JP5607441B2 - Conductive polymer fine particles, conductive polymer fine particle dispersions and methods for producing them - Google Patents

Description

  The present invention relates to a conductive polymer fine particle and a conductive polymer fine particle dispersion in which the fine particle is dispersed in a dispersion medium. More specifically, the present invention relates to a conductive polymer fine particle having high conductivity and excellent dispersibility in a dispersion medium. The present invention relates to a conductive polymer fine particle dispersion that is excellent in dispersion uniformity and dispersion stability using the fine particles, can form a transparent and uniform coating film with high conductivity, and a method for producing the same.

  Since π-conjugated conductive polymers such as polyaniline, polypyrrole, polythiophene have excellent stability and conductivity, various antistatic agents, electrolytes for solid electrolytic capacitors, anticorrosion paints, EMI shields, chemical sensors, display elements Application to non-linear materials, plating primers, etc. is expected.

  However, these π-conjugated conductive polymer substances generally have a problem that they are insoluble or hardly soluble in a solvent and are infusible, so that they are difficult to mold and process.

  Therefore, a technique for improving the moldability and workability by pulverizing the conductive polymer into fine particles or fillers and dispersing it in a dispersion medium such as water or an organic solvent is known.

  However, the conductive polymer substance fine particles generally tend to aggregate in the dispersion medium, and it is very difficult to obtain a dispersion having good dispersion uniformity and dispersion stability. And a highly transparent conductive film (conductive layer) could not be formed. On the other hand, when trying to improve the dispersibility by lowering the solid content concentration of the conductive polymer fine particles, it is necessary to repeat the coating process multiple times to obtain a thick conductive film. It has been difficult to apply to applications that require thick conductive films such as electrolytes.

  Thus, techniques for improving the dispersion stability and conductivity of conductive polymer particles have been proposed so far.

  For example, Patent Document 1 discloses a conductive composition in which a π-conjugated conductive polymer doped with a polyanion is dispersed in an organic solvent containing a basic organic compound serving as an ion pair with the polyanion. Although this electroconductive composition has improved dispersion stability to some extent, the electroconductivity of the formed film was not sufficient.

  Patent Document 2 discloses a conductive polymer substance obtained by wet-grinding a conductive polymer substance having an electric conductivity of 10 S / cm or more into particles having an average particle diameter of 1000 nm or less in an organic solvent and dispersing the particles in the organic solvent. An organic solvent dispersion is disclosed.

  However, the conductive polymer particles themselves used in this dispersion are not different from those conventionally known in composition and properties, so that they still tend to agglomerate and the dispersion stability is not sufficient.

  Patent Document 3 describes that a conductive coating composition that can be easily formed can be obtained by blending a binder resin into an organic solvent dispersion of a conductive polymer. However, even with this technique, it has been difficult to obtain a dispersion excellent in dispersion stability and conductivity.

JP 2007-254730 A JP-A-2005-068166 JP 2007-324142 A

  This invention is made | formed in view of the said subject, and makes it a subject to provide the conductive polymer fine particle which has the outstanding electroconductivity and dispersibility, and its manufacturing method. In addition, the present invention utilizes such conductive polymer fine particles, is excellent in dispersion uniformity and dispersion stability, has high conductivity, high transparency, and can form a uniform coating film. It is an object of the present invention to provide a functional polymer fine particle dispersion and a method for producing the same.

  The present inventors combined a polyester resin compound having a sulfonic acid group in the molecular structure and a low molecular weight aromatic sulfonic acid compound as dopant components, and dispersed them by doping them into a π-conjugated conductive polymer. Conductive polymer fine particles having excellent conductivity and conductivity can be obtained, and the fine particle dispersion can form a conductive film having excellent transparency and conductivity while maintaining a good dispersion state for a long period of time. As a result, the present invention has been completed.

That is, the present invention provides conductive polymer fine particles obtained by doping a π-conjugated conductive polymer with a dopant component, and the dopant component is at least the following components (a) and (b);
(A) Polyester resin compound having a sulfonic acid group (b) A conductive polymer fine particle comprising a low molecular weight aromatic sulfonic acid compound.

（上式中、Ｒはグリコール残基を示し、Ａは、スルホン酸基を除く置換基を有していてもよい多価カルボン酸残基を示す。ｎは１あるいは２を示す。）
で示される繰り返し単位及び、下記一般式（２）

（上式中、Ｒはグリコール残基を示し、Ｂは芳香環を示す。ｎは１或いは２を示す。）
で示される繰り返し単位を含む共重合体のものである。 In the present invention, the (a) polyester resin compound having a sulfonic acid group is
The following general formula (1)

(In the above formula, R represents a glycol residue, A represents a polyvalent carboxylic acid residue which may have a substituent other than a sulfonic acid group. N represents 1 or 2.)
And a repeating unit represented by the following general formula (2)

(In the above formula, R represents a glycol residue, B represents an aromatic ring, and n represents 1 or 2.)
It is a copolymer containing the repeating unit shown by these.

  Further, the present invention is a conductive polymer fine particle dispersion obtained by dispersing or dissolving the conductive polymer fine particles in a solvent.

  Further, the present invention provides the following general formula (3)

（式中、Ｘは、酸素原子又は硫黄原子を示す。Ｚは、それぞれ同一であっても異なっていても良い酸素原子又は硫黄原子を表す。Ｒは、直鎖状又は分岐鎖状の炭素数１〜６のアルキレン基を示す。）
で示されるモノマー化合物、（ａ）スルホン酸基を有するポリエステル樹脂系化合物、（ｂ）低分子芳香族スルホン酸化合物および化学酸化重合触媒を含有するモノマー溶液に、酸化剤含有液を添加することを特徴とする導電性高分子微粒子の製造方法である。

(In the formula, X represents an oxygen atom or a sulfur atom. Z represents an oxygen atom or a sulfur atom which may be the same as or different from each other. R represents a linear or branched carbon number. 1 to 6 alkylene groups are shown.)
An oxidant-containing liquid is added to the monomer compound containing (a) a polyester resin compound having a sulfonic acid group, (b) a low molecular weight aromatic sulfonic acid compound, and a chemical oxidative polymerization catalyst. This is a method for producing conductive polymer fine particles.

  Furthermore, the present invention is a method for producing a conductive polymer fine particle dispersion, characterized in that a conductive polymer fine particle-containing liquid in which the conductive polymer fine particles, a dispersant and a solvent are mixed is dispersed by wet pulverization. .

  According to the present invention, conductive polymer fine particles having excellent conductivity and dispersibility can be obtained. The conductive polymer fine particle dispersion in which the conductive polymer fine particles are dispersed or dissolved in a dispersion medium is excellent in dispersion uniformity and dispersion stability, and can maintain a uniform dispersion state for a long period of time. And by apply | coating this dispersion | distribution on a board | substrate, electroconductivity is high, it is excellent in transparency, and a uniform electroconductive film can be formed. Furthermore, since this dispersion is excellent in dispersion uniformity and dispersion stability, the solid content concentration of the conductive polymer fine particles can be increased, and a thick conductive film can be easily formed.

  Further, according to the production method of the present invention, the particle size of the conductive polymer fine particles can be controlled, and uniform and highly dispersible fine particles can be obtained in a simple process with a high yield.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

  The conductive polymer fine particles of the present invention are obtained by doping a π-conjugated conductive polymer with (a) a polyester resin compound having a sulfonic acid group and (b) a low molecular weight aromatic sulfonic acid compound as a dopant component. is there.

  Among the dopant components, the component (a) polyester resin-based compound having a sulfonic acid group is a polyester resin having a polyester skeleton portion substituted with a sulfonic acid group, and a linear polyester is particularly preferable.

  The linear polyester is obtained by polymerizing a reactive raw material composed of a compound having an ester-forming functional group. The ester-forming functional group means a functional group that reacts with a carboxyl group or a hydroxyl group to form an ester bond, and specifically includes a carboxyl group, a hydroxyl group, an ester-forming derivative group of a carboxyl group, and a hydroxyl group. Of the ester-forming derivative. An ester-forming derivative group of a carboxyl group is a group derived from a carboxyl group that has been anhydrideized, esterified, acid chlorided or halogenated and reacts with a hydroxyl group to form an ester bond. . The ester-forming derivative group of a hydroxyl group is a group that is derived, for example, by acetylation of a hydroxyl group and reacts with other carboxyl groups to form an ester bond. In particular, when the ester-forming functional group is a carboxyl group or a hydroxyl group, it is preferable in that the reactivity during production of the polyester resin is good.

  The amount of each compound contained in the reactive raw material is such that the total number of carboxyl groups and ester forming derivative groups contained in each compound and the total number of hydroxyl groups and ester forming derivative groups are 1: It is preferable to adjust so that it may become the range of 1-2.5.

  In order to adjust the molecular weight, the reactive raw material contains an appropriate amount of a known polyfunctional compound such as pentaerythritol, trimethylolpropane, dimethylolbutanoic acid, a trifunctional or higher functional carboxylic acid. May be. Furthermore, for example, p-hydroxybenzoic acid, monovalent aliphatic alcohol, and the like may be used together.

  As such a linear polyester, a linear polyester having a polyvalent carboxylic acid component and a glycol component as constituent components is preferably used. The polyvalent carboxylic acid component includes a divalent or higher polyvalent carboxylic acid and an ester-forming derivative in which a carboxyl group in the polyvalent carboxylic acid is substituted with the ester-forming inducing group derived from the carboxyl group. Furthermore, the polyvalent carboxylic acid component includes polyvalent carboxylic acids having a sulfonic acid group, ester-forming derivatives thereof, and alkali metal salts thereof. Examples of the polyvalent carboxylic acid include dicarboxylic acids such as aromatic dicarboxylic acids and aliphatic dicarboxylic acids. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, diphenic acid, naphthalic acid, 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 2,6. -A naphthalene dicarboxylic acid etc. can be mentioned, As aromatic dicarboxylic acid which has a sulfonic acid group, 5-sulfoisophthalic acid, 2-sulfoisophthalic acid, 4-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfonaphthalene- Examples include 2,6-dicarboxylic acid. On the other hand, examples of the aliphatic dicarboxylic acid include linear, branched and alicyclic oxalic acid, malonic acid, succinic acid, maleic acid, itaconic acid, glutaric acid, adipic acid, pimelic acid, and 2,2-dimethylglutaric acid. , Suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, diglycolic acid, thiodipropionic acid and the like.

  The polyvalent carboxylic acid component may be used singly or in combination of two or more, but an aromatic dicarboxylic acid having a sulfonic acid group and an ester-forming derivative thereof and alkali metal salts thereof ( Hereinafter, these are collectively referred to as “aromatic dicarboxylic acids having a sulfonic acid group”, and aromatic dicarboxylic acids and ester-forming derivatives thereof (hereinafter collectively referred to as “aromatic dicarboxylic acids”). In particular, it is preferable to use only the aromatic dicarboxylic acids and aromatic dicarboxylic acids having these sulfonic acid groups as the polyvalent carboxylic acid component, or to use them as the main component. .

  On the other hand, the glycol component includes glycol and ester-forming derivatives in which a hydroxyl group in the glycol is substituted with an ester-forming derivative group derived from the hydroxyl group. Examples of glycols include ethylene glycol and diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, and other polyethylene glycols, as well as propylene glycol and dipropylene glycol, tripropylene glycol, Polypropylene glycol such as tetrapropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl- 1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, , 2,4-trimethyl-1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1 , 3-cyclobutanediol, 4,4′-dihydroxybiphenol, 4,4′-methylenediphenol, 4,4′-isopropylidenediphenol, 1,5-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,2 -Bis (4-hydroxyphenyl) propane (bisphenol A), bisphenol S and the like.

  These glycols and their ester-forming derivatives may be used alone or in combination. In particular, ethylene glycol; diethylene glycol; butanediols such as 1,4-butanediol; hexanediols such as 1,6-hexanediol; 1,4-cyclohexanedimethanols; neopentyl glycol; glycols such as bisphenol A; And ester-forming derivatives of these glycols are preferably used.

  (A) The polyester resin type compound which has a sulfonic acid group is manufactured by the well-known polyester manufacturing method using the said reactive raw material. For example, a polyester resin is produced by a direct esterification reaction in which a polyvalent carboxylic acid component and a glycol component are reacted in a one-step reaction. On the other hand, when the polyvalent carboxylic acid component contains an ester-forming derivative of polyvalent carboxylic acid and the glycol component contains glycol, this is an ester exchange reaction between the ester-forming derivative of polyvalent carboxylic acid and glycol. The polyester resin may be produced through a first stage reaction and a second stage reaction in which the reaction product of the first stage reaction is polycondensed. In the first stage reaction, all the reactive raw materials may be contained in the reaction system from the beginning, or may be added to the reaction system during the polycondensation reaction. In the case of batch preparation, for example, the reaction system is gradually heated to 150 to 260 ° C. under an atmospheric pressure condition under an inert gas atmosphere such as nitrogen gas, whereby the transesterification reaction proceeds. The second stage reaction proceeds in a temperature range of 160 to 280 ° C. under a reduced pressure of, for example, 6.7 hPa (5 mmHg) or less. In the first stage reaction and the second stage reaction, conventionally known titanium, antimony, lead, zinc, magnesium, calcium, manganese, alkali metal compounds and the like may be added to the reaction system at any time as a catalyst.

  The intrinsic viscosity of the polyester resin compound having a sulfonic acid group thus obtained is preferably in the range of 0.03 to 1.0, and is particularly dispersed if it is in the range of 0.05 to 0.6. An effect excellent in stability can be obtained. Intrinsic viscosity is a measure of the rate at which one molecule of solute contributes to the viscosity of a solution.The concentration is zero when the specific viscosity of a solution is measured by varying the concentration in a dilute state of the polymer and the specific viscosity of the solution is divided by the concentration. It is a value extrapolated to the state of. The specific viscosity was measured at 20 ° C. with an Ostwald viscometer using o-chlorophenol as a solvent.

  (A) As the polyester resin compound having a sulfonic acid group, a copolymer having a repeating unit represented by the following general formulas (1) and (2) is preferable.

  The repeating unit represented by the general formula (1) is as follows.

  In the above formula, R represents a glycol residue, and A represents a polyvalent carboxylic acid residue that may have a substituent other than the sulfonic acid group. n represents 1 or 2. Here, the glycol residue means a portion excluding the hydroxyl group of the glycol component, and the polyvalent carboxylic acid residue means a portion excluding the carboxyl group of the polyvalent carboxylic acid.

  Preferred as R is an alkylene group having 1 to 6 carbon atoms or an alkylene group having 2 to 12 carbon atoms and having an ether bond between them, and particularly preferably an alkylene group having 1 to 4 carbon atoms or 2 to 2 carbon atoms. 8 is an alkylene group having an ether bond therebetween.

  Examples of A include aromatic rings such as a benzene ring, a naphthalene ring, and an anthracene ring, and a naphthalene ring is particularly preferable. Moreover, as a substituent which A has, a C1-C4 alkyl group etc. can be illustrated.

  Since the component (a) has a repeating structure represented by the general formula (1), the compatibility with the π-conjugated conductive polymer is improved, so that the dispersibility of the conductive polymer fine particles is improved. There is an effect.

  On the other hand, the repeating unit represented by the general formula (2) is as follows.

  In the general formula (2), R represents a glycol residue, and B represents an aromatic ring. n represents 1 or 2. The glycol residue has the same meaning as above. R is preferably an alkylene group having 1 to 6 carbon atoms or an alkylene group having 2 to 12 carbon atoms and having an ether bond therebetween, and particularly preferably an alkyl group having 1 to 4 carbon atoms or 2 to 2 carbon atoms. 8 is an alkylene group having an ether bond therebetween.

  By having the repeating unit represented by the general formula (2) in the component (a), the miscibility and compatibility with the π-conjugated conductive polymer is good as in the repeating unit of the general formula (1). Therefore, the dispersibility of the conductive polymer fine particles is improved. Moreover, since it has a sulfonic acid group, it functions as a dopant anion of the conductive polymer, and has the effect of improving the conductivity of the conductive polymer fine particles.

  In the copolymer having the repeating units represented by the general formulas (1) and (2), the repeating unit represented by the general formula (1) is preferably contained in an amount of 30 to 80 mol%, and 50 to 70. Mole% is more preferable. This range is preferable because of excellent dispersibility.

  In the copolymer having the repeating units represented by the general formulas (1) and (2), the repeating unit represented by the general formula (2) is preferably contained at least 20 mol%, more preferably 20%. It is -70 mol%, Most preferably, it is 30-60 mol%. That is, when the mole percentage of the repeating unit having a sulfonic acid group of the general formula (2) in the copolymer is a sulfonation rate, the sulfonation rate is preferably at least 20% or more, and 20 to 70%. Is more preferable, and 30 to 50% is particularly preferable. If the sulfonation rate is less than 20%, sufficient dispersibility may not be obtained.

  As the copolymer having a repeating unit represented by the general formulas (1) and (2), a copolymer having a repeating unit represented by the following general formula (1a) and / or (1b) and (2a) is particularly preferable. It is a polymer.

（上式中、ｎは１或いは２を示す。）

(In the above formula, n represents 1 or 2.)

（上式中、ｎは１或いは２を示す。）

(In the above formula, n represents 1 or 2.)

（上式中、ｎは１或いは２を示す。）

(In the above formula, n represents 1 or 2.)

  In this copolymer, the repeating unit represented by the general formula (2a) is preferably contained at least 20 mol%, more preferably 20 to 70 mol%, particularly preferably 30 to 50 mol%. That is, the sulfonation rate is preferably at least 20% or more, more preferably 20 to 70%, and particularly preferably 30 to 50%. If the sulfonation rate is less than 20%, sufficient dispersibility may not be obtained. As a copolymer having a sulfonation rate of 40%, Plus Coat Z-4000-100 manufactured by Kyoyo Chemical Co., Ltd. is commercially available, and can be suitably used in the present invention.

  Specifically, the copolymer having the repeating units represented by the above general formulas (1a) and / or (1b) and (2a) contains 20 dimethyl 2,6-naphthalenedicarboxylate as the polyvalent carboxylic acid component. ~ 60 mol%, dimethyl terephthalate 0-40 mol%, 5-sulfoisophthalic acid dimethylsodium 40 mol%, ethylene glycol 70-100 mol%, diethylene glycol 0-30 mol% as glycol components The polyhydric carboxylic acid component and the glycol component were mixed at a molar ratio of 1: 2 and charged into the transesterification reactor. To this, 0.01% by mass of titanium potassium oxalate was added as a catalyst, and a nitrogen atmosphere was added. By raising the temperature to 250 ° C. under the above, the transesterification reaction proceeds and the by-product methanol is added. It is removed by. Next, when the temperature in the reactor is raised to 255 to 260 ° C., the pressure is reduced to 1 mmHg (1.3 hPa), the polycondensation reaction proceeds as appropriate, and the diol as a by-product is recovered to recover the sulfone. A polyester resin having a conversion rate of 40% can be obtained.

  The intrinsic viscosity of this copolymer is preferably in the range of 0.03 to 1.0, more preferably in the range of 0.05 to 0.6, from the viewpoint of dispersion stability.

  On the other hand, as a dopant component (b) low molecular weight aromatic sulfonic acid compound, for example, benzenesulfonic acid, p-toluenesulfonic acid, isopropylbenzenesulfonic acid, dodecylbenzenesulfonic acid, benzenedisulfonic acid, etc. Alkyl-substituted or unsubstituted benzene mono- or disulfonic acid, 2-naphthalenesulfonic acid, 1,7-naphthalenedisulfonic acid, 2,6-naphthalenedisulfonic acid, 2,7-naphthalenedisulfonic acid, 1,3,6-naphthalenetri C1-C20 alkyl-substituted or unsubstituted naphthalene monosulfonic acid, C1-C20 alkyl-substituted or unsubstituted naphthalene disulfonic acid, C1-C20 alkyl-substituted, such as sulfonic acid and alkylnaphthalene sulfonic acid Or unsubstituted naphthalenetri 1 to 20 carbon atoms such as sulfonic acid, alkyl substituted or unsubstituted naphthalene tetrasulfonic acid having 1 to 20 carbon atoms, anthracene sulfonic acid, anthraquinone sulfonic acid, anthraquinone disulfonic acid, biphenyl sulfonic acid, alkylbiphenyl sulfonic acid, biphenyl disulfonic acid, etc. 20 alkyl-substituted or unsubstituted anthracene monosulfonic acid, C1-C20 alkyl-substituted or unsubstituted anthracene disulfonic acid, C1-C20 alkyl-substituted or unsubstituted anthracene sulfonic acid, C1-C1 20 alkyl-substituted or unsubstituted anthracene tetrasulfonic acid, C1-C20 alkyl-substituted or unsubstituted anthraquinone monosulfonic acid, C1-C20 alkyl-substituted or unsubstituted anthraquinone disulfate Acid, C1-C20 alkyl-substituted or unsubstituted anthraquinone trisulfonic acid, C1-C20 alkyl-substituted or unsubstituted anthraquinone tetrasulfonic acid, C1-C20 alkyl-substituted or unsubstituted biphenyl Monosulfonic acid, alkyl substituted or unsubstituted biphenyl disulfonic acid having 1 to 20 carbon atoms, alkyl substituted or unsubstituted biphenyl trisulfonic acid having 1 to 20 carbon atoms, alkyl substituted or unsubstituted biphenyl having 1 to 20 carbon atoms Tetrasulfonic acid is mentioned.

  Among these, from the viewpoint of dispersibility and conductivity, an alkyl-substituted or unsubstituted benzene monosulfonic acid having 1 to 20 carbon atoms and an alkyl-substituted or unsubstituted naphthalene monosulfonic acid having 1 to 20 carbon atoms are particularly preferable. P-toluenesulfonic acid and 2-naphthalenesulfonic acid are preferred.

  In addition, the low molecular weight aromatic sulfonic acid compound of the dopant component (b) can be used alone or in combination of a plurality of types.

  The molar ratio of the sulfonic acid group in the dopant component (a) to (b) in the conductive polymer fine particles of the present invention is preferably 50:50 to 10:90, and 40:60 to 20:80. It is more preferable. When the molar ratio of the sulfonic acid group in the dopant component (a) is less than 10%, sufficient transparency cannot be obtained when the obtained conductive polymer fine particle dispersion is applied to the substrate, In some cases, sufficient dispersion stability of the conductive polymer fine particles cannot be obtained. If it exceeds 50%, sufficient conductivity may not be obtained, and dispersion of the conductive polymer fine particles may be difficult.

  The π-conjugated conductive polymer that can be used in the present invention is not particularly limited. For example, polypyrroles, polythiophenes, polyanilines, and the like can be used. However, the conductivity and dispersion stability are improved. Since an excellent conductive polymer fine particle dispersion can be obtained and the transparency of the conductive film formed by this dispersion is excellent, the polymer should be a polymer of the compound represented by the following general formula (3). preferable.

  In the above formula (3), X represents an oxygen atom or a sulfur atom. Z represents an oxygen atom or a sulfur atom which may be the same or different. R represents a linear or branched alkylene group having 1 to 6 carbon atoms.

  Specific examples of the compound represented by the above formula (3) include 3,4-ethylenedioxythiophene, methyl-3,4-ethylenedioxythiophene, ethyl-3,4-ethylenedioxythiophene, and propyl-3. , 4-ethylenedioxythiophene, 3,4-propylenedioxythiophene, methyl-3,4-propylenedioxythiophene, ethyl-3,4-propylenedioxythiophene, propyl-3,4-propylenedioxythiophene, 3,4-ethylenedioxyfuran, methyl-3,4-ethylenedioxyfuran, ethyl-3,4-ethylenedioxyfuran, propyl-3,4-ethylenedioxyfuran, 3,4-propylenedioxyfuran , Methyl-3,4-propylenedioxyfuran, ethyl-3,4-propylenedioxyfuran Propyl-3,4-propylenedioxyfuran, 3,4-ethylenedithiathiophene, methyl-3,4-ethylenedithiathiophene, ethyl-3,4-ethylenedithiathiophene, propyl-3,4-ethylenedi Examples include thiathiophene, 3,4-propylene dithiathiophene, methyl-3,4-propylene dithiathiophene, ethyl-3,4-propylene dithiathiophene, and propyl-3,4-propylene dithiathiophene.

  Among these, a conductive polymer fine particle dispersion excellent in dispersion stability can be obtained, and since the conductivity and transparency of the conductive film formed thereby are excellent, 3,4-ethylenedioxythiophene, Methyl-3,4-ethylenedioxythiophene and ethyl-3,4-ethylenedioxythiophene are particularly preferred.

  In the conductive polymer fine particles of the present invention, a monomer compound constituting a π-conjugated conductive polymer such as the compound represented by the general formula (3) is chemically treated in the presence of the dopant components (a) and (b). It can be obtained by oxidative polymerization or electrolytic oxidative polymerization.

  Chemical oxidation polymerization may be performed by reacting the monomer compound with an appropriate oxidizing agent, and electrolytic polymerization is performed by electrolytic oxidation in an electrolytic solution containing the monomer compound and an appropriate supporting electrolyte. It can be carried out. Among these, chemical oxidative polymerization is preferably used from the viewpoint of mass productivity and the shape of the conductive polymer fine particles.

  Preferable specific examples of the method for producing the conductive polymer fine particles of the present invention include the following methods.

  That is, a monomer compound constituting a π-conjugated conductive polymer such as the monomer compound represented by the general formula (3), (a) a polyester resin compound having a sulfonic acid group, and (b) a low-molecular aromatic sulfonic acid In this method, conductive polymer fine particles are obtained by adding an oxidant-containing solution to a monomer solution containing a compound and a chemical oxidative polymerization catalyst, followed by chemical oxidative polymerization.

  As the chemical oxidation polymerization catalyst, a transition metal compound is preferably used, for example, a salt of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, molybdenum, ruthenium, etc. Salts such as sulfuric acid, hydrochloric acid, nitric acid and acetic acid are preferred, and preferred examples thereof include ferrous sulfate, cuprous sulfate, cuprous chloride, molybdenum chloride, tungsten chloride, ferrous sulfate, cuprous nitrate and the like. In particular, ferrous sulfate is preferable because conductive polymer fine particles can be obtained with high yield.

  As the solvent used in the monomer solution, water, methanol, ethanol, a mixed solvent thereof or the like can be used, but water is preferable from the viewpoint of the conductivity of the obtained conductive polymer fine particles.

  The concentration of the monomer compound in the monomer solution is preferably 0.01 to 3 mol / L, and more preferably 0.1 to 1 mol / L. The addition amount of the dopant component (b) is preferably 0.1 to 3 mol, more preferably 0.3 to 2 mol as a sulfonic acid group with respect to 1 mol of this monomer compound. On the other hand, the addition amount of the dopant component (a) is preferably 0.1 to 10 mol, more preferably 0.2 to 2 mol, relative to 1 mol of the monomer compound. The addition amount of the chemical oxidation polymerization catalyst is 0.0001 to 0.5 mol, more preferably 0.001 to 0.1 mol, relative to 1 mol of the monomer compound. When the above transition metal compound is used as the chemical oxidative polymerization catalyst, the transition metal compound can also act as an oxidizing agent, but it is preferable that the concentration of such a catalyst is used, thereby dispersibility of the conductive polymer fine particles. Can be improved.

  The oxidant is not particularly limited as long as it is an oxidant capable of chemically oxidatively polymerizing the monomer compound. For example, halides such as iodine, bromine, bromine iodide, chlorine dioxide, iodic acid, periodic acid, and chlorous acid. Metal halides such as antimony pentafluoride, phosphorus pentachloride, phosphorus pentafluoride, aluminum chloride, molybdenum chloride, permanganate, dichromate, chromic anhydride, ferric salt, cupric salt, etc. High valence state metal ion salt, sulfuric acid, nitric acid, trifluoromethanesulfuric acid and other proton acids, sulfur trioxide, nitrogen dioxide and other oxygen compounds, hydrogen peroxide, ammonium persulfate, peroxo acids such as sodium perborate, Examples thereof include salts of the peroxo acids, heteropolyacids such as molybdophosphoric acid, tungstophosphoric acid, tungstomolybdophosphoric acid, and salts of the heteropolyacid.

Among these, it is preferable to use a peroxosulfate such as ammonium persulfate or sodium persulfate, and more preferably ammonium persulfate since fine particles having an appropriate particle diameter can be obtained.

  As a solvent used for the oxidizing agent-containing solution, water is preferable. In particular, an aqueous solution containing 0.3 to 5 gram equivalent of an oxidizing agent at a concentration of 5 to 40% by mass with respect to 1 mol of the monomer compound is preferable.

  In adding the oxidant-containing solution to the monomer solution, it is preferable to drop the oxidant-containing solution while stirring the monomer solution and perform the polymerization reaction while controlling the input amount of the oxidant-containing solution. Usually, the oxidant-containing solution is added continuously or intermittently over a period of 0.1 to 50 hours, preferably 0.2 to 10 hours with respect to the total amount of the monomer solution, and the polymerization reaction is usually 0 ° C to 100 ° C. Preferably, it is carried out in the range of 5 ° C. to 60 ° C. for 0.2 to 60 hours, more preferably 1 to 12 hours.

  After the reaction, the precipitate is filtered by a known method, and if necessary, washed and dried to obtain the conductive polymer fine particles of the present invention.

  According to the above production method, the oxidant concentration is less likely to be unevenly distributed, and the generation of a local polymerization reaction can be suppressed. Therefore, the average particle diameter of the generated conductive polymer fine particles can be controlled to a desired value. Thus, a more uniform and good dispersible product can be obtained in a high yield. For example, conductive polymer fine particles having a primary average particle diameter of 10 to 1000 nm can be obtained in a yield of 80 to 300% based on the weight of the monomer compound used.

  The conductive polymer fine particle dispersion of the present invention is obtained by dispersing or dissolving the conductive polymer fine particles obtained as described above in a dispersion medium. A preferred method for producing this dispersion includes a method of dispersing a conductive polymer fine particle solution in which conductive polymer fine particles, a dispersant and a solvent are mixed, by wet grinding.

  As the dispersion medium, water or an organic solvent can be used.

  As the organic solvent, alcohols, ketones, esters, ethers, cellosolves, aromatic hydrocarbons, aliphatic hydrocarbons and the like can be used.

  Examples of alcohols include methanol, ethanol, 1-propanol, isopropyl alcohol, n-butanol, s-butanol, t-butanol, n-amyl alcohol, s-amyl alcohol, t-amyl alcohol, allyl alcohol, isoamyl alcohol, and isobutyl. Alcohol, 2-ethylbutanol, 2-octanol, n-octanol, cyclohexanol, tetrahydrofurfuryl alcohol, furfuryl alcohol, n-hexanol, n-heptanol, 2-heptanol, 3-heptanol, benzyl alcohol, methylcyclohexanol, Examples include ethylene glycol, ethylene glycol monomethyl ether, glycerin, diethylene glycol, and propylene glycol.

  Examples of ketones include acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, methyl isobutyl ketone, and methyl-n-propyl ketone.

  Esters include ethyl acetoacetate, ethyl benzoate, methyl benzoate, isobutyl formate, ethyl formate, propyl formate, methyl formate, isobutyl acetate, ethyl acetate, propyl acetate, methyl acetate, methyl salicylate, diethyl oxalate, diethyl tartrate , Dibutyl tartrate, ethyl phthalate, methyl phthalate, butyl phthalate, γ-butyrolactone, ethyl malonate, methyl malonate and the like.

  Examples of cellosolves include methyl cellosolve and ethyl cellosolve.

  Aromatic hydrocarbons include benzene, toluene, xylene and the like.

  Examples of aliphatic hydrocarbons include hexane and cyclohexane.

  As the dispersant, a polymer dispersant having an amine value, a polymer dispersant having an acid value, a polymer dispersant having an amine value and an acid value, and the like can be used. Examples of these commercially available products include Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk-166, Disperbyk-182, Disperyk-183, Disperbyk-184 (manufactured by BYK Chemie), Solsperse-17000, 20000, Solsperse-24000, Solsperse-32000 (manufactured by Nihon Lubrizol Corporation), Ajisper PB711, Azisper PB821, Azisper PB822, Azisper PB824 (manufactured by Ajinomoto Co., Inc.), EFKA4046, EFKA4300, EFKA4510 (manufactured, EFKA4510) These may be used alone or in combination. It can be.

  Among these, it is particularly preferable from the viewpoint of dispersion stability to use a polymer dispersant having an amine value (Disperbyk-161, Disperbyk-182, etc.).

  The addition amount of the dispersing agent is preferably 1 to 10000% by weight, preferably 10 to 1000% by weight, based on the conductive polymer fine particles.

  For the wet pulverization, a ball mill, an attritor, a sand mill, a bead mill or the like can be used, and it may be a batch type or a continuous type. For example, after stirring and mixing with a homogenizer as a premix, zirconia beads or the like can be dispersed using a bead mill as a medium.

  As described above, a dispersion of 0.1 to 15% by mass, preferably 2 to 10% by mass of the conductive polymer fine particles as a solid content concentration can be prepared. Thus, since the thing of a high solid content concentration is obtained, the conductive film with a film thickness can be formed easily.

  In addition, a dispersion in which the 50% cumulative particle diameter of the conductive polymer fine particles in the dispersion medium is 10 to 1000 nm can be prepared. The 50% cumulative particle size is a value measured by the method described in the examples.

  A conductive film can be formed on a substrate using the conductive polymer fine particle dispersion thus obtained. Examples of the method for forming the conductive film include a method in which the conductive polymer fine particle dispersion is directly coated on the substrate by spin coating or the like and dried.

Moreover, the electroconductivity of the obtained electroconductive film can be improved more by adding a electroconductivity improver to the electroconductive polymer fine particle dispersion of this invention.
The conductivity improver interacts with a dopant of a π-conjugated conductive polymer or a π-conjugated conductive polymer to improve the conductivity of the π-conjugated conductive polymer.
Examples of the conductivity improver include a nitrogen-containing aromatic cyclic compound, a compound having two or more hydroxyl groups, a compound having two or more carboxyl groups, a compound having an amide group, a compound having an imide group, and a lactam. Examples thereof include compounds and compounds having a glycidyl group.

  In addition, the conductive polymer fine particle dispersion of the present invention can be mixed with an appropriate binder resin and used as a coating composition or an ink composition.

The binder resin may be a thermosetting resin or a thermoplastic resin. For example, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyimides; polyamide imides; polyamides such as polyamide 6, polyamide 6, 6, polyamide 12, and polyamide 11; polyvinylidene fluoride, polyvinyl fluoride, polytetrafluoroethylene Fluoropolymers such as ethylene tetrafluoroethylene copolymer and polychlorotrifluoroethylene; vinyl resins such as polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, polyvinyl acetate, and polyvinyl chloride; epoxy resins; xylene resins; aramid resins; Polyurea; polyurea; melamine resin; phenol resin; polyether; acrylic resin and copolymers thereof.
These binder resins may be preliminarily dissolved in an organic solvent, may be provided with a functional group such as a sulfonic acid group or a carboxylic acid group, may be in an aqueous solution, or may be dispersed in water such as emulsification. Good.

  Among binder resins, one or more of polyurethane, polyester, acrylic resin, polyamide, polyimide, epoxy resin, and polyimide silicone are preferable because they can be easily mixed. Acrylic resins are suitable for applications such as optical filters because of their high hardness and excellent transparency.

The acrylic resin preferably contains a liquid polymer that is cured by heat energy and / or light energy.
Here, examples of the liquid polymer that is cured by thermal energy include a reactive polymer and a self-crosslinking polymer.
The reactive polymer is a polymer in which a monomer having a substituent is polymerized, and examples of the substituent include a carboxyl group, an acid anhydride, an oxetane group, a glycidyl group, and an amino group. Specific monomers include malonic acid, succinic acid, glutamic acid, pimelic acid, ascorbic acid, phthalic acid, acetylsalicylic acid, adipic acid, isophthalic acid, benzoic acid, m-toluic acid and other carboxylic acid compounds, anhydrous Maleic acid, phthalic anhydride, dodecyl succinic anhydride, dichloromaleic anhydride, tetrachlorophthalic anhydride, tetrahydrophthalic anhydride, acid anhydrides such as pimelic anhydride, 3,3-dimethyloxetane, 3,3-dichloromethyloxetane Oxetane compounds such as 3-methyl-3-hydroxymethyloxetane and azidomethylmethyloxetane, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, phenol novolac polyglycidyl ether, N, N-diglycidyl-p-aminophenol Glycidyl ether compounds such as cidyl ether, tetrabromobisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether (ie, 2,2-bis (4-glycidyloxycyclohexyl) propane), N, N-diglycidylaniline, tetra Glycidylamine compounds such as glycidyldiaminodiphenylmethane, N, N, N, N-tetraglycidyl-m-xylylenediamine, triglycidyl isocyanurate, N, N-diglycidyl-5,5-dialkylhydantoin, diethylenetriamine, triethylenetetramine, Dimethylaminopropylamine, N-aminoethylpiperazine, benzyldimethylamine, tris (dimethylaminomethyl) phenol, DHP30-tri (2-ethylhexoate), Amine compounds such as taphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, dicyandiamide, boron trifluoride, monoethylamine, menthanediamine, xylenediamine, ethylmethylimidazole, etc. Among compounds containing two or more oxirane rings in one molecule And glycidyl compound of epichlorohydrin of bisphenol A, or the like.

In the reactive polymer, at least a bifunctional or higher functional crosslinking agent is used. Examples of the crosslinking agent include melamine resin, epoxy resin, metal oxide and the like. Examples of the metal oxide include basic metal compounds Al (OH) ₃ , Al (OOC · CH ₃ ) ₂ (OOCH), Al (OOC · CH ₃ ) ₂ , ZrO (OCH ₃ ), Mg (OOC · CH _3). ), Ca (OH) ₂ , Ba (OH) _{3 and the} like can be used as appropriate.

  The self-crosslinking polymer is self-crosslinking between functional groups by heating, and examples thereof include those containing a glycidyl group and a carboxyl group, and those containing both an N-methylol and a carboxyl group.

  Examples of the liquid polymer that is cured by light energy include oligomers or prepolymers such as polyester, epoxy resin, oxetane resin, polyacryl, polyurethane, polyimide, polyamide, polyamideimide, and polyimide silicone. Examples of monomer units constituting a liquid polymer that is cured by light energy include bisphenol A / ethylene oxide-modified diacrylate, dipentaerythritol hexa (penta) acrylate, dipentaerythritol monohydroxypentaacrylate, and dipropylene glycol diacrylate. Acrylate, trimethylolpropane triacrylate, glycerin propoxytriacrylate, 4-hydroxybutyl acrylate, 1,6-hexanediol diacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, polyethylene glycol diacrylate, Pentaerythritol triacrylate, tetrahydrofurfuryl acrylate, trimethylolpropane tria Relates, acrylates such as tripropylene glycol diacrylate, tetraethylene glycol dimethacrylate, alkyl methacrylate, allyl methacrylate, 1,3-butylene glycol dimethacrylate, n-butyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, diethylene glycol dimethacrylate, 2- Such as ethylhexyl methacrylate, glycidyl methacrylate, 1,6-hexanediol dimethacrylate, 2-hydroxyethyl methacrylate, isobornyl methacrylate, lauryl methacrylate, phenoxyethyl methacrylate, t-butyl methacrylate, tetrahydrofurfuryl methacrylate, trimethylolpropane trimethacrylate, etc. Methacrylates Glycidyl ethers such as allyl glycidyl ether, butyl glycidyl ether, higher alcohol glycidyl edel, 1,6-hexanediol glycidyl ether, phenyl glycidyl ether, stearyl glycidyl ether, diacetone acrylamide, N, N-dimethylacrylamide, dimethylaminopropyl acrylamide , Dimethylaminopropylmethacrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, acryloylmorpholine, N-vinylformamide, N-methylacrylamide, N-isopropylacrylamide, Nt-butylacrylamide, N-phenyl Acrylics such as acrylamide, acryloylpiperidine, 2-hydroxyethylacrylamide ( Methacryl) amides, 2-chloroethyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, hydroxybutyl vinyl ether, isobutyl vinyl ether, vinyl ethers such as triethylene glycol vinyl ether, carboxylic acid vinyl esters such as vinyl butyrate, vinyl monochloroacetate and vinyl pivalate And monofunctional monomers as well as polyfunctional monomers.

A liquid polymer that is cured by light energy is cured by a photopolymerization initiator. Examples of the photopolymerization initiator include acetophenones, benzophenones, Michler benzoylbenzoate, tetramethylthiuram monosulfide, and thioxanthones. Furthermore, n-butylamine, triethylamine, tri-n-butylphosphine, or the like can be mixed as a photosensitizer.
Examples of the cationic polymerization initiator include aryldiazonium salts, diarylhalonium salts, triphenylsulfonium salts, silanol / aluminum chelates, α-sulfonyloxyketones, and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, this invention is not restrict | limited at all by an Example.

Example 1
(Synthesis of conductive polymer fine particles (1))
A polyester resin having a sulfonic acid group in 100 ml of ion-exchanged water, plus coat Z-4000-100 (manufactured by Kyoyo Chemical Industry Co., Ltd., sulfonation rate 40%) as the amount of sulfonic acid group is 16 mmol, 2-naphthalenesulfonic acid 24 mmol, sulfuric acid Ferrous iron (0.4 mmol) was added and stirred. Next, 40 mmol of 3,4-ethylenedioxythiophene was added as a polymerizable monomer and stirred. While stirring this solution, 34 g of an aqueous 30% ammonium persulfate solution (45 mmol as ammonium persulfate) was slowly added and reacted at 40 ° C. for 4 hours. The obtained precipitate is filtered, washed with ion-exchanged water until the pH of the filtrate becomes near neutral, then washed with acetone and then dried to give 12 indigo conductive polymer fine particles (1). .9 g was obtained. In addition, this indigo polymer (1) was molded into a disk-like pellet (diameter 13 mm, thickness 0.6 mm) with a tablet molding machine, and then an electric conductivity meter (Lorestar GP (MCP-T600) manufactured by Mitsubishi Chemical Corporation). As a result of measuring the electrical conductivity using the slab, it was 7.0 S / cm.

(Preparation of conductive polymer fine particle dispersion (1a))
The obtained conductive polymer fine particles (1) 3.5 g, methyl ethyl ketone 60.2 g, dispersant Disperbyk 161 (manufactured by Big Chemie, 30% active ingredient, amine value 11 mg KOH / g) 6.3 g bead mill (stock) DYNO MILL MULTI LAB made by Shinmaru Enterprises Co., Ltd.) Conductive polymer fine particle dispersion by stirring and mixing zirconia beads having a diameter of 0.3 mm with a filling rate of 80% and a slurry temperature of 20 ° C. or less for 6 hours (1a) was obtained.
When the particle size of the obtained conductive polymer fine particle dispersion (1a) was measured with a particle size distribution analyzer (Nanotrack UPA-EX150, manufactured by Nikkiso Co., Ltd.), the 50% cumulative particle size was 600 nm. Further, when the particle size was measured similarly one month after the preparation of the conductive polymer fine particle dispersion (storage condition: 25 ° C.), the 50% cumulative particle size was 770 nm.

(Preparation of conductive polymer fine particle dispersion (1b))
The obtained conductive polymer fine particles (1) (3.5 g), isopropyl alcohol (62.0 g), dispersant Disperbyk 182 (produced by Big Chemie, active ingredient 43%, amine value 13 mgKOH / g) 4.5 g and a bead mill (disperser) DYNO MILL MULTI LAB made by Shinmaru Enterprises Co., Ltd.) Conductive polymer fine particle dispersion by stirring and mixing zirconia beads having a diameter of 0.3 mm with a filling rate of 80% and a slurry temperature of 20 ° C. or less for 6 hours The body (1b) was obtained.
When the particle size of the obtained conductive polymer fine particle dispersion (1b) was measured with a particle size distribution analyzer (Nanotrack UPA-EX150, manufactured by Nikkiso Co., Ltd.), the 50% cumulative particle size was 500 nm. Further, when the particle diameter was measured similarly one month after the preparation of the conductive polymer fine particle dispersion (storage condition: 25 ° C.), the 50% cumulative particle diameter was 550 nm.

(Applying conductive polymer fine particle dispersion to glass plate)
The obtained conductive polymer fine particle dispersion (1a) was diluted 5 times with methyl ethyl ketone, spin-coated on a glass plate (2000 rpm, 10 seconds), and dried at 100 ° C. for 3 minutes with a blower dryer. A glass plate coated with the molecular fine particle dispersion was obtained. The surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 8 × 10 ⁶ Ω / □, the total light transmittance was 87.0%, and the haze value was 1.2%.
Further, when the conductive polymer fine particle dispersion one month after the production was applied in the same manner, the surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 9 × 10 ⁶ Ω / □, The transmittance was 86.5% and the haze value was 1.4%.
Here, the surface resistance value was measured using a surface resistance measuring machine (Hirester UP (MCP-HT450) manufactured by Mitsubishi Chemical Corporation), and the total light transmittance and haze value were measured using a haze meter (Nippon Denshoku Industries Co., Ltd.). ) NDH5000).

Similarly, the conductive polymer fine particle dispersion (1b) obtained was diluted 5 times with isopropyl alcohol, spin-coated on a glass plate (2000 rpm, 10 seconds), and dried at 100 ° C. for 3 minutes with a blow dryer. A glass plate coated with the conductive polymer fine particle dispersion was obtained. The surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 9 × 10 ⁶ Ω / □, the total light transmittance was 88.0%, and the haze value was 1.3%.
Further, when the conductive polymer fine particle dispersion one month after the production was applied in the same manner, the surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 1 × 10 ⁷ Ω / □, The transmittance was 87.5% and the haze value was 1.4%.

(Preparation of conductive ink composition (1c))
Conductive polymer fine particle dispersion (1b) obtained above (2.0 g), dipentaerythritol hexaacrylate (NK ester A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) 1.5 g, ethyl acetate 2.3 g, isopropyl A conductive ink composition (1c) was prepared by stirring and mixing 3.6 g of alcohol, 0.5 g of N-methyl-2-pyrrolidone, and 0.1 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy).

(Application of conductive ink composition (1c) to film)
The conductive ink composition (1c) was applied to a 50 μm thick polyethylene terephthalate film (Diafoil T-600E, manufactured by Mitsubishi Plastics Co., Ltd.) with a bar coater No. 4 was applied, dried at 100 ° C. for 1 minute, and then irradiated with ultraviolet rays under the condition of a light amount of 50 mJ / cm ² to obtain a film coated with the conductive ink composition. The surface resistance value of the surface coated with the conductive ink composition was 5 × 10 ⁶ Ω / □, the total light transmittance was 89.0%, and the haze value was 1.2%.

Example 2
(Synthesis of conductive polymer fine particles (2))
To 100 ml of ion-exchanged water, 12 mmol, 28 mmol of 2-naphthalenesulfonic acid and 0.4 mmol of ferrous sulfate were added and stirred with PLUSCOAT Z-4000-100 as the amount of sulfonic acid group. Next, 40 mmol of 3,4-ethylenedioxythiophene was added as a polymerizable monomer and stirred. While stirring this solution, 34 g of an aqueous 30% ammonium persulfate solution (45 mmol as ammonium persulfate) was slowly added and reacted at 40 ° C. for 4 hours. The obtained precipitate was filtered, washed with ion exchange water until the pH of the filtrate was close to neutral, then washed with acetone and then dried to give indigo conductive polymer fine particles (2) 11 .5 g was obtained. Moreover, it was 7.6 S / cm as a result of measuring electrical conductivity similarly to Example 1. FIG.

(Preparation of conductive polymer fine particle dispersion (2a))
Using the obtained conductive polymer fine particles (2), a conductive polymer fine particle dispersion (2a) was obtained in the same manner as in the preparation of the conductive polymer fine particle dispersion (1a) of Example 1.
When the particle size of the obtained conductive polymer fine particle dispersion was measured with a particle size distribution analyzer (Nanotrack UPA-EX150, manufactured by Nikkiso Co., Ltd.), the 50% cumulative particle size was 650 nm. Further, when the particle size was measured similarly one month after the preparation of the conductive polymer fine particle dispersion (storage condition: 25 ° C.), the 50% cumulative particle size was 660 nm.

(Preparation of conductive polymer fine particle dispersion (2b))
Using the obtained conductive polymer fine particles (2), a conductive polymer fine particle dispersion (2b) was obtained in the same manner as in the preparation of the conductive polymer fine particle dispersion (1b) of Example 1.
When the particle size of the obtained conductive polymer fine particle dispersion was measured with a particle size distribution analyzer (Nanotrack UPA-EX150, manufactured by Nikkiso Co., Ltd.), the 50% cumulative particle size was 450 nm. Further, when the particle size was measured similarly one month after preparation of the conductive polymer fine particle dispersion (storage condition: 25 ° C.), the 50% cumulative particle size was 470 nm.

(Application of conductive polymer fine particle dispersion (2a) to glass plate)
In the same manner as in Example 1, a glass plate coated with the conductive polymer fine particle dispersion (2a) was obtained. The surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 6 × 10 ⁶ Ω / □, the total light transmittance was 87.6%, and the haze value was 1.2%.
Further, when the conductive polymer fine particle dispersion one month after the production was applied in the same manner, the surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 8 × 10 ⁶ Ω / □, The transmittance was 87.0% and the haze value was 1.3%.

(Application of conductive polymer fine particle dispersion (2b) to glass plate)
In the same manner as in Example 1, a glass plate coated with the conductive polymer fine particle dispersion (2b) was obtained. The surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 7 × 10 ⁶ Ω / □, the total light transmittance was 87.0%, and the haze value was 1.3%.
Further, when the conductive polymer fine particle dispersion one month after the production was applied in the same manner, the surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 9 × 10 ⁶ Ω / □, The transmittance was 86.0% and the haze value was 1.4%.

(Preparation of conductive ink composition (2c))
In the same manner as in Example 1, a conductive ink composition (2c) was prepared.

(Application of conductive ink composition (2c) to film)
In the same manner as in Example 1, a film coated with the conductive ink composition was obtained. The surface resistance value of the surface coated with the conductive ink composition was 2 × 10 ⁶ Ω / □, the total light transmittance was 88.2%, and the haze value was 1.3%.

Example 3
(Synthesis of conductive polymer fine particles (3))
To 100 ml of ion-exchanged water, 8 mmol, 32 mmol of 2-naphthalenesulfonic acid, and 0.4 mmol of ferrous sulfate were added and stirred with PLUSCOAT Z-4000-100 as the amount of sulfonic acid group. Next, 40 mmol of 3,4-ethylenedioxythiophene was added as a polymerizable monomer and stirred. While stirring this solution, 34 g of an aqueous 30% ammonium persulfate solution (45 mmol as ammonium persulfate) was slowly added and reacted at 40 ° C. for 4 hours. The obtained precipitate is filtered, washed with ion-exchanged water until the pH of the filtrate becomes near neutral, then washed with acetone and then dried to obtain indigo conductive polymer fine particles (3) of 10 .3 g was obtained. Moreover, as a result of measuring electrical conductivity similarly to Example 1, it was 9.8 S / cm.

(Preparation of conductive polymer fine particle dispersion (3a))
Using the obtained conductive polymer fine particles (3), a conductive polymer fine particle dispersion (3a) was obtained in the same manner as in the preparation of the conductive polymer fine particle dispersion (1a) of Example 1.
When the particle size of the obtained conductive polymer fine particle dispersion was measured with a particle size distribution measuring device (Nanotrack UPA-EX150, manufactured by Nikkiso Co., Ltd.), the 50% cumulative particle size was 600 nm. Further, when the particle size was measured similarly one month after the preparation of the conductive polymer fine particle dispersion (storage condition: 25 ° C.), the 50% cumulative particle size was 630 nm.

(Preparation of conductive polymer fine particle dispersion (3b))
Using the obtained conductive polymer fine particles (3), a conductive polymer fine particle dispersion (3b) was obtained in the same manner as in the preparation of the conductive polymer fine particle dispersion (1b) of Example 1.
When the particle size of the obtained conductive polymer fine particle dispersion was measured with a particle size distribution analyzer (Nanotrack UPA-EX150, manufactured by Nikkiso Co., Ltd.), the 50% cumulative particle size was 400 nm. Further, when the particle size was measured similarly one month after the preparation of the conductive polymer fine particle dispersion (storage condition: 25 ° C.), the 50% cumulative particle size was 430 nm.

(Application of conductive polymer fine particle dispersion (3a) to glass plate)
In the same manner as in Example 1, a glass plate coated with the conductive polymer fine particle dispersion (3a) was obtained. The surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 3 × 10 ⁶ Ω / □, the total light transmittance was 86.6%, and the haze value was 1.4%.
Further, when the conductive polymer fine particles one month after the production were applied in the same manner, the surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 4 × 10 ⁶ Ω / □, and the total light transmission was achieved. The rate was 86.0% and the haze value was 1.6%.

(Application of conductive polymer fine particle dispersion (3b) to glass plate)
In the same manner as in Example 1, a glass plate coated with the conductive polymer fine particle dispersion (3b) was obtained. The surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 5 × 10 ⁶ Ω / □, the total light transmittance was 87.0%, and the haze value was 1.3%.
Further, when the conductive polymer fine particle dispersion one month after the production was applied in the same manner, the surface resistance value of the surface on which the conductive polymer fine particle dispersion was applied was 6 × 10 ⁶ Ω / □, The transmittance was 86.0% and the haze value was 1.4%.

(Preparation of conductive ink composition (3c))
In the same manner as in Example 1, a conductive ink composition (3c) was prepared.

(Application of conductive ink composition (3c) to film)
In the same manner as in Example 1, a film coated with the conductive ink composition was obtained. The surface resistance value of the surface coated with the conductive ink composition was 1 × 10 ⁶ Ω / □, the total light transmittance was 88.0%, and the haze value was 1.3%.

Example 4
(Synthesis of conductive polymer fine particles (4))
In 100 ml of ion-exchanged water, 4 mmol, 36 mmol of 2-naphthalenesulfonic acid, and 0.4 mmol of ferrous sulfate were added and stirred with PLUSCOAT Z-4000-100 as the amount of sulfonic acid group. Next, 40 mmol of 3,4-ethylenedioxythiophene was added as a polymerizable monomer and stirred. While stirring this solution, 34 g of an aqueous 30% ammonium persulfate solution (45 mmol as ammonium persulfate) was slowly added and reacted at 40 ° C. for 4 hours. The obtained precipitate is filtered, washed with ion-exchanged water until the pH of the filtrate becomes near neutral, then washed with acetone and then dried to obtain 8 conductive blue fine polymer particles (4). .9 g was obtained. Further, the conductivity was measured in the same manner as in Example 1 and found to be 49 S / cm.

(Preparation of conductive polymer fine particle dispersion (4a))
Using the obtained conductive polymer fine particles (4), a conductive polymer fine particle dispersion (4a) was obtained in the same manner as in the production of the conductive polymer fine particle dispersion (1a) of Example 1.
When the particle size of the obtained conductive polymer fine particle dispersion was measured with a particle size distribution analyzer (Nanotrack UPA-EX150, manufactured by Nikkiso Co., Ltd.), the 50% cumulative particle size was 740 nm. Further, when the particle diameter was measured similarly one month after the preparation of the conductive polymer fine particle dispersion (storage condition: 25 ° C.), the 50% cumulative particle diameter was 850 nm.

(Preparation of conductive polymer fine particle dispersion (4b))
Using the obtained conductive polymer fine particles (4), a conductive polymer fine particle dispersion (4b) was obtained in the same manner as in the preparation of the conductive polymer fine particle dispersion (1b) of Example 1.
When the particle size of the obtained conductive polymer fine particle dispersion was measured with a particle size distribution measuring device (Nanotrack UPA-EX150, manufactured by Nikkiso Co., Ltd.), the 50% cumulative particle size was 600 nm. Further, when the particle size was measured similarly one month after the preparation of the conductive polymer fine particle dispersion (storage condition: 25 ° C.), the 50% cumulative particle size was 750 nm.

(Application of conductive polymer fine particle dispersion (4a) to glass plate)
In the same manner as in Example 1, a glass plate coated with the conductive polymer fine particle dispersion (4a) was obtained. The surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 9 × 10 ⁵ Ω / □, the total light transmittance was 84.0%, and the haze value was 1.6%.
In addition, when the conductive polymer fine particle dispersion one month after preparation (storage condition: 25 ° C.) was applied in the same manner, the surface resistance value of the surface on which the conductive polymer fine particle dispersion was applied was 2 × 10 ^6. The total light transmittance was 82.0%, and the haze value was 1.8%.

(Application of conductive polymer fine particle dispersion (4b) to glass plate)
In the same manner as in Example 1, a glass plate coated with the conductive polymer fine particle dispersion (4b) was obtained. The surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 1 × 10 ⁶ Ω / □, the total light transmittance was 84.0%, and the haze value was 1.6%.
In addition, when the conductive polymer fine particle dispersion one month after preparation (storage condition: 25 ° C.) was applied in the same manner, the surface resistance value of the surface on which the conductive polymer fine particle dispersion was applied was 2 × 10 ^6. The total light transmittance was 82.0%, and the haze value was 1.8%.

(Preparation of conductive ink composition (4c))
In the same manner as in Example 1, a conductive ink composition (4c) was prepared.

(Application of conductive ink composition (4c) to film)
In the same manner as in Example 1, a film coated with the conductive ink composition was obtained. The surface resistance value of the surface coated with the conductive ink composition was 5 × 10 ⁵ Ω / □, the total light transmittance was 86.5%, and the haze value was 1.5%.

Example 5
(Synthesis of conductive polymer fine particles (5))
Resin synthesized by reducing the sulfonation rate of Pluscoat Z-4000-100 to 30% in 100 ml of ion-exchanged water (Plus Coat GX-580, manufactured by Kyoyo Chemical Industry Co., Ltd.) 8 mmol, 2-naphthalene as the amount of sulfonic acid group 32 mmol of sulfonic acid and 0.4 mmol of ferrous sulfate were added and stirred. Next, 40 mmol of 3,4-ethylenedioxythiophene was added as a polymerizable monomer and stirred. While stirring this solution, 34 g of an aqueous 30% ammonium persulfate solution (45 mmol as ammonium persulfate) was slowly added and reacted at 40 ° C. for 4 hours. The obtained precipitate is filtered, washed with ion-exchanged water until the pH of the filtrate becomes near neutral, then washed with acetone and then dried to give 12 indigo conductive polymer fine particles (5). .5 g was obtained. Moreover, as a result of measuring electrical conductivity similarly to Example 1, it was 9.5 S / cm.

(Preparation of conductive polymer fine particle dispersion (5a))
Using the obtained conductive polymer fine particles (5), a conductive polymer fine particle dispersion (5a) was obtained in the same manner as in the preparation of the conductive polymer fine particle dispersion (1a) of Example 1.
When the particle size of the obtained conductive polymer fine particle dispersion was measured with a particle size distribution analyzer (Nanotrack UPA-EX150, manufactured by Nikkiso Co., Ltd.), the 50% cumulative particle size was 700 nm. Moreover, when the particle diameter was measured similarly one month after preparation of the conductive polymer fine particle dispersion (storage condition: 25 ° C.), the 50% cumulative particle diameter was 800 nm.

(Preparation of conductive polymer fine particle dispersion (5b))
Using the obtained conductive polymer fine particles (5), a conductive polymer fine particle dispersion (5b) was obtained in the same manner as in the preparation of the conductive polymer fine particle dispersion (1b) of Example 1.
When the particle size of the obtained conductive polymer fine particle dispersion was measured with a particle size distribution measuring device (Nanotrack UPA-EX150, manufactured by Nikkiso Co., Ltd.), the 50% cumulative particle size was 600 nm. Moreover, when the particle diameter was measured similarly one month after preparation of the conductive polymer fine particle dispersion (storage condition: 25 ° C.), the 50% cumulative particle diameter was 660 nm.

(Application of conductive polymer fine particle dispersion (5a) to glass plate)
By performing the same treatment as in Example 1, a glass plate coated with the conductive polymer fine particle dispersion (5a) was obtained. The surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 4 × 10 ⁶ Ω / □, the total light transmittance was 87.0%, and the haze value was 1.4%.
Further, when the conductive polymer fine particle dispersion one month after the production was applied in the same manner, the surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 5 × 10 ⁶ Ω / □, The light transmittance was 86.5% and the haze value was 1.6%.

(Application of conductive polymer fine particle dispersion (5b) to glass plate)
By performing the same treatment as in Example 1, a glass plate coated with the conductive polymer fine particle dispersion (5b) was obtained. The surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 5 × 10 ⁶ Ω / □, the total light transmittance was 86.0%, and the haze value was 1.5%.
Further, when the conductive polymer fine particle dispersion one month after the production was applied in the same manner, the surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 6 × 10 ⁶ Ω / □, The light transmittance was 85.5% and the haze value was 1.7%.

(Preparation of conductive ink composition (5c))
In the same manner as in Example 1, a conductive ink composition (5c) was prepared.

(Application of conductive ink composition (5c) to film)
In the same manner as in Example 1, a film coated with the conductive ink composition was obtained. The surface resistance value of the surface coated with the conductive ink composition was 2 × 10 ⁶ Ω / □, the total light transmittance was 88.0%, and the haze value was 1.3%.

Example 6
(Synthesis of conductive polymer fine particles (6))
To 100 ml of ion-exchanged water, 8 mmol, p-toluenesulfonic acid 32 mmol, and ferrous sulfate 0.4 mmol were added and stirred with PLUSCOAT Z-4000-100 as the amount of sulfonic acid group. Next, 40 mmol of 3,4-ethylenedioxythiophene was added as a polymerizable monomer and stirred. While stirring this solution, 34 g of an aqueous 30% ammonium persulfate solution (45 mmol as ammonium persulfate) was slowly added and reacted at 40 ° C. for 4 hours. The obtained precipitate was filtered, washed with ion exchange water until the pH of the filtrate was close to neutral, then washed with acetone and then dried to obtain indigo conductive polymer fine particles (6) 9 0.0 g was obtained. Moreover, as a result of measuring electrical conductivity similarly to Example 1, it was 5.0 S / cm.

(Preparation of conductive polymer fine particle dispersion (6a))
Using the obtained conductive polymer fine particles (6), a conductive polymer fine particle dispersion (6a) was obtained in the same manner as the production of the conductive polymer fine particle dispersion (1a) of Example 1.
When the particle size of the obtained conductive polymer fine particle dispersion was measured with a particle size distribution measuring device (Nanotrack UPA-EX150, manufactured by Nikkiso Co., Ltd.), the 50% cumulative particle size was 600 nm. Moreover, when the particle diameter was measured similarly one month after preparation of the conductive polymer fine particle dispersion (storage condition: 25 ° C.), the 50% cumulative particle diameter was 660 nm.

(Preparation of conductive polymer fine particle dispersion (6b))
Using the obtained conductive polymer fine particles (6), a conductive polymer fine particle dispersion (6b) was obtained in the same manner as in the preparation of the conductive polymer fine particle dispersion (1b) of Example 1.
When the particle size of the obtained conductive polymer fine particle dispersion was measured with a particle size distribution analyzer (Nanotrack UPA-EX150, manufactured by Nikkiso Co., Ltd.), the 50% cumulative particle size was 400 nm. Further, when the particle diameter was measured similarly one month after preparation of the conductive polymer fine particle dispersion (storage condition: 25 ° C.), the 50% cumulative particle diameter was 450 nm.

(Application of conductive polymer fine particle dispersion (6a) to glass plate)
By performing the same treatment as in Example 1, a glass plate coated with the conductive polymer fine particle dispersion (6a) was obtained. The surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 2 × 10 ⁷ Ω / □, the total light transmittance was 87.5%, and the haze value was 1.3%.
Moreover, when the conductive polymer fine particle dispersion one month after the production was applied in the same manner, the surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 3 × 10 ⁷ Ω / □, The light transmittance was 87.0%, and the haze value was 1.4%.

(Application of conductive polymer fine particle dispersion (6b) to glass plate)
By carrying out the same treatment as in Example 1, a glass plate coated with the conductive polymer fine particle dispersion (6b) was obtained. The surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 3 × 10 ⁷ Ω / □, the total light transmittance was 87.0%, and the haze value was 1.4%.
Further, when the conductive polymer fine particle dispersion one month after the production was applied in the same manner, the surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 4 × 10 ⁷ Ω / □, The light transmittance was 87.5%, and the haze value was 1.5%.

(Preparation of conductive ink composition (6c))
In the same manner as in Example 1, a conductive ink composition (6c) was prepared.

(Application of conductive ink composition (6c) to film)
In the same manner as in Example 1, a film coated with the conductive ink composition was obtained. The surface resistance value of the surface coated with the conductive ink composition was 2 × 10 ⁷ Ω / □, the total light transmittance was 88.5%, and the haze value was 1.3%.

Comparative Example 1
(Synthesis of conductive polymer fine particles (7))
To 100 ml of ion-exchanged water, 40 mmol of 2-naphthalenesulfonic acid and 0.4 mmol of ferrous sulfate were added and stirred. Next, 40 mmol of 3,4-ethylenedioxythiophene was added as a polymerizable monomer and stirred. While stirring this solution, 34 g of an aqueous 30% ammonium persulfate solution (45 mmol as ammonium persulfate) was slowly added and reacted at 40 ° C. for 4 hours. The obtained precipitate was filtered, washed with ion-exchanged water until the pH of the filtrate was close to neutral, then washed with acetone and then dried to obtain 6 indigo conductive polymer fine particles (7). .9 g was obtained. As a result of measuring the electrical conductivity in the same manner as in Example 1, it was 90 S / cm.

(Preparation of conductive polymer fine particle dispersion (7a))
Using the obtained conductive polymer fine particles (7), a conductive polymer fine particle dispersion (7a) was obtained in the same manner as in the preparation of the conductive polymer fine particle dispersion (1a) of Example 1.
When the particle size of the obtained conductive polymer fine particle dispersion was measured with a particle size distribution analyzer (Nanotrack UPA-EX150, manufactured by Nikkiso Co., Ltd.), the 50% cumulative particle size was 680 nm. However, when the particle diameter was measured similarly one month after the preparation of the conductive polymer fine particle dispersion (storage condition: 25 ° C.), the 50% cumulative particle diameter was 1100 nm. Moreover, the sediment which can be confirmed visually was seen.

(Preparation of conductive polymer fine particle dispersion (7b))
Using the obtained conductive polymer fine particles (7), a conductive polymer fine particle dispersion (7b) was obtained in the same manner as in the preparation of the conductive polymer fine particle dispersion (1b) of Example 1.
When the particle size of the obtained conductive polymer fine particle dispersion was measured with a particle size distribution measuring device (Nanotrack UPA-EX150, manufactured by Nikkiso Co., Ltd.), the 50% cumulative particle size was 600 nm. However, when the particle size was measured similarly one month after the preparation of the conductive polymer fine particle dispersion (storage condition: 25 ° C.), the 50% cumulative particle size was 1050 nm. Moreover, the sediment which can be confirmed visually was seen.

(Application of conductive polymer fine particle dispersion (7a) to glass plate)
By carrying out the same treatment as in Example 1, a glass plate coated with the conductive polymer fine particle dispersion (7a) was obtained. The surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 3 × 10 ⁵ Ω / □, the total light transmittance was 80.0%, and the haze value was 1.7%.
In addition, when the conductive polymer fine particle dispersion one month after the production was applied in the same manner, the surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 7 × 10 ⁵ Ω / □, The transmittance was 77.0% and the haze value was 2.0%.

(Application of conductive polymer fine particle dispersion (7b) to glass plate)
By carrying out the same treatment as in Example 1, a glass plate coated with the conductive polymer fine particle dispersion (7b) was obtained. The surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 4 × 10 ⁵ Ω / □, the total light transmittance was 79.0%, and the haze value was 1.8%.
Further, when the conductive polymer fine particle dispersion one month after the production was applied in the same manner, the surface resistance value of the surface on which the conductive polymer fine particle dispersion was applied was 8 × 10 ⁵ Ω / □, The transmittance was 76.0% and the haze value was 2.1%.

(Preparation of conductive ink composition (7c))
In the same manner as in Example 1, a conductive ink composition (7c) was prepared.

(Application of conductive ink composition (7c) to film)
In the same manner as in Example 1, a film coated with the conductive ink composition was obtained. The surface resistance value of the surface coated with the conductive ink composition was 3 × 10 ⁵ Ω / □, the total light transmittance was 83.0%, and the haze value was 1.7%.

Comparative Example 2
(Synthesis of conductive polymer fine particles (8))
To 100 ml of ion-exchanged water, 40 mmol of p-toluenesulfonic acid and 0.4 mmol of ferrous sulfate were added and stirred. Next, 40 mmol of 3,4-ethylenedioxythiophene was added as a polymerizable monomer and stirred. While stirring this solution, 34 g of an aqueous 30% ammonium persulfate solution (45 mmol as ammonium persulfate) was slowly added and reacted at 40 ° C. for 4 hours. The obtained precipitate was filtered, washed with ion-exchanged water until the pH of the filtrate became near neutral, then washed with acetone and then dried to obtain 5 indigo conductive polymer fine particles (8). 0.7 g was obtained. Moreover, as a result of measuring electrical conductivity similarly to Example 1, it was 6.0 S / cm.

(Preparation of conductive polymer fine particle dispersion (8a))
Using the obtained conductive polymer fine particles (8), a conductive polymer fine particle dispersion (8a) was obtained in the same manner as in the preparation of the conductive polymer fine particle dispersion (1a) of Example 1.
When the particle size of the obtained conductive polymer fine particle dispersion was measured with a particle size distribution analyzer (Nanotrack UPA-EX150, manufactured by Nikkiso Co., Ltd.), the 50% cumulative particle size was 490 nm. However, when the particle diameter was measured similarly one month after the preparation of the conductive polymer fine particle dispersion (storage condition: 25 ° C.), the 50% cumulative particle diameter was 1200 nm. Moreover, the sediment which can be confirmed visually was seen.

(Preparation of conductive polymer fine particle dispersion (8b))
Using the obtained conductive polymer fine particles (8), a conductive polymer fine particle dispersion (8b) was obtained in the same manner as in the preparation of the conductive polymer fine particle dispersion (1b) of Example 1.
When the particle size of the obtained conductive polymer fine particle dispersion was measured with a particle size distribution analyzer (Nanotrack UPA-EX150, manufactured by Nikkiso Co., Ltd.), the 50% cumulative particle size was 450 nm. However, when the particle diameter was measured similarly one month after the preparation of the conductive polymer fine particle dispersion (storage condition: 25 ° C.), the 50% cumulative particle diameter was 1100 nm. Moreover, the sediment which can be confirmed visually was seen.

(Coating of conductive polymer fine particle dispersion (8a) to glass plate)
By carrying out the same treatment as in Example 1, a glass plate coated with the conductive polymer fine particle dispersion (8a) was obtained. The surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 4 × 10 ⁷ Ω / □, the total light transmittance was 79.0%, and the haze value was 1.7%.
Further, when the conductive polymer fine particle dispersion one month after the production was applied in the same manner, the surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 9 × 10 ⁷ Ω / □, The transmittance was 76.0% and the haze value was 2.0%.

(Application of conductive polymer fine particle dispersion (8b) to glass plate)
By carrying out the same treatment as in Example 1, a glass plate coated with the conductive polymer fine particle dispersion (8b) was obtained. The surface resistance value of the surface coated with the conductive polymer fine particle dispersion was 5 × 10 ⁷ Ω / □, the total light transmittance was 79.0%, and the haze value was 1.8%.
Further, when the conductive polymer fine particle dispersion one month after the production was applied in the same manner, the surface resistance value of the surface on which the conductive polymer fine particle dispersion was applied was 1 × 10 ⁸ Ω / □, The transmittance was 76.0% and the haze value was 2.1%.

(Preparation of conductive ink composition (8c))
In the same manner as in Example 1, a conductive ink composition (8c) was prepared.

(Application of conductive ink composition (8c) to film)
In the same manner as in Example 1, a film coated with the conductive ink composition was obtained. The surface resistance value of the surface coated with the conductive ink composition was 3 × 10 ⁷ Ω / □, the total light transmittance was 84.0%, and the haze value was 1.7%.

Comparative Example 3
(Synthesis of conductive polymer fine particles (9))
To 200 ml of ion-exchanged water, 40 mmol and 0.4 mmol of ferrous sulfate were added and stirred with PLUSCOAT Z-4000-100 as the amount of sulfonic acid group. Next, 40 mmol of 3,4-ethylenedioxythiophene was added as a polymerizable monomer and stirred. While stirring this solution, 34 g of an aqueous 30% ammonium persulfate solution (45 mmol as ammonium persulfate) was slowly added and reacted at 40 ° C. for 4 hours. The obtained precipitate was filtered, washed with ion-exchanged water until the pH of the filtrate was close to neutral, then washed with acetone and then dried to give 15 indigo conductive polymer fine particles (9). 0.0 g was obtained. Moreover, as a result of measuring electrical conductivity similarly to Example 1, it was 3.0 S / cm.

(Preparation of conductive polymer fine particle dispersion)
Using the obtained cyan polymer, an attempt was made to produce a conductive polymer fine particle dispersion in the same manner as in Example 1. However, reaggregation was observed and a uniform dispersion could not be obtained.

Comparative Example 4
(Synthesis of conductive polymer fine particles (10))
12 mmol, 2-naphthalenesulfonic acid 28 mmol, and ferrous sulfate 0.4 mmol were added to and stirred with 100 ml of ion-exchanged water using polystyrene sulfonic acid (manufactured by Aldrich, average molecular weight 75000) as the sulfonic acid group amount. Next, 40 mmol of 3,4-ethylenedioxythiophene was added as a polymerizable monomer and stirred. While stirring this solution, 34 g of an aqueous 30% ammonium persulfate solution (45 mmol as ammonium persulfate) was slowly added and reacted at 40 ° C. for 4 hours. The obtained precipitate was filtered, washed with ion-exchanged water, then washed with acetone and then dried to obtain 7.4 g of a blue polymer. Moreover, as a result of measuring electrical conductivity similarly to Example 1, it was 51 S / cm.

(Preparation of conductive polymer fine particle dispersion)
Using the obtained cyan polymer, an attempt was made to produce a conductive polymer fine particle dispersion in the same manner as in Example 1. However, reaggregation was observed and a uniform dispersion could not be obtained.

  The production conditions and evaluation results of the conductive polymer fine particle dispersions shown in Examples 1 to 6 and Comparative Examples 1 to 4 are summarized in Table 1 below.

  As shown in the above table, those of Examples 1 to 6 were excellent in dispersion stability, with no significant change in the particle size even after 1 month of preparation of the dispersion. On the other hand, those shown in Comparative Examples 1 and 2 showed an increase in particle size due to reaggregation of fine particles.

  Further, Examples 1 to 6 had low surface resistance, excellent total light transmittance, and low haze. On the other hand, the thing of the comparative example 1 was a thing with a small transmittance | permeability and a large haze. The thing of the comparative example 2 was a thing with a high surface resistance value and a large haze.

  From the above results, it was shown that the conductive polymer fine particle dispersion of the present invention is excellent in all of dispersion stability, conductivity and transparency.

  The conductive polymer fine particle dispersion of the present invention is excellent in dispersion stability and can form a film having high conductivity and excellent transparency, so that it can be used for antistatic films, anticorrosion paints, EMI shields, plating primers, etc. Is available.

Claims (9)

Conductive polymer fine particles obtained by doping a π-conjugated conductive polymer with a dopant component, wherein the dopant component is at least the following components (a) and (b);
(A) viewing contains a polyester resin-based compound (b) low molecular aromatic sulfonic acid compound having a sulfonic acid group,
Component (a) polyester resin compound having a sulfonic acid group,
The following general formula (1)

(In the above formula, R represents a glycol residue, A represents a polyvalent carboxylic acid residue optionally having a substituent other than a sulfonic acid group, and n represents 1 or 2.)
And a repeating unit represented by the following general formula (2)

(In the above formula, R represents a glycol residue, B represents an aromatic ring, and n represents 1 or 2.)
Conductive polymer fine particles characterized by being a copolymer containing a repeating unit represented by the formula: 2. The conductive polymer fine particle according to claim 1 , wherein the repeating unit represented by the general formula (2) in the component (a) polyester resin compound having a sulfonic acid group is at least 20 mol% or more. The conductive polymer fine particle according to claim 1 or 2 , wherein the molar ratio of the sulfonic acid group in the component (a) to the component (b) is in the range of 40:60 to 20:80. The π-conjugated conductive polymer is represented by the following general formula (3)

(In the formula, X represents an oxygen atom or a sulfur atom. Z represents an oxygen atom or a sulfur atom which may be the same as or different from each other. R represents a linear or branched carbon number. 1 to 6 alkylene groups are shown.)
The conductive polymer fine particles according to any one of claims 1 to 3 , which is a polymer of a monomer compound represented by formula (1). The following general formula (3)

(In the formula, X represents an oxygen atom or a sulfur atom. Z represents an oxygen atom or a sulfur atom which may be the same as or different from each other. R represents a linear or branched carbon number. 1 to 6 alkylene groups are shown.)
Adding an oxidant-containing solution to a monomer solution containing (a) a polyester resin compound having a sulfonic acid group, (b) a low molecular weight aromatic sulfonic acid compound and a chemical oxidative polymerization catalyst. A method for producing conductive polymer fine particles. The method for producing conductive polymer fine particles according to claim 5 , wherein the molar ratio of the sulfonic acid group in the component (a) to the component (b) in the monomer solution is in the range of 40:60 to 20:80. A conductive polymer fine particle dispersion obtained by dispersing or dissolving the conductive polymer fine particles according to any one of claims 1 to 4 in a dispersion medium. Conductive polymer fine particle-containing liquid obtained by mixing the conductive polymer fine particles according to any one of claims 1 to 4 , a dispersing agent, and a dispersion medium is dispersed by wet pulverization. A method for producing a fine particle dispersion. A conductive ink composition comprising the conductive polymer fine particle dispersion according to claim 7 .