JP6291419B2 - Method for producing dispersion containing conductive polymer composition and dispersion containing conductive polymer composition - Google Patents

Description

  The present invention relates to a method for producing a dispersion containing a conductive polymer composition. More specifically, the present invention produces a low-viscosity dispersion comprising a conductive polymer composition comprising a conjugated conductive polymer excellent in transparency and conductivity and a polyanion doped therein. Regarding the method.

  Conductive paint, antistatic agent, electromagnetic shielding material, solid electrolyte, transparent conductive material, battery material, capacitor material, sensor material, conductive adhesive, electrophotographic material, photosensitive member, transfer member, etc. A polymer is used.

  As the conjugated conductive polymer, polythiophene, polypyrrole, polyaniline, polyacetylene, polyphenylene, poly (p-phenylene-vinylene), polyacene, polythiophene vinylene and the like are known. A technique of doping a polyanion such as polystyrene sulfonic acid as a counter anion of a conjugated conductive polymer is also known.

  For example, Patent Document 1 or Patent Document 2 discloses a method for producing a conductive composition characterized by oxidative polymerization of a monomer for obtaining a conjugated conductive polymer in the presence of a polyanion, and a polyanion; A method for producing a conductive composition is disclosed in which a monomer for obtaining a conjugated conductive polymer is oxidatively polymerized in the presence of an organic sulfonic acid. Further, Patent Document 3 discloses a conductive property comprising polymerizing the monomer by irradiating ultrasonic waves onto an aqueous or non-aqueous dispersion or solution containing a polyanion and a monomer for obtaining a conjugated conductive polymer. A method for producing a polymer composition is described.

JP 2005-76016 A Japanese Patent Laid-Open No. 7-90060 Special table 2011-510141 gazette

  By the way, the conductive polymer easily aggregates in the liquid medium, and the dispersion containing the conductive polymer may have a high viscosity. High viscosity dispersions are inconvenient for industrial handling. In addition, higher conductivity is required for conductive polymers for application to high-performance products.

  An object of the present invention is to provide a low-viscosity dispersion containing a conductive polymer composition comprising a conjugated conductive polymer excellent in conductivity and a polyanion doped therein.

  The present invention includes the following forms.

[1] a step of polymerizing a monomer for obtaining a conjugated conductive polymer in a liquid medium; and
A method for producing a dispersion comprising a conductive polymer composition comprising a step of adding a polyanion during the polymerization.
[2] The method for producing a dispersion containing the conductive polymer composition according to [1], further comprising dispersing a conjugated conductive polymer to be produced in the course of the polymerization.
[3] The method for producing a dispersion containing the conductive polymer composition according to [2], wherein the dispersion treatment is performed by ultrasonic irradiation.

[4] The method further comprises mixing a monomer for obtaining a conjugated conductive polymer with a polyanion before emulsification of the polymer, and emulsifying the mixture in a liquid medium. 3] The manufacturing method of the dispersion liquid containing the conductive polymer composition as described in any one of 3).
[5] The method for producing a dispersion containing the conductive polymer composition according to [4], wherein the emulsification is performed by ultrasonic irradiation.

[6] A method for producing a dispersion containing the conductive polymer composition according to any one of [1] to [5], wherein the polyanion is a polymer having a sulfonic acid group.
[7] A method for producing a dispersion containing the conductive polymer composition according to any one of [1] to [5], wherein the polyanion is polystyrene sulfonic acid.
[8] A method for producing a dispersion containing the conductive polymer composition according to any one of [1] to [7], wherein the polyanion has a molecular weight of 1,000 to 1,000,000.

[9] The monomer for obtaining the conjugated conductive polymer is from pyrrole which may have a substituent, aniline which may have a substituent, and thiophene which may have a substituent. The manufacturing method of the dispersion liquid containing the conductive polymer composition as described in any one of [1]-[8] which is at least one chosen from the group which consists of.
[10] The conductive polymer according to any one of [1] to [8], wherein the monomer for obtaining the conjugated conductive polymer contains a compound represented by the formula (I) A method for producing a dispersion containing the composition.

（式（I）中、Ｒ¹およびＲ²は、各々独立に、水素原子、置換基を有してもよい炭素数１〜１８のアルキル基、置換基を有してもよい炭素数１〜１８のアルコキシ基、若しくは置換基を有してもよい炭素数１〜１８のアルキルチオ基を表し、または、Ｒ¹とＲ²とが結合し且つＲ¹とＲ²が結合する各炭素原子と一緒になって、置換基を有してもよい炭素数３〜１０の脂環、置換基を有してもよい炭素数６〜１０の芳香環、置換基を有してもよい炭素数２〜１０の酸素原子含有複素環、置換基を有してもよい炭素数２〜１０のイオウ原子含有複素環、若しくは置換基を有してもよい炭素数２〜１０のイオウ原子および酸素原子含有複素環を形成してもよい。）

(In Formula (I), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms which may have a substituent, or an optionally substituted 1 to 1 carbon atom. 18 alkoxy group, or also represents an alkylthio group having 1 to 18 carbon atoms have a substituent, or, together with R ¹ and R ² are bonded and the carbon atom to which R ¹ and R ² are attached The alicyclic ring having 3 to 10 carbon atoms which may have a substituent, the aromatic ring having 6 to 10 carbon atoms which may have a substituent, and 2 carbon atoms which may have a substituent. 10 oxygen atom-containing heterocycles, optionally substituted sulfur atom-containing heterocycles having 2 to 10 carbon atoms, or optionally substituted sulfur atoms having 2 to 10 carbon atoms and oxygen atom-containing heterocycles A ring may be formed.)

[11] The conductive polymer composition according to any one of [1] to [8], wherein the monomer for obtaining the conjugated conductive polymer contains a compound represented by the formula (II). A method for producing a dispersion containing a product.

（式（II）中、Ｒ³およびＲ⁴は、各々独立に、水素原子または置換基を有してもよい炭素数１〜４のアルキル基を表し、または、Ｒ³とＲ⁴とが結合し且つＯＲ³とＯＲ⁴が結合する各炭素原子と一緒になって、置換基を有してもよい炭素数３〜６の酸素原子含有複素環を形成してもよい。）
〔１２〕共役系導電性重合体を得るための単量体が、３，４−エチレンジオキシチオフェンを含むものである、〔１〕〜〔８〕のいずれかひとつに記載の導電性重合体組成物を含む分散液の製造方法。

(In formula (II), R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent, or R ³ and R ⁴ are bonded to each other. And together with each carbon atom to which OR ³ and OR ⁴ are bonded, an oxygen atom-containing heterocyclic ring having 3 to 6 carbon atoms which may have a substituent may be formed.)
[12] The conductive polymer composition according to any one of [1] to [8], wherein the monomer for obtaining a conjugated conductive polymer contains 3,4-ethylenedioxythiophene. The manufacturing method of the dispersion liquid containing this.

[13] The liquid medium contains water,
A dispersion containing the conductive polymer composition according to any one of [1] to [12], wherein the polymerization is performed using at least one oxidizing agent selected from the group consisting of peroxodisulfuric acid and a salt thereof. Manufacturing method.

[14] A dispersion containing a conductive polymer composition obtained by the production method according to any one of [1] to [13].
[15] The dispersion according to [14], further comprising an electrical conductivity improver.
[16] The dispersion according to [15], wherein the electrical conductivity improver is at least one selected from the group consisting of ethylene glycol, propylene glycol and glycerin.

  According to the production method of the present invention, a low-viscosity dispersion containing a conductive polymer composition excellent in conductivity and comprising a conjugated conductive polymer and a polyanion doped therein is easily obtained. be able to.

It is a figure which shows the viscosity change of the reaction liquid from the polymerization start in Example 3 and the comparative example 2 to the completion | finish of superposition | polymerization.

  The production method according to an embodiment of the present invention includes a step of polymerizing a monomer for obtaining a conjugated conductive polymer in a liquid medium, and a step of adding a polyanion during the polymerization.

  The conjugated conductive polymer obtained by polymerization in the production method of the present invention is not particularly limited as long as the main chain is an organic polymer composed of a π-conjugated system. Examples include polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, polythiophene vinylenes, and copolymers thereof. Of these, polypyrroles, polythiophenes and polyanilines are preferred, and polythiophenes are more preferred. As the conjugated conductive polymer, those having a substituent such as an alkyl group, a carboxylic acid group, a sulfonic acid group, an alkoxyl group, a hydroxyl group, and a cyano group are preferable in that high conductivity can be obtained.

  Specific examples of preferable conjugated conductive polymers include polypyrrole, polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propyl). Pyrrole), poly (3-butylpyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4) -Dibutylpyrrole), poly (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole) , Poly (3-hydroxypyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxy) Pyrrole), poly (3-hexyloxy-pyrrole), poly (3-methyl-4-hexyloxy-pyrrole) and poly (3-methyl-4-hexyloxy-pyrrole) can be mentioned;

  Examples of polythiophenes include polythiophene, poly (3-methylthiophene), poly (3-hexylthiophene), poly (3-heptylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3- Dodecylthiophene), poly (3-octadecylthiophene), poly (3-bromothiophene), poly (3-chlorothiophene), poly (3-iodothiophene), poly (3-cyanothiophene), poly (3-phenylthiophene) ), Poly (3,4-dimethylthiophene), poly (3,4-dibutylthiophene), poly (3-hydroxythiophene), poly (3-methoxythiophene), poly (3-ethoxythiophene), poly (3- Butoxythiophene), poly (3-hexyloxythiophene), poly (3- Butyloxythiophene), poly (3-octyloxythiophene), poly (3-decyloxythiophene), poly (3-dodecyloxythiophene), poly (3-octadecyloxythiophene), poly (3,4-dihydroxythiophene) , Poly (3,4-dimethoxythiophene), poly (3,4-diethoxythiophene), poly (3,4-dipropoxythiophene), poly (3,4-dibutoxythiophene), poly (3,4 Dihexyloxythiophene), poly (3,4-diheptyloxythiophene), poly (3,4-dioctyloxythiophene), poly (3,4-didecyloxythiophene), poly (3,4-didodecyloxythiophene) ), Poly (3,4-ethylenedioxythiophene), poly (3,4-propylenedio Cithiophene), poly (3,4-butylenedioxythiophene), poly (3-methyl-4-methoxythiophene), poly (3-methyl-4-ethoxythiophene), poly (3-carboxythiophene), poly ( 3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly (3-methyl-4-carboxybutylthiophene) and poly (3,4-ethyleneoxythiathiophene). ;

  Examples of polyanilines include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-aniline sulfonic acid), and poly (3-aniline sulfonic acid).

  Among these, it is selected from the group consisting of polypyrrole, polythiophene, poly (N-methylpyrrole), poly (3-methylthiophene), poly (3-methoxythiophene), and poly (3,4-ethylenedioxythiophene). At least one is preferable from the viewpoint of conductivity. Poly (3,4-ethylenedioxythiophene) is more preferable because it has higher conductivity and excellent heat resistance.

  The monomer for obtaining the conjugated conductive polymer is selected from the group consisting of pyrrole which may have a substituent, aniline which may have a substituent, and thiophene which may have a substituent. At least one selected is preferably used. Specific examples of such monomers include pyrrole, N-methylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, 3-octylpyrrole, 3-decylpyrrole, 3 -Dodecylpyrrole, 3,4-dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxylpyrrole, 3-methyl-4-carboxylpyrrole, 3-methyl-4-carboxyethylpyrrole, 3-methyl-4-carboxybutyl Pyrrole, 3-hydroxypyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole, 3-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole;

  Thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3-butylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-octylthiophene, 3-decylthiophene, 3-dodecylthiophene, 3-octadecyl Thiophene, 3-bromothiophene, 3-chlorothiophene, 3-iodothiophene, 3-cyanothiophene, 3-phenylthiophene, 3,4-dimethylthiophene, 3,4-dibutylthiophene, 3-hydroxythiophene, 3-methoxythiophene 3-ethoxythiophene, 3-butoxythiophene, 3-hexyloxythiophene, 3-heptyloxythiophene, 3-octyloxythiophene, 3-decyloxythiophene, 3-dodecyloxythiophene, 3- Kutadecyloxythiophene, 3,4-dihydroxythiophene, 3,4-dimethoxythiophene, 3,4-diethoxythiophene, 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene 3,4-diheptyloxythiophene, 3,4-dioctyloxythiophene, 3,4-didecyloxythiophene, 3,4-didodecyloxythiophene, 3,4-ethylenedioxythiophene, 3,4-propylene Dioxythiophene, 3,4-butylene dioxythiophene, 3-methyl-4-methoxythiophene, 3-methyl-4-ethoxythiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3-methyl-4 -Carboxyethylthiophene, 3-methyl-4 Carboxybutyl thiophene, 3,4-ethyleneoxythiathiophene;

  Examples include aniline, 2-methylaniline, 3-isobutylaniline, 2-aniline sulfonic acid, and 3-aniline sulfonic acid. These can be used alone or in combination of two or more.

  The monomer for obtaining the conjugated conductive polymer preferably contains a compound represented by the formula (I), more preferably a compound represented by the formula (II), and most preferably 3, 4 -Including ethylenedioxythiophene.

In formula (I), R ¹ and R ² are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, or an optionally substituted carbon atom having 1 to 18 carbon atoms. It represents an alkoxy group or an alkylthio group having 1 to 18 carbon atoms which may have a substituent, or, together with R ¹ and R ² are bonded and the carbon atom to which R ¹ and R ² are attached An alicyclic ring having 3 to 10 carbon atoms which may have a substituent, an aromatic ring having 6 to 10 carbon atoms which may have a substituent, and 2 to 10 carbon atoms which may have a substituent. An oxygen atom-containing heterocyclic ring, a C 2-10 sulfur atom-containing heterocyclic ring which may have a substituent, or a C 2-10 sulfur atom and an oxygen atom-containing heterocyclic ring which may have a substituent May be formed.

Examples of the oxygen atom-containing heterocycle include an oxirane ring, an oxetane ring, a furan ring, a hydrofuran ring, a pyran ring, a pyrone ring, a dioxane ring, and a trioxane ring.
Examples of the sulfur atom-containing heterocycle include a thiirane ring, a thietane ring, a thiophene ring, a thiane ring, a thiopyran ring, a thiopyrylium ring, a benzothiopyran ring, a dithian ring, a dithiolane ring, and a trithian ring.
Examples of the sulfur atom and oxygen atom-containing heterocycle include an oxathiolane ring and an oxathian ring.

In formula (II), R ³ and R ⁴ each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 4 carbon atoms, or R ³ and R ⁴ are bonded to each other. Moreover, together with each carbon atom to which OR ³ and OR ⁴ are bonded, a C 3-6 oxygen atom-containing heterocyclic ring which may have a substituent may be formed.
R ³ and R ⁴ preferably have ³ to 6 carbon atoms which may have a substituent together with the carbon atoms to which R ³ and R ⁴ are bonded and to which OR ³ and OR ⁴ are bonded. To form an oxygen atom-containing heterocycle. Examples of the oxygen atom-containing heterocycle include an oxirane ring, an oxetane ring, a furan ring, a hydrofuran ring, a pyran ring, a pyrone ring, a dioxane ring, and a trioxane ring, and a dioxane ring is preferable.

  The polyanion used in the present invention is a polymer having an anionic group. Examples of the anionic group include a group consisting of a sulfonic acid or a salt thereof, a group consisting of a phosphoric acid or a salt thereof, a monosubstituted phosphate group, a group consisting of a carboxylic acid or a salt thereof, a monosubstituted sulfate group. Among these, a strongly acidic group is preferable, a group consisting of sulfonic acid or a salt thereof, a group consisting of phosphoric acid or a salt thereof is more preferable, and a group consisting of sulfonic acid or a salt thereof is most preferable. The anionic group may be directly bonded to the polymer main chain or may be bonded to the side chain. When an anionic group is bonded to the side chain, the doping effect is more remarkably achieved. Therefore, the anionic group is preferably bonded to the end of the side chain.

  The polyanion may have a substituent other than the anionic group. Examples of the substituent include alkyl group, hydroxy group, alkoxy group, phenol group, cyano group, phenyl group, hydroxyphenyl group, ester group, halogeno group, alkenyl group, imide group, amide group, amino group, oxycarbonyl group, A carbonyl group etc. are mentioned. Among these, an alkyl group, a hydroxy group, a cyano group, a phenol group, and an oxycarbonyl group are preferable, and an alkyl group, a hydroxy group, and a cyano group are more preferable. The substituent may be directly bonded to the polymer main chain or may be bonded to the side chain. When the substituent is bonded to the side chain, the substituent is preferably bonded to the end of the side chain in order to perform each function of the substituent.

  The alkyl group that can be substituted in the polyanion can be expected to have an effect of increasing the solubility and dispersibility in the liquid medium, the compatibility and dispersibility with the conjugated conductive polymer, and the like. Examples of the alkyl group include a chain alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, and a dodecyl group; a cyclopropyl group, Examples thereof include cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group. In view of solubility in a liquid medium, dispersibility in a conjugated conductive polymer, steric hindrance, and the like, an alkyl group having 1 to 12 carbon atoms is more preferable.

  The hydroxy group that can be substituted in the polyanion facilitates the formation of hydrogen bonds with other hydrogen atoms, and has high solubility in liquid media, high compatibility with conjugated conductive polymers, dispersibility, and adhesion. Can be expected. The hydroxy group is preferably bonded to the terminal of an alkyl group having 1 to 6 carbon atoms bonded to the polymer main chain.

  The cyano group and hydroxyphenyl group that can be substituted in the polyanion can be expected to have an effect of increasing the compatibility with the conjugated conductive polymer, the solubility in the liquid medium, and the heat resistance. The cyano group is directly bonded to the polymer main chain, bonded to the terminal of the alkyl group having 1 to 7 carbon atoms bonded to the polymer main chain, or the terminal of the alkenyl group having 2 to 7 carbon atoms bonded to the polymer main chain. Those bonded to are preferred.

  The oxycarbonyl group that can be substituted in the polyanion is preferably an alkyloxycarbonyl group, an aryloxycarbonyl group, or an alkyloxycarbonyl group or an aryloxycarbonyl group that is directly bonded to the polymer main chain with another functional group interposed therebetween.

  The polymer main chain of the polyanion is not particularly limited. Examples of the polymer main chain include polyalkylene, polyimide, polyamide, and polyester. Of these, polyalkylene is preferable from the viewpoint of synthesis and availability.

  Polyalkylene is a polymer composed of repeating units of ethylenically unsaturated monomers. The polyalkylene may have a carbon-carbon double bond in the main chain. Examples of the polyalkylene include polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyvinyl alcohol, polyvinylphenol, poly (3,3,3-trifluoropropylene), polyacrylonitrile, polyacrylate, polymethacrylate, polystyrene, polybutadiene, poly And isoprene.

  As polyimide, pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, 2,2,3,3-tetracarboxydiphenyl ether dianhydride, 2,2- [4,4 Examples include those obtained by polycondensation reaction of acid anhydrides such as' -di (dicarboxyphenyloxy) phenyl] propane dianhydride and diamines such as oxydianiline, paraphenylenediamine, metaphenylenediamine, and benzophenonediamine. .

  Examples of the polyamide include polyamide 6, polyamide 6,6, polyamide 6,10 and the like.

  Examples of the polyester include polyethylene terephthalate and polybutylene terephthalate.

  Specific examples of the polymer having a sulfonic acid group suitably used as a polyanion include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, and poly (2-acrylamide). -2-methylpropanesulfonic acid), polyisoprenesulfonic acid and salts thereof. These may be homopolymers or two or more types of copolymers. Of these, polystyrenesulfonic acid, polyisoprenesulfonic acid, polyacrylic acid ethylsulfonic acid, polyacrylic acid butylsulfonic acid, and salts thereof are preferable. Polyanions, especially polymers with sulfonic acid groups, can alleviate the thermal decomposition of conjugated conductive polymers and improve the dispersibility of monomers to obtain conjugated conductive polymers in liquid media And function as a dopant for the conjugated conductive polymer.

  The polyanion used in the present invention has a weight average molecular weight of preferably 1,000 to 1,000,000, more preferably 5,000 to 300,000. When the weight average molecular weight is within this range, the solubility of the polyanion in the liquid medium and the compatibility between the polyanion and the conjugated conductive polymer are improved. A weight average molecular weight is measured as a polystyrene conversion molecular weight using gel permeation chromatography.

  The polyanion may have the above properties selected from commercially available products, or may be obtained by synthesis by a known method. Examples of the method for synthesizing polyanions include the method described in Houben-Weyl, “Methoden derorganischen Chemle” Vol. E20, Makromolekulare Stoffe, No. 2 (1987) p1141-, the methods described in Patent Documents 1 to 3 and the like. Can be mentioned.

  The amount of the polyanion used is a monomer 1 for obtaining a conjugated conductive polymer in which the anionic group in the polyanion is combined with the one prepared in advance before the start of polymerization and the one added during the polymerization. The amount is preferably 0.25 to 10 mol, more preferably 0.8 to 8 mol, and still more preferably 0.8 to 5 mol, relative to mol. The mass of the polyanion with respect to 100 parts by mass of the conjugated conductive polymer obtained by the production method of the present invention is preferably 10 to 10000 parts by mass, more preferably 50 to 5000 parts by mass, and further preferably 100 to 1000 parts by mass. . If the amount of the polyanion is too large, the conductivity of the conductive polymer composition tends to decrease, and if the amount of the polyanion is too small, the dispersibility of the conductive polymer composition in the liquid medium tends to decrease. .

  The liquid medium used in the present invention is not particularly limited as long as it can disperse a conductive polymer composition comprising a conjugated conductive polymer and a polyanion doped therein. Examples of liquid media include water; amides such as N-vinylpyrrolidone, hexamethylphosphortriamide, N-vinylformamide, and N-vinylacetamide; phenols such as cresol, phenol, and xylenol; dipropylene glycol, 1,3 -Polyhydric alcohols such as butylene glycol, 1,4-butylene glycol, diglycerin, isoprene glycol, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol Carbonate compounds such as ethylene carbonate and propylene carbonate; dioxane, diethyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol di Ethers such as Ruki ethers; heterocyclic compounds such as 3-methyl-2-oxazolidinone; acetonitrile, glutarodinitrile, methoxy acetonitrile, propionitrile, and the like nitriles such as benzonitrile. These solvents can be used alone or in combination of two or more. Among these, it is preferable to use a liquid medium containing 1 to 99% by mass of water, more preferably 50 to 99% by mass of water, and still more preferably using water alone. Substances that can be used as the liquid medium include those that can also be used as additives such as an electrical conductivity improver described later. When such a liquid medium is used, an additive such as an electric conductivity improving agent of a type different from the liquid medium may be added.

  The amount of the liquid medium to be used is preferably 1 to 50000 parts by mass, more preferably 50 to 10000 parts by mass, with respect to 100 parts by mass in total of the monomer and polyaniline for obtaining the conjugated conductive polymer. If the amount of liquid medium used is too small, the viscosity of the dispersion tends to increase. When the amount of the liquid medium used is too large, it takes time to remove the liquid medium from the dispersion liquid, and the production efficiency of articles such as a film using the dispersion liquid of the present invention tends to decrease.

  In order to polymerize a monomer for obtaining a conjugated conductive polymer in a liquid medium, first, the monomer and, if necessary, an additive are added to the liquid medium and dissolved, emulsified or dispersed. A monomer solution, emulsion or dispersion (hereinafter sometimes referred to as monomer solution) is obtained. The monomer solution may be prepared by a powerful stirring device such as a homogenizer, but it is preferably by ultrasonic irradiation. The ultrasonic irradiation energy is not particularly limited as long as a uniform monomer liquid can be obtained. The ultrasonic irradiation is preferably performed at a power consumption of 5 to 500 W / L for 0.1 to 2 hours / L.

  The monomer solution before the start of polymerization may contain a part of a predetermined amount of polyanion to be doped into the conjugated conductive polymer from the viewpoint of suppressing aggregation of the conjugated conductive polymer generated during the polymerization. preferable. The polyanion can be contained in a monomer liquid by mixing with a monomer for obtaining a conjugated conductive polymer and dissolving, emulsifying or dispersing the resulting mixture in a liquid medium. The amount of the polyanion to be contained in the monomer liquid before the start of polymerization is preferably 0 to 99% by mass, more preferably 10 to 90% by mass, and further preferably 20 to 80% by mass of the total amount of polyanions used.

  For example, in the case of producing a dispersion containing polypyrroles or polythiophenes as a conjugated conductive polymer, the polymerization of the monomer is started by bringing the monomer to a predetermined temperature in the presence of an oxidizing agent. Examples of oxidizing agents include peroxodisulfates such as ammonium peroxodisulfate, sodium peroxodisulfate, and potassium peroxodisulfate; metal halides such as boron trifluoride; ferric chloride, ferric sulfate, and chloride. Transition metal compounds such as cupric; metal oxides such as silver oxide and cesium oxide; peroxides such as hydrogen peroxide and ozone; organic peroxides such as benzoyl peroxide; oxygen and the like. Of these, peroxodisulfate is preferred.

  The temperature during the polymerization is usually 5 to 80 ° C. When the temperature during polymerization is within this range, polymerization can be carried out at an appropriate reaction rate, increase in viscosity can be suppressed, and production of a dispersion containing a conductive polymer composition can be carried out stably and economically. It can be performed in a reasonable time, and the conductivity of the resulting conductive polymer composition tends to be high. The temperature at the time of superposition | polymerization can be managed by using a well-known heater and a cooler. Moreover, you may superpose | polymerize, changing temperature within the said range as needed.

  In the production method of the present invention, a polyanion is added to the polymerization reaction solution during the polymerization. By this method, the mechanism by which a conjugated conductive polymer excellent in conductivity can be obtained without excessively increasing the viscosity during polymerization is estimated as follows: When polymerization is performed in the presence of a polyanion A conjugated conductive polymer having a short main chain during growth is doped with a polyanion. If the polymerization further proceeds as it is, the amount of polyanion becomes relatively small, so that a conjugated conductive polymer that continues to grow the main chain without being doped increases. A conjugated conductive polymer having a long main chain tends to aggregate and the viscosity of the polymerization reaction solution tends to increase. When a polyanion is added thereto, the conjugated conductive polymer having a long main chain is doped with the polyanion, and aggregation of the conjugated conductive polymer can be prevented. Furthermore, since the conjugated conductive polymer grows to some extent and is doped with polyanions, a film having high electrical conductivity can be obtained by applying and drying the resulting dispersion.

  The addition of the polyanion is preferably performed continuously or intermittently in order to suppress a rapid increase in the polyanion concentration. In order to uniformly mix the polyanions added to the polymerization reaction solution, it is preferable to add the polyanions in a solution. It is preferable to use a solution containing a liquid medium used for the polymerization reaction solution as the solvent. Since the addition rate of the polyanion varies depending on the scale of the reaction apparatus, it cannot be generally determined, but is usually 1 to 1000 parts by mass / 100 parts by mass with respect to 100 parts by mass of the monomer for obtaining the conjugated conductive polymer. It's time.

  In the production method of the present invention, it is preferable that the polymerization further includes dispersing the conjugated conductive polymer to be produced. This dispersion treatment can be performed by a powerful stirring device such as a homogenizer, but is preferably performed by ultrasonic irradiation. By this dispersion treatment, aggregation of the conjugated conductive polymer having a long main chain can be suppressed. The ultrasonic irradiation energy is not particularly limited as long as aggregation of the conjugated conductive polymer can be suppressed. The ultrasonic irradiation is preferably performed until the end of the reaction with a power consumption of 5 to 500 W / L.

  According to the production method of the present invention, since the conjugated conductive polymer having a long main chain grown is surely doped into the polyanion, a conductive polymer composition having high conductivity can be obtained. Moreover, since the desorption of polyanions that may be caused by the external environment such as humidity and heat hardly occurs, a conductive polymer composition excellent in heat resistance and moisture resistance can be obtained.

  If necessary, an additive may be added to the monomer solution or polymerization reaction solution used in the production method of the present invention, or to the dispersion liquid containing the conductive polymer composition obtained by the production method of the present invention. it can. The additive is not particularly limited as long as it can be mixed with the conjugated conductive polymer and the polyanion. Examples thereof include water-soluble polymer compounds, water-dispersible compounds, alkaline compounds, surfactants, antifoaming agents, coupling agents, antioxidants, and electrical conductivity improvers.

  The water-soluble polymer compound is a water-soluble polymer having a cationic group or a nonionic group in the main chain or side chain of the polymer. Specific examples of the water-soluble polymer compound include, for example, polyoxyalkylene, water-soluble polyurethane, water-soluble polyester, water-soluble polyamide, water-soluble polyimide, water-soluble polyacryl, water-soluble polyacrylamide, polyvinyl alcohol, polyacrylic acid and the like. Is mentioned. Of these, polyoxyalkylene is preferred.

  Specific examples of polyoxyalkylene include diethylene glycol, triethylene glycol, oligopolyethylene glycol, triethylene glycol monochlorohydrin, diethylene glycol monochlorohydrin, oligoethylene glycol monochlorohydrin, triethylene glycol monobromohydrin, diethylene glycol monobromhydrin, Oligoethylene glycol monobromohydrin, polyethylene glycol, glycidyl ethers, polyethylene glycol glycidyl ethers, polyethylene oxide, triethylene glycol / dimethyl ether, tetraethylene glycol / dimethyl ether, diethylene glycol / dimethyl ether, diethylene glycol / diethyl ether / diethylene glycol / Butyl ether, dipropylene glycol, tripropylene glycol, polypropylene glycol, polypropylene dioxide, polyoxyethylene alkyl ethers, polyoxyethylene glycerol fatty acid esters, polyoxyethylene fatty acid amides.

  A water-dispersible compound is a compound in which a part of a low hydrophilic compound is substituted with a highly hydrophilic functional group, or a compound having a highly hydrophilic functional group adsorbed around a low hydrophilic compound (E.g., an emulsion) that is dispersed without being precipitated in water. Specific examples include polyester, polyurethane, acrylic resin, silicone resin, and emulsions of these polymers. The water-soluble polymer compound and the water-dispersible compound can be used singly or in combination of two or more. When a water-soluble polymer compound and a water-dispersible compound are added, the dispersion containing the conductive polymer composition can be thickened or the coating performance can be improved.

  The amount of the water-soluble polymer compound and the water-dispersible compound is preferably 1 to 4000 parts by mass, more preferably 50 to 2000 parts by mass with respect to a total of 100 parts by mass of the conjugated conductive polymer and the polyanion. . If the amount of the water-soluble polymer compound and the water-dispersible compound is too large, the conductivity tends to be low.

An alkaline compound may be added to the dispersion liquid containing the conductive polymer composition. By adding an alkaline compound, it is possible to impart corrosion resistance to an article to which the dispersion is applied.
As the alkaline compound, known inorganic alkaline compounds and organic alkaline compounds can be used. Examples of the inorganic alkaline compound include ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia and the like. Examples of the organic alkaline compound include aromatic amines, aliphatic amines, and alkali metal alkoxides.

Of the aromatic amines, nitrogen-containing heteroaryl ring compounds are preferred. The nitrogen-containing heteroaryl ring compound is a nitrogen-containing heterocyclic compound that exhibits aromaticity. In aromatic amines, the nitrogen atom contained in the heterocycle has a conjugated relationship with other atoms.
Examples of the nitrogen-containing heteroaryl ring compound include pyridines, imidazoles, pyrimidines, pyrazines, and triazines. Of these, pyridines, imidazoles, and pyrimidines are preferable from the viewpoint of solvent solubility and the like.

  Examples of the aliphatic amine include ethylamine, n-octylamine, diethylamine, diisobutylamine, methylethylamine, trimethylamine, triethylamine, allylamine, 2-ethylaminoethanol, 2,2′-iminodiethanol, N-ethylethylenediamine, and the like. It is done.

  Examples of the alkali metal alkoxide include sodium alkoxide such as sodium methoxide and sodium ethoxide, potassium alkoxide, calcium alkoxide and the like.

  The pH of the dispersion liquid containing the conductive polymer composition can be adjusted by adding the alkaline compound. For example, it is preferable to adjust the pH to 3 to 13 in order to impart corrosion resistance to an article made of metal and metal oxide.

  Surfactants include anionic surfactants such as carboxylates, sulfonates, sulfates and phosphates; cationic surfactants such as amine salts and quaternary ammonium salts; carboxybetaines and aminocarboxylic acids Examples include amphoteric surfactants such as salts and imidazolium betaines; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, ethylene glycol fatty acid esters, and polyoxyethylene fatty acid amides.

Examples of the antifoaming agent include silicone resin, polydimethylsiloxane, and silicone resin.
Examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, saccharides, vitamins and the like.

  The electrical conductivity improver is not particularly limited as long as it increases the electrical conductivity of the dispersion containing the conductive polymer composition. Examples of the electrical conductivity improver include compounds containing an ether bond such as tetrahydrofuran; compounds containing a lactone group such as γ-butyrolactone and γ-valerolactone; caprolactam, N-methylcaprolactam, N, N-dimethylacetamide, N -Compounds containing amide or lactam groups such as methylacetamide, N, N-dimethylformamide, N-methylformamide, N-methylformanilide, N-methylpyrrolidone, N-octylpyrrolidone, pyrrolidone; tetramethylenesulfone, dimethylsulfoxide, etc. A saccharide or saccharide derivative such as sucrose, glucose, fructose or lactose; a sugar alcohol such as sorbitol or mannitol; a succinimide, Imides such as Reimido; 2-furan carboxylic acid, 3-furan furan derivatives such as carboxylic acid, ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethylene glycol, and the like dialcohol or polyalcohols such as glycerol. Of these, tetrahydrofuran, N-methylformamide, N-methylpyrrolidone, ethylene glycol, propylene glycol, dimethyl sulfoxide, sorbitol, and glycerin are preferable from the viewpoint of improving electrical conductivity, and from the group consisting of ethylene glycol, propylene glycol, and glycerin. At least one selected is particularly preferred. An electrical conductivity improver can be used individually by 1 type or in combination of 2 or more types.

  After the dispersion obtained by the production method of the present invention is attached to the article, the liquid medium is removed to give the article a function such as conductivity. Examples of the attaching means include application, spraying, and immersion. By removing the liquid medium from the dispersion obtained by the production method of the present invention, a molded article such as a film of the conductive polymer composition can be obtained. As a method for removing the liquid medium, known methods such as room temperature drying, hot air drying, and far-infrared irradiation drying can be used. The liquid medium is not completely removed by the above method, and a part of the liquid medium may remain in the molded product depending on the type of the liquid medium used.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

The solid content concentration, viscosity, pH and conductivity were measured by the following methods, respectively. (Solid content concentration)
Approximately 2 g of the dispersion was weighed in a sample container and allowed to stand in a dryer at 105 ° C. for 1 hour, and then the mass of the sample in the sample container was measured, (mass before drying−mass after drying) / mass before drying. Was defined as the solid content concentration.

(viscosity)
B type viscometer, rotor no. 2 was measured.

(PH)
The measurement was performed using a pH meter (Model HM-30G manufactured by Toa DKK Co., Ltd .: glass electrode).

(conductivity)
While stirring 100 g of the dispersion containing the conductive polymer composition, ammonia water was added to the dispersion. Then 10 g of ethylene glycol was added. A dispersion with pH 4.5 was obtained. In accordance with JIS K 7194, a pH 4.5 dispersion was poured on a glass plate and dried with hot air at 100 ° C. to form a 10 μm thick film. The conductivity of the film was measured with Loresta (Mitsubishi Chemical Corporation).

Example 1
Sodium polystyrene sulfonate by dissolving sodium polystyrene sulfonate (trade name Polynas (PS-50): weight average molecular weight 2.3 × 10 ⁵ ) manufactured by Tosoh Organic Chemical Co., Ltd. in water to a concentration of 2% by mass. A 2% by weight aqueous solution was prepared.
4288 parts by weight of ion-exchanged water, 7498 parts by weight of a 2% by weight aqueous solution of sodium polystyrenesulfonate, and 420 parts by weight of a 2% by weight aqueous solution of iron (III) p-toluenesulfonate hexahydrate (manufactured by Sigma-Aldrich) at 27 ° C. And mixed. To this solution, 100 parts by mass of 3,4-ethylenedioxythiophene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and mixed while irradiating ultrasonic waves at 27 ° C.
While stirring with a stirring blade and ultrasonic irradiation at 27 ° C., 210 parts by mass of sodium peroxodisulfate (manufactured by Kanto Chemical Co., Inc.) was added to the resulting mixture to initiate the polymerization reaction. Next, 4999 parts by mass of a 2% by weight aqueous sodium polystyrenesulfonate solution was added dropwise over 4 hours. Then, it was made to react, stirring with a stirring blade and ultrasonic irradiation for 4 hours at 27 degreeC.
After completion of the reaction, 1100 parts by mass of cation exchange resin and 1100 parts by mass of anion exchange resin are added to the resulting reaction solution, and the reaction solution is stirred for 12 hours, thereby removing unreacted monomers, oxidizing agent and oxidation catalyst Adsorbed on an ion exchange resin. The ion exchange resin was separated by filtration to obtain a dispersion containing a conductive polymer composition containing poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid doped therein. The dispersion had a solid content concentration of 2.0% by mass, a viscosity of 150 mPa · s, and a pH of 1.9. The conductivity of the film obtained by the dispersion adjusted to pH 4.5 was 220 S / cm. The results are summarized in Table 1.

Examples 2 to 5 and Comparative Examples 1 to 3
A dispersion containing the conductive polymer composition was produced in the same manner as in Example 1 except that the polymerization reaction formulation shown in Table 1 was used. The results are summarized in Table 1. Moreover, the viscosity change of the reaction liquid from the polymerization start to the completion | finish of superposition | polymerization measured in Example 3 and Comparative Example 2 is shown in FIG.

The meanings of the abbreviations in the table are as follows.
PSS-Na: Sodium polystyrene sulfonate PSS-Na (PS-50) 2 mass% Aqueous solution: Sodium polystyrene sulfonate (manufactured by Tosoh Organic Chemical Co., Ltd., trade name Polynas (PS-50): Weight average molecular weight 2.3 × 10 ⁵ ) aqueous polystyrene polystyrene sulfonate solution prepared by dissolving in water to a concentration of 2 mass% PSS-Na (PS-50) 3 mass% aqueous solution: sodium polystyrene sulfonate (manufactured by Tosoh Organic Chemical Co., Ltd.) Polystyrene (PS-50): Polystyrene sodium sulfonate aqueous solution PSS-Na (PS-1) 3 mass prepared by dissolving a weight average molecular weight 2.3 × 10 ⁵ ) in water to a concentration of 3 mass% % Aqueous solution: sodium polystyrene sulfonate (manufactured by Tosoh Organic Chemical Co., Ltd., trade name Polynas (PS-1): Heavy Polystyrene sulfonate aqueous solution prepared by dissolving a weight average molecular weight of 5.0 × 10 ⁴ ) in water to a concentration of 3% by mass EDOT: 3,4-ethylenedioxythiophene Fe (OTs) ₃ 2% by mass aqueous solution : P-toluenesulfonic acid iron (III) hexahydrate 2 mass% aqueous solution (manufactured by Sigma-Aldrich)

  As shown in Table 1, the dispersion containing the conductive polymer composition obtained according to the production method of the present invention can be obtained by the conventional method even if the conjugated conductive polymer and the polyanion have the same mass ratio. It can be seen that a conductive polymer composition having high conductivity is included. In addition, when a dispersion liquid containing a conductive polymer composition is produced according to the present invention, the viscosity of the reaction liquid changes low during the period from the start of polymerization to the end of polymerization as shown in FIG. Is advantageous.

Claims (15)

A step of polymerizing a monomer for obtaining a conjugated conductive polymer in a liquid medium ;
Adding a polyanion course of the polymerization, and
In the course of the polymerization, the resulting conjugated conductive polymer is dispersed by ultrasonic irradiation ,
A method for producing a dispersion containing a conductive polymer composition. A step of polymerizing a monomer for obtaining a conjugated conductive polymer in a liquid medium ;
Adding a polyanion course of the polymerization, and
Mixing a monomer for obtaining a conjugated conductive polymer and a polyanion before emulsification of the mixture in a liquid medium before the start of the polymerization ,
A method for producing a dispersion containing a conductive polymer composition. The manufacturing method of the dispersion liquid containing the conductive polymer composition of Claim 2 which further includes carrying out the dispersion | distribution process of the conjugated system conductive polymer to produce | generate in the said polymerization process. The manufacturing method of the dispersion liquid containing the conductive polymer composition of Claim 3 which performs the said dispersion | distribution process by ultrasonic irradiation. The manufacturing method of the dispersion liquid containing the conductive polymer composition as described in any one of Claims 2-4 which performs the said emulsification by ultrasonic irradiation.   The manufacturing method of the dispersion liquid containing the conductive polymer composition as described in any one of Claims 1-5 whose said polyanion is a polymer which has a sulfonic acid group.   The manufacturing method of the dispersion liquid containing the conductive polymer composition as described in any one of Claims 1-5 whose said polyanion is polystyrene sulfonic acid.   The manufacturing method of the dispersion liquid containing the conductive polymer composition as described in any one of Claims 1-7 whose weight average molecular weights of the said polyanion are 1000-1 million.   The monomer for obtaining the conjugated conductive polymer is selected from the group consisting of pyrrole which may have a substituent, aniline which may have a substituent, and thiophene which may have a substituent. The manufacturing method of the dispersion liquid containing the conductive polymer composition as described in any one of Claims 1-8 which is at least one chosen. The dispersion containing the conductive polymer composition according to any one of claims 1 to 8, wherein the monomer for obtaining the conjugated conductive polymer contains a compound represented by the formula (I). Liquid manufacturing method.

(In Formula (I), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms which may have a substituent, or an optionally substituted 1 to 1 carbon atom. 18 alkoxy group, or also represents an alkylthio group having 1 to 18 carbon atoms have a substituent, or, together with R ¹ and R ² are bonded and the carbon atom to which R ¹ and R ² are attached The alicyclic ring having 3 to 10 carbon atoms which may have a substituent, the aromatic ring having 6 to 10 carbon atoms which may have a substituent, and 2 carbon atoms which may have a substituent. 10 oxygen atom-containing heterocycles, optionally substituted sulfur atom-containing heterocycles having 2 to 10 carbon atoms, or optionally substituted sulfur atoms having 2 to 10 carbon atoms and oxygen atom-containing heterocycles A ring may be formed.) The dispersion containing the conductive polymer composition according to any one of claims 1 to 8, wherein the monomer for obtaining the conjugated conductive polymer contains a compound represented by the formula (II). Liquid manufacturing method.

(In formula (II), R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent, or R ³ and R ⁴ are bonded to each other. And together with each carbon atom to which OR ³ and OR ⁴ are bonded, an oxygen atom-containing heterocyclic ring having 3 to 6 carbon atoms which may have a substituent may be formed.)   The dispersion liquid containing the conductive polymer composition according to any one of claims 1 to 8, wherein the monomer for obtaining the conjugated conductive polymer contains 3,4-ethylenedioxythiophene. Production method. The liquid medium includes water;
Production of a dispersion containing a conductive polymer composition according to any one of claims 1 to 12, wherein the polymerization is performed using at least one oxidizing agent selected from the group consisting of peroxodisulfuric acid and salts thereof. Method. The manufacturing method of the dispersion liquid containing the conductive polymer composition as described in any one of Claims 1-13 which further includes adding an electrical conductivity improver. The manufacturing method of the dispersion liquid containing the conductive polymer composition of Claim 14 whose electrical conductivity improver is at least 1 chosen from the group which consists of ethylene glycol, propylene glycol, and glycerol.

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