WO2004114326A1 - Process for preparing electroconductive coatings - Google Patents
Process for preparing electroconductive coatings Download PDFInfo
- Publication number
- WO2004114326A1 WO2004114326A1 PCT/EP2004/051073 EP2004051073W WO2004114326A1 WO 2004114326 A1 WO2004114326 A1 WO 2004114326A1 EP 2004051073 W EP2004051073 W EP 2004051073W WO 2004114326 A1 WO2004114326 A1 WO 2004114326A1
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- WIPO (PCT)
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- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000004984 smart glass Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- CJNYCXOZPQVMIV-UHFFFAOYSA-M sodium;4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-3-ylmethoxy)butane-1-sulfonate Chemical compound [Na+].O1C(COCCCCS(=O)(=O)[O-])COC2=CSC=C21 CJNYCXOZPQVMIV-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical class OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
Definitions
- the present invention relates to a process for preparing electroconductive coatings .
- Polythiophenes have been studied extensively due to their interesting electrical and/or optical properties. Polythiophenes become electrically conducting upon chemical or electrochemical oxidation or reduction. Their ultimately achievable electrical conductivity is determined by their chemical composition, the stereoregularity of the polymerization of the thiophene monomers in the polythiophene chain and by their ⁇ -conjuga ion lengths. Such stereoregularity problems do not arise when unsubstituted thiophenes or thiophenes substituted in the 3- and 4-positions with identical groups are polymerized. . :
- EP-A 339 340 discloses a polythiophene containing structural units of the formula:
- A denotes an optionally substituted Cl-C4-alkylene radical and its preparation by oxidative polymerization of the corresponding thiophene.
- EP-A 440 957 discloses dispersions of polythiophenes, constructed from structural units of formula (I) :
- R 1 and R 2 independently of one another represent hydrogen or a C1-C4 alkyl group or together form an optionally substituted Cl-C4-alkylene residue, in the presence of a polyanion compound and specifically discloses in Examples the polymerization of 3,4- ethylenedioxythiophene [EDOT] in the presence of poly(styrene sulphonic acid) at a weight ratio of 1:1.29 (Example 2), 1:2.2 (Examples 7 and 8), 1:4 (Examples 1, 3, 4 and 10), 1:6 (Example 5) and 1:8.33 (Example 6) in water.
- EDOT 3,4- ethylenedioxythiophene
- Aqueous dispersions of PEDOT/PSS are commercially available from BAYER as BAYTRONTM P.
- Table 1 Table 1 :
- PEDOT/PSS prepared from aqueous and acetonitrile (AN) solutions of EDOT and NaPPS with PSS to PEDOT ratios ranging from 0.24 to 3.33 increased with decreasing PSS: PEDOT ratio as would be intuitively expected by one skilled in the art, due to the higher concentration of the intrinsically conductive component PEDOT.
- EP-A-686 662 discloses mixtures of A) neutral polythiophenes with the repeating structural unit of formula (I) ,
- R 1 and R 2 independently of one another represent hydrogen or a C1-C4 alkyl group or together represent an optionally substituted C1-C4 alkylene residue, preferably an optionally with alkyl group substituted methylene, an optionally with Cl-C12-alkyl or phenyl group substituted 1,2-ethylene residue or a 1,2- cyclohexene residue, and B) a di- or polyhydroxy- and/or carboxy groups or amide or lactam group containing organic compound; and conductive coatings therefrom which are tempered to increase their resistance preferably to ⁇ 300 ohm/square.
- EP-A 686 662 disclose the polymerization of EDOT in the presence of poly(styrene sulphonic acid) at a weight ratio of 1:3.57 in water.
- WO 03/001299A discloses a material for making an electroconductive pattern, said material comprising a support and a light-exposure differentiable element, characterized in that said light-exposure differentiable element comprises an outermost layer containing a polyanion and a polymer or copolymer of a substituted or unsubstituted thiophene, and optionally a second layer contiguous with said outermost layer; and wherein said outermost layer and/or said optional second layer contains a light-sensitive component capable upon exposure of changing the removability of the exposed parts of said outermost layer relative to the unexposed parts of said outermost layer.
- conductivity enhancement refers to a process in which the conductivity is enhanced e.g. by contact with high boiling point liquids such as di- or polyhydroxy- and/or carboxy groups or amide or lactam group containing organic compound optionally followed by heating at elevated temperature, preferably between 100 and 250 °C, during preferably 1 to 90 seconds, results in conductivity increase.
- high boiling point liquids such as di- or polyhydroxy- and/or carboxy groups or amide or lactam group containing organic compound optionally followed by heating at elevated temperature, preferably between 100 and 250 °C, during preferably 1 to 90 seconds, results in conductivity increase.
- temperatures below 100°C can be used.
- Such conductivity enhancement is observed with polythiophenes and can take place during the preparation of the outermost layer or subsequently.
- Particularly preferred liquids for such treatment are N-methyl-pyrrolidinone and diethylene glycol such as disclosed in EP-A 686 662 and EP-A 1 003 179.
- the PEDOT/PSS dispersion used in all the EXAMPLES of WO 03/001299A had a PEDOT: PSS weight ratio of 1:2.4 and had a narrow particle size distribution determined by CPS disc centrifuge measurements with a maximum at 25 nm and an average particle size of 30-50 nm.
- EP-A 1 003 179 discloses a method for producing a polymeric conductive layer on an object comprising the steps of: providing an aqueous composition containing a polythiophene, a polyanion compound and an aprotic compound with a dielectric constant, ⁇ , > 15; applying said composition to said object forming a layer; and drying said layer to form a conductive polymeric layer on said object, characterized in that said object and said layer are kept at a temperature below 100°C and said conductive polymeric layer has a resistivity of at most 2 k ⁇ /square. Furthermore, the examples in EP 1 003 179 disclose the polymerization of EDOT in the presence of poly(styrene sulphonic acid) at a weight ratio of 1:2.46 in water.
- a general drawback of conductive polymers which have been prepared and studied up to now, is that their conductivities are still too low for certain applications, their visible light transmittances are insufficiently high and/or they are not processable.
- R and R independently of one another represent hydrogen or a C_ 5 ⁇ alkyl group or together form an optionally substituted C - 5-alkylene residue and at least one polyanion compound
- said latex having a primary particle size of less than 40 nm and said dispersion contains an organic compound containing a di- or polyhydroxy- and/or carboxy groups or amide or lactam group or an aprotic compound with a dielectric constant, ⁇ , > 15, characterized in that said latex particles contain said at least one polyanion compound and said polymer in a weight ratio of at least 4.
- aspects of the present invention are also realized by a process for preparing an electroconductive coating comprising the steps of: preparing an aqueous solution or dispersion of a polymer consisting of structural units including monomer units according to formula (I) :
- aspects of the present invention are also realized by a process for preparing an electroconductive coating comprising the steps of: preparing an aqueous solution or dispersion of a polymer consisting of structural units including monomer units according to formula (I) :
- polymer includes homopolymers, copolymers, terpolymers, graft polymers and block copolymers and both chain and condensation polymers .
- C ⁇ - 5 -alkylene group represents methylenedioxy, 1,2- ethylenedioxy, 1, 3-propylenedioxy, 1, 4-butylenedioxy and 1,5- pentylenedioxy groups .
- initiator means a species capable of initiating polymerization .
- alkyl means all variants possible for each number of carbon atoms in the alkyl group i.e. for three carbon atoms: n- propyl and isopropyl; for four carbon atoms: n-butyl, isobutyl and tertiary-butyl; for five carbon atoms: n-pentyl, 1,1-dimethyl-- propyl, 2,2-dimethylpropyl and 2-methyl-butyl etc.
- aqueous medium for the purposes of the present invention means a liquid containing at least 60% by volume of water, preferably at least 80% by volume of water, and optionally containing water-miscible organic solvents such as alcohols e.g. methanol, ethanol, 2-propanol, butanol, iso-amyl alcohol, octanol, cetyl alcohol etc.; glycols e.g. ethylene glycol; glycerine; N- methyl pyrrolidinone; methoxypropanol; and ketones e.g. 2-propanone and 2-butanone etc.
- non-aqueous medium for the purposes of the present invention means all liquids not included in the term aqueous medium.
- electroconductive means having a surface resistance below 10 ⁇ /square.
- ⁇ conductivity enhancement refers to a process in which the conductivity is enhanced e.g. by contact with high boiling point liquids such as di- or polyhydroxy- and/or carboxy groups or amide or lactam group containing organic compound optionally followed by heating at elevated temperature, preferably between 100 and 250°C, during preferably 1 to 90 seconds, results in conductivity increase.
- high boiling point liquids such as di- or polyhydroxy- and/or carboxy groups or amide or lactam group containing organic compound optionally followed by heating at elevated temperature, preferably between 100 and 250°C, during preferably 1 to 90 seconds
- elevated temperature preferably between 100 and 250°C, during preferably 1 to 90 seconds
- temperatures below 100°C can be used.
- Such conductivity enhancement is observed with polythiophenes and can take place during the preparation of the outermost layer or subsequently.
- liquids for such treatment are N-methyl-pyrrolidinone and diethylene glycol such as disclosed in EP-A 0 686 662 and EP-A 1 003 179.
- PEDOT as used in the present disclosure represents poly (3,4- ethylenedioxythiophene) .
- EDOT as used in the present disclosure represents 3,4- ethylenedioxythiophene .
- ADOT as used in the present disclosure represents 3,4- alkylenedioxythiophene) .
- PSS as used in the present disclosure represents poly (styrenesulphonic acid) or poly (styrenesulphonate) .
- PET as used in the present disclosure represents poly (ethylene terephthalate) .
- said latex has a primary particle size of less than 30 nm.
- the weight ratio of said at least one polyanion compound to said polymer corresponds to the weight ratio of said structural units to said at least one polyanion compound during the preparation thereof.
- said latex particles contain said at least one polyanion compound and said polymer in a weight ratio of greater than 4 and less than 20.
- aqueous dispersion of a latex wherein said latex is prepared in a reaction medium with less than 8500 mg of oxygen/L of said reaction medium when the initiator is added.
- aqueous dispersion of a latex wherein said latex is prepared in a reaction medium with less than 2000 mg of oxygen/L of said reaction medium when the initiator is added.
- aqueous dispersion of a latex wherein said latex is prepared in a reaction medium with less than 1000 mg of oxygen/L of said reaction medium when the initiator is added.
- a seventh embodiment of the aqueous dispersion of a latex wherein said latex is prepared in a reaction medium with less than 500 mg of oxygen/L of said reaction medium when the initiator is added.
- aqueous dispersion of a latex wherein said latex is prepared in a reaction medium with less than 100 mg of oxygen/L of said reaction medium when the initiator is added.
- aqueous dispersion of a latex wherein said latex is prepared in a reaction medium with less than 3 mg of oxygen/L of said reaction medium when the initiator is added.
- aqueous dispersion of a latex wherein said latex is prepared in a reaction medium with less than 1.5 mg of oxygen/L of said reaction medium when the initiator is added.
- the monomer units according to formula (I) are selected from the group consisting of optionally alkyl group-substituted 3, -methylenedioxy-thiophene units, optionally alkyl or aryl-group-substituted 3,4- ethylenedioxythiophene units, optionally alkyl or aryl-group- substituted 3,4-ethylenedioxythiophene units, a unit according to
- R and R are together a 1,2-cyclohexene group, optionally alkyl or aryl-group-substituted 3,4- propylenedioxythiophene units, optionally alkyl or aryl-group- substituted 3,4-butylenedioxythiophene units and optionally alkyl or aryl-group-substituted 3, 4-pentylenedioxythiophene units.
- the polymer is a copolymer of at least one 3, -alkylenedioxythiophene compound with a solubility in water at 25 °C of less than 2.2 g/L with at least one 3, 4-alkylenedioxythiophene compound with a solubility in water at 25°C of at least 2.2 g/L.
- the polymer is a copolymer of at least one 3, -alkylenedioxythiophene compound with a solubility in water at 25 °C of less than 2.2 g/L with at least one 3,4-alkylene-dioxythiophene compound with a solubility in water at 25°C of at least 2.2 g/L and the 3,4-alkylenedioxy-thio ⁇ hene compound with a solubility in water at 25 C C of at least 2.2 g/L is selected from the group consisting of: 3, 4-dihydro-21f-thieno [3,4- b] [l,4]dioxin-2-yl)methanol, 3, 4-dihydro-2H-thieno [3,4- b] [1, 4] dioxepin-3-ol, (2, 3-dihydro-thieno [3, 4-i>] [1, 4
- a step in the processes, according to the present invention is the preparation of an aqueous solution or dispersion of a polymer consisting of structural units including monomer units according to formula (I) :
- the molar ratio of polymer or copolymer of (3, 4-dialkoxythiophene) to at least one polyanion compound in the solution or dispersion is in the range of 1:5 to 1:8.0.
- said monomer units according to formula (I) are present in a concentration of 60 mM or less in said reaction medium.
- the concentration of oxygen in the reaction medium can be regulated by any means e.g. freeze-thaw techniques, prolonged bubbling of an inert gas such as argon, nitrogen or helium through the reaction medium, consumption of oxygen in a sacrificial reaction under an inert gas blanket.
- an inert gas such as argon, nitrogen or helium
- the inert atmosphere is a nitrogen, helium or argon atmosphere.
- the oxidation agents used for the oxidative polymerisation of pyrrole such as described for example in Journal of the American Chemical Society, volume 85, pages 454-458 (1963) and J. Polymer Science Part A Polymer Chemistry, volume 26, pages 1287-1294 (1988) , can be utilized for the oxidative polymerization of thiophenes .
- the polymerization is oxidative and the inexpensive and easily accessible oxidation agents used for initiating the polymerization are selected from the group consisting of iron (III) salts such as FeCl 3 , the iron (III) salts of organic acids, e.g. Fe(OTs) 3 , H 2 ⁇ 2 , K 2 Cr 2 ⁇ 7 , alkali and ammonium persulphates, alkali perborates and potassium permanganate.
- iron (III) salts such as FeCl 3
- the iron (III) salts of organic acids e.g. Fe(OTs) 3 , H 2 ⁇ 2 , K 2 Cr 2 ⁇ 7
- alkali and ammonium persulphates alkali perborates and potassium permanganate.
- oxidative polymerization of thiophenes requires 2.25 equivalents of oxidation agent per mole thiophene of formula (I) [see e.g. J. Polymer Science Part A Polymer Chemistry, volume 26, pages 1287-1294 (1988)]. In practice an excess of 0.1 to 2 equivalents of oxidation agent is used per polymerizable unit. The use of persulphates and iron (III) salts has the great technical advantage that they do not act corrosively. Furthermore, in the presence of particular additives oxidative polymerization of the thiophene compounds according to formula (I) proceeds so slowly that the thiophenes and oxidation agent can be brought together as a solution or paste and applied to the substrate to be treated. After application of such solutions or pastes the oxidative polymerization can be accelerated by heating the coated substrate as disclosed in US 6,001,281 and WO 00/14139 herein incorporated by 5 reference .
- Reductive polymerization can be performed using the Stille (organotin) or Suzuki (organoboron) routes described in 2002 by Appperloo et al. in Chem. Eur. Journal, volume 8, pages 2384-2396, and as disclosed in 2001 in Tetrahedron Letters, volume 42, pages 10 155-157 and in 1998 in Macromolecules, volume 31, pages 2047-2056 respectively or with nickel complexes as disclosed in 1999 in Bull. Chem. Soc. Japan, volume 72, page 621 and in 1998 in Advanced Materials, volume 10, pages 93-116.
- Polymers containing monomer units according to formula (I) may is also be prepared by chemically copolymerizing monomer units according to formula (I) with other poly erizable heterocyclic compounds such as pyrrole.
- the oxygen concentration can be measured with a Knick Process Unit 73 0 2 , using InPro 6000 Series 0 2 sensors, available from Mettler Toledo. These sensors are based on a polarographic oxygen measurement.
- the Clark polarographic sensor consists basically of a
- the transmitter supplies a constant polarization voltage to the cathode, needed to reduce oxygen.
- the oxygen molecules that migrate through the membrane are reduced at the
- the amount of oxygen in an aqueous 6wt% aqueous solution of pol (styrenesulphonic acid) determined via this technique is 6.5mg/L .
- a poly (styrenesulphonic acid) solution at 25°C and 1013 mbar 0 saturated with oxygen by bubbling oxygen through it has an oxygen content of 38,45mg/L. This value may be regarded as the max solubility of oxygen in a poly (styrenesulphonic acid) solution at 25°C and 1013mbar.
- Polymers containing monomer units according to formula (I) can be prepared by electrochemical polymerization. Electrochemical oxidative polymerization of thiophene compounds according to formula (I) carried out at temperatures from -78 °C to the boiling point of the solvent employed, temperatures between -20°C and 60°C is preferred. The reaction time, depending upon the particular thiophene, is generally between a few seconds and several hours. Electrochemical polymerization of thiophene compounds was described in 1994 by Dietrich et al. in Journal Electroanalytical Chemistry, volume 369, pages 87-92.
- Inert liquids suitable for use during electrochemical oxidation of thiophene compounds according to formula (I) are: water, alcohols such as methanol and ethanol, ketones such as acetophenone, halogenated hydrocarbons such as methylene chloride, chloroform, tetrachloromethane and fluorohydrocarbons, esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, heptane and cyclohexane, nitriles such as acetonitrile and benzonitrile, sulfoxides such as dimethylsulfoxide, sulfones such as dimethylsulfone, phenylmethylsulfone and sulfolan, liquid aliphatic amides such as methyl acetamide, dimethyl acetamide
- Electrolyte additives for use in the electrochemical polymerization of thiophene compounds according to formula (I) are preferably free acids or the usual conducting salts, which exhibit a certain solubility in the solvent used.
- Particularly suitable electrolytes are alkali, alkaline earth or optionally alkylated ammonium, phosphonium, sulfonium or oxonium cations in combination with perchlorate, tosylate, tetrafluoroborate or hexafluorophosphonate anions .
- the electrolyte additives are used in such quantities, that a current of at least 0.1 mA flows during electrochemical oxidation.
- Electrochemical polymerization can be carried out continuously or discontinuously.
- Known electrode materials are ITO-covered glass, precious metal or steel mesh, carbon-filled polymers, evaporated metal-coated insulator layers and carbon felt .
- Current densities during electrochemical oxidation may vary within wide limits. According to an eighth embodiment of the present invention the current densities is 0.0001 to 100 mA/cm 2 . According to a ninth embodiment of the present invention the current density is 0.01 to 40 mA/cm 2 . At these current densities voltages of ca. 0.1 to 50 V are set up.
- Polymers containing monomer units according to formula (I) may also be prepared by electroche ically copolymerizing monomer units according to formula (I) with other polymerizable heterocyclic compounds such as pyrrole .
- polyanion compounds for use in the dispersion according to the present invention are disclosed in EP-A 440 957 and include polymeric carboxylic acids, e.g. polyacrylic acids, polymethacrylic acids, or polymaleic acids and polysulphonic acids, e.g. poly(styrene sulphonic acid) .
- polycarboxylic acids and polysulphonic acids can also be copolymers of vinylcarboxylic acids and vinylsulphonic acids with other polymerizable monomers, e.g. acrylic acid esters, methacrylic acid esters and styrene.
- the at least one polyanion compound includes polystyrene sulphonic acid.
- Polymers containing monomer units according to formula (I) exhibit high electrical conductivity together with low absorption of visible light and high absorption to infrared radiation. Therefore layers thereof are highly electrically conducting, highly transparent to visible light and heat shielding.
- Such polythiophenes can be applied to a wide variety of rigid and flexible substrates, e.g. ceramics, glass and plastics, and are particularly suitable for flexible substrates such as plastic sheeting and the substrates can be substantially bent and deformed without the polythiophene layer losing its electrical conductivity.
- Such polythiophenes can therefore be utilized in photovoltaic devices, batteries, capacitors and organic and inorganic electroluminescent devices, in electromagnetic shielding layers, in heat shielding layers, in antistatic coatings for a wide variety of products including photographic film, thermographic recording materials and photothermographic recording materials, in smart windows, in electrochromic devices, in sensors for organic and bio- organic materials, in field effect transistors, in printing plates, in conductive resin adhesives and in free-standing electrically conductive films [see also chapter 10 of the Handbook of Oligo- and Polythiophenes, Edited by D. Fichou, Wiley-VCH, Weinheim (1999)].
- Subbing layer Nr. 01 used in the EXAMPLES has the composition:
- the concentration of oxygen in this solution as measured with a Knick Process Unit 73 0 2 , using InPro 6000 Series 0 2 is given in Table 2.
- the quantities of Fe 2 (S0 4 ) 3 .9H 2 O and a 2 S 2 ⁇ s corresponding to concentrations of 0.13 and 41.6 mM respectively were then added to initiate the polymerization reaction.
- the concentration of EDOT in the reaction mixtures was 30 mM and that of PSS was 57 mM.
- the reaction mixtures were then stirred at 25°C for 7h, after which a further quantity of a 2 S 2 ⁇ 8 for the particular PEDOT-type was added corresponding to a concentration of 6.95 mM.
- the reaction mixtures were treated twice with ion exchanger (300mL LewatitTM S100MB + 500mL LewatitTM M600MB) .
- the resulting mixtures were further thermally treated at 95°C for 2h and the resulting viscous mixture treated with high shear [microfluidizer at 60 MPa (600Bar)].
- Coating dispersions were produced by adding 3-glycidoxypropyl- trimethoxysilane, ZONYL® FSO100, a copolymer latex of vinylidene chloride, methacrylate and itaconic acid (88/10/2) and N-methyl pyrrolidinone to the dispersions of EXAMPLE 1 so as to produce layers of type 1, upon doctor blade-coating onto a subbed 175 ⁇ m poly (ethylene terephthalate) support and drying at 45°C for 3.5 minutes, with the following composition:
- the optical density of the layers was determined by measuring a stack of 10 strips with a Macbeth® TD904 densitometer using a visible filter and then obtaining therefrom the optical density of a single strip.
- the values given in Table 3 include the optical density of the PET-support.
- the surface resistance of the layers was measured in a room conditioned to a temperature of 25°C and 30% relative humidity by contacting the printed layer with parallel copper electrodes each 35 mm long and 35 mm apart capable of forming line contacts, the electrodes being separated by a Teflon® insulator. This enabled a direct measurement of the surface resistance to be realized.
- Table 3 The results are also summarized in Table 3.
- the concentration of oxygen in this solution was ⁇ 1. Omg/L as measured with a Knick Process Unit 73 0 2 , using InPro 6000 Series 0 2 .
- the quantities of Fe 2 (S0 4 ) 3 .9H 2 0 and Na 2 S 2 ⁇ 8 corresponding to concentrations of 0.13 and 41.6 mM respectively were then added to initiate the polymerization reaction.
- the concentration of EDOT in the reaction mixtures was 30 mM and that of PSS was 57 mM.
- the reaction mixtures were then stirred at 25°C for 7h, after which a further quantity of Na 2 S 2 0s for the particular PEDOT-type was added corresponding to a concentration of 6.95 mM.
- the reaction mixtures were treated twice with ion exchanger (300mL LewatitTM S100MB + 500mL LewatitTM M600MB) .
- the resulting mixtures were further thermally treated at 95°C for 2h and the resulting viscous mixture treated with high shear [microfluidizer at 60 MPa (600Bar)].
- the concentration of oxygen in this solution was ⁇ l.Omg/L as measured with a Knick Process Unit 73 O 2 , using InPro 6000 Series O 2 .
- PEDOT EDOT PSS Fe 2 (S0 ) 3 Na 2 S 2 0 8 Na 2 S 2 0 8 Water type weight weight of final con9H 2 0 weight initially added weight
- reaction mixtures were then stirred at 25°C for 7h, after which a further quantity of Na 2 S 2 0s f ° r the particular PEDOT- type was added corresponding to a concentration of 6.95 mM.
- reaction mixtures were treated twice with ion exchanger (300mL LewatitTM SIOOMB + 500mL LewatitTM M600MB) .
- the resulting mixtures were further thermally treated at 95°C for 2h and the resulting viscous mixture treated with high shear [microfluidizer at 60 MPa (600Bar) ] .
- the resulting PSS PEDOT weight and molar ratios
- PEDOT/PSS-concentrations viscosity as measured in an Ubbelohde viscometer in a bath thermostatted at 25°C, the peak particle sizes in the bimodal size distribution and the number of particles per mL with a particle size greater than 1 ⁇ m are given in Table 7.
- Table 7 Table 7:
- Aqueous gel permeation chromatography using UV-vis absorption detection was used to determine the relative quantity of PSS, bound or unbound, as the area of the peak at 254 nm, A 2 5 4 , and the relative quantity of bound PEDOT, otherwise no transport could take place and the PEDOT could not be detected, as the area of the peak at 785 nm, 85 - A 254 / 8 gives the relative molar quantity of PSS to the bound PEDOT.
- the molecular weight of the PEDOT relative to sodium poly(styrene sulphonate) standards was determined at the same time. The results are summarized in Table 8.
- the electroconductive layers of type 1 with dispersions based on the dispersions of EXAMPLE 3 were prepared in which the quantities of ZONYL® FSO100, 3-glycidoxypro ⁇ ryl- trimethoxysilane, copolymer latex and N-methylpyrrolidinone were held constant and the quantity of latex varied to yield a constant coverage of PEDOT [28.9 mg/m 2 .
- These layers were characterized as described for the dispersions of EXAMPLE 1 and the results are given in Table 9.
- the results in Table 9 surprisingly show that the surface resistance decreased with increasing PSS: PEDOT ratio for layers containing PEDOT/PSS produced in the substantial absence of oxygen, according to the present invention.
- Coating dispersions were produced by adding 3-glycidoxypropyl- trimethoxysilane, ZONYLTM FSO100 and diethylene glycol to the aqueous PEDOT/PSS-dispersions produce coverages upon coating on a poly (ethylene terephthalate) support subbed with subbing layer 1 and then drying for 1 minute at 140°C, with the following composition:
- PEDOT/PSS quantity was varied to maintain a constant PEDOT
- ZONYLTM FSO 100 11 mg/m 2 diethylene glycol [DEG] (theoretical) 1.33 mL/m 2
- Samples of the PEDOT-dispersions of types 10, 13, 17 and 19/20 were freeze dried were freeze dried under high vacuum (0.7 mbar) in a CHRIST BETA2-16 shelf freeze-dryer until all of the water was evaporated (i.e. until the temperature of the shelves was equal to room temperature) and dry powders were obtained.
- the resulting freeze-dried samples were then analysed by 13 C CP/MAS with a 200 MHz spectrometer at 11 different contact times in the ms range at a spin speed of 6.4 kHz, each measurement being repeated 3000 times to increase the signal to noise ratio.
- the C-shift from the EDOT ring (68 ppm) is well-separated from the aliphatic PSS signals (around 40 ppm).
- the In (Intensity) versus contact time (CT) characteristics were analyzed according to the relationship:
- the T lp H relaxation times are different for each signal and also different for each sample. Quantitative results require such long measurement sequence.
- the T lp H relaxation times for aromatic PSS carbon atoms, aliphatic PSS carbon atoms and carbon atoms of the PEDOT-ether group for each PEDOT-type are given in Table 11 below.
- the concentration of oxygen in this solution was ⁇ l.Omg/L as measured with a Knick Process Unit 73 O 2 , using InPro 6000 Series 0 2 .
- the quantities of Fe 2 (SO 4 ) 3 .9H 2 0 and a 2 S 2 ⁇ 8 corresponding to concentrations of 0.13 and 41.6 mM respectively were then added to initiate the polymerization reaction.
- the concentration of EDOT in the reaction mixtures was 30 mM and that of PSS was 46 mM for PEDOT-type 24, 37 mM for PEDOT-type 25, 57 mM for PEDOT-type 26, 69 mM for PEDOT-type 27 and 93 mM for PEDOT-type 28.
- the reaction mixtures were then stirred at 25°C for 7h, after which a further quantity of Na 2 S 2 ⁇ s for the particular PEDOT-type was added corresponding to a concentration of 6.94 mM.
- reaction mixtures were treated twice with ion exchanger (300mL LewatitTM SIOOMB + 500mL LewatitTM M600MB) .
- the resulting mixtures were further thermally treated at 95°C for 2h and the resulting viscous mixture treated with high shear [microfluidizer at 60 MPa (600Bar) ] .
- the electroconductive layers of type 1 with dispersions based on the dispersions of EXAMPLE 4 were prepared and characterized as described for the dispersions of EXAMPLE 3. The results are summarized in Table 15 for the type 1 electroconductive layers .
- the quantity of EDOT for the particular PEDOT-type given in Table 15 was then added to this solution, giving a EDOT-concentration of 30 mM.
- the concentration of oxygen in this solution was measured with a Knick Process Unit 73 O 2 , using InPro 6000 Series O 2 .
- the quantities of Fe 2 (SO 4 ) 3 .9H 2 O and a 2 S 2 ⁇ s corresponding to concentrations of 0.13 and 41.6 mM respectively were then added to initiate the polymerization reaction.
- the concentration of EDOT in the reaction mixtures was 30 mM and the final concentration of PSS in the reaction medium is given in Table 16 for the particular PEDOT-type.
- the reaction mixtures were then stirred at 25°C for 7h, after which a further quantity of a 2 S 2 ⁇ 8 for the particular PEDOT-type was added corresponding to a concentration of 6.94 mM. After an additional reaction time of 16h the reaction mixtures were treated twice with ion exchanger (300mL LewatitTM SIOOMB + 500mL LewatitTM M600MB) .
- the resulting mixtures were further thermally treated at 95°C for 2h and the resulting viscous mixture treated with high shear [microfluidizer at 60 MPa (600Bar) ] .
- the molecular weights of the PEDOT in PEDOT-dispersions type 26 to 30 was determined by aqueous gel permeation chromatography as described in EXAMPLE 3 are given in Table 17.
- the present invention may include any feature or combination of features disclosed herein either implicitly or explicitly or any generalisation thereof irrespective of whether it relates to the presently claimed invention.
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Abstract
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JP2006516142A JP2007526925A (en) | 2003-06-20 | 2004-06-09 | Method for producing an electrically conductive coating |
CN200480023731A CN100594560C (en) | 2003-06-20 | 2004-06-09 | Process for preparing electroconductive coatings |
EP04741766A EP1639607A1 (en) | 2003-06-20 | 2004-06-09 | Process for preparing electroconductive coatings |
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Cited By (7)
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WO2008002481A1 (en) * | 2006-06-23 | 2008-01-03 | Eastman Kodak Company | Conductive polymer coating with improved aging stability |
EP1798785A3 (en) * | 2005-12-14 | 2010-07-21 | H.C. Starck GmbH | Transparent Polymer Electrode for Electro-Optical Devices |
EP2391186A1 (en) * | 2009-01-22 | 2011-11-30 | Sumitomo Chemical Company, Limited | Ink-jet printing ink for organic electroluminescent element, and process for production of organic electroluminescent element |
US8663505B2 (en) | 2007-09-04 | 2014-03-04 | Heraeus Precious Metals Gmbh & Co. Kg | Process for producing conducting polymers |
US8721928B2 (en) | 2008-01-22 | 2014-05-13 | Heraeus Precious Metals Gmbh & Co. Kg | Method for the production of conductive polymers |
EP2079792B1 (en) | 2006-11-06 | 2015-08-05 | Agfa-Gevaert N.V. | Layer configuration with improved stability to sunlight exposure |
EP3419033A1 (en) * | 2010-10-01 | 2018-12-26 | Heraeus Deutschland GmbH & Co KG | A solid polymer capacitor having improve electrical parameters at low temperature |
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KR101035694B1 (en) * | 2008-09-02 | 2011-05-19 | 한국기계연구원 | Forming method of electroconductive polymer layer having nano pattern |
JP6434906B2 (en) * | 2013-04-18 | 2018-12-05 | 国立大学法人山梨大学 | Method for producing solution or dispersion of conductive polythiophene compound |
CN106967257B (en) * | 2015-12-14 | 2021-05-18 | 新加坡科技研究局 | Method of forming polythiophene polysulfonate complexes |
US10658121B2 (en) * | 2017-10-18 | 2020-05-19 | Kemet Electronics Corporation | Process for forming a solid electrolytic capacitor |
CN112521587B (en) * | 2020-12-07 | 2023-08-11 | 南京浩瀚高分子新型材料有限公司 | Method for preparing aqueous polymer with assistance of polytetrafluoroethylene micropowder |
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EP0440957A2 (en) * | 1990-02-08 | 1991-08-14 | Bayer Ag | New polythiophene dispersions, their preparation and their use |
EP0686662A2 (en) * | 1994-05-06 | 1995-12-13 | Bayer Ag | Conductive coatings |
US5766515A (en) * | 1994-05-06 | 1998-06-16 | Bayer Aktiengessellschaft | Conductive coatings |
EP0991303A2 (en) * | 1998-09-12 | 2000-04-05 | Bayer Aktiengesellschaft | Auxiliary layers for electroluminescent devices |
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DE69321567T2 (en) * | 1992-12-17 | 1999-06-02 | Agfa Gevaert Nv | Antistatic, permanent primer |
JP3937113B2 (en) * | 1998-06-05 | 2007-06-27 | 日産化学工業株式会社 | Organic-inorganic composite conductive sol and method for producing the same |
DE69919661T2 (en) * | 1998-11-17 | 2005-09-22 | Agfa-Gevaert | Process for the preparation of a layer of conductive polythiophene at low temperature |
WO2003048227A1 (en) * | 2001-12-04 | 2003-06-12 | Agfa-Gevaert | Process for preparing an aqueous or non-aqueous solution or dispersion of a polythiophene or thiophene copolymer |
-
2004
- 2004-06-09 EP EP04741766A patent/EP1639607A1/en not_active Withdrawn
- 2004-06-09 WO PCT/EP2004/051073 patent/WO2004114326A1/en active Application Filing
- 2004-06-09 CN CN200480023731A patent/CN100594560C/en not_active Expired - Fee Related
- 2004-06-09 KR KR1020057024380A patent/KR100995561B1/en active IP Right Grant
- 2004-06-09 JP JP2006516142A patent/JP2007526925A/en active Pending
Patent Citations (4)
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EP0440957A2 (en) * | 1990-02-08 | 1991-08-14 | Bayer Ag | New polythiophene dispersions, their preparation and their use |
EP0686662A2 (en) * | 1994-05-06 | 1995-12-13 | Bayer Ag | Conductive coatings |
US5766515A (en) * | 1994-05-06 | 1998-06-16 | Bayer Aktiengessellschaft | Conductive coatings |
EP0991303A2 (en) * | 1998-09-12 | 2000-04-05 | Bayer Aktiengesellschaft | Auxiliary layers for electroluminescent devices |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1798785A3 (en) * | 2005-12-14 | 2010-07-21 | H.C. Starck GmbH | Transparent Polymer Electrode for Electro-Optical Devices |
US7938986B2 (en) | 2005-12-14 | 2011-05-10 | H.C. Starck Gmbh & Co. Kg | Transparent polymeric electrodes for electro-optical structures, processes for producing the same, and dispersions used in such processes |
EP2731160A1 (en) * | 2005-12-14 | 2014-05-14 | Heraeus Precious Metals GmbH & Co. KG | Transparent polymer electrode for electro-optical devices |
WO2008002481A1 (en) * | 2006-06-23 | 2008-01-03 | Eastman Kodak Company | Conductive polymer coating with improved aging stability |
EP2079792B1 (en) | 2006-11-06 | 2015-08-05 | Agfa-Gevaert N.V. | Layer configuration with improved stability to sunlight exposure |
EP2079792B2 (en) † | 2006-11-06 | 2018-09-12 | Agfa-Gevaert N.V. | Layer configuration with improved stability to sunlight exposure |
US8663505B2 (en) | 2007-09-04 | 2014-03-04 | Heraeus Precious Metals Gmbh & Co. Kg | Process for producing conducting polymers |
US8721928B2 (en) | 2008-01-22 | 2014-05-13 | Heraeus Precious Metals Gmbh & Co. Kg | Method for the production of conductive polymers |
EP2391186A1 (en) * | 2009-01-22 | 2011-11-30 | Sumitomo Chemical Company, Limited | Ink-jet printing ink for organic electroluminescent element, and process for production of organic electroluminescent element |
EP2391186A4 (en) * | 2009-01-22 | 2013-09-25 | Sumitomo Chemical Co | Ink-jet printing ink for organic electroluminescent element, and process for production of organic electroluminescent element |
EP3419033A1 (en) * | 2010-10-01 | 2018-12-26 | Heraeus Deutschland GmbH & Co KG | A solid polymer capacitor having improve electrical parameters at low temperature |
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CN1839448A (en) | 2006-09-27 |
CN100594560C (en) | 2010-03-17 |
EP1639607A1 (en) | 2006-03-29 |
JP2007526925A (en) | 2007-09-20 |
KR20060015654A (en) | 2006-02-17 |
KR100995561B1 (en) | 2010-11-22 |
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