US20060071201A1 - Novel polythiophene dispersions - Google Patents

Novel polythiophene dispersions Download PDF

Info

Publication number
US20060071201A1
US20060071201A1 US11/288,703 US28870305A US2006071201A1 US 20060071201 A1 US20060071201 A1 US 20060071201A1 US 28870305 A US28870305 A US 28870305A US 2006071201 A1 US2006071201 A1 US 2006071201A1
Authority
US
United States
Prior art keywords
dispersion
solution
polythiophene
water
integer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US11/288,703
Inventor
Friedrich Jonas
Stephan Kirchmeyer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Heraeus Deutschland GmbH and Co KG
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=7677127&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=US20060071201(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Individual filed Critical Individual
Priority to US11/288,703 priority Critical patent/US20060071201A1/en
Publication of US20060071201A1 publication Critical patent/US20060071201A1/en
Assigned to H.C. STARCK GMBH & CO. KG reassignment H.C. STARCK GMBH & CO. KG CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: H.C. STARCK GMBH
Assigned to H. C. STARCK GMBH & CO. KG reassignment H. C. STARCK GMBH & CO. KG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BAYER BETEILIGUNGSVERWALTUNG GOSLAR GMBH
Assigned to BAYER BETEILIGUNGSVERWALTUNG GOSLAR GMBH reassignment BAYER BETEILIGUNGSVERWALTUNG GOSLAR GMBH CORRECTIVE ASSIGNMENT TO CORRECT THE THE ASSIGNEE NEED TO BE CHANGED TO BAYER BETEILIGUNGSVERWALTUNG GOSLAR GMBH PREVIOUSLY RECORDED ON REEL 018766 FRAME 0488. ASSIGNOR(S) HEREBY CONFIRMS THE CHANGE OF NAME. Assignors: H.C. STARK GMBH
Assigned to H.C. STARCK GMBH reassignment H.C. STARCK GMBH MERGER (SEE DOCUMENT FOR DETAILS). Assignors: H.C. STARCK GMBH & CO. KG
Assigned to HERAEUS CLEVIOS GMBH reassignment HERAEUS CLEVIOS GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: H.C. STARCK GMBH
Assigned to HERAEUS PRECIOUS METALS GMBH & CO. KG reassignment HERAEUS PRECIOUS METALS GMBH & CO. KG MERGER (SEE DOCUMENT FOR DETAILS). Assignors: HERAEUS CLEVIOS GMBH
Priority to US13/665,029 priority patent/US20130059953A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention relates to the preparation and use of dispersions or solutions comprising optionally substituted polythiophenes in anhydrous or low-water-content organic solvents.
  • Conductive polymers based on substituted thiophenes are increasingly being used in industry, e.g., in the through-plating of circuit boards (EP-A 553671), the antistatic finishing of photographic films and plastic moldings (EP-A 440957) or for electrodes in solid-electrolyte capacitors (EP-A 340512).
  • dispersions of ⁇ -conjugated, polymeric compounds of this type are preferably employed.
  • Aqueous dispersions or solutions of polythiophene + An ⁇ ion complexes have proven to be particularly suitable for such purposes since they have both high stability and result in coatings having excellent conductivity.
  • An ⁇ ion complexes may consist of ⁇ -conjugated polythiophenes, whose positive charges are delocalized over the entire molecule, and anions of, for example, organic polyacids, which compensate for these positive charges.
  • EP-A 440957 states that polythiophene + An ⁇ ion complexes are formed as aqueous dispersions which consist of 3,4-polyalkylenedioxythiophenes and anions of polystyrenesulfonic acid. These dispersions can be employed directly for the above-mentioned purposes.
  • An improved variant for the preparation of aqueous dispersions or solutions of this type is the use of ion exchangers for removing the inorganic salt content, or part thereof, originating predominantly from the chemical oxidation (DE-A 19 627 071).
  • This desalination step prevents the formation of cloudiness and inhomogeneities (for example in the production of thin antistatic layers) and helps form highly transparent, clear layers.
  • EP-A 203 438 discloses polymers of substituted thiophenes which are dispersed in organic solvents.
  • the disadvantage of the process described therein is the preparation of the polythiophenes from substituted 2,5-dihalothiophenes with the aid of magnesium in the presence of a nickel catalyst. It is not practicable to carry out the reaction in this way on a relatively large scale, and the content of carcinogenic and allergenic nickel prevents the use of the solution without prior, complex work-up steps.
  • EP-A 253 994 likewise describes a method for the preparation of solutions or dispersions of polythiophene + An ⁇ ion complexes consisting of polythiophenes and anions of the conductive salts used therein, in organic solvents.
  • the polymerization of the monomeric thiophenes takes place through chemical oxidation in the organic solvent itself.
  • the desired product precipitates out of the reaction solution and therefore cannot be used, for example, for the production of transparent films.
  • dispersions comprising 3,4-polyalkylenedioxythiophenes can be prepared directly in organic solvents, but the inorganic salt content, predominantly originating from the chemical oxidation, remains in solution in such cases, which may lead to the above-mentioned undesired effects in the production of coatings.
  • the invention relates to a process for preparing a dispersion or a solution containing an optionally substituted polythiophene in an organic solvent, comprising a) adding a water-miscible organic solvent or a water-miscible solvent mixture to an aqueous dispersion or solution comprising optionally substituted polythiophenes, and b) removing at least some of the water from the mixture resulting from step a).
  • the invention relates to a process for preparing a dispersion or a solution containing polythiophene + An ⁇ ion complexes in organic solvents, comprising
  • step 1) preference is given to dispersions or solutions comprising polythiophene + An ⁇ ion complexes, where polythiophene + is a polymer which comprises recurring units of the formula (I) at least some of which are positively charged and in which
  • An ⁇ is an anion of an organic polyacid, or where polythiophene +
  • An ⁇ is a polymer which comprises recurring units of the formula (II) in which at least some of the thiophene rings carry a positive charge and in which
  • polythiophenes of the formulae (I) and (II) are in polycationic form.
  • the positive charges are delocalized over the entire molecule and are therefore not shown in the formulae.
  • M + in the formula (II) may be not only, for example, a metal ion, proton or optionally substituted ammonium ion, but is preferably also, for example, a cationic unit of the polythiophene. Preference is likewise given to alkali metal ions and ammonium ions as well as protons.
  • step 1) particular preference is given to dispersions or solutions of polythiophene + An ⁇ ion complexes where polythiophene + is a polymer which comprises recurring units of the formula (I), at least some of which are positively charged and in which
  • Y is —(CH 2 ) m —CR 1 R 2 (CH 2 ) n — or a 1,2-cyclohexylene radical, R 1 and R 2 , independently of one another, are hydrogen, hydroxymethyl, C 1 -C 8 -alkyl or phenyl,
  • An ⁇ is an anion of a polyacrylic acid, polysulfonic acid, polystyrenesulfonic acid, a mixture thereof or a copolymer of the parent monomers or copolymers with acid-free monomers,
  • polythiophene + An ⁇ is a polymer which comprises recurring units of the formula (II), in which at least some of the thiophene rings carry a positive charge and in which
  • Z is —(CH 2 ) m —CR 1 R 2 (CH 2 ) n —,
  • R 3 is hydrogen
  • R 4 is —(CH 2 ) s —O—(CH 2 ) p —SO 3 ⁇ M + ,
  • n and n are identical or different and are an integer from 0 to 3,
  • M + is a cation
  • s 0, 1 or 2
  • p 4 or5.
  • polythiophene + is a polymer which comprises recurring units of the formula (I), at least some of which are positively charged and in which
  • Y is a 1,2-ethylene radical
  • An ⁇ is an anion of a polystyrenesulfonic acid
  • polythiophene+An ⁇ is a polymer which comprises recurring units of the formula (II), in which at least some of the thiophene rings carry a positive charge and in which
  • Z is —(CH 2 ) m —CR 3 R 4 (CH 2 ) n —,
  • R 3 is hydrogen
  • R 4 is —(CH 2 ) s —O—(CH 2 ) p —SO 3 ⁇ M + ,
  • n 0 or 1
  • n 0 or 1
  • M + is a cation
  • s is 0 or 1
  • the amount of the water-miscible solvent or water-miscible organic solvent mixture added is, for example, from about 5 to about 1000% by weight, based on the aqueous ion complex dispersions or solutions that are employed.
  • Suitable solvents include but are not limited to: amidic solvents, such as formamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-methylcaprolactam and N-methylformamide.
  • Alcohols and ethers such as ethylene glycol, glycerol, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether or dioxane.
  • Water-soluble solvent mixtures consisting of solvents which are water-miscible per se and solvents which are not water-miscible per se are likewise included.
  • the solvents may be added individually or in the form of a mixture or in the form of a mixture together with sugar alcohols, such as sorbitol or mannitol.
  • amidic solvents and solvents which have a boiling point of above about 100° C. at atmospheric pressure and water-miscible solvents or water-miscible solvent mixtures which form an azeotrope with water.
  • Step 2) can be carried out, for example, by membrane process, such as ultrafiltration, or by distillation. Distillation is preferred here and can be carried out, for example, at a temperature of from about 0 to about 200° C., preferably from about 20 to about 100° C.
  • the pressure selected for the distillation can be atmospheric pressure or reduced pressure. Reduced pressure down to about 0.001 mbar is preferred here.
  • Step 3) can be carried out if desired.
  • the solvents employed for the dilution may be the solvents or solvent mixtures described in step 1).
  • the following solvents for example, are suitable: aliphatic alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, amyl alcohol, isoamyl alcohol and neopentyl alcohol, aliphatic ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone and methyl tert-butyl ketone, ethers, such as tetrahydrofuran and methyl tert-butyl ether, esters of aliphatic and aromatic carboxylic acids, such as ethyl acetate, butyl acetate, glycol monomethyl ether acetate and butyl phthalate, aliphatic and
  • the solvent can be employed alone or in the form of a mixture.
  • ion complex dispersions which have a water content of from 0 to about 20% by weight, preferably from 0 to about 5% by weight.
  • the content of the ion complexes in the dispersions can be from about 0.01 to about 20% by weight, preferably from about 0.2 to about 5% by weight.
  • the ion complex dispersions prepared in accordance with the invention can be used, for example, for the production of rechargeable batteries, light-emitting diodes, sensors, electrochromic windows, coatings of copier drums, cathode ray tubes, electrically conductive and antistatic coatings on plastic films, plastic moldings or on photographic materials.
  • the invention is a dispersion or a solution having an inorganic salt that is less than about 40% of the amount originally employed for the preparation of the polythiophene + An ⁇ by oxidative polymerization.
  • the polythiophene + can be prepared in accordance to the procedures described in EP-A 440957.
  • the invention is a process for providing a substrate with conductivity comprising applying a dispersion or a solution, made in accordance to the invention, to a substrate.
  • the invention is a process for the antistatic finishing of substrates comprising applying to a substrate a dispersion or a solution comprising a polythiophene + An ⁇ ion complex made in accordance to the invention.
  • the invention is a process for the antistatic finishing of photographic material comprising applying to a photographic material a dispersion or a solution made in accordance to the invention.
  • the dispersions or solutions according to the invention can furthermore be used for data storage, optical signal conversion, suppression of electromagnetic interference (EMI) and conversion of solar energy.
  • EMI electromagnetic interference
  • Coatings can be produced, for example, by known process, such as, spraying, gravure printing, offset printing, curtain coating, spin coating, roller coating, brushing and dipping.
  • binders and/or crosslinking agents such as, for example, polyurethanes or dispersions thereof, polyacrylates, polyolefin dispersions and epoxysilanes, such as 3-glycidoxypropyltrialkoxysilanes, to the dispersions prepared in accordance with the invention.
  • silane hydrolysates such as those based on tetraethoxysilane
  • the ion exchangers were removed by filtration. A ready-to-use solution having a solids content of about 1.2% by weight was obtained.
  • Example 2 100 g of the solution prepared in accordance with Example 1 were introduced into a 500 ml three-necked flask fitted with stirrer and internal thermometer. 200 g of dimethylacetamide were added over the course of 15 minutes with stirring, and 122 g of a mixture of water and dimethylacetamide were subsequently distilled off at 40° C. and a pressure of 18 mbar.
  • the solution had a water content of 3.9% (determined by the Karl Fischer method) and a solids content of 0.8% (determined by drying at 140° C. for 12 hours).
  • Example 1 70 g of the solution prepared in accordance with Example 1 were introduced into a 500 ml three-necked flask fitted with stirrer and internal thermometer. 130 g of N-methylpyrrolidone were added over the course of 10 minutes with stirring, and 67 g of a mixture of water and N-methylpyrrolidone were subsequently distilled off at 20° C. and a pressure of 8 mbar.

Abstract

A process for the preparation of dispersions or solutions comprising polythiophene+An− ion complexes in anhydrous or low-water-content organic solvents, characterized in that at least one water-miscible organic solvent or a water-miscible solvent mixture is added to an aqueous dispersion or solution comprising optionally substituted polythiophenes, all or some of the water is removed, and the resultant dispersion or solution is, if desired, diluted with organic solvents.

Description

    BACKGROUND
  • The invention relates to the preparation and use of dispersions or solutions comprising optionally substituted polythiophenes in anhydrous or low-water-content organic solvents.
  • Conductive polymers based on substituted thiophenes are increasingly being used in industry, e.g., in the through-plating of circuit boards (EP-A 553671), the antistatic finishing of photographic films and plastic moldings (EP-A 440957) or for electrodes in solid-electrolyte capacitors (EP-A 340512). For uses of this type, dispersions of π-conjugated, polymeric compounds of this type are preferably employed.
  • Aqueous dispersions or solutions of polythiophene+An− ion complexes have proven to be particularly suitable for such purposes since they have both high stability and result in coatings having excellent conductivity.
  • These polythiophene+An− ion complexes may consist of π-conjugated polythiophenes, whose positive charges are delocalized over the entire molecule, and anions of, for example, organic polyacids, which compensate for these positive charges.
  • In the oxidative polymerization of substituted 3,4-alkylenedioxythiophenes using potassium peroxodisulfate as an oxidant in the presence of polystyrenesulfonic acid, EP-A 440957 states that polythiophene+An− ion complexes are formed as aqueous dispersions which consist of 3,4-polyalkylenedioxythiophenes and anions of polystyrenesulfonic acid. These dispersions can be employed directly for the above-mentioned purposes.
  • The oxidative polymerization of substituted 3,4-alkylenedioxythiophenes which are substituted in the alkylene unit by radicals carrying acid groups likewise results in the formation of dispersions or solutions of polythiophene+An− ion complexes, but in which the positive charges of the conjugated π-system are compensated by the acid anions likewise already present in the molecule.
  • An improved variant for the preparation of aqueous dispersions or solutions of this type is the use of ion exchangers for removing the inorganic salt content, or part thereof, originating predominantly from the chemical oxidation (DE-A 19 627 071). This desalination step prevents the formation of cloudiness and inhomogeneities (for example in the production of thin antistatic layers) and helps form highly transparent, clear layers.
  • However, it has been found that, in spite of the good properties of aqueous dispersions or solutions, the different wetting ability compared with water and the differentiated drying behavior of organic solvents is advantageous for some applications, e.g., for the application of conductive layers to the support material.
  • Simple drying or removal of the water from the above-mentioned dispersions or solutions by distillation gives powders which cannot be redispersed in a simple manner by addition of organic solvents.
  • EP-A 203 438 discloses polymers of substituted thiophenes which are dispersed in organic solvents. However, the disadvantage of the process described therein is the preparation of the polythiophenes from substituted 2,5-dihalothiophenes with the aid of magnesium in the presence of a nickel catalyst. It is not practicable to carry out the reaction in this way on a relatively large scale, and the content of carcinogenic and allergenic nickel prevents the use of the solution without prior, complex work-up steps.
  • EP-A 253 994 likewise describes a method for the preparation of solutions or dispersions of polythiophene+An− ion complexes consisting of polythiophenes and anions of the conductive salts used therein, in organic solvents. In these cases, the polymerization of the monomeric thiophenes takes place through chemical oxidation in the organic solvent itself. In this process, however, the desired product precipitates out of the reaction solution and therefore cannot be used, for example, for the production of transparent films.
  • According to EP-A 440 957, dispersions comprising 3,4-polyalkylenedioxythiophenes can be prepared directly in organic solvents, but the inorganic salt content, predominantly originating from the chemical oxidation, remains in solution in such cases, which may lead to the above-mentioned undesired effects in the production of coatings.
  • There was therefore a need to find a method of combining the excellent conductivity and coating properties of the fully or partially desalinated, aqueous dispersions or solutions of the polythiophene+An− ion complexes with the widely variable wetting and drying properties of organic solvents.
    • SUMMARY
  • The invention relates to a process for preparing a dispersion or a solution containing an optionally substituted polythiophene in an organic solvent, comprising a) adding a water-miscible organic solvent or a water-miscible solvent mixture to an aqueous dispersion or solution comprising optionally substituted polythiophenes, and b) removing at least some of the water from the mixture resulting from step a).
  • In one embodiment, the invention relates to a process for preparing a dispersion or a solution containing polythiophene+ An− ion complexes in organic solvents, comprising
      • a) adding a water-miscible organic solvent or a water-miscible organic solvent mixture to an aqueous dispersion or solution of polythiophene+An− ion complexes, wherein polythiophene+ is a polymer which comprises recurring units of the formula (I)
        Figure US20060071201A1-20060406-C00001
      • at least some of which are positively charged and wherein
      • Y is —(CH2)m—CR1R2(CH2)n— or an optionally substituted 1,2-C3-C8-cycloalkylene radical, and
      • R1 and R2, independently of one another, are hydrogen, hydroxymethyl, an optionally substituted C1-C20-alkyl radical or an optionally substituted C6-C14-aryl radical, and
      • m and n are identical or different and are an integer from 0 to 3,
      • and wherein
      • An− is an anion of an organic polyacid,
      • or wherein
      • polythiophene+An− is a polymer which comprises recurring units of the formula (II)
        Figure US20060071201A1-20060406-C00002
        in which at least some of the thiophene rings carry a positive charge and wherein
      • Z is —(CH2)m—CR3R4(CH2)n—,
      • R3 is hydrogen or —(CH2)s—O—(CH2)p—SO3 −M+,
      • R4 is —(CH2)s—O—(CH2)p—SO3 −M+,
      • m and n are an integer from 0 to 3,
      • M+ is a cation,
      • s is an integer from 0 to 10, and
      • p is an integer from 1 to 18,
        and b) removing water from the mixture resulting in step a).
  • These and other features, aspects, and advantages of the present invention will become better understood with reference to the following description and appended claims.
    • DESCRIPTION
  • A process has now been found for the preparation of dispersions or solutions comprising optionally substituted polythiophenes in organic solvents, which is characterized in that
      • 1) a water-miscible organic solvent or a water-miscible solvent mixture is added to an aqueous dispersion or solution comprising optionally substituted polythiophenes, and
      • 2) at least some of the water is removed from the resultant mixtures, and
      • 3) the mixtures are, if desired, diluted with organic solvents.
  • For step 1), preference is given to dispersions or solutions comprising polythiophene+An− ion complexes, where polythiophene+ is a polymer which comprises recurring units of the formula (I)
    Figure US20060071201A1-20060406-C00003
    at least some of which are positively charged and in which
      • Y is —(CH2)m—CR1R2(CH2)n— or an optionally substituted 1,2-C3-C8— cycloalkylene radical, and
      • R1 and R2, independently of one another, are hydrogen, hydroxymethyl, an optionally substituted C1-C20-alkyl radical or an optionally substituted C6-C14-aryl radical,
      • and
      • m and n are identical or different and are an integer from 0 to 3, and where
  • An− is an anion of an organic polyacid, or where polythiophene+An− is a polymer which comprises recurring units of the formula (II)
    Figure US20060071201A1-20060406-C00004
    in which at least some of the thiophene rings carry a positive charge and in which
    • Z is —(CH2)m—CR3R4(CH2)n—,
    • R3 is hydrogen or —(CH2)s—O—(CH2)p—SO3 −M+,
    • R4 is —(CH2)s—O—(CH2)p—SO3 −M+,
    • M+ is a cation,
    • s is an integer from 0 to 10, and
    • p is an integer from 1 to 18.
  • The polythiophenes of the formulae (I) and (II) are in polycationic form. The positive charges are delocalized over the entire molecule and are therefore not shown in the formulae.
  • M+ in the formula (II) may be not only, for example, a metal ion, proton or optionally substituted ammonium ion, but is preferably also, for example, a cationic unit of the polythiophene. Preference is likewise given to alkali metal ions and ammonium ions as well as protons.
  • For step 1), particular preference is given to dispersions or solutions of polythiophene+An− ion complexes where polythiophene+ is a polymer which comprises recurring units of the formula (I), at least some of which are positively charged and in which
  • Y is —(CH2)m—CR1R2(CH2)n— or a 1,2-cyclohexylene radical, R1 and R2, independently of one another, are hydrogen, hydroxymethyl, C1-C8-alkyl or phenyl,
      • m and n are identical or different and are 0 or 1, and where
  • An− is an anion of a polyacrylic acid, polysulfonic acid, polystyrenesulfonic acid, a mixture thereof or a copolymer of the parent monomers or copolymers with acid-free monomers,
  • or where polythiophene+An− is a polymer which comprises recurring units of the formula (II), in which at least some of the thiophene rings carry a positive charge and in which
  • Z is —(CH2)m—CR1R2(CH2)n—,
  • R3 is hydrogen,
  • R4 is —(CH2)s—O—(CH2)p—SO3 −M+,
  • m and n are identical or different and are an integer from 0 to 3,
  • M+ is a cation,
  • s is 0, 1 or 2,
  • p is 4 or5.
  • Very particular preference is given to dispersions or solutions of polythiophene+An− ion complexes where polythiophene+ is a polymer which comprises recurring units of the formula (I), at least some of which are positively charged and in which
  • Y is a 1,2-ethylene radical, and where
  • An− is an anion of a polystyrenesulfonic acid,
  • or where polythiophene+An− is a polymer which comprises recurring units of the formula (II), in which at least some of the thiophene rings carry a positive charge and in which
  • Z is —(CH2)m—CR3R4 (CH2)n—,
  • R3 is hydrogen,
  • R4 is —(CH2)s—O—(CH2)p—SO3 −M+,
  • m is 0 or 1,
  • n is 0 or 1,
  • M+ is a cation,
  • s is 0 or 1, and
  • p is 4.
  • In this first step, the amount of the water-miscible solvent or water-miscible organic solvent mixture added is, for example, from about 5 to about 1000% by weight, based on the aqueous ion complex dispersions or solutions that are employed. Suitable solvents here include but are not limited to: amidic solvents, such as formamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-methylcaprolactam and N-methylformamide. Alcohols and ethers, such as ethylene glycol, glycerol, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether or dioxane. Water-soluble solvent mixtures consisting of solvents which are water-miscible per se and solvents which are not water-miscible per se are likewise included.
  • The solvents may be added individually or in the form of a mixture or in the form of a mixture together with sugar alcohols, such as sorbitol or mannitol.
  • Preference is given to amidic solvents and solvents which have a boiling point of above about 100° C. at atmospheric pressure and water-miscible solvents or water-miscible solvent mixtures which form an azeotrope with water.
  • Step 2) can be carried out, for example, by membrane process, such as ultrafiltration, or by distillation. Distillation is preferred here and can be carried out, for example, at a temperature of from about 0 to about 200° C., preferably from about 20 to about 100° C. The pressure selected for the distillation can be atmospheric pressure or reduced pressure. Reduced pressure down to about 0.001 mbar is preferred here.
  • Step 3) can be carried out if desired. The solvents employed for the dilution may be the solvents or solvent mixtures described in step 1). In addition, the following solvents, for example, are suitable: aliphatic alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, amyl alcohol, isoamyl alcohol and neopentyl alcohol, aliphatic ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone and methyl tert-butyl ketone, ethers, such as tetrahydrofuran and methyl tert-butyl ether, esters of aliphatic and aromatic carboxylic acids, such as ethyl acetate, butyl acetate, glycol monomethyl ether acetate and butyl phthalate, aliphatic and aromatic hydrocarbons, such as pentane, hexane, cyclohexane, octane, isooctane, decane, toluene, o-xylene, m-xylene and p-xylene.
  • For the dilution, the solvent can be employed alone or in the form of a mixture.
  • In accordance with the invention, ion complex dispersions are obtained which have a water content of from 0 to about 20% by weight, preferably from 0 to about 5% by weight.
  • The content of the ion complexes in the dispersions can be from about 0.01 to about 20% by weight, preferably from about 0.2 to about 5% by weight.
  • The ion complex dispersions prepared in accordance with the invention can be used, for example, for the production of rechargeable batteries, light-emitting diodes, sensors, electrochromic windows, coatings of copier drums, cathode ray tubes, electrically conductive and antistatic coatings on plastic films, plastic moldings or on photographic materials.
  • In one embodiment, the invention is a dispersion or a solution having an inorganic salt that is less than about 40% of the amount originally employed for the preparation of the polythiophene+An− by oxidative polymerization. In one embodiment the polythiophene+ can be prepared in accordance to the procedures described in EP-A 440957.
  • In one embodiment, the invention is a process for providing a substrate with conductivity comprising applying a dispersion or a solution, made in accordance to the invention, to a substrate. In another embodiment, the invention is a process for the antistatic finishing of substrates comprising applying to a substrate a dispersion or a solution comprising a polythiophene+An− ion complex made in accordance to the invention. In another embodiment, the invention is a process for the antistatic finishing of photographic material comprising applying to a photographic material a dispersion or a solution made in accordance to the invention.
  • The dispersions or solutions according to the invention can furthermore be used for data storage, optical signal conversion, suppression of electromagnetic interference (EMI) and conversion of solar energy.
  • In addition, they can be used, for example, for the production of solid electrolytes in solid-state capacitors, of electroluminescent displays and of transparent electrodes, e.g., in touch screens.
  • Coatings can be produced, for example, by known process, such as, spraying, gravure printing, offset printing, curtain coating, spin coating, roller coating, brushing and dipping.
  • If desired, it is furthermore possible to add binders and/or crosslinking agents, such as, for example, polyurethanes or dispersions thereof, polyacrylates, polyolefin dispersions and epoxysilanes, such as 3-glycidoxypropyltrialkoxysilanes, to the dispersions prepared in accordance with the invention.
  • In order to increase the scratch resistance of coatings, it is furthermore possible to add silane hydrolysates, such as those based on tetraethoxysilane, to the dispersions according to the invention (see, inter alia, EP-A 825 219).
  • The invention is further described in the following illustrative examples in which all parts and percentages are by weight unless otherwise indicated.
    • EXAMPLES Example 1
  • Preparation of an Aqueous Suspension of a Polythiophene+An− Ion Complex
  • 20 g of free polystyrenesulfonic acid (Mn about 40,000), 21.4 g of potassium peroxodisulfate and 50 mg of iron(III) sulfate were introduced with stirring into 2000 ml of water. 8.0 g of 3,4-ethylenedioxythiophene were added with stirring. The solution was stirred at room temperature for 24 hours. 100 g of anion exchanger (Lewatit MP 62, commercial product from Bayer AG) and 100 g of cation exchanger (Lewatit S 100, commercial product from Bayer AG), both water-moist, were subsequently added, and the mixture was stirred for 8 hours.
  • The ion exchangers were removed by filtration. A ready-to-use solution having a solids content of about 1.2% by weight was obtained.
    • Example 2
  • 100 g of the solution prepared in accordance with Example 1 were introduced into a 500 ml three-necked flask fitted with stirrer and internal thermometer. 200 g of dimethylacetamide were added over the course of 15 minutes with stirring, and 122 g of a mixture of water and dimethylacetamide were subsequently distilled off at 40° C. and a pressure of 18 mbar.
  • The solution had a water content of 3.9% (determined by the Karl Fischer method) and a solids content of 0.8% (determined by drying at 140° C. for 12 hours).
  • In order to produce coatings, in each case 10 g of the solution were diluted with the amounts of ethanol indicated in the table. The solutions were subsequently applied to polyester films in a wet-film thickness of 24 μm using a spiral doctor blade and dried at 60° C. for 15 minutes, and the surface resistance values were determined. The values measured are shown in Table 1. In all cases, conductive, transparent, clear coatings were obtained.
    TABLE 1
    Experiment No. Ethanol [g] Surface resistance [Ω/]
    1 5 4200
    2 10  68*103
    3 50  895*103
    4 100    3.6*107
    • Example 3
  • 70 g of the solution prepared in accordance with Example 1 were introduced into a 500 ml three-necked flask fitted with stirrer and internal thermometer. 130 g of N-methylpyrrolidone were added over the course of 10 minutes with stirring, and 67 g of a mixture of water and N-methylpyrrolidone were subsequently distilled off at 20° C. and a pressure of 8 mbar.
  • In order to produce coatings, the solution was applied to polyester films in a wet-film thickness of 24 μm using a spiral doctor blade and dried at 40 or 100° C. for 12 hours, and the surface resistance values were determined. The values measured are shown in Table 2. In both cases, conductive, transparent, clear coatings were obtained.
    TABLE 2
    Experiment No. Drying temperature [° C.] Surface resistance [Ω/]
    1 40 1.8*103
    2 100 7.8*103
  • Although the present invention has been described in detail with reference to certain preferred versions thereof, other variations are possible. Therefore, the spirit and scope of the appended claims should not be limited to the description of the versions contained therein.

Claims (12)

1. A process for preparing a dispersion or a solution containing an optionally substituted polythiophene in an organic solvent, comprising:
a) adding a water-miscible organic solvent or a water-miscible solvent mixture to an aqueous dispersion or solution comprising optionally substituted polythiophenes; and
b) removing at least some of the water from the mixture resulting from step a), and thereby forming the dispersion of the solution.
2. The process according to claim 1, wherein the process further comprises diluting the dispersion or the solution resulting from the process with an organic solvent or a mixture of organic solvents subsequent to step b).
3-10. (canceled)
11. A dispersion or a solution comprising:
(a) a polythiophene+An− ion complex, wherein the polythiophene+ is a polymer comprising recurring units represented by formula (I).
Figure US20060071201A1-20060406-C00005
at least some of which are positively charged and wherein,
Y is —(CH2)m—CR1R2(CH2)n— or an optionally substituted 1,2-C3-C8-cycloalkylene radical, and
R1 and R2, independently of one another, are hydrogen, hydroxymethyl, an optionally substituted C1-C20-alkyl radical or an optionally substituted C6-C14-aryl, and
m and n are identical or different and are an integer from 0 to 3, and further wherein,
An− is an anion of an organic polyacid; and
(b) a solvent selected from the group consisting of low-water-content solvent and anhydrous organic solvent.
12. The dispersion or the solution according to claim 11, wherein the dispersion or the solution has an inorganic salt content that is less than about 40% of the amount originally employed for the preparation of the An−polythiophene+.
13. The dispersion or the solution according to claim 11, wherein the dispersion or the solution has a water content ranging from 0 to about 5% by weight.
14. A dispersion or a solution comprising:
(a) a polythiophene+An− ion complex, wherein the polythiophene+An− is a polymer comprising recurring units represented by formula (II)
Figure US20060071201A1-20060406-C00006
wherein at least some of the thiophene rings carry a positive charge, and wherein,
Z is —(CH2)m—CR3R4(CH2)n—,
R3 is hydrogen or —(CH2)s—O—(CH2)p—SO3 −M+,
R4 is —(CH2)s—O—(CH2)p—SO3 −M+,
m and n are an integer from 0 to 3,
M+ is a cation,
s is an integer from 0 to 10, and
p is an integer from 1 to 18; and
(b) a solvent selected from the group consisting of low-water-content solvent and anhydrous organic solvent.
15. The dispersion or the solution according to claim 14, wherein the dispersion or the solution has an inorganic salt content that is less than about 40% of the amount originally employed for the preparation of the An−polythiophene+.
16. The dispersion of claim 14, wherein the solution or the dispersion has a water content is from 0 to about 5% by weight.
17. A process for providing a substrate with conductivity comprising applying a dispersion or a solution to a substrate,
wherein the dispersion or the solution comprises a polythiophene+An− ion complex in organic solvents, and the solution or the dispersion being prepared by a process comprising,
a) adding a water-miscible organic solvent or a water-miscible organic solvent mixture to an aqueous dispersion or a solution of a polythiophene+An− ion complex,
wherein polythiophene+ is a polymer comprising recurring units selected from the group consisting of recurring units represented by the following formula (I) and formula (II)
Figure US20060071201A1-20060406-C00007
at least some of which are positively charged and for formula (I),
Y is —(CH2)m—CR1R2(CH2)n— or an optionally substituted 1,2-C3-C8-cycloalkylene radical, and
R1 and R2, independently of one another, are hydrogen, hydroxymethyl, an optionally substituted C1-C20-alkyl radical or an optionally substituted C6-C14-aryl radical, and
m and n are identical or different and are an integer from 0 to 3, and further wherein, and
An− is an anion of an organic polyacid, and for formula (II)
Figure US20060071201A1-20060406-C00008
at least some of the thiophene rings carry a positive charge, and
Z is —(CH2)m—CR3R4(CH2)n—,
R3 is hydrogen or —(CH2)s—O—(CH2)p—SO3 −M+,
R4 is —(CH2)s—O—(CH2)p—SO3 −M+,
m and n are an integer from 0 to 3,
M+ is a cation,
s is an integer from 0 to 10, and
p is an integer from 1 to 18, and
b) removing water from the mixture resulting in step a).
18. A process for antistatic finishing of substrates comprising applying a dispersion or a solution comprising a polythiophene+An− ion complex to a substrate,
wherein the dispersion or the solution contains a polythiophene+An− ion complex in an organic solvent, and the solution or the dispersion being prepared by a process comprising,
a) adding a water-miscible organic solvent or a water-miscible organic solvent mixture to an aqueous dispersion or a solution of a polythiophene+An− ion complex,
wherein polythiophene+ is a polymer comprising recurring units selected from the group consisting of recurring units represented by the following formula (I) and formula (II),
Figure US20060071201A1-20060406-C00009
at least some of which are positively charged and in which for formula (I),
Y is —(CH2)m—CR1R2(CH2)n— or an optionally substituted 1,2-C3-C8-cycloalkylene radical, and
R1 and R2, independently of one another, are hydrogen,
hydroxymethyl, an optionally substituted C1-C20-alkyl radical or an optionally substituted C6-C14-aryl radical, and
m and n are identical or different and are an integer from 0 to 3, and further wherein,
An− is an anion of an organic polyacid, and for formula (II),
Figure US20060071201A1-20060406-C00010
at least some of the thiophene rings carry a positive charges and
Z is —(CH2)m—CR3R4(CH2)n—,
R3 is hydrogen or —(CH2)s—O—(CH2)p—SO3 −M+,
R4 is —(CH2)s—O—(CH2)p—SO3 −M+,
m and n are an integer from 0 to 3,
M+ is a cation,
s is an integer from 0 to 10, and
p is an integer from 1 to 18, and
b) removing water from the mixture resulting in step a).
19. A process for the antistatic finishing of photographic material comprising applying a dispersion or a solution to a photographic material,
wherein the dispersion or the solution contains a polythiophene+An− ion complex in an organic solvent, and the solution or the dispersion prepared by a process comprising,
a) adding a water-miscible organic solvent or a water-miscible organic solvent mixture to an aqueous dispersion or a solution of polythiophene+An− ion complex,
wherein the polythiophene+ is a polymer comprising recurring units selected from the group consisting of recurring units represented by the following formula (I) and formula (II),
Figure US20060071201A1-20060406-C00011
at least some of which are positively charged and in which for formula (I).
Y is —(CH2)m—CR1R2(CH2)n— or an optionally substituted 1,2-C3-C8-cycloalkylene radical, and
R1 and R2, independently of one another, are hydrogen, hydroxymethyl, an optionally substituted C1-C20-alkyl radical or an optionally substituted C6-C14-aryl radical, and
m and n are identical or different and are an integer from 0 to 3, and further wherein,
An− is an anion of an organic polyacid, and for formula (II)
Figure US20060071201A1-20060406-C00012
at least some of the thiophene rings carry a positive charge, and
Z is —(CH2)m—CR3R4(CH2)n—,
R3 is hydrogen or —(CH2)s—O—(CH2)p—SO3 −M+,
R4 is —(CH2)s—O—(CH2)p—SO3 −M+,
m and n are an integer from 0 to 3,
M+ is a cation,
s is an integer from 0 to 10, and
p is an integer from 1 to 18, and
b) removing water from the mixture resulting in step a).
US11/288,703 2001-03-12 2005-11-29 Novel polythiophene dispersions Abandoned US20060071201A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US11/288,703 US20060071201A1 (en) 2001-03-12 2005-11-29 Novel polythiophene dispersions
US13/665,029 US20130059953A1 (en) 2001-03-12 2012-10-31 Novel polythiophene dispersions

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE10111790A DE10111790A1 (en) 2001-03-12 2001-03-12 New polythiophene dispersions
DE10111790.6 2001-03-12
US10/093,219 US7008562B2 (en) 2001-03-12 2002-03-07 Method of forming polythiophene dispersions
US11/288,703 US20060071201A1 (en) 2001-03-12 2005-11-29 Novel polythiophene dispersions

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US10/093,219 Division US7008562B2 (en) 2001-03-12 2002-03-07 Method of forming polythiophene dispersions

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/665,029 Division US20130059953A1 (en) 2001-03-12 2012-10-31 Novel polythiophene dispersions

Publications (1)

Publication Number Publication Date
US20060071201A1 true US20060071201A1 (en) 2006-04-06

Family

ID=7677127

Family Applications (3)

Application Number Title Priority Date Filing Date
US10/093,219 Expired - Fee Related US7008562B2 (en) 2001-03-12 2002-03-07 Method of forming polythiophene dispersions
US11/288,703 Abandoned US20060071201A1 (en) 2001-03-12 2005-11-29 Novel polythiophene dispersions
US13/665,029 Abandoned US20130059953A1 (en) 2001-03-12 2012-10-31 Novel polythiophene dispersions

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US10/093,219 Expired - Fee Related US7008562B2 (en) 2001-03-12 2002-03-07 Method of forming polythiophene dispersions

Family Applications After (1)

Application Number Title Priority Date Filing Date
US13/665,029 Abandoned US20130059953A1 (en) 2001-03-12 2012-10-31 Novel polythiophene dispersions

Country Status (12)

Country Link
US (3) US7008562B2 (en)
EP (1) EP1373356B1 (en)
JP (2) JP4225785B2 (en)
KR (1) KR100856954B1 (en)
CN (1) CN1219807C (en)
AT (1) ATE294828T1 (en)
DE (2) DE10111790A1 (en)
ES (1) ES2240731T3 (en)
HK (1) HK1063641A1 (en)
RU (1) RU2299893C2 (en)
TW (1) TWI247016B (en)
WO (1) WO2002072660A1 (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020136923A1 (en) * 2001-01-26 2002-09-26 Friedrich Jonas Electroluminescent arrangements
US20070147857A1 (en) * 2005-12-23 2007-06-28 Samsung Electronics Co., Ltd. Apparatus for detecting developer level in developing unit
US20100038596A1 (en) * 2006-08-10 2010-02-18 Nissan Chemical Industries , Ltd. Process for producing dispersion liquid of intrinsic electroconductive polymer in organic solvent
WO2010127253A1 (en) * 2009-05-01 2010-11-04 Plextronics, Inc. Replacing aqueous with non-aqueous solvent
US20110024692A1 (en) * 2007-09-04 2011-02-03 H.C. Starck Clevios Gmbh Process for producing conducting polymers
US20110049433A1 (en) * 2008-01-22 2011-03-03 H.C. Starck Clevios Gmbh Method for the production of conductive polymers
US20110135939A1 (en) * 2008-07-29 2011-06-09 Tadayuki Isaji Conductive coating composition
US20110168946A1 (en) * 2008-05-09 2011-07-14 H.C. Starck Clevios Gmbh Novel polythiophene polyanion complexes in homopolar organic solvents
US20130059953A1 (en) * 2001-03-12 2013-03-07 Heraeus Clevios Gmbh Novel polythiophene dispersions

Families Citing this family (52)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6692662B2 (en) * 2001-02-16 2004-02-17 Elecon, Inc. Compositions produced by solvent exchange methods and uses thereof
WO2003048229A1 (en) 2001-12-04 2003-06-12 Agfa-Gevaert Composition containing a polymer or copolymer of a 3,4-dialkoxythiophene and non-aqueous solvent
US7122130B2 (en) 2001-12-04 2006-10-17 Agfa Gevaert Composition containing a polymer or copolymer of a 3,4-dialkoxythiophene and non-aqueous solvent
EP1514318A2 (en) * 2002-06-14 2005-03-16 Konarka Technologies, Inc. Material for a functional layer of an organic electronic component, method for the production thereof, and use thereof
US20050234280A1 (en) * 2002-06-14 2005-10-20 Georg Wittmann Material for a thin and low-conductive funtional layer for an oled and production method therefor
EP1513902A1 (en) * 2002-06-14 2005-03-16 Siemens Aktiengesellschaft Material for the production of a conductive organic functional layer and use thereof
US7317048B2 (en) 2003-01-06 2008-01-08 E.I. Du Pont De Nemours And Company Variable resistance poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) for use in electronic devices
US7179534B2 (en) * 2003-01-31 2007-02-20 Princeton University Conductive-polymer electronic switch
US6656763B1 (en) * 2003-03-10 2003-12-02 Advanced Micro Devices, Inc. Spin on polymers for organic memory devices
DE102004006583A1 (en) * 2004-02-10 2005-09-01 H.C. Starck Gmbh Polythiophene formulations for improving organic light-emitting diodes
WO2006087969A1 (en) * 2005-02-16 2006-08-24 Nissan Chemical Industries, Ltd. Method for producing intrinsically conductive polymer dispersion in organic solvent
JP2007297637A (en) * 2005-02-16 2007-11-15 Nissan Chem Ind Ltd Dispersion of intrinsically electroconductive polymer in organic solvent
EP1950246A4 (en) * 2005-11-16 2009-11-25 Nagase Chemtex Corp Conductive resin composition, conductive film comprising the same, and resistive-film switch employing the same
US20080097009A1 (en) * 2006-02-10 2008-04-24 Tadayuki Isaji Method for production of organic solvent dispersion of intrinsically conductive polymer
JP4945157B2 (en) * 2006-03-27 2012-06-06 株式会社東芝 Reproducible foam molded article having excellent restoring force, method for producing the same, and method for regenerating the same
JP5429652B2 (en) * 2006-07-18 2014-02-26 荒川化学工業株式会社 Process for producing conductive polymer / dopant complex organic solvent dispersion
WO2008022908A1 (en) 2006-08-21 2008-02-28 Agfa-Gevaert Uv-photopolymerizable composition for producing organic conductive layers, patterns or prints
WO2008132955A1 (en) * 2007-04-16 2008-11-06 Shin-Etsu Polymer Co., Ltd. Method for producing conductive polymer solution
DE102007041039A1 (en) * 2007-08-29 2009-03-05 H.C. Starck Gmbh Production of conductive coatings by ink jet printing
DE102008059389A1 (en) 2008-11-27 2010-06-02 Ormecon Gmbh Preparing coating having conductive polymer derived from thiophene, useful to prepare article e.g. transparent substrates, comprises applying aqueous/organic dispersion, drying formed layer and contacting with polar solvent
DE102008003251A1 (en) 2008-01-04 2009-07-09 Ormecon Gmbh Preparing a coating with increased conductivity by adding a dispersion or solution containing conductive polymer with thiophene on a substrate, drying the formed layer, and contacting a polar solvent with the forming or formed layer
WO2009086902A1 (en) * 2008-01-04 2009-07-16 Ormecon Gmbh Process for the preparation of coatings exhibiting increased conductivity based on polythiophene and its derivatives
EP2105458A1 (en) 2008-03-27 2009-09-30 Agfa-Gevaert Dispersable polythiophene composition.
JP4993380B2 (en) * 2008-04-14 2012-08-08 ソニーケミカル＆インフォメーションデバイス株式会社 Electromagnetic wave suppressor and method for producing the same
JP5470831B2 (en) * 2008-12-17 2014-04-16 東洋インキＳｃホールディングス株式会社 Polythiophene composition, conductive film using the same, and laminate
KR20110122677A (en) 2009-02-04 2011-11-10 닛산 가가쿠 고교 가부시키 가이샤 Conductive coating composition
JP5455211B2 (en) * 2009-11-05 2014-03-26 テイカ株式会社 Conductive auxiliary agent composition for lithium ion battery, method for producing the same, electrode mixture composition for lithium ion battery, method for producing the same, and lithium ion battery
JP5371710B2 (en) 2009-11-20 2013-12-18 三洋電機株式会社 Manufacturing method of solid electrolytic capacitor
US9378859B2 (en) 2010-08-20 2016-06-28 Rhodia Operations Polymer compositions, polymer films, polymer gels, polymer foams, and electronic devices containing such films, gels and foams
JP5759008B2 (en) 2010-11-03 2015-08-05 ヘレウス プレシャス メタルズ ゲーエムベーハー ウント コンパニー カーゲー PEDOT dispersion in organic solvent
DE102013008460A1 (en) 2013-05-21 2014-11-27 Heraeus Precious Metals Gmbh & Co. Kg Nonpolar solvents as adhesion promoter additive in PEDOT / PSS dispersions
JP6379523B2 (en) * 2013-04-04 2018-08-29 東ソー株式会社 Conductive polymer aqueous solution and conductive polymer film
JP6311355B2 (en) * 2014-01-27 2018-04-18 東ソー株式会社 Conductive polymer aqueous solution and conductive polymer film
JP6427887B2 (en) * 2014-02-05 2018-11-28 東ソー株式会社 Conductive polymer aqueous solution and conductive polymer film
US9428603B2 (en) 2014-03-18 2016-08-30 Council Of Scientific & Industrial Research Polymeric dispersion of thiophene copolymers and a process for preparation thereof
EP2940079B1 (en) 2014-04-30 2017-08-23 Agfa-Gevaert Non-aqueous dispersions of a conductive polymer
JP7167570B2 (en) * 2017-11-09 2022-11-09 東ソー株式会社 Conductive polymer aqueous solution, conductive polymer film, and coated article
EP3587506B1 (en) * 2018-06-28 2023-04-05 Heraeus Deutschland GmbH & Co. KG Liquid compositions comprising particles of a conductive polymer and an organic solvent forming an azeotrope with water
US11114250B2 (en) 2018-08-10 2021-09-07 Avx Corporation Solid electrolytic capacitor formed from conductive polymer particles
CN112805798A (en) 2018-08-10 2021-05-14 阿维科斯公司 Solid electrolytic capacitor containing polyaniline
EP3834217A4 (en) 2018-08-10 2022-05-11 KYOCERA AVX Components Corporation Solid electrolytic capacitor containing an intrinsically conductive polymer
US11955294B2 (en) 2018-12-11 2024-04-09 KYOCERA AVX Components Corporation Solid electrolytic capacitor containing an intrinsically conductive polymer
US11315740B2 (en) 2019-05-17 2022-04-26 KYOCERA AVX Components Corporation Solid electrolytic capacitor
DE112020004416T5 (en) 2019-09-18 2022-06-15 KYOCERA AVX Components Corporation Solid electrolytic capacitor for use at high voltages
CN114787951A (en) 2019-12-10 2022-07-22 京瓷Avx元器件公司 Tantalum capacitor with enhanced stability
JP2023506714A (en) 2019-12-10 2023-02-20 キョーセラ・エイブイエックス・コンポーネンツ・コーポレーション Solid electrolytic capacitor containing precoat and intrinsically conductive polymer
RU2770151C2 (en) * 2020-01-31 2022-04-14 Федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский государственный университет" (СПбГУ) Polymer polyquinone-polythiophene compositions for electrochemical current sources
CN111393678B (en) * 2020-03-27 2023-03-28 徐宁 Method for preparing organic solvent dispersion liquid of aqueous polymer
EP4134388A1 (en) 2020-04-06 2023-02-15 Shin-Etsu Chemical Co., Ltd. Conductive polymer composition, substrate, and method for producing substrate
US20210380738A1 (en) 2020-06-03 2021-12-09 Shin-Etsu Chemical Co., Ltd. Conductive polymer composition, substrate, and method for producing substrate
US11631548B2 (en) 2020-06-08 2023-04-18 KYOCERA AVX Components Corporation Solid electrolytic capacitor containing a moisture barrier
JP2022155819A (en) 2021-03-31 2022-10-14 信越化学工業株式会社 Conductive polymer composition, substrate, and method for producing substrate

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4711742A (en) * 1985-05-31 1987-12-08 Allied Corporation Solution processible forms of neutral and electrically conductive poly(substituted heterocycles)
US4910645A (en) * 1988-04-30 1990-03-20 Bayer Aktiengesellschaft Solid electrolytes, and electrolyte capacitors containing same
US5300575A (en) * 1990-02-08 1994-04-05 Bayer Aktiengesellschaft Polythiophene dispersions, their production and their use
US5403467A (en) * 1992-01-29 1995-04-04 Bayer Ag Process for through-hole plating of two-layer circuit boards and multilayers
US6084040A (en) * 1996-08-19 2000-07-04 Bayer Ag Scratch-resistant conductive coatings
US6358437B1 (en) * 1997-12-23 2002-03-19 Bayer Aktiengesellschaft Screen printing paste for producing electrically conductive coatings
US6429248B2 (en) * 1999-08-30 2002-08-06 Eastman Kodak Company Coating composition containing electrically-conductive polymer and solvent mixture
US6632472B2 (en) * 2000-06-26 2003-10-14 Agfa-Gevaert Redispersable latex comprising a polythiophene
US6692662B2 (en) * 2001-02-16 2004-02-17 Elecon, Inc. Compositions produced by solvent exchange methods and uses thereof
US20050186403A1 (en) * 1998-03-17 2005-08-25 Seiko Epson Corporation Method of forming thin film patterning substrate including formation of banks

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0253594A3 (en) 1986-07-16 1989-10-11 COOKSON GROUP plc Polymerisable thiophene monomers, their production and polymers prepared therefrom
DE19627071A1 (en) 1996-07-05 1998-01-08 Bayer Ag Electroluminescent devices
EP1081548A1 (en) * 1999-08-30 2001-03-07 Eastman Kodak Company Coating composition containing polythiophene and solvent mixture
DE60140129D1 (en) * 2000-06-26 2009-11-19 Agfa Gevaert REDISPERIBLE LATEX CONTAINS A POLYTHIOPHONE
EP2289964A3 (en) * 2000-11-22 2014-01-01 Heraeus Precious Metals GmbH & Co. KG Dispersible polymer powders
US6692663B2 (en) * 2001-02-16 2004-02-17 Elecon, Inc. Compositions produced by solvent exchange methods and uses thereof
DE10111790A1 (en) * 2001-03-12 2002-09-26 Bayer Ag New polythiophene dispersions
JP4049744B2 (en) * 2001-12-04 2008-02-20 アグフア−ゲヴエルト，ナームローゼ・フエンノートシヤツプ Process for producing aqueous or non-aqueous solution or dispersion of polythiophene or thiophene copolymer

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4711742A (en) * 1985-05-31 1987-12-08 Allied Corporation Solution processible forms of neutral and electrically conductive poly(substituted heterocycles)
US4910645A (en) * 1988-04-30 1990-03-20 Bayer Aktiengesellschaft Solid electrolytes, and electrolyte capacitors containing same
US5300575A (en) * 1990-02-08 1994-04-05 Bayer Aktiengesellschaft Polythiophene dispersions, their production and their use
US5403467A (en) * 1992-01-29 1995-04-04 Bayer Ag Process for through-hole plating of two-layer circuit boards and multilayers
US6084040A (en) * 1996-08-19 2000-07-04 Bayer Ag Scratch-resistant conductive coatings
US6358437B1 (en) * 1997-12-23 2002-03-19 Bayer Aktiengesellschaft Screen printing paste for producing electrically conductive coatings
US20050186403A1 (en) * 1998-03-17 2005-08-25 Seiko Epson Corporation Method of forming thin film patterning substrate including formation of banks
US6429248B2 (en) * 1999-08-30 2002-08-06 Eastman Kodak Company Coating composition containing electrically-conductive polymer and solvent mixture
US6632472B2 (en) * 2000-06-26 2003-10-14 Agfa-Gevaert Redispersable latex comprising a polythiophene
US6692662B2 (en) * 2001-02-16 2004-02-17 Elecon, Inc. Compositions produced by solvent exchange methods and uses thereof

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7923475B2 (en) * 2001-01-26 2011-04-12 H. C. Starck Gmbh Electroluminescent arrangements
US20020136923A1 (en) * 2001-01-26 2002-09-26 Friedrich Jonas Electroluminescent arrangements
US20130059953A1 (en) * 2001-03-12 2013-03-07 Heraeus Clevios Gmbh Novel polythiophene dispersions
US20070147857A1 (en) * 2005-12-23 2007-06-28 Samsung Electronics Co., Ltd. Apparatus for detecting developer level in developing unit
US7480468B2 (en) * 2005-12-23 2009-01-20 Samsung Electronics Co., Ltd. Apparatus for detecting developer level in developing unit
US8158030B2 (en) * 2006-08-10 2012-04-17 Nissan Chemical Industries, Ltd. Process for producing dispersion liquid of intrinsic electroconductive polymer in organic solvent
US20100038596A1 (en) * 2006-08-10 2010-02-18 Nissan Chemical Industries , Ltd. Process for producing dispersion liquid of intrinsic electroconductive polymer in organic solvent
US20110024692A1 (en) * 2007-09-04 2011-02-03 H.C. Starck Clevios Gmbh Process for producing conducting polymers
US8663505B2 (en) 2007-09-04 2014-03-04 Heraeus Precious Metals Gmbh & Co. Kg Process for producing conducting polymers
US20110049433A1 (en) * 2008-01-22 2011-03-03 H.C. Starck Clevios Gmbh Method for the production of conductive polymers
US8721928B2 (en) 2008-01-22 2014-05-13 Heraeus Precious Metals Gmbh & Co. Kg Method for the production of conductive polymers
US20110168946A1 (en) * 2008-05-09 2011-07-14 H.C. Starck Clevios Gmbh Novel polythiophene polyanion complexes in homopolar organic solvents
US8721929B2 (en) 2008-05-09 2014-05-13 Heraeus Precious Metals Gmbh & Co. Kg Polythiophene polyanion complexes in homopolar organic solvents
US20110135939A1 (en) * 2008-07-29 2011-06-09 Tadayuki Isaji Conductive coating composition
US20120097898A1 (en) * 2009-05-01 2012-04-26 Plextronices, Inc. Replacing aqueous with non-aqueous solvent
WO2010127253A1 (en) * 2009-05-01 2010-11-04 Plextronics, Inc. Replacing aqueous with non-aqueous solvent

Also Published As

Publication number Publication date
JP2009046687A (en) 2009-03-05
EP1373356B1 (en) 2005-05-04
US20020173579A1 (en) 2002-11-21
ES2240731T3 (en) 2005-10-16
JP5183395B2 (en) 2013-04-17
DE10111790A1 (en) 2002-09-26
DE50203008D1 (en) 2005-06-09
JP2004532298A (en) 2004-10-21
EP1373356A1 (en) 2004-01-02
CN1219807C (en) 2005-09-21
RU2003130279A (en) 2005-04-10
CN1496382A (en) 2004-05-12
HK1063641A1 (en) 2005-01-07
KR20030082974A (en) 2003-10-23
KR100856954B1 (en) 2008-09-04
TWI247016B (en) 2006-01-11
US20130059953A1 (en) 2013-03-07
ATE294828T1 (en) 2005-05-15
US7008562B2 (en) 2006-03-07
JP4225785B2 (en) 2009-02-18
WO2002072660A1 (en) 2002-09-19
RU2299893C2 (en) 2007-05-27

Similar Documents

Publication Publication Date Title
US7008562B2 (en) Method of forming polythiophene dispersions
KR101493761B1 (en) Process for producing conducting polymers
US6635729B1 (en) Process for the preparation of water-soluble π-conjugated polymers
JP4077675B2 (en) Aqueous dispersion of complex of poly (3,4-dialkoxythiophene) and polyanion and method for producing the same
US8721928B2 (en) Method for the production of conductive polymers
TWI522386B (en) Dispersions comprising polythiophenes with a defined content of thiophene monomer
KR101174515B1 (en) Specific oxidation agents for producing conductive polymers
US20030161941A1 (en) Transparent polythiophene layers of high conductivity
US20120175565A1 (en) Polymer coatings containing conductive polymers
US20120119154A1 (en) Electroconductive Coating Composition And Process For Production Of Electroconductive Coating Film
KR20100110836A (en) Process for the preparation of coatings exhibiting increased conductivity based on polythiophene and its derivatives
US20230135022A1 (en) Conductive composition and production method therefor, and water-soluble polymer and production method therefor
US20220348712A1 (en) Polythiophenes in organic solvents
EP4332146A1 (en) Polythiophene compound and conductive material composition

Legal Events

Date Code Title Description
AS Assignment

Owner name: H.C. STARCK GMBH & CO. KG,GERMANY

Free format text: CHANGE OF NAME;ASSIGNOR:H.C. STARCK GMBH;REEL/FRAME:018766/0488

Effective date: 20060926

Owner name: H.C. STARCK GMBH & CO. KG, GERMANY

Free format text: CHANGE OF NAME;ASSIGNOR:H.C. STARCK GMBH;REEL/FRAME:018766/0488

Effective date: 20060926

AS Assignment

Owner name: H. C. STARCK GMBH & CO. KG,GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:BAYER BETEILIGUNGSVERWALTUNG GOSLAR GMBH;REEL/FRAME:019197/0734

Effective date: 20070321

Owner name: H. C. STARCK GMBH & CO. KG, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:BAYER BETEILIGUNGSVERWALTUNG GOSLAR GMBH;REEL/FRAME:019197/0734

Effective date: 20070321

AS Assignment

Owner name: BAYER BETEILIGUNGSVERWALTUNG GOSLAR GMBH, GERMANY

Free format text: CORRECTIVE ASSIGNMENT TO CORRECT THE THE ASSIGNEE NEED TO BE CHANGED TO BAYER BETEILIGUNGSVERWALTUNG GOSLAR GMBH PREVIOUSLY RECORDED ON REEL 018766 FRAME 0488;ASSIGNOR:H.C. STARK GMBH;REEL/FRAME:019604/0833

Effective date: 20060926

Owner name: BAYER BETEILIGUNGSVERWALTUNG GOSLAR GMBH,GERMANY

Free format text: CORRECTIVE ASSIGNMENT TO CORRECT THE THE ASSIGNEE NEED TO BE CHANGED TO BAYER BETEILIGUNGSVERWALTUNG GOSLAR GMBH PREVIOUSLY RECORDED ON REEL 018766 FRAME 0488. ASSIGNOR(S) HEREBY CONFIRMS THE CHANGE OF NAME;ASSIGNOR:H.C. STARK GMBH;REEL/FRAME:019604/0833

Effective date: 20060926

Owner name: BAYER BETEILIGUNGSVERWALTUNG GOSLAR GMBH, GERMANY

Free format text: CORRECTIVE ASSIGNMENT TO CORRECT THE THE ASSIGNEE NEED TO BE CHANGED TO BAYER BETEILIGUNGSVERWALTUNG GOSLAR GMBH PREVIOUSLY RECORDED ON REEL 018766 FRAME 0488. ASSIGNOR(S) HEREBY CONFIRMS THE CHANGE OF NAME;ASSIGNOR:H.C. STARK GMBH;REEL/FRAME:019604/0833

Effective date: 20060926

AS Assignment

Owner name: H.C. STARCK GMBH, GERMANY

Free format text: MERGER;ASSIGNOR:H.C. STARCK GMBH & CO. KG;REEL/FRAME:019681/0705

Effective date: 20070604

Owner name: H.C. STARCK GMBH,GERMANY

Free format text: MERGER;ASSIGNOR:H.C. STARCK GMBH & CO. KG;REEL/FRAME:019681/0705

Effective date: 20070604

AS Assignment

Owner name: HERAEUS CLEVIOS GMBH, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:H.C. STARCK GMBH;REEL/FRAME:027727/0334

Effective date: 20111111

AS Assignment

Owner name: HERAEUS PRECIOUS METALS GMBH & CO. KG, GERMANY

Free format text: MERGER;ASSIGNOR:HERAEUS CLEVIOS GMBH;REEL/FRAME:027734/0357

Effective date: 20110718

STCB Information on status: application discontinuation

Free format text: ABANDONED -- AFTER EXAMINER'S ANSWER OR BOARD OF APPEALS DECISION