1.00, and it is preferable to react all of the isocyanate groups with amino groups having active hydrogen. From the viewpoint of the design of the dispersant that is the final product (the balance between the carbon material adsorption site and the solvent affinity site), 0.35 to 0.9 is more preferable, and the conductivity using the dispersant that is the final product From the viewpoint of dispersion stability of the composition, 0.5 to 0.8 is most preferable.

  If the blending equivalent ratio is less than 0.25, the amount of urea bonds in the dispersant, which is the final product, decreases, and the dispersibility may deteriorate. On the other hand, if the blending equivalent ratio is larger than 1.00, an isocyanate group having a high reaction activity remains, which reacts with water and the like, resulting in a high molecular weight and a high viscosity, which is not preferable. When the blending equivalent is 1.00, for example, in the reaction of polyamine (C2) having two amino groups having active hydrogen and diisocyanate (D2) having two isocyanate groups, the molecular weight is theoretically. Is not preferable from the viewpoint of molecular weight control.

  Furthermore, when primary and / or secondary amino groups (amino groups having active hydrogen) in addition to tertiary amino groups and urea bonds are present in the dispersant skeleton, the adsorptivity to the carbon material is improved and the solvent affinity is increased. The balance with the sex site is also improved, and the dispersibility and its stability over time are also improved.

  That is, as described above, when the compounding equivalent ratio is 0.35 to 0.9, preferably 0.5 to 0.8, tertiary amino groups, urea bonds, amino groups having active hydrogen, and solvent affinity. The balance of the parts is improved and excellent dispersion stability is exhibited.

  The polymer (G2) having a basic functional group constituting the composition of the present invention is a first step for producing a polymer (A2) having one or two (meth) acryloyl groups in one terminal region. And a polyamine (B2) containing a (meth) acryloyl group and one or more primary and / or secondary amino groups of the polymer (A2) having one or two (meth) acryloyl groups in one end region. A first step of producing a polymer (C2) having an amino group, and a primary and / or second step of producing a polymer (C2) having an amino group. It can be produced by a production method comprising a third step of reacting a primary amino group with an isocyanate group of a polyisocyanate (D2) containing at least two or more isocyanate groups.

  The synthesis method and conditions for each step are as described above.

  The weight average molecular weight (Mw) of the polymer (G2) having a basic functional group constituting the conductive composition is preferably 1,000 to 100,000, more preferably 1,500 to 50,000. Particularly preferred is 2,000 to 30,000. If the weight average molecular weight is less than 1,000, the stability of the conductive composition may decrease. If the weight average molecular weight exceeds 100,000, the interaction between the resins becomes strong, and the viscosity of the conductive composition is increased. It may happen. Moreover, it is preferable that the amine value of the obtained dispersing agent is 5-100 mgKOH / g, More preferably, it is 10-70 mgKOH / g, More preferably, it is 20-50 mgKOH / g. If the amine value is less than 5 mgKOH / g, the functional group adsorbing to the carbon material may be insufficient, and it may be difficult to contribute to the carbon material dispersion. If the amine value exceeds 100 mgKOH / g, the carbon materials may aggregate. Insufficient viscosity lowering effect and defects in the appearance of the coating film may occur.

<Vinylamide resin>
The conductive composition may contain a vinylamide resin in order to obtain good dispersion and dispersion stability of the carbon material. Vinylamide resins are generally known to have an adsorption interaction with anionic species. Strictly speaking, the vinylamide resin does not correspond to a resin having a basic functional group, but its pH is slightly basic. Therefore, in this specification, it is treated as a resin having a basic functional group.
The vinyl amide resin to be used is not particularly limited, and examples thereof include polyvinyl acetamide, polyacrylamide, polyvinyl pyrrolidone, alkylated polyvinyl pyrrolidone, polyvinyl pyrrolidone graft copolymer, and a copolymer of vinyl pyrrolidone and a comonomer. Can be mentioned.

  Comonomers that can be copolymerized with vinylpyrrolidone include α-olefin, vinyl acetate, ethyl acrylate, methyl acrylate, methyl methacrylate, dimethylaminomethyl methacrylate, acrylamide, methacrylamide, acrylonitrile, ethylene, styrene, maleic anhydride, Examples include acrylic acid, sodium vinyl sulfate, vinyl chloride, vinyl pyrrolidine, trimethylsiloxy vinyl silane, vinyl propionate, vinyl caprolactam, and methyl vinyl ketone.

  In addition, an acid-modified product obtained by treating the vinylamide resin with an organic acid or an inorganic acid can be used.

  Among the above-mentioned vinylamide resins, in particular, a treatment with an almost neutral vinylamide resin such as polyvinylpyrrolidone, vinylpyrrolidone-1-butene copolymer, or vinylpyrrolidone-styrene copolymer, or an organic acid or an inorganic acid. An acid-modified product of polyvinyl pyrrolidone is preferably used.

  The vinylamide resin is effective in dispersing the carbon material because the solvent used has excellent wettability with respect to the solvent regardless of whether the solvent used is water, water-based solvent, or solvent-based solvent. It is presumed that this is because the process proceeds smoothly and the aggregation of the carbon materials is extremely reduced. In particular, when a highly polar solvent is used, the dispersion effect is extremely high.

<Combined effect of vinylamide resin and various derivatives having basic or acidic functional groups>
In order for the conductive composition to further obtain good dispersion and dispersion stability of the carbon material, it is preferable to use various derivatives having a basic or acidic functional group in combination with the vinylamide resin. As one of the effects of the above-mentioned various derivatives having basic or acidic functional groups (hereinafter sometimes simply referred to as “derivatives”), a derivative further added to increase the wettability of the vinylamide resin with a solvent is a carbon material. By acting on the surface (for example, adsorption), it is considered that dispersion proceeds due to a synergistic effect.

  Therefore, in the present invention, by using the above-mentioned vinylamide resin and various derivatives having basic or acidic functional groups, functional groups are not directly introduced (covalently bonded) to the surface of the carbon material, and further, no dispersion resin is used. Good dispersion can be obtained. From these, good dispersion can be obtained without reducing the conductivity of the carbon material, and a wiring sheet in which the carbon material is uniformly dispersed can be produced.

  In addition, in the conductive composition, there are various derivatives having a functional group on the surface of the carbon material, so that the wettability of the carbon material with respect to the binder and the like is improved. Storage stability and coatability are improved.

  The resin having a basic functional group is not limited to the above-described three types, and other than the three types, polyvinyl type, polyurethane type, polyester type, polyether type, formalin condensate, silicone type, and These composite polymers are exemplified. Furthermore, two or more kinds of resins having these basic functional groups can be used in combination.

<Pigment derivative having acidic functional group (II-1)>
In order to obtain good dispersion and dispersion stability of the carbon material, the conductive composition is an organic dye derivative having an acidic functional group, an anthraquinone derivative having an acidic functional group, an acidic functional group as an organic compound having an acidic functional group. One or more derivatives selected from an acridone derivative having an acidic functional group or a triazine derivative having an acidic functional group may be contained.

  In particular, use of a triazine derivative represented by the following formula (27) or an organic dye derivative represented by the following formula (30) is preferable.

In equation (27),
X ¹⁰¹ _{is, -NH -, - O -,} - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH-, or ^-X 103 ^-Y 101 ^{-X 104} - a and,
X ¹⁰² and X ¹⁰⁴ are each independently —NH— or —O—;
X ¹⁰³ represents —CONH—, —SO ₂ NH—, —CH ₂ NH—, —NHCO—, or —NH
SO ₂ −
Y ¹⁰¹ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
Z ¹⁰¹ is —SO ₃ M, —COOM, or —P (O) (— OM) ₂ ;
M ¹⁰¹ is one equivalent of a monovalent to trivalent cation,
Q ¹⁰¹ is —O—R ¹⁰² , —NH—R ¹⁰² , a halogen group, —X ¹⁰¹ —R ¹⁰¹ , or —X ¹⁰² —Y ¹⁰¹ —Z ¹⁰¹ ,
R ¹⁰² is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group,
n ¹⁰¹ is an integer of 1 to 4,
R ¹⁰¹ is an organic dye residue, a substituted or unsubstituted heterocyclic residue, a substituted or unsubstituted aromatic ring residue, or a group represented by the following formula (28).

In formula (28),
X ²⁰¹ is —NH— or —O—;
X ²⁰² and X ²⁰³ each independently represent —NH—, —O—, —CONH—, —SO ₂ N
H—, —CH ₂ NH—, or —CH ₂ NHCOCH ₂ NH—,
R ^201, and ^{R 202} are each independently an organic pigment residue, a heterocyclic residue, substituted or unsubstituted, substituted or unsubstituted aromatic ring residue, or a ^-Y 201 ^{-Z 201,}
Y ²⁰¹ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
Z ²⁰¹ is —SO ₃ M ²⁰¹ , —COOM ²⁰¹ , or —P (O) (— OM ²⁰¹ ) ₂ ;
^M201 is one equivalent of a trivalent cation.

Examples of the organic dye residue represented by R ^{101 in} the formula (27) and R ²⁰¹ and R ²⁰² in the formula (28) include, for example, diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, and polyazo, Phthalocyanine dyes, diaminodianthraquinones, anthrapyrimidines, flavantrons, anthanthrone, indanthrone, pyranthrone, violanthrone and other anthraquinone dyes, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes , Isoindoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, metal complex dyes, and the like. In particular, in order to increase the effect of suppressing the short circuit of the battery due to metal, it is preferable to use an organic dye residue that is not a metal complex dye, among which an azo dye, a diketopyrrolopyrrole dye, a metal-free phthalocyanine dye, The use of a quinacridone dye or a dioxazine dye is preferable because of excellent dispersibility.

Examples of the heterocyclic residue and aromatic ring residue represented by R ^{101 in} formula (27) and R ²⁰¹ and R ²⁰² in formula (28) include thiophene, furan, pyridine, pyrazole, pyrrole, and imidazole. , Isoindoline, isoindolinone, benzimidazolone, benzthiazole, benztriazole, indole, quinoline, carbazole, acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene, or anthraquinone. In particular, the use of a heterocyclic residue containing at least one of S, N, and O heteroatoms is preferable because of excellent dispersibility.

Y ^{101 in} formula (27) and Y ^{201 in} formula (28) represent a substituted or unsubstituted alkylene group, alkenylene group or arylene group having 20 or less carbon atoms, preferably a substituted or unsubstituted phenylene group or biphenylene. Group, a naphthylene group, or an alkylene group which may have a side chain having 10 or less carbon atoms.

The substituted or unsubstituted alkyl group or alkenyl group represented by R ¹⁰² contained in Q ^{101 of} formula (27) preferably has 20 or less carbon atoms, and more preferably has 10 or less carbon atoms. Examples thereof include an alkyl group which may have a chain. In the alkyl group or alkenyl group having a substituent, the hydrogen atom of the alkyl group or alkenyl group is substituted with a halogen group such as a fluorine atom, a chlorine atom, or a bromine atom, a hydroxyl group, or a mercapto group. Is.

M ^{101 in the} formula (27) and M ^{201 in the} formula (28) represent one equivalent of a monovalent to trivalent cation, for example, any one of a hydrogen atom (proton), a metal cation, or a quaternary ammonium cation. . Moreover, when it has two or more M in a dispersing agent structure, M may be only any one of a proton, a metal cation, or a quaternary ammonium cation, and these may be combined.

  Examples of the metal include lithium, sodium, potassium, calcium, barium, magnesium, aluminum, nickel, and cobalt.

  The quaternary ammonium cation is a single compound having a structure represented by the formula (29) or a mixture.

In Formula (29), R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ³⁰⁴ are any of hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group It is.

R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ^{304 in} formula (29) may be the same or different. Moreover, when R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ³⁰⁴ have a carbon atom, the number of carbon atoms is 1 to 40, preferably 1 to 30, and more preferably 1 to 20. When carbon number exceeds 40, the electroconductivity of a conductive layer may fall.

  Specific examples of the quaternary ammonium include dimethylammonium, trimethylammonium, diethylammonium, triethylammonium, hydroxyethylammonium, dihydroxyethylammonium, 2-ethylhexylammonium, dimethylaminopropylammonium, laurylammonium, and stearylammonium. However, it is not limited to these.

In equation (30),
X ^401, a direct bond, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH-
^{_{, -CH 2 NHCOCH 2 NH -,}} - X 402 -Y-, or ^-X 402 ^{-Y-X 403} - a and,
X ⁴⁰² represents —CONH—, —SO ₂ NH—, —CH ₂ NH—, —NHCO—, or —NH
SO ₂ −
X ⁴⁰³ is —NH— or —O—;
Y ⁴⁰¹ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
Z ⁴⁰¹ is —SO ₃ M ⁴⁰¹ , —COOM ⁴⁰¹ , or —P (O) (— OM ⁴⁰¹ ) ₂ ;
M ⁴⁰¹ is one equivalent of a monovalent to trivalent cation,
R ⁴⁰¹ is an organic dye residue,
n ⁴⁰¹ is an integer of 1 to 4.

Examples of the organic dye residue represented by R ⁴⁰¹ in the formula (30) include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantrons, Anthraquinone dyes such as anthanthrone, indanthrone, pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes Examples thereof include dyes, selenium dyes, and metal complex dyes. The organic dye residue represented by R ₉ includes a light yellow anthraquinone residue that is not generally called a dye. In particular, the use of azo dyes, diketopyrrolopyrrole dyes, metal-free phthalocyanine dyes, quinacridone dyes, or dioxazine dyes is preferable because of excellent dispersibility.

M ^{401 in} the formula of formula (30) represents one equivalent of a monovalent to trivalent cation, for example, a hydrogen atom (proton), a metal cation, or a quaternary ammonium cation. When Ar has two or more M dispersant structure, M ⁴⁰¹ is a proton, metal cation or quaternary ammonium may be only one of a cation, or a combination thereof.

  Examples of the metal include lithium, sodium, potassium, calcium, barium, magnesium, aluminum, nickel, and cobalt.

  The quaternary ammonium cation is a single compound having a structure represented by the formula (29) or a mixture.

In Formula (29), R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ³⁰⁴ are any of hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group It is.

R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ^{304 in} formula (29) may be the same or different. Moreover, when R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ³⁰⁴ have a carbon atom, the number of carbon atoms is 1 to 40, preferably 1 to 30, and more preferably 1 to 20. When carbon number exceeds 40, the electroconductivity of a conductive layer may fall.

  Specific examples of the quaternary ammonium include dimethylammonium, trimethylammonium, diethylammonium, triethylammonium, hydroxyethylammonium, dihydroxyethylammonium, 2-ethylhexylammonium, dimethylaminopropylammonium, laurylammonium, and stearylammonium. However, it is not limited to these.

  The method for synthesizing the dispersing agent is not particularly limited. For example, Japanese Patent Publication No. 39-28884, Japanese Patent Publication No. 45-11026, Japanese Patent Publication No. 45-29755, Japanese Patent Publication No. 64-5070. It can synthesize | combine by the method described in gazette or Unexamined-Japanese-Patent No. 2004-217842. The disclosure by the above publication is incorporated as part of the present specification.

  As one of the effects of the various derivatives having an acidic functional group, it is considered that the added derivative exerts a dispersion effect by acting (for example, adsorbing) on the surface of the carbon material.

  That is, at least one derivative selected from the group consisting of an organic dye derivative having an acidic functional group and a triazine derivative having an acidic functional group (hereinafter sometimes abbreviated as “derivative having an acidic functional group” or “derivative”). Is completely or partially dissolved in a solvent or water, and a carbon material is added and mixed in the solution. As a result, the action (for example, adsorption) of these derivatives on the carbon material advances, and the wettability of the carbon material surface to the solvent or water is accelerated by the polarity of the acidic functional group of the derivative that acts on the surface of the carbon material (for example, adsorption). Therefore, it is considered that the aggregation of the carbon material is easily solved.

  In addition, by interacting the acidic functional group possessed by the above derivative with a cation component such as amine (for example, formation of ion pairs by neutralization (salt formation) and polarization or dissociation of ion pairs (salts)), It is considered that electrostatic repulsion on the surface of the carbon material is promoted and the dispersion stability of the carbon material is further increased.

  Further, the adhesion between the carbon material and the resin component is improved by the interaction (for example, acid-base interaction) between the acidic functional group of the derivative and the basic functional group of the resin having the basic functional group. At the same time, it is considered that the dispersion stability of the carbon material is further increased.

  Furthermore, since the carbon material and the binder resin are in close contact with each other through the resin having the basic functional group, it is considered that the adhesion between the substrate of the wiring sheet and the conductive layer is also improved.

<II-2. Resin having acidic functional group>
In order to obtain good dispersion and dispersion stability of the carbon material, the conductive composition contains a resin having an acidic functional group. Preferred acidic functional groups are a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The resin having an acidic functional group is preferably the following three types of resins (H1) to (H3) from the viewpoint of dispersion stability.

  The resin having an acidic functional group also functions as a binder for binding carbon materials together. The resin having an acidic functional group is selected from the group consisting of an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a triazine derivative having a basic functional group. By using together with one or more selected derivatives, it is possible to further improve the dispersion stability of the carbon material and the coating property and the adhesion to the substrate when it is used as a conductive composition.

That is, an organic dye derivative having a basic functional group acting on (for example, adsorbing on) a carbon material surface, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, or a triazine derivative having a basic functional group Interaction between basic functional group and acidic functional group of resin having acidic functional group (for example, acid-base interaction), organic dye derivative having basic functional group, anthraquinone derivative having basic functional group, An acridone derivative having a basic functional group or a triazine derivative having a basic functional group and a resin having an acidic functional group are adsorbed on the carbon material surface while interacting (for example, acid-base interaction). As a result, the adsorption of the resin having an acidic functional group to the surface of the carbon material is promoted, the adhesion between the carbon material and the resin component is improved, and the dispersion stability of the carbon material is improved by repulsion due to the steric hindrance of the resin. It is thought to improve. Moreover, since the adhesiveness between the carbon material and the binder is improved, it can be expected that the amount of the binder used is reduced. Hereinafter, resins (H1) to (H3) suitable as resins having an acidic functional group in the present invention will be described.

<Polyvinyl resin (H1) having acidic functional group>
As shown in the formula (31), the first step for producing the polyvinyl resin (H1) having an acidic functional group is a compound (s) having two hydroxyl groups and one thiol group in the molecule. Is a step of radically polymerizing the ethylenically unsaturated monomer (m) to produce a vinyl polymer (a) having two hydroxyl groups at one end. The solvent-affinity vinyl polymer site (the ethylenically unsaturated monomer (m) is polymerized by the thiol group of the compound (s) having two hydroxyl groups and one thiol group in the molecule acting as a chain transfer agent ( A vinyl polymer (a) in which two hydroxyl groups are introduced via S atoms at the terminal of M) is synthesized.

  Examples of the compound (s) having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto- 1,2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propane Examples include diol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and 2-mercaptoethyl-2-ethyl-1,3-propanediol.

  A compound (s) having two hydroxyl groups and one thiol group in the molecule is adjusted with the ethylenically unsaturated monomer (m), optionally in accordance with the molecular weight of the target vinyl polymer (a). A vinyl polymer (a) can be obtained by mixing and heating a polymerization initiator. Preferably, bulk polymerization or solution polymerization is performed using 1 to 30 parts by weight of the compound (s) having a hydroxyl group and a thiol group with respect to 100 parts by weight of the ethylenically unsaturated monomer. The reaction temperature is 40 to 150 ° C., preferably 50 to 110 ° C., and the reaction time is 3 to 30 hours, preferably 5 to 20 hours.

  In the polymerization, 0.001 to 5 parts by weight of a polymerization initiator can be arbitrarily used with respect to 100 parts by weight of the ethylenically unsaturated monomer (m). As the polymerization initiator, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), and 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) ) Propane] and the like.

  Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more.

  In the case of solution polymerization, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and N-methyl are used as polymerization solvents. Pyrrolidone or the like is used, but is not particularly limited thereto. Two or more kinds of these polymerization solvents may be mixed and used.

  Examples of the ethylenically unsaturated monomer (m) include the following general ethylenically unsaturated monomer (m1). Common ethylenically unsaturated monomers (m1) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) Alkyl (meth) acrylates such as acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, and lauryl (meth) acrylate; cyclohexyl (meth) acrylate , (Meth) acrylates having an aliphatic ring such as isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate; (meth) acrylates having a heterocycle such as tetrahydrofurfuryl (meth) acrylate; (Meth) acrylates having aromatic rings such as (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxydiethylene glycol (meth) acrylate; methoxypolypropylene glycol (meth) acrylate, and ethoxypolyethylene glycol Alkoxypolyalkylene glycol (meth) acrylates such as (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, dye N-substituted (meth) acrylamides such as acetone (meth) acrylamide and acryloylmorpholine; N, N-dimethylaminoethyl (meth) acrylate, and N, N- Amino group-containing (meth) acrylates such as ethylaminoethyl (meth) acrylate; nitriles such as (meth) acrylonitrile; styrenes such as styrene and α-methylstyrene; ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n -Vinyl ethers such as butyl vinyl ether and isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate and vinyl propionate. However, it is not particularly limited to the above polymer, and two or more types may be used in combination, or the following monomers may be used in combination as required.

  As one of the ethylenically unsaturated monomers (m), a carboxyl group-containing ethylenically unsaturated monomer (m2) can be used in combination. Examples of the ethylenically unsaturated monomer (m2) having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, crotonic acid, acrylic acid dimer, and caprolactone of acrylic acid. One type or two or more types can be selected from an adduct (addition mole number is 1 to 5), a caprolactone adduct of methacrylic acid (addition mole number is 1 to 5), and the like.

  In this invention, it is preferable to use 20 to 70 weight% of benzyl (meth) acrylate among the ethylenically unsaturated monomer (m) illustrated above. If it is less than 20% by weight, the affinity for the solvent is low, and sufficient steric repulsion effect cannot be obtained, and the dispersibility of the carbon material may be lowered. If it exceeds 70% by weight, the solvent itself dissolves in the solvent. As a result, the adsorption to the carbon material may be insufficient, or the viscosity of the conductive composition may increase due to the entanglement between the solvent affinity parts.

  In the present invention, the ethylenically unsaturated monomer (m3) having a blocked isocyanate group, the ethylenically unsaturated monomer having an oxetane group, together with the ethylenically unsaturated monomer (m) exemplified above. A vinyl polymer (a) can be produced using an ethylenically unsaturated monomer selected from at least one of a body (m4) and an ethylenically unsaturated monomer (m5) having a t-butyl group. I can do it. By using these monomers, the crosslinkable functional groups (blocked isocyanate group, oxetane group, and t-butyl group, respectively) in the monomer are crosslinked by heating. When forming the layer, the chemical resistance, solvent resistance, heat resistance and alkali resistance can be further improved after thermosetting by hot pressing.

  Examples of the ethylenically unsaturated monomer (m3) having a blocked isocyanate group include Karenz MOI-BM and Karenz MOI-BP (manufactured by Showa Denko). Examples of the ethylenically unsaturated monomer (m4) having an oxetane group include ETERNACOLL OXMA (manufactured by Ube Industries). Examples of the ethylenically unsaturated monomer (m5) having a t-butyl group include t-butyl methacrylate and t-butyl acrylate.

  The blocked isocyanate group of the monomer is more preferable because it crosslinks with the hydroxyl group when used in combination with the hydroxyl group, and the oxetane group is more preferable because it crosslinks with the carboxyl group when used in combination with the carboxyl group. When used together with a group, it undergoes a crosslinking reaction with a hydroxyl group, and when used together with an oxetane group, a crosslinking reaction occurs with an oxetane group.

  In the case of combining carboxyl groups, in the curable dispersant, a carboxyl group derived from tetracarboxylic dianhydride (b) can be used as a curable site, but an ethylenically unsaturated monomer having a carboxyl group is ethylenic. By using together as an unsaturated monomer (m2), a carboxyl group can be easily introduced into the curable dispersant.

  Examples of the ethylenically unsaturated monomer (m2) having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, crotonic acid, acrylic acid dimer, and caprolactone of acrylic acid. One type or two or more types can be selected from an adduct (addition mole number is 1 to 5), a caprolactone adduct of methacrylic acid (addition mole number is 1 to 5), and the like.

  Moreover, when combining a hydroxyl group, a hydroxyl group can also be introduce | transduced into a curable dispersing agent by using together the ethylenically unsaturated monomer (m6) which has a hydroxyl group as an ethylenically unsaturated monomer.

As the ethylenically unsaturated monomer (m6) having a hydroxyl group, any monomer having a hydroxyl group and having an ethylenically unsaturated double bond may be used.
2-hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3, or 4) -hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, and glycerol ( Hydroxyalkyl (meth) acrylates such as meth) acrylate; N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, and N- (2-hydroxybutyl) (meta) ) N- (hydroxyalkyl) (meth) acrylamides such as acrylamide; 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, and 2- (or 3- or 4-) hydroxybutyl vinyl ether Hydroxy And alkylalkyl allyl ethers such as 2-hydroxyethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ether, and 2- (or 3-, or 4-) hydroxybutyl allyl ether. It is done.

  Also, ethylenic unsaturation obtained by adding alkylene oxide or lactone to the above hydroxyalkyl (meth) acrylates, N- (hydroxyalkyl) (meth) acrylamides, hydroxyalkyl vinyl ethers, and hydroxyalkyl allyl ethers. A monomer can also be used as an ethylenically unsaturated monomer having a hydroxyl group used in the present invention. As the alkylene oxide to be added, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide, and a combination system of two or more of these are used. When two or more kinds of alkylene oxide are used in combination, the bonding form may be random and / or block. As the lactone to be added, δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and a combination system of two or more of these are used. What added both alkylene oxide and lactone may be used.

  In the present invention, an unsaturated bond can be introduced into the vinyl polymer (a). As a method for introducing an unsaturated bond into the vinyl polymer (a), a hydroxyl group is introduced into the vinyl polymer (a), and then an ethylenically unsaturated monomer (m7) having an isocyanate group is reacted. A method, a method of introducing a carboxyl group into the vinyl polymer (a), and then reacting an ethylenically unsaturated monomer having an epoxy group (m8); an epoxy group being introduced into the vinyl polymer (a); And a method of reacting an ethylenically unsaturated monomer (m2) having a carboxyl group later.

  Examples of the ethylenically unsaturated monomer (m7) having an isocyanate group include Karenz MOI (2-methacryloyloxyethyl isocyanate manufactured by Showa Denko) and Karenz AOI (2-acryloyloxyethyl isocyanate manufactured by Showa Denko). . Examples of the ethylenically unsaturated monomer (m8) having an epoxy group include glycidyl (meth) acrylate and cyclomer M100 (3,4-epoxycyclohexyl (meth) acrylate manufactured by Daicel Chemical Industries).

  As shown in the following formula (32), the second step for producing a polyvinyl resin (H2) having an acidic functional group is a vinyl polymer having two hydroxyl groups at one end obtained in the first step. This is a step of reacting the union (a) with the tetracarboxylic dianhydride (b).

  Assuming that the molar ratio of the vinyl polymer (a) having two hydroxyl groups at one end is α and the molar ratio of the tetracarboxylic dianhydride (b) is β, the molecular weight is theoretically infinite when α = β. Therefore, it is often the case that α> β or α <β is changed to change the α / β ratio to control the target molecular weight. For example, when α = β + 1, both ends are hydroxyl groups, the molecular weight is not increased any more, and a polyvinyl resin (H2-1) having an acidic functional group can be synthesized stably. On the other hand, when β = α + 1, both ends become acid anhydride groups and the stability is deteriorated. Therefore, the acid anhydride group is hydrolyzed to have a polyvinyl resin (H2 -2) can be synthesized.

  Next, each component in the 2nd manufacturing process of the polyvinyl resin (H2) which has an acidic functional group is demonstrated.

The tetracarboxylic dianhydride (b) used in the present invention reacts with a vinyl polymer (a) having two hydroxyl groups at one end to form an ester bond, and on the resulting polyester main chain Pendant carboxyl groups can be left. If the acid anhydride group remaining in the product of formula (32) is hydrolyzed, the product of this reaction will have 2 or 3 carboxyl groups in the X ₁ moiety in the structural formula. The plurality of carboxyl groups are effective as adsorption sites for the carbon material.

However, in the case where the carboxyl group bound to X ⁰ is only one, high dispersibility, fluidity, and unfavorable not express storage stability. X ⁰ in the present invention is a reaction residue after the tetracarboxylic dianhydride (b) has reacted with the vinyl polymer (a) having two hydroxyl groups at one end. Preferably, it is a reaction residue after the tetracarboxylic dianhydride represented by the following formula (33) or formula (34) has reacted with the vinyl polymer (a) having a hydroxyl group.

  In the above formula (33), k is 1 or 2.

In the above formula (34), Q ⁰ is a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CF ₃ ) ₂ —, the following formula (35) or It is group represented by (36).

In the present invention, the vinyl polymer (a) having two hydroxyl groups at one end is reacted with tetracarboxylic dianhydride (b) to bond to X ⁰ in the product in the above formula (32). The plurality of carboxyl group parts function as an adsorbing part for the carbon material, and the vinyl polymer part functions as a solvent-affinity part.

  The weight average molecular weight of the vinyl polymer (a) having two hydroxyl groups at one end is preferably 1,000 to 10,000, and this part becomes an affinity part for the solvent as a dispersion medium. When the weight average molecular weight of the vinyl polymer (a) is less than 1,000, the effect of steric repulsion due to the solvent-affinity portion is reduced, and it becomes difficult to prevent aggregation of the carbon material, resulting in insufficient dispersion stability. There is. On the other hand, if it exceeds 10,000, the absolute amount of the solvent-affinity part increases, and the dispersibility effect itself may decrease. Furthermore, the viscosity of the conductive composition may increase.

  The vinyl polymer (a) can easily adjust the molecular weight to the above range, and also has good affinity for the solvent. As explained in the first step of the polyvinyl resin (H1) having an acidic functional group, the weight average molecular weight of the vinyl polymer (a) having two hydroxyl groups at one end is determined by the ethylenically unsaturated monomer. Use of compound (s) having two hydroxyl groups and one thiol group in the molecule for (m), reaction temperature, reaction time, used as needed for ethylenically unsaturated monomer (m) It can be controlled by the weight of the polymerization initiator used, the type of polymerization solvent used as required, and the ethylenically unsaturated monomer (m) concentration during polymerization.

  Examples of the tetracarboxylic dianhydride (b) include 1,2,3,4-butanetetracarboxylic anhydride, 1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,3-dimethyl-1, 2,3,4-cyclobutanetetracarboxylic anhydride, 1,2,3,4-cyclopentanetetracarboxylic anhydride, 2,3,5-tricarboxycyclopentylacetic anhydride, 3,5,6-tricarboxy Norbornane-2-acetic anhydride, 2,3,4,5-tetrahydrofurantetracarboxylic anhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Anhydrides, and aliphatic tetracarboxylic anhydrides such as bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic anhydride; and pyromelli Toic anhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic anhydride, 3 , 3 ′, 4,4′-biphenylsulfonetetracarboxylic anhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic acid anhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic acid anhydride, 3,3 ', 4,4'-tetraphenylsilane tetracarboxylic acid Anhydride, 1,2,3,4-furantetracarboxylic anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) Diphenyl sulfide anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane anhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride, bis (phthalic acid) phenylphosphine oxide anhydride, p-phenylene-bis (tri Phenylphthalic acid anhydride, m-phenylene-bis (triphenylphthalic acid) anhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether anhydride, bis (triphenylphthalic acid) -4,4 ′ -Diphenylmethane anhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic anhydride, 9,9-bis [4- ( 3,4-dicarboxyphenoxy) phenyl] fluorenic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic anhydride, and 3,4-dicarboxy-1, And aromatic tetracarboxylic anhydrides such as 2,3,4-tetrahydro-6-methyl-1-naphthalene succinic anhydride.

  The tetracarboxylic dianhydride (b) that can be used in the present invention is not limited to the compounds exemplified above, and may have any structure as long as it has two carboxylic anhydride groups. These may be used alone or in combination. Further, what is preferably used in the present invention is an aromatic tetracarboxylic acid anhydride represented by the formula (34) or the formula (35) from the viewpoint of reducing the viscosity of the conductive composition, A tetracarboxylic anhydride having two or more aromatic rings is preferred. Further, a compound having one carboxylic anhydride group in the molecule or a compound having three or more can be used in combination.

  The catalyst used in the second step of preparing the polyvinyl resin (H1) having the acidic functional group may be a known catalyst. The catalyst is preferably a tertiary amine compound such as triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, and 1 , 5-diazabicyclo- [4.3.0] -5-nonene.

  The polyvinyl resin (H1) having an acidic functional group that can be used in the present invention can be produced using only the above raw materials, but avoids problems such as high viscosity and non-uniform reaction. Therefore, it is preferable to use a solvent. A well-known thing can be used as a solvent. Examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and N-methylpyrrolidone. The solvent used for the reaction can be removed by an operation such as distillation after completion of the reaction, or can be used as a part of the product as it is.

  The polyvinyl resin (H1) having an acidic functional group that can be used in the present invention is obtained by reacting a vinyl polymer (a) having two hydroxyl groups at one end and a tetracarboxylic dianhydride (b). can get. The molar ratio of the acid anhydride group in the tetracarboxylic acid anhydride (b) to the hydroxyl group in the vinyl polymer (a) is such that the molar ratio of the vinyl polymer (a) is α, and the tetracarboxylic dianhydride ( When the molar ratio of b) is β, 2β / 2α = β / α = 0.3 to 1.2 is preferable, more preferably β / α = 0.5 to 1.0, and most preferably β / α. = 0.6 to 0.8. When the reaction is carried out with β / α> 1, the remaining acid anhydride group may be hydrolyzed with a necessary amount of water and used. If it is less than 0.3, the acid anhydride residue, which is an adsorbing part to the carbon material, may decrease, and the acid value of the resin may also decrease. On the other hand, if it exceeds 1.2, the polyester will have a high molecular weight, and when used as a conductive composition, the interaction between the resins will be strong and the viscosity may increase.

  The reaction temperature in the second step of the polyvinyl resin (H1) having an acidic functional group is 80 ° C. to 180 ° C., preferably 90 ° C. to 160 ° C. When the reaction temperature is 80 ° C. or lower, the reaction rate is slow, and when it is 180 ° C. or higher, the carboxyl group undergoes an esterification reaction, which may cause a decrease in acid value or gelation. Ideally, the reaction is stopped until the absorption of the acid anhydride is eliminated by infrared absorption, but when the acid value of the polyester is in the range of 5 to 200, or the hydroxyl value is 20 to 200. The reaction may be stopped when entering the range.

  The weight average molecular weight of the obtained polyvinyl resin (H2) having an acidic functional group is preferably 2,000 to 25,000. If the weight average molecular weight is less than 2,000, the stability of the conductive composition may be lowered. On the other hand, when it exceeds 25,000, the interaction between resins becomes strong, and the viscosity of the conductive composition may increase. Moreover, as for the acid value of the obtained polyvinyl-type resin (H1) which has an acidic functional group, 5-200 mgKOH / g is preferable. More preferably, it is 5-150 mgKOH / g, Most preferably, it is 5-100 mgKOH / g. If the acid value is less than 5, the adsorptivity to the carbon material may be reduced, and there may be a problem in dispersibility. If the acid value exceeds 200 mgKOH / g, the interaction between the resins becomes strong and the viscosity of the conductive composition is high. There is a case.

<Polyester resin having acidic functional group (H2)>
As long as the polyester-based resin (H2) having an acidic functional group that can be used in the present invention has a structure represented by the following formula (1), its chemical structure and production method are not particularly limited. The production method includes, for example, a first step of producing a polyester having a hydroxyl group at one end by ring-opening polymerization of a lactone using a monoalcohol as an initiator, a polyester having a hydroxyl group at one end, a tetra A method comprising a second step of reacting carboxylic dianhydride is preferred.

Formula (37):
(HOOC-) _m -R ²¹ -(-COO-[-R ²³ -COO-] _n -R ²² ) _t

In the above formula (37), R ²¹ is a tetravalent tetracarboxylic acid compound residue, R ²² is a monoalcohol residue, R ²³ is a lactone residue, and m is 2 or 3 Where n is an integer from 1 to 50 and t is (4-m).

In the present invention, preferred compounds as polyester resin (H3) having an acidic functional group represented by the above formula ^{(37), R 21} is a group represented by the later-described formula (38) - (42), R ²² is an aliphatic alkyl group having 8 to 20 carbon atoms, or a terminal ether group or ester polyoxyalkylene (alkylene moiety having 2 to 4 carbon atoms) group having a molecular weight of 200 to 1500, and R ²³ is , A hexamethylene group, a pentamethylene group, or an alkyl-substituted hexamethylene group, m is 2 or 3, n is an integer of 3 to 20, and t is (4-m) It is a certain resin.

Note that in the polyester resin (H3) having an acidic functional group represented by the above formula ^{(37), R 21} is preferably any one of groups represented by the following formula (38) - (40).

In the above formula (40), A ⁰ is a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ). _2— A group represented by the following formula (41) or (42).

  The monoalcohol that can be used for the production of the polyester-based resin (H2) having an acidic functional group is not particularly limited as long as it is a compound having one hydroxyl group. The aliphatic monoalcohol is, for example, preferably a linear or branched substituted or unsubstituted saturated aliphatic monoalcohol having 1 to 30 carbon atoms (more preferably 1 to 25 carbon atoms), or a carbon atom. Examples thereof include substituted or unsubstituted saturated alicyclic monoalcohols having 1 to 30 (more preferably 1 to 25 carbon atoms). Examples of the substituent of the saturated aliphatic monoalcohol or saturated alicyclic monoalcohol include a carboxyl group.

  Examples of aliphatic monoalcohols are methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, tert-butanol, 1-pentanol, isopentanol, 1-hexanol, 4-methyl-2-pentanol. 1-heptanol, 1-octanol, isooctanol, 2-ethylhexanol, 1-nonanol, isononanol, 1-decanol, 1-dodecanol, 1-myristyl alcohol, cetyl alcohol, 1-stearyl alcohol, isostearyl alcohol, 2- Examples include octyl decanol, 2-octyl decanol, 2-hexyl decanol, behenyl alcohol, and oleyl alcohol. Examples of the alicyclic monoalcohol include cyclohexanol.

  As the aliphatic monoalcohol, a branched aliphatic monoalcohol is preferable, and examples thereof include 8 to 20 carbon atoms such as 2-ethylhexanol, isostearyl alcohol, 2-octyldecanol, 2-octyldodecanol, and 2-hexyldecanol. Are preferred.

  As the monoalcohol, a substituted or unsubstituted aromatic monoalcohol having 6 to 30 carbon atoms (more preferably 6 to 25 carbon atoms), for example, phenol or cumylphenol can be used. A saturated aliphatic monoalcohol having an aliphatic group having 1 to 6 carbon atoms and substituted with an aromatic group having 6 to 10 carbon atoms, such as benzyl alcohol, can also be used.

  Furthermore, as the monoalcohol, a monoalkylene glycol monoether having a hydroxyl group at one end or a polyalkylene glycol monoether having a hydroxyl group at one end can be used. As these monoalkylene glycol monoethers or polyalkylene glycol monoethers, preferably, mono or polyethylene glycol or mono or polypropylene glycol alkyl monoethers having 1 to 8 carbon atoms can be mentioned. Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Monopropyl ether, propylene glycol monobutyl ether, propylene Glycol monohexyl ether, propylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monohexyl ether, dipropylene glycol mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, trie Lenglycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monohexyl ether, triethylene glycol mono-2-ethylhexyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, triethylene glycol Propylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monohexyl ether, tripropylene glycol mono-2-ethylhexyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetra Ethylene glycol monob Chill ether, tetraethylene glycol monohexyl ether, tetraethylene glycol mono-2-ethylhexyl ether, tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl ether, tetrapropylene glycol monobutyl ether, tetrapropylene glycol monohexyl Mention may be made of alkylene glycol monoalkyl ethers such as ether, tetrapropylene glycol mono-2-ethylhexyl ether, and tetradiethylene glycol monomethyl ether.

  Furthermore, examples of the monoalcohol that can be used for the production of the polyester-based resin (H2) having an acidic functional group include monoalcohols having one or more ethylenically unsaturated double bonds. Examples of the ethylenically unsaturated double bond include a vinyl group or a (meth) acryloyl group, and a (meth) acryloyl group is preferable. These can be compounds having different types of double bonds in one compound.

  As the monoalcohol having the ethylenically unsaturated double bond, for example, an unsaturated monoalcohol compound having one, two, or three or more ethylenically unsaturated double bonds can be used. Examples of monoalcohols having one ethylenically unsaturated double bond include hydroxyalkyl esters of (meth) acrylic acid having 1 to 8 carbon atoms, such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl ( (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ethyl 2- (hydroxymethyl) acrylate, 2 -Hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate and the like can be mentioned.

  Examples of the monoalcohol having two ethylenically unsaturated double bonds include 2-hydroxy-3-acryloyloxypropyl methacrylate or glycerin di (meth) acrylate. Examples of the monoalcohol having three ethylenically unsaturated double bonds include pentaerythritol triacrylate, and examples of the monoalcohol having five ethylenically unsaturated double bonds include dipentaerythritol pentaacrylate. be able to.

  Alcohol obtained by addition polymerization of alkylene oxide starting from the hydroxyl group of the aliphatic monoalcohol, aromatic monoalcohol, and monoalcohol having an ethylenically unsaturated double bond exemplified above, that is, one terminal is Etherified or esterified polyalkylene glycol can also be used for the production of a polyester-based resin (H2) having an acidic functional group. As the alkylene oxide used for the addition polymerization, for example, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide, or a mixture of two or more thereof is used. be able to. When two or more kinds of alkylene oxide are used in combination, the bonding form may be random and / or block. The addition number of alkylene oxide is usually 1 to 300, preferably 2 to 250, and particularly preferably 5 to 100 in one molecule.

  The addition of alkylene oxide can be carried out by a known method, for example, at a temperature of 100 to 200 ° C. in the presence of an alkali catalyst. Commercially available products of the addition polymerization product thus obtained include Nippon Oil & Fats Uniox series or Nippon Oil & Fats Bremer series.

  Specifically, UNIOX M-400, M-550, M-2000, BLEMMER PE-90, PE-200, PE-350, AE-90, AE-200, AE-400, PP-1000, PP -500, PP-800, AP-150, AP-400, AP-550, AP-800, 50PEP-300, 70PEP-350B, AEP series, 55PET-400, 30PET-800, 55PET-800, AET series, 30PPT -800, 50PPT-800, 70PPT-800, APT series, 10PPB-500B, and 10APB-500B.

  The monoalcohol that can be used for the production of the polyester-based resin (H2) having an acidic functional group is not limited to the above examples, and any compound can be used as long as it is a compound having one hydroxyl group. These can be used alone or in combination of two or more.

  Among the above monoalcohols, for example, 4-methyl-2-pentanol, isopentanol, isooctanol, 2-ethylhexanol, isononanol, isostearyl alcohol, 2-octyldecanol, 2-octyldodecanol, or 2-hexyldecanol By using a branched aliphatic monoalcohol such as polyalkylene glycol having a hydroxyl group at one end, the crystallinity is lowered and may become liquid at room temperature. It is preferable in terms of compatibility.

  By performing ring-opening polymerization of a lactone using the monoalcohol as an initiator, a polyester having a hydroxyl group at one end and usable for the production of the resin-type dispersant can be obtained. The lactone that can be used in the ring-opening polymerization is preferably a 4-membered to 10-membered ring, more preferably a 5- to 7-membered lactone, and the ring-constituting carbon atom is substituted or unsubstituted. Can be. Examples of the substituent of the ring-constituting carbon atom include an alkyl group having 1 to 4 carbon atoms. Also, an unsaturated lactone containing one or more ethylene bonds in the ring, or a condensed lactone with an aromatic compound (for example, benzene) can be used.

  Specific examples of suitable lactones include β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, and alkyl-substituted ε-caprolactone. Of these, δ-valerolactone, ε-caprolactone, or alkyl-substituted ε-caprolactone is preferably used from the viewpoint of ring-opening polymerizability. Examples of the alkyl substituent include an alkyl group having 1 to 4 carbon atoms, particularly a methyl group or an ethyl group, and the alkyl substituent can be substituted with one or more of these alkyl substituents.

  The lactone can be used without being limited to the above examples, and can be used alone or in combination of two or more. When two or more types are used in combination, the crystallinity is lowered and may become liquid at room temperature, which is preferable in terms of workability and compatibility with other resins.

  The ring-opening polymerization of the monoalcohol and the lactone can be carried out in a known manner, for example, by charging the monoalcohol, the lactone, and the polymerization catalyst into a reactor connected with a dehydrating tube and a condenser, and under a nitrogen stream. . When a low-boiling monoalcohol is used as the monoalcohol, the reaction can be performed under pressure using an autoclave. Moreover, when using the compound which has an ethylenically unsaturated double bond as said monoalcohol, it is preferable to add a polymerization inhibitor and to react in the flow of dry air.

  The number of moles of the lactone added to 1 mole of the monoalcohol is 1 to 50 moles, preferably 3 to 20 moles, and most preferably 4 to 16 moles. If the number of added moles is less than 1 mole, the effect of dispersing the carbon material cannot be obtained, and if it exceeds 50 moles, the molecular weight becomes too large and the dispersibility of the carbon material and the fluidity of the conductive composition are lowered. Invite.

  Examples of the polymerization catalyst for the ring-opening polymerization include tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethyl. Quaternary ammonium salts such as ammonium bromide and benzyltrimethylammonium iodide; tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodide, tetrabutylphosphonium iodide, benzyltrimethylphosphonium chloride, Benzyltrimethylphosphonium bromide Quaternary phosphonium salts such as benzyltrimethylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, and tetraphenylphosphonium iodide; phosphorus compounds such as triphenylphosphine; potassium acetate, sodium acetate, potassium benzoate, and sodium benzoate Organic carboxylates such as sodium alcoholates, alkali metal alcoholates such as sodium alcoholates and potassium alcoholates; tertiary amines; organotin compounds; organoaluminum compounds; organotitanate compounds; and zinc compounds such as zinc chloride . The catalyst is used in an amount of 0.1 ppm to 3000 ppm, preferably 1 ppm to 1000 ppm. When the catalyst amount is 3000 ppm or more, the polyester resin (H3) having an acidic functional group is intensely colored, which adversely affects the stability of the product. On the contrary, if the amount of the catalyst used is 0.1 ppm or less, the rate of ring-opening polymerization of the cyclic ester is extremely slow, which is not preferable.

  The ring-opening polymerization reaction can be carried out without a solvent, or a suitable dehydrated organic solvent can be used. The solvent used in the ring-opening polymerization reaction can be used after removal of the reaction by an operation such as distillation.

  The ring-opening polymerization reaction is preferably carried out in the range of 100 to 220 ° C, more preferably 110 to 210 ° C. If the reaction temperature is less than 100 ° C., the reaction rate is very slow. .

  The radical polymerization inhibitor used when using a monoalcohol having an ethylenically unsaturated double bond is hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, p-benzoquinone, 2,4-dimethyl-6-t-butylphenol. And phenothiazine are preferable, and these can be used alone or in combination, and the amount used is preferably 0.01% to 6%, more preferably 0.05% to 1.0%. .

  The polyester-based resin (H2) having an acidic functional group used in the present invention reacts a hydroxyl group of a polyester having a hydroxyl group at one end obtained in the first step with a tetracarboxylic dianhydride. It is preferable to obtain by (second step).

  Examples of tetracarboxylic dianhydrides used in the second step include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, and heterocyclic tetracarboxylic acids. Mention may be made of acid dianhydrides and polycyclic tetracarboxylic dianhydrides.

  Specifically, aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3 -Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, Fats such as 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride and bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride Cyclic tetracarboxylic dianhydride; and 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, and 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1 , 2- It can be mentioned heterocyclic tetracarboxylic acid anhydrides such as carboxylic acid dianhydride.

  Further, pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid Dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic Acid dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4 , 4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis 3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) Diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidene diphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) Phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′- Diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, 9,9-bis (3,4-dicarbo) Ciphenyl) fluorene dianhydride, aromatic tetracarboxylic dianhydride such as 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 3,4-dicarboxy- 1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride, etc. Of polycyclic tetracarboxylic dianhydrides.

  As the aromatic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride having two or more aromatic rings is particularly preferable, and in particular, 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride. Products, ethylene glycol ditrimellitic anhydride ester, and 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride.

  The tetracarboxylic dianhydride that can be used for the production of the polyester-based resin (H2) having an acidic functional group is not limited to the compounds exemplified above, and any one having two carboxylic anhydride moieties in the molecule. Such a structure may be used. These may be used alone or in combination. Furthermore, the tetracarboxylic dianhydride which can be used suitably for manufacture of the polyester-type resin (H2) which has an acidic functional group is an aromatic tetracarboxylic dianhydride from a viewpoint of low viscosity of an electroconductive composition. And more preferably tetracarboxylic dianhydride having two or more aromatic rings (particularly 2 to 4).

  The reaction ratio in the second step is the ratio of the number of moles <N> of the anhydrous ring of the tetracarboxylic acid anhydride to the number of moles <H> of the hydroxyl group of the polyester having a hydroxyl group at one end [<H> / <N>] is preferably 0.5 <H> / <N> <1.2, more preferably 0.7 <H> / <N> <1.1, and most preferably <H> / <N> = 1. When the reaction is performed with <H> / <N> <1, the remaining acid anhydride may be hydrolyzed with a necessary amount of water and used.

  A catalyst may be used in the second step. As the catalyst, tertiary amine compounds include, for example, triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, and 1,8-diazabicyclo- [5.4.0] -7-undecene, Examples include 1,5-diazabicyclo- [4.3.0] -5-nonene.

  Both the first step and the second step may be performed without a solvent, or an appropriate dehydrated organic solvent may be used. The solvent used for the reaction can be removed by an operation such as distillation after completion of the reaction, or can be used as a part of the product as it is.

  The reaction temperature is 80 ° C to 180 ° C, preferably 90 ° C to 160 ° C. When the reaction temperature is 80 ° C. or lower, the reaction rate is slow, and when the reaction temperature is 180 ° C. or higher, the half-esterified product again forms a cyclic anhydride, making it difficult to complete the reaction.

In the above formula (1), n is preferably an integer of 1 to 30, more preferably an integer of 2 to 20. In the above formula (1), when at least one of n and t is 2 or more, the plurality of R ²³ present in the above formula (1) are all the same group or a plurality of groups. Can be included.

  The resin having an acidic functional group is not limited to only the above two types (H1) to (H2), and other than the two types, polyvinyl, polyurethane, polyester, polyether, formalin condensate, Silicone-based and composite polymers thereof may be used. Furthermore, two or more kinds of resins having these acidic functional groups can be used in combination.

<Resins (H3) having other commercially available acidic functional groups>
Although it does not specifically limit as resin which has a commercially available acidic functional group, For example, the following are mentioned. These may be used alone or in combination.
As the resin having an acidic functional group manufactured by Big Chemie, Anti-Terra-U, U100, 203, 204, 205, Disperbyk-101, 102, 106, 107, 110, 111, 140, 142, 170, 171, 174 180, 2001, BYK-P104, P104S, P105, 9076, and 220S.

  Examples of the resin having an acidic functional group manufactured by Nippon Lubrizol include SOLPERSE 3000, 21000, 26000, 36000, 36600, 41000, 41090, 43000, 44000, and 53095.

  Examples of the resin having an acidic functional group manufactured by Efka Additives include EFKA4510, 4530, 5010, 5044, 5244, 5054, 5055, 5063, 5064, 5065, 5066, 5070, and 5071.

  Examples of the resin having an acidic functional group manufactured by Ajinomoto Fine Techno Co. include Ajisper PN411 and Azisper PA111.

  Examples of the resin having an acidic functional group manufactured by ELEMENTIS include Nuosperse FX-504, 600, 605, FA620, 2008, FA-196, and FA-601.

  Examples of the resin having an acidic functional group manufactured by Lion Corporation include Politi A-550 and Politi PS-1900.

  As resins having an acidic functional group manufactured by Enomoto Kasei Co., Ltd., Disparon 2150, KS-860, KS-873SN, 1831, 1860, PW-36, DA-1200, DA-703-50, DA-7301, DA-325 DA-375, DA-234, and the like.

  Examples of the resin having an acidic functional group manufactured by BASF Japan include JONCRYL67, 678, 586, 611, 680, 682, 683, 690, 52J, 57J, 60J, 61J, 62J, 63J, 70J, HPD-96J, 501J, 354J, 6610, PDX-6102B, 7100, 390, 711, 511, 7001, 741, 450, 840, 74J, HRC-1645J, 734, 852, 7600, 775, 537J, 1535, PDX-7630, 352J, 252D, 538J7640, 7641, 631, 790, 780, and 7610.

  Examples of the resin having an acidic functional group manufactured by Mitsubishi Rayon include Dianal BR-60, 64, 73, 77, 79, 83, 87, 88, 90, 93, 102, 106, 113, and 116. .

Without limiting to the above-mentioned dispersants, commercially available organic solvent-based dispersants can also be used, and examples thereof include the following.
Dispersbyk-103, 108, 109, 112, 116, 130, 161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2050 2070, 2096, 2150, BYK-9077, and the like.
As a dispersant manufactured by Nippon Lubrizol Corporation, SOLPERSE 5000, 9000, 13240, 13650, 13940, 17000, 18000, 19000, 22000, 24000SC, 24000GR28000, 31845, 32000, 32500, 32600, 33500, 34750, 35100, 35200, 37500 38500.
As the dispersant manufactured by Efka Additives, EFKA 1500, 1501, 1502, 1503, 4008, 4009, 4010, 4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4330, 4400, 4401, 4402, 4403, 4406, 4520, 4570, 4800, 5207, and the like.
Examples of the dispersant manufactured by Ajinomoto Fine Techno Co. include Ajisper PB711, PB821, and PB822.
Examples of the dispersant manufactured by ISP Japan include polyvinylpyrrolidone PVP K-15, K-30, K-60, K-90, or K-120.
Examples of the dispersant manufactured by Kawaken Fine Chemicals include Hinoact KF-1000, 1300M, 1500, 1700, T-6000, 8000, 8000E, or 9100.

Moreover, although a commercially available aqueous dispersing agent is not specifically limited, For example, the following are mentioned.
Examples of the dispersant manufactured by Big Chemie include Disperbyk-180, 183, 184, 185, 187, 190, 191, 192, 193, 198, 2090, 2091, 2095, 2096, or BYK-154.
Examples of the dispersant manufactured by Nippon Lubrizol include SOLPERSE 12000, 20000, 27000, 41000, 41090, 43000, 44000, or 45000.
Examples of the dispersant manufactured by Efka Additives include EFKA1101, 1120, 1125, 1500, 1503, 4500, 4510, 4520, 4530, 4540, 4550, 4560, 4570, 4580, and 5071.
As the dispersant manufactured by BASF Japan, JONCRYL67, 678, 586, 611, 680, 682, 683, 690, 52J, 57J, 60J, 61J, 62J, 63J, 70J, HPD-96J, 501J, 354J, 6610, PDX-6102B, 7100, 390, 711, 511, 7001, 741, 450, 840, 74J, HRC-1645J, 734, 852, 7600, 775, 537J, 1535, PDX-7630, 352J, 252D, 538J, 7640, 7641, 631, 790, 780, 7610, JDX-C3000, JDX-3020, JDX-6500, etc. are mentioned. Moreover, Luvitec K17, K30, K60, K80, K85, K90, K115, VA64W, VA64, VPI55K72W, VPC55K65W, etc. are mentioned.
Examples of the dispersant manufactured by Kawaken Fine Chemicals include Hinoact A-110, 300, 303, or 501.
Examples of the dispersant manufactured by Nitto Bo Medical include PAA series, PAS series, amphoteric series PAS-410C, 410SA, 84, 2451, or 2351.
Examples of the dispersant manufactured by ISP Japan include polyvinylpyrrolidone PVP K-15, K-30, K-60, K-90, or K-120.
Examples of the dispersant manufactured by Maruzen Petrochemical Co., Ltd. include polyvinylimidazole PVI.

Next, the solvent will be described. When the binder resin (A) in the conductive layer and the conductive carbon material (B) are uniformly mixed, a solvent can be appropriately used. Examples of such a solvent include an organic solvent and water.
Organic solvents include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol methyl ether, diethylene glycol methyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc. Suitable for the composition of the conductive composition from among ethers such as hexane, heptane, octane and other hydrocarbons, benzene, toluene, xylene, cumene and other aromatics, ethyl acetate, butyl acetate and other esters Can be used. Two or more solvents may be used.
In addition, when employ | adopting the printing coating system as which viscosity more than fixed is required for electroconductive compositions, such as screen printing, the viscosity at the time of 25 degreeC of an organic solvent has preferable 30mPa * s-75000mPa * s. If the viscosity is less than 30 mPa · s, the resin content is low due to the high conductivity, so the viscosity and conductivity of the carbon material suitable for coating cannot be obtained, and the coating property is insufficient. When the viscosity exceeds 75000 mPa · s, the dispersibility of the carbon material is significantly lowered because the viscosity is too high. Examples include terpineol, dihydroterpineol, 2,4-diethyl-1,5-pentanediol, 1,3-butylene glycol, and isobornylcyclohexanol. The high-viscosity solvents shown here may be used in combination of two or more, and may be used in combination with a low-viscosity solvent having a viscosity at 25 ° C. of less than 30 mPa · s, such as methyl ethyl ketone, toluene, and isopropyl alcohol. Is possible.

Next, other components will be described. In the conductive composition of the present invention, an ultraviolet absorber, an ultraviolet stabilizer, a radical scavenger, a filler, a thixotropy imparting agent, an anti-aging agent, and an antioxidant are added to the conductive composition of the present invention, as necessary. Agent, antistatic agent, flame retardant, thermal conductivity improver, plasticizer, anti-sagging agent, antifouling agent, antiseptic, disinfectant, antifoaming agent, leveling agent, anti-blocking agent, curing agent, thickener, Various additives such as a pigment dispersant and a silane coupling agent may be added.

(Disperser / Mixer)
As an apparatus used for obtaining the conductive composition, a disperser or a mixer that is usually used for pigment dispersion or the like can be used.

  For example, mixers such as dispersers, homomixers, or planetary mixers; homogenizers such as “Clearmix” manufactured by M Technique, or “fillmix” manufactured by PRIMIX; paint conditioner (manufactured by Red Devil), ball mill, sand mill (Shinmaru Enterprises "Dynomill", etc.), Attritor, Pearl Mill (Eirich "DCP Mill", etc.), or Coball Mill, etc .; Media type dispersers; Wet Jet Mill (Genus, "Genus PY", Sugino Media-less dispersers such as “Starburst” manufactured by Machine, “Nanomizer” manufactured by Nanomizer, etc., “Claire SS-5” manufactured by M Technique, or “MICROS” manufactured by Nara Machinery; or other roll mills, etc. Although The present invention is not limited to these.

  For example, when using a media-type disperser, a disperser in which the agitator and vessel are made of a ceramic or resin disperser, or the surface of the metal agitator and vessel is treated with tungsten carbide spraying or resin coating. Is preferably used. As the media, it is preferable to use glass beads, ceramic beads such as zirconia beads or alumina beads. Only one type of dispersion device may be used, or a plurality of types of devices may be used in combination.

(Conductive wiring sheet)
The conductive wiring sheet of the present invention has a conductive layer formed from a conductive composition on a substrate.

(Sheet substrate)
Although the shape of the sheet-like base material used for an electroconductive wiring sheet is not specifically limited, An insulating resin film is preferable and what suited various uses can be selected suitably.

  For example, examples of the material include PET (polyethylene terephthalate), PEN (polyethylene naphthalate), polyimide, polyvinyl chloride, polyamide, nylon, OPP (stretched polypropylene), CPP (unstretched polypropylene), and the like. There is nothing.

  In general, a film on a flat plate is used as the shape, but a roughened surface, a primer-treated one, a perforated one, and a mesh-like substrate can also be used.

  There is no restriction | limiting in particular as a method of coating an electroconductive composition on a sheet-like base material, A well-known method can be used.

Specific examples include die coating method, dip coating method, roll coating method, doctor coating method, knife coating method, spray coating method, gravure coating method, screen printing method or electrostatic coating method, and the like. Examples of methods that can be used include standing drying, blower dryers, hot air dryers, infrared heaters, and far-infrared heaters, but are not particularly limited thereto.
In addition, rolling may be performed with a lithographic press or a calender roll after coating, or may be performed while heating in order to soften the conductive layer and facilitate pressing.

(Conductive layer density)
The density in the conductive layer of the present invention is 1.2 to 2.0 g / cm ³ , preferably 1.5 to 2.0 g / cm ³ .
Since the density of the conductive layer is 1.2 to 2.0 g / cm ³ , the contact between the conductive carbon materials in the conductive layer becomes good, and the conductive network in the conductive layer becomes good. Thus, it is possible to obtain a conductive wiring sheet having good adhesion to the base material while ensuring high conductivity. When the density of the conductive layer is less than 1.2 g / cm ³ , the contact between the conductive carbon materials in the conductive layer becomes insufficient, and the conductivity of the conductive layer becomes poor. In addition, when the density of the conductive layer exceeds 2.0 g / cm ³ , the adhesion between the carbon materials is likely to be separated due to expansion of the material or the like due to poor adhesion to the base material or storage at a high temperature. Therefore, the conductivity is poor and the durability is poor.

(Thickness of conductive layer)
The thickness of the conductive layer of the present invention is 10 to 500 μm, preferably 20 to 200 μm, and more preferably 50 to 150 μm.

(Volume resistivity of conductive layer)
The volume resistivity of the conductive layer of the present invention is preferably less than 1 × 10 ⁻² Ω · cm. Since the volume resistivity is less than 1 × 10 ⁻² Ω · cm, it can be suitably used as a wiring for an electronic device or the like.

(Composition of conductive layer)
The ratio of the binder resin (A) in the conductive layer of the present invention is 5 to 75% by mass, preferably 10 to 50% by mass, and more preferably 20 to 35% by mass. If the amount of the binder resin (A) is too small, the surface properties and adhesion of the conductive layer may not be maintained. On the other hand, if the amount of the binder resin (A) is too large, the conductivity of the conductive layer may be reduced. .
Moreover, the ratio of the electroconductive carbon material (B) which occupies in the electroconductive layer of this invention is 25-95 mass%, Preferably it is 50-90 weight%, More preferably, it is 65-80 mass%. If the amount of the conductive carbon material (B) is too small, the conductivity of the conductive layer may be insufficient. On the other hand, if the amount of the conductive carbon material (B) is too large, the adhesiveness of the conductive layer is reduced. There is a case.
Furthermore, when using a dispersing agent (C) together, it is 0.1-15 mass% in an electroconductive layer, Preferably it is 0.1-10 mass%, More preferably, it is 0.1-5 mass%.

  EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples and comparative examples, “part” represents “part by mass”, Mw represents a weight average molecular weight, and Tg represents a glass transition temperature.

<Synthesis of Binder Resin A-1>
Polyester polyol (made by Kuraray Co., Ltd.) obtained from terephthalic acid, adipic acid and 3-methyl-1,5-pentanediol in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping device, and nitrogen introduction tube “Kuraray polyol P-2011”, Mn = 2011) 455.5 parts, dimethylolbutanoic acid 16.5 parts, isophorone diisocyanate 105.2 parts, and toluene 140 parts were charged and reacted in a nitrogen atmosphere at 90 ° C. for 3 hours. 360 parts of toluene was added to a urethane prepolymer solution having an isocyanate group. Next, 19.9 parts of isophorone diamine, 0.63 parts of di-n-butylamine, 294.5 parts of 2-propanol, and 335.5 parts of toluene were mixed with the urethane prepolymer solution having an isocyanate group. 969.5 parts were added, reacted at 50 ° C. for 3 hours and subsequently at 70 ° C. for 2 hours, diluted with 126 parts of toluene and 54 parts of 2-propanol, Mw = 61,000, acid value = 10 mgKOH / g, A solution of polyurethane resin A-1 was obtained in which the total equivalent of amino groups in the polyamino compound and the reaction terminator was 0.98 with respect to the free isocyanate groups at both ends of the polymer.

<Synthesis of Binder Resin A-2>
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, 156.2 g of Pripol 1009 as a polybasic acid compound, 5.5 g of 5-hydroxyisophthalic acid, and preamine as a polyamine compound 146.4 g of 1074 and 100 g of ion-exchanged water were charged and stirred until the temperature of heat generation became constant. When the temperature was stabilized, the temperature was raised to 110 ° C., and after confirming the outflow of water, the temperature was raised to 120 ° C. after 30 minutes, and then the dehydration reaction was continued while raising the temperature by 10 ° C. every 30 minutes. . When the temperature reached 230 ° C., the reaction was continued for 3 hours at the same temperature, and kept for 1 hour under a vacuum of about 2 kPa to lower the temperature. Finally, an antioxidant was added to obtain a polyamide resin A-2 having a weight average molecular weight of 24,000, an acid value of 13.2 KOHmg / g, a hydroxyl value of 5.5 KOHmg / g, and a glass transition temperature of −32 ° C.

In addition, evaluation of resin was performed as follows.
<Measurement method of weight average molecular weight (Mw)>
For measurement of Mw, GPC (gel permeation chromatography) “HPC-8020” manufactured by Tosoh Corporation was used. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent (THF; tetrahydrofuran) based on the difference in molecular size. For the measurement in the present invention, “LF-604” (manufactured by Showa Denko KK: GPC column for rapid analysis: 6 mm ID × 150 mm size) is connected in series to the column, the flow rate is 0.6 ml / min, the column temperature. It carried out on the conditions of 40 degreeC, and the determination of the weight average molecular weight (Mw) was performed in polystyrene conversion.
<Measurement of acid value>
About 1 g of a sample is accurately weighed in a stoppered Erlenmeyer flask, and 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution is added and dissolved. To this is added phenolphthalein reagent as an indicator and held for 30 seconds. Thereafter, the solution is titrated with a 0.1N alcoholic potassium hydroxide solution until the solution becomes light red. The acid value was determined by the following formula (unit: mgKOH / g). Acid value (mgKOH / g) = (5.611 × a × F) / S
However,
S: Sample collection amount (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution <Measuring method of hydroxyl value>
The hydroxyl value represents the amount of hydroxyl group contained in 1 g of the hydroxyl group-containing resin in terms of the amount (mg) of potassium hydroxide necessary for neutralizing acetic acid bonded to the hydroxyl group when the hydroxyl group is acetylated. It is. The hydroxyl value was measured according to JISK0070. In the present invention, the hydroxyl value is calculated in consideration of the acid value as shown in the following formula.
<Measurement of hydroxyl value>
About 1 g of a sample is accurately weighed in a stoppered Erlenmeyer flask, and 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution is added and dissolved. Further, exactly 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml) was added and stirred for about 1 hour. To this, phenolphthalein reagent is added as an indicator and lasts for 30 seconds. Thereafter, the solution is titrated with a 0.1N alcoholic potassium hydroxide solution until the solution becomes light red.
The hydroxyl value was determined by the following formula (unit: mgKOH / g).
Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.05} / S] + D
However,
S: Sample collection amount (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: Consumption of 0.1N alcoholic potassium hydroxide solution in the empty experiment (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution D: Acid value (mgKOH / g)
<Measuring method of glass transition temperature>
The binder resin from which the solvent was removed by drying was measured by using a DSC-1 manufactured by METTLER TOLEDO Co., Ltd. and raising the temperature from -80 to 150 ° C. at 2 ° C./min.

<Adjustment of binder resin>
The binder resin used in the Examples and Comparative Examples was adjusted to a solution having a solid content of 20% using the solvent shown below. The composition ratio of the mixed solvent is described as a mass ratio.
-Binder resin A-1-1 solution: The binder resin A-1 solution was diluted with toluene / methyl ethyl ketone / 2-propanol (1/1/1) to obtain a binder resin A-1-1 solution.
-Binder resin A-2-1 solution: The binder resin A-2 solution was diluted with toluene / methyl ethyl ketone / 2-propanol (1/1/1) to obtain a binder resin A-2-1 solution.
-Binder resin A-3-1 solution: Binder resin A-3: Byron 200 (manufactured by Toyobo Co., Ltd., polyester resin) is diluted with toluene / methyl ethyl ketone / 2-propanol (1/1/1) to form a binder. A solution of Resin A-3-1 was obtained.

<Wiring sheet>
Example 1
200 parts of a solution of A-1-1 as a binder resin (resin solid content 40 parts), B-1 as an electrically conductive carbon material: 60 parts of artificial graphite PAG-5 (manufactured by Nippon Graphite Co., Ltd.), toluene / 240 parts of methyl ethyl ketone / 2-propanol (1/1/1) was placed in a mixer and mixed, and further dispersed in a sand mill to obtain a conductive composition (1). The degree of dispersion of the obtained dispersion was determined by determination with a grind gauge (in accordance with JISK5600-2-5). The evaluation results are shown in Table 1. The numbers in the table indicate the size of the coarse particles, and the smaller the value, the better the dispersibility, and the more uniform and good state.
And after apply | coating this electroconductive composition (1) on a PET (polyethylene terephthalate) film of thickness 100 micrometers used as a sheet-like base material using a doctor blade, it heat-dried. Further, pressing was performed to produce a wiring sheet (1) having a conductive layer thickness of 100 μm and a density of 1.43 g / cm ³ . The conductive carbon material contained in the conductive layer is 60% by mass.
The obtained wiring sheet was evaluated by the following method. The evaluation results are shown in Table 1.

(Conductive layer density)
The density of the conductive layer was evaluated from the mass and volume of the conductive layer. Specifically, the mass and thickness of a 10 cm square wiring sheet (area: 100 cm ² ) and the mass and thickness of a 10 cm square PET film (area: 100 cm ² ) were measured, and a 10 cm square conductive layer (area: 100 cm). The mass and thickness of ² ) were calculated. Next, the density of the conductive layer was calculated by dividing the mass of the conductive layer by the volume (area × thickness).

(Volume resistivity of conductive layer)
The volume resistivity of the conductive layer was determined by measuring (JIS-K7194) by a four-terminal method using Loresta GP (manufactured by Mitsubishi Chemical Analytech Co., Ltd.). The evaluation results are shown in Table 1.
A: “Volume resistivity is less than 5 × 10 ⁻³ Ω · cm (very good)”
○: “Volume resistivity is 5 × 10 ⁻³ Ω · cm or more and less than 1 × 10 ⁻² Ω · cm (good)”
○ △: “Volume resistivity is 1 × 10 ⁻² Ω · cm or more and less than 5 × 10 ⁻² Ω · cm (can be used)”
Δ: “Volume resistivity is 5 × 10 ⁻² Ω · cm or more and less than 1 × 10 ⁻¹ Ω · cm (defect)”
×: “Volume resistivity is 1 × 10 ⁻¹ Ω · cm or more (very poor)”

(Durability of conductive layer)
The durability of the conductive layer is determined by the rate of change in volume resistivity before and after the wiring sheet was left in an oven at a temperature of 80 ° C. for 1 month (volume resistivity before being left in the oven / after being left in the oven for 1 month). (Percentage of volume resistivity ratio). The volume resistivity was measured in the same manner as described above. The evaluation results are shown in Table 1.

○: “Change rate is 120% or less (good)”
○ △: “Change rate is higher than 120% and 200% or less (usable)”
Δ: “Change rate is higher than 200% and 300% or less (defect)”
X: “Change rate is 300% or more. Practical problem (defect)”

(Surface properties of conductive layer)
The surface property in the conductive layer of the wiring sheet produced above was determined by visual observation. The evaluation results are shown in Table 1. The surface property is better as the material does not crack. If the surface properties of the conductive layer are poor and cracks are likely to occur, it becomes difficult to handle the wiring sheet, leading to loss of the conductive layer during handling or resistance change during long-term use. .
○: “No cracking (practical problem-free level)”
○ △: “In rare cases, cracks are seen (there is a problem, but the usable level)”
Δ: “Partial cracks are seen”
×: “Overall cracks are seen”

(Adhesiveness of conductive layer)
The conductive layer produced above was cut into 6 grids in the vertical and horizontal directions at intervals of 2 mm using a knife from the surface of the conductive layer to the depth reaching the substrate. An adhesive tape was applied to the cut and immediately peeled off, and the degree of the conductive layer falling off was determined by visual judgment. The evaluation results are shown in Table 1, and the evaluation criteria are shown below.
○: “No peeling (practical problem-free level)”
○ △: “Slightly peeled (problem but usable level)”
△: “About half peel”
×: “Peeling at most parts”

(Examples 2 to 19 and Comparative Examples 1 to 6)
Conductive compositions (2) to (19) and (a) to (f) were obtained by the same method as that for the conductive composition (1) at the composition ratio shown in Table 1. Also, the wiring sheet (2) of the examples and comparative examples were respectively the same as the wiring sheet (1) except that the coating amount of the conductive composition and the pressing conditions were changed so as to obtain the thickness and density shown in Table 1. To (19) and (a) to (f) were obtained.

The materials used in the examples are shown below.
<Binder resin (A)>
A-1: Polyurethane resin A-2: Polyamide resin A-3: Polyester resin Byron 200 (manufactured by Toyobo Co., Ltd.)
<Conductive carbon material (B)>
B-1: Artificial graphite PAG-5 (manufactured by Nippon Graphite Co., Ltd., average particle size 30 μm)
B-2: scale-like graphite 10099M (manufactured by Nishimura Graphite, average particle size 65 μm)
B-3: exfoliated graphite CMX (manufactured by Nippon Graphite Co., Ltd., average particle size 40 μm)
B-4: Spherical graphite CGC-20 (manufactured by Nippon Graphite Co., Ltd., average particle size 20 μm)
<Dispersant (C)>
C-1: Organic dye derivative having a basic functional group (Table 2)
C-2: Triazine derivative having a basic functional group (Table 2)
C-3: Polyvinylpyrrolidone PVP K-30 (made by ISP Japan)
C-4: Organic dye derivative having an acidic functional group (Table 2)
C-5: Triazine derivative having an acidic functional group (Table 2)

As shown in Table 1, in the wiring sheet of the present invention, the conductivity could be greatly improved without causing problems in the surface properties and adhesion of the conductive layer. The volume resistivity of the conductive layer tends to be better when the density of the conductive layer is larger, but if the density of the conductive layer is too high as in Comparative Example 2, it may lead to problems such as durability and adhesion of the conductive layer. confirmed. When the density of the conductive layer was too small as in Comparative Examples 1, 3, 4, and 5, it was also confirmed that the adhesion of the conductive layer tends to be poor. From these, it can be seen that the density of the conductive layer is important. Moreover, the tendency for the adhesiveness of a conductive layer to fall was confirmed, when the thickness of a conductive layer became thick like Examples 14, 15 and the comparative example 6. Furthermore, it can be seen that when the dispersant is used, the value of the grind gauge is smaller than when the same carbon material is used, and it is considered that the carbon material is uniformly distributed in the conductive layer.
When flaky graphite or a dispersant was used, it was confirmed that particularly good characteristics were exhibited. A comparison of Examples 3 and 17 shows that the volume resistivity of the conductive layer is better when flaky graphite is used. This is thought to be because the use of flaky graphite led to the improvement of the conductive network by making the contact between the carbon materials planar. When Examples 10 and 11 were compared, it was confirmed that the surface properties and adhesion of the conductive layer were good, and when Examples 16 and 17 were compared, the volume resistivity of the conductive layer was good. These are considered to have led to the improvement of the conductive layer because the use of the dispersant enabled the carbon material to be uniformly dispersed without agglomeration. On the other hand, when Comparative Examples 3 and 5 were compared, it was confirmed that sufficient conductivity could not be obtained even when a dispersant was used in combination. This confirms that even if the carbon material was uniformly dispersed without agglomeration, the conductive network was not formed because the contact between the carbon materials was insufficient when the density of the conductive layer was low. It is thought that there is. Moreover, when Examples 1-18 were compared, when flaky graphite and a dispersing agent were used, it turned out that durability of a conductive layer is favorable. These are considered to be due to the use of flaky graphite and a dispersing agent to improve the durability as a result of the good contact between the carbon materials and the improvement of the conductive layer.
As described above, in the conductive layer composed of the binder resin and the conductive carbon material, it has been found that good contact of the carbon material can be obtained by setting a predetermined density in order to form an appropriate conductive network. . Further, when flaky graphite or a dispersant was used, particularly good characteristics were shown.

Claims (5)

A conductive wiring sheet having a sheet-like base material and a conductive layer disposed on the sheet-like base material,
The conductive layer includes a binder resin (A) and a conductive carbon material (B),
A wiring sheet having a density of the conductive layer of 1.2 to 2.0 g / cm ³ and a thickness of the conductive layer of 500 μm or less. The wiring sheet according to claim 1, wherein the volume resistivity of the conductive layer is less than 1 × 10 ⁻² Ω · cm.   The wiring sheet according to claim 1 or 2, wherein the content of the conductive carbon material (B) in the conductive layer is 50 to 90 mass%.   4. The wiring sheet according to claim 1, wherein the conductive carbon material (B) contains flaky graphite. The wiring sheet according to claim 1, wherein the conductive layer further contains a dispersing agent (C).