Conductive polymer dispersion

Abstract

A conductive polymer composition comprising a conductive polymer and a polymer binder, wherein the polymer binder comprises an aqueous dispersion of a polymer mixture, and the polymer mixture comprises a first polymer that is water-dispersible and a second polymer that is water-insoluble.

Description

Technical Field

[0001] The present invention relates to a conductive polymer dispersion and a conductive polymer formulation prepared therefrom. Specifically, the present invention relates to a conductive polymer formulation used for preparing a conductive coating liquid and / or printing ink for various substrates. The present invention also relates to a method for preparing such a conductive polymer dispersion and / or formulation.

Background Art

[0002] As a well-known and widely used conductive polymer coating liquid and / or printing ink, there is a poly(3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (PEDOT / PSS) type.

[0003] In many applications, such PEDOT / PSS-based coatings or printing inks have insufficient adhesion while maintaining a sufficiently high conductivity (i.e., low surface resistivity) to various substrates.

[0004] In order to improve the adhesion to the substrate, a so-called binder is often added to the coating liquid or printing ink. Such a binder typically contains a polymer that is miscible with the dispersion medium of the PEDOT / PSS coating liquid or printing ink. Since the PEDOT / PSS-based coating liquid or printing ink is preferably prepared from an aqueous PEDOT / PSS dispersion, in such a case, the binder polymer is a water-miscible polymer.

[0005] Patent Document 1 (AGFA GEVAERT NV) discloses an aqueous PEDOT / PSS composition containing a non-Newtonian binder. Examples of the non-Newtonian binder include a homopolymer or copolymer of acrylic acid crosslinked with a polyalkenyl polyether.

[0006] Patent document 2 (AGFA GEVAERT NV) discloses an aqueous PEDOT / PSS flexographic printing ink containing a latex binder. Suitable latex binders include, for example, carboxylated polyolefins, or homopolymers or copolymers of monomers selected from the group consisting of styrene, (meth)acrylate, and diene.

[0007] Patent Document 3 (HEREAUS) discloses an aqueous PEDOT / PSS screen printing ink. This ink contains a water-soluble or water-dispersible polymer, particularly a partially sulfonated polymer, as a binder to improve the water miscibility of the ink.

[0008] Patent Document 4 (DAINIPPON INK & CHEMICALS) discloses an aqueous screen printing ink comprising PEDOT / PSS, a water-soluble resin, and a solvent. The water-soluble resin is preferably a cellulose resin.

[0009] In this specification, the term "water-miscible polymer" includes both water-soluble polymers and water-dispersible polymers. When a water-soluble polymer is used as a binder in a conductive polymer dispersion / compound, the water resistance of the coating or print prepared from the dispersion / compound can be expected to be degraded. In contrast, water-dispersible polymers generally have little effect on the water resistance of the coating.

[0010] Water-miscible polymers are often prepared by combining water-miscible comonomers or polymer segments with water-insoluble comonomers or polymer segments. To obtain a well-defined submicron dispersion, the polymer is preferably The dispersion contains a sufficient amount of water-miscible comonomer or polymer segment, or a sufficient amount of surfactant or stabilizer. The presence of such water-miscible comonomer or polymer segment often improves adhesion to various plastic substrates. However, in most cases, its presence also reduces the water resistance of the coating.

[0011] There is a need for a conductive polymer composition that does not contain a high-boiling point solvent and that can be used to prepare a coating having sufficient water resistance, surface resistance, and adhesion to various substrates. [Prior art documents] [Patent Documents]

[0012] [Patent Document 1] WO2002 / 079316 [Patent Document 2] WO2003 / 000765 [Patent Document 3] US6358437 [Patent Document 4] JP2010 / 265450 [Overview of the project]

[0013] The object of the present invention is to provide a conductive polymer composition that does not contain a high-boiling point solvent and that can be used to prepare a coating having sufficient water resistance, surface resistance, and adhesion to various substrates.

[0014] The object of the present invention is realized by a conductive polymer composition as defined in claim 1.

[0015] Further objects of the present invention will become apparent from the following description herein. [Modes for carrying out the invention]

[0016] definition The term "monofunctional" means, for example, that a polymerizable compound has one polymerizable group, as in the case of a monofunctional polymerizable compound.

[0017] The term "bifunctional" means, for example, in the case of a bifunctional polymerizable compound, that the polymerizable compound has two polymerizable groups.

[0018] The term "polyfunctional" means, for example, in the case of a polyfunctional polymerizable compound, that the polymerizable compound has more than two polymerizable groups.

[0019] The term "alkyl" means all possible variants for alkyl groups of each number of carbon atoms, that is, methyl, ethyl, for those with 3 carbon atoms, n-propyl and isopropyl, for those with 4 carbon atoms, n-butyl, isobutyl, and tert-butyl, for those with 5 carbon atoms, n-pentyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, and 2-methylbutyl, etc.

[0020] Unless otherwise specified, a substituted or unsubstituted alkyl group is preferably a C1-C6-alkyl group.

[0021] Unless otherwise specified, a substituted or unsubstituted alkenyl group is preferably a C2-C6-alkenyl group.

[0022] Unless otherwise specified, a substituted or unsubstituted alkynyl group is preferably a C2-C6- alkynyl group.

[0023] Unless otherwise specified, a substituted or unsubstituted aralkyl group is preferably a phenyl or naphthyl group having one, two, three, or more C1-C6-alkyl groups.

[0024] Unless otherwise specified, a substituted or unsubstituted aralkyl group is preferably a C7-C 20 -alkyl group having a phenyl group or a naphthyl group.

[0025] Unless otherwise specified, a substituted or unsubstituted aryl group is preferably a phenyl group or a naphthyl group.

[0026] Unless otherwise specified, substituted or unsubstituted heteroaryl groups are preferably five- or six-membered rings substituted with one, two, or three oxygen, nitrogen, sulfur, selenium atoms, or a combination thereof.

[0027] Unless otherwise specified, substituted or unsubstituted alkylene groups are preferably C1-C6 alkylene groups.

[0028] The term "substituted" means, for example, that the alkyl group can be substituted with an atom other than the atoms normally present in such a group (i.e., carbon and hydrogen). For example, a substituted alkyl group may contain a halogen atom or a thiol group. An unsubstituted alkyl group contains only carbon and hydrogen atoms.

[0029] Unless otherwise specified, substituted alkyl groups, substituted alkenyl groups, substituted alkynyl groups, substituted aralkyl groups, substituted alkaryl groups, substituted aryl groups, and substituted heteroaryl groups are preferably substituted with one or more components selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl, esters, amides, amines, ethers, thioethers, ketones, aldehydes, sulfoxides, sulfones, sulfonic acid esters, sulfonamides, -Cl, -Br, -I, -OH, -SH, -CN, and -NO2.

[0030] Conductive polymer composition The conductive polymer composition according to the present invention is as follows: - Conductive polymers and, - Polymer binders, The present invention is characterized by comprising a polymer binder, wherein the polymer binder comprises a polymer mixture in an aqueous dispersion, and this polymer mixture comprises a first polymer that is water-dispersible and a second polymer that is water-insoluble.

[0031] A composition containing a conductive polymer is referred to herein as a conductive polymer composition.

[0032] In this specification, "polymer binder" refers to a binder comprising one or more polymers. Binders are typically added to optimize the film-forming or printable properties of a composition, and to optimize the mechanical properties of a coating or pattern of the composition on a substrate.

[0033] As described below, the water-dispersible polymer mixture possesses the properties of both a water-dispersible polymer (first polymer) and a water-insoluble polymer (second polymer). In this way, the properties of a water-insoluble polymer can be introduced into an aqueous dispersion.

[0034] There are two preferred methods for preparing polymer mixtures.

[0035] In the first method, the second polymer, dissolved in an organic solvent, is added to an aqueous dispersion of the first polymer, and then the organic solvent is evaporated.

[0036] In the second method, a second polymer, dissolved in an organic solvent, is added to a first polymer, also dissolved in an organic solvent. The two organic solvents can be different or the same. Water is then added to the organic solution containing the first and second polymers, followed by evaporation of the organic solvent(s).

[0037] Both methods yield a polymer mixture according to the present invention. This polymer mixture can be either homogeneous or heterogeneous. If the first and second polymers are not completely miscible, or if the organic solvent in which the second polymer is dissolved does not allow for complete swelling of the first polymer, the polymer mixture dispersion may exhibit particle phase separation, such as a core-shell morphology. If the first and second polymers are miscible and the organic solvent(s) used are good solvents for both polymers, the polymer mixture dispersion can be a homogeneous interpenetration network of both the first and second polymers.

[0038] The first method is suitable when controlling the particle size of the polymer mixture dispersion is important. The second method is suitable when using water-dispersible polymers that are sold as solid products or as solutions in organic solvents. The second method also makes it easier to obtain homogeneous polymer mixtures.

[0039] Examples of water-dispersible polymers include polyurethanes, polyesters, and polyacrylates.

[0040] The production of polyurethane dispersions that provide sufficient chemical resistance and mechanical performance typically involves the use of aprotic solvents such as N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP). However, due to their high boiling points, solvents like NMP and NEP are difficult to remove from dispersions and coatings containing such dispersions. The presence of these solvents can negatively affect the properties of the coating, such as reduced adhesion, cohesiveness, abrasion resistance, and scratch resistance. Furthermore, solvents like NMP are unsuitable for the manufacturing environment due to their toxicity. To obtain good film-forming properties without the need for such aprotic, typically high-boiling-point solvents, larger quantities of dispersed comonomers, such as dimethylolpropionic acid or polyethylene glycol-functionalized diols, e.g., Ymer® N120 or Ymer® N90, may be used. The presence of larger amounts of such hydrophilic comonomers eliminates the need for aprotic solvents as binders or softeners, but reduces water resistance. By adding a water-insoluble secondary polymer to compensate for the reduced water resistance, the polymer mixture according to the present invention can be obtained.

[0041] Polyester dispersions are typically prepared by polycondensation of dicarboxylic acids, methyl dicarboxylic acid esters, or activated dicarboxylic acid esters with diols, or by ring-opening polymerization of lactones. Typically, water-dispersible co-polyesters are obtained by incorporating hydrophilic comonomers, such as sulfisophthalic acid or its corresponding sodium salt. A large amount of such hydrophilic comonomers is required to obtain a stable aqueous dispersion. However, a large amount of such hydrophilic comonomers can also reduce the water resistance of such polyester copolymers. Furthermore, semi-crystalline... When polyester is modified with a hydrophilic comonomer, its crystallinity often decreases. By adding a water-insoluble secondary polymer to compensate for this decrease in physical properties, the polymer mixture according to the present invention can be obtained.

[0042] Acrylic dispersions are typically prepared by conventional emulsion polymerization. Polymerization nucleation is usually established via micelles or homogeneous nucleation. During polymerization, the particle size of the acrylic dispersion increases while the amount of monomer present in the monomer droplets decreases. For efficient emulsion polymerization, the monomers must have limited water solubility to allow them to move from the monomer droplets towards the polymerization field. Therefore, hydrophobic and water-insoluble monomers are difficult to polymerize by conventional emulsion polymerization techniques, or such monomers can only be incorporated in small amounts. Examples of hydrophobic monomers include stearyl (meth)acrylate, behenyl methacrylate, hexadecyl acrylate, 9-vinylfluorene, N-vinylcarbazole, N-allylcarbazole, 9-vinylanthracene, 1-vinylnaphthalene, and 2-vinylnaphthalene. Although the incorporation of hydrophobic monomers is often of interest, if this cannot be achieved by emulsion copolymerization, such monomers can be introduced via a water-insoluble secondary polymer to obtain the polymer mixture according to the present invention.

[0043] Similarly, UV stabilizers such as 2-(2'-hydroxy-5'-methacrylateoxyethylphenyl)-2H-benzotriazole [RUVA-93, CAS registry number 96478-09-0] can also be incorporated by emulsion polymerization. However, even in this case, incorporating large quantities of such monomers can be difficult. The technique of adding a water-insoluble secondary polymer can solve this problem because it allows for the acquisition of larger quantities of UV absorbers.

[0044] Polyacrylic dispersions can also be prepared by mini-emulsification polymerization, which allows the use of hydrophobic monomers, particularly when monomer droplets are converted into polymer particles. However, mini-emulsification polymerization is not possible for all types of monomers, and particle size control is more difficult. In the case of polyacrylic dispersions prepared by mini-emulsification polymerization, the addition of a water-insoluble secondary polymer can also broaden the range of polymer properties that can be incorporated using the polyacrylic dispersion. Furthermore, the secondary polymer can be added not only after the preparation of the polyacrylic dispersion, but also during preparation by dissolving the water-insoluble secondary polymer in the acrylic monomer used in the mini-emulsification.

[0045] In both conventional emulsion polymerization and polyacrylate dispersions prepared via mini-emulsification, particle size control is more difficult when bulky, water-insoluble monomers are used. Adding these monomers to a water-insoluble secondary polymer can be a solution to this problem. This allows emulsion polymerization only with monomers such as methyl methacrylate and / or styrene, enabling very good particle size control.

[0046] The median particle diameter (d50) of the water-dispersible polymer mixture described above is preferably 10 to 2000 nm, more preferably 20 to 1000 nm, and most preferably 30 to 500 nm.

[0047] The aqueous conductive composition may contain one or more other polymer binders in addition to the polymer binders described above. Such additional binders are preferably water-dispersible or soluble polymers and can be selected from the group consisting of polymers or copolymers containing hydroxyl groups, carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, or salts thereof, or oligoethylene glycol polymers or copolymers.

[0048] Polymer mixture The above-mentioned water-dispersible polymer mixture includes a first polymer that is water-dispersible and a second polymer that is water-insoluble.

[0049] Daiichi Polymer The polymer referred to as the "first polymer" above is water-dispersible.

[0050] When used herein, a water-dispersible polymer means that the polymer is dispersible in an aqueous medium, preferably water.

[0051] When preparing a conductive composition according to the present invention, the first polymer can be added to the composition as an aqueous dispersion or as a water-dispersible solid polymer.

[0052] When used as a solid polymer, the polymer has water-stabilized polymer segments or monomers. These water-stabilized polymer segments or monomers can be anionic, cationic, amphoteric, or nonionic. The solid polymer can also be a precursor of a polymer that becomes water-dispersible after pH adjustment, for example, by converting carboxylic acids to carboxyl salts by increasing the pH, or by converting amines to ammonium groups by decreasing the pH.

[0053] The first polymer is preferably selected from the group consisting of polyurethane, polyacrylate, polyacrylamide, polyamine, polyether, polyester, polycarbonate, polyvinyl ether, polyvinyl ester, polyvinyl acetal, polyacetal, polyketone, olefin, polyvinyl halide, polyvinylidene halide, polycarbodiimide, phenolic resin, cellulose derivative, and polysaccharides, or mixtures thereof.

[0054] The first polymer is more preferably selected from the group consisting of polyurethane, polyacrylate, and polyester, or mixtures thereof.

[0055] Examples of primary polymers available as aqueous dispersions include: -Examples of polyurethane dispersions include Vondic 2210, Vondic 1980 NE, Vondic 1672 NE, Vondic EXP3829, Hydran AP40N, Hydran AP20, Ruco coat EC4811, Hauthane L-2877, Incorez W835 / 364, NeoRez R9930, and NeoRez R985, etc. -Examples of polyester dispersions include Skybon® EM660, Skybon® EM110, Eastek® 1100, Eastek® 1400, Vylonal® MD1480, Vylonal® MS1200, Plascoat® Z687, and Plascoat® Z-690, etc. -Examples of polyvinyl acetal dispersions include S LEC(registered trademark) KW-10 and S LEC(registered trademark) KW-M; -Examples of polyacrylate dispersions include Neocryl® XK37, Bonron PS002, Neocryl® XK151, Neocryl® D2101, Joncryl® OH 8312, Joncryl® HSL 9011, Joncryl® HSL700, and Carboset® 514H, etc. -Examples of vinyl ester dispersions include Alcotex® WD100, Vinnapas® EP1, and Sumikaflex S900HL; -Examples of vinyl halide dispersions include Sumikaflex S850 HQ; Examples of vinylidene chloride dispersions include Daran SL159, Diofan P520, and Daran SL128; - Examples of polycarbodiimide dispersions include Desmodur 2802.

[0056] Examples of primary polymers available as water-dispersible solid polymers include Joncryl® 682, Joncryl® 690, Joncryl® 586, Joncryl® 680, Eudragit® L-100-55, Isobam® 600, Ceramer® 1608, Lithene® ultra PM4-7.5MA, Carboset® 525, Carboset® 527, Carboset® GA1164, Bykjet® 9152, Aquaflex® XL30, SSMA® 1000 HNa, SMA® 1000 MA, SMA® 1550 H, SMA® 1440 F, SMA® 2625 P, SMA® 1000 I, and Pluronic® PE There is 6400.

[0057] Second polymer The second polymer mentioned above is water-insoluble.

[0058] When used herein, a water-insoluble polymer means that the polymer's solubility in an aqueous medium, preferably water, is less than 20% by weight, preferably less than 5% by weight, and most preferably less than 2% by weight.

[0059] The second polymer can be water-dispersible, however, it is preferable that the second polymer is not water-dispersible.

[0060] The second polymer is preferably selected from the group consisting of polyurethane, polyacrylate, polyacrylamide, polyamine, polyether, polyester, polycarbonate, polyvinyl ether, polyolefin, styrene copolymer, polyvinyl ester, polyvinyl acetal, polyacetal, polyketone, polyvinyl halide, polyvinylidene halide, polycarbodiimide, polysiloxane, phenolic resin, cellulose derivative, and polysaccharides, or mixtures thereof.

[0061] When preparing the polymer mixture according to the present invention, the second polymer can be used as a solid polymer, but it can also be used as a solution of an organic solvent, such as ethyl acetate, acetone, or MEK.

[0062] Examples of secondary polymers include: -Polyesters include Dynacol® 7150, Vylon® 220, Stepanpol® PD-195, Stepanpol® PD-56, CAPA® polyols, e.g., CAPA® 2205, CAPA® 2402, CAPA® 2054, and CAPA® 3050, etc., and Dai Nippon INK & Chemicals polyester polyols, e.g., OD-X-2044, OD-X-2692, OD-X-2420, OD-X-2376, OD-X-355, and OD-X-2018, etc. -Examples of polyketones include Carilon® D26VM100, Ketone Resin 575, Ketone Resin 725, Ketone Resin 730, and Ketone Resin 610; -Polyacrylate resins include Neocryl(registered trademark) B 300, Neocr yl(registered trademark) B 805, Neocryl(registered trademark) B 814, Degalan(registered trademark) M920, Elvacite(registered trademark) 2041, Neocryl(registered trademark) B-728, etc. -Polyethers include PolyTHF® grade, manufactured by BASF, etc. -Examples of polyvinyl acetal resins include Mowital® B 14 S, Pioloform® BL16, Mowital® BA55HH, S LEC® BX 35-Z, S LEC® B5 HPZ, S LEC® BH-6, S LEC® BH-A, and S LEC® BH-3, etc. -Examples of cellulose derivatives include Eastman cellulose acetate butyrate (e.g., CAB-381-2, CAB-381-0.1, or CAB-381-0.5); Examples of polycarbodiimides include Stabilizer 7000, Stabilizer G 900, and Stabilizer G 500; -Examples of polycarbonate include Eternacoll® UM90, Eternacoll® PH200D, Eternacoll® UH100, and Eternacoll® UH200.

[0063] The second polymer can be a block copolymer or a graft copolymer, such as the acrylic resin Nanostrength® M22 PE.

[0064] Water-insoluble polymers available as organic solutions that can be used as secondary polymers include, for example, CK232, CK233, and CK234, phenolic resins dissolved in ethyl acetate, manufactured by Allnex.

[0065] The second polymer can also be a reactive polymer, such as an isocyanate-terminated polymer. Examples of isocyanate-terminated polyesters include Ucopol M630, Ucopol M631, and Ucupol 571-01 (all soluble in ethyl acetate), Desmodur® LU D80, Desmodur® LU D95, Polurcast PET85A-01, and Polurcast PET88A-01. Examples of isocyanate-terminated polycarbonates available as solid resins include Eternathane® 400-7 and Eternathane® 400-12. Examples of isocyanate-terminated polyethers include Desmodur® XP2617, Desmodur® E 15, Desmodur® LU T80, and Desmodur® LU T95. Examples of isocyanate-terminated silicones include Silmer®NCO Di-10 and Silmer®NCO Di-50.

[0066] The reactive group can be incorporated into an acrylic polymer, for example, by using reactive acrylic monomers such as hydroxyethyl acrylate, hydroxyethyl methacrylate, glycidyl methacrylate, isocyanatoethyl methacrylate, maleic anhydride, etc.

[0067] The reactive groups of the second polymer may improve the adhesion, scratch resistance, chemical resistance, and mechanical resistance of the aqueous conductive polymer dispersion when it is coated onto a substrate.

[0068] Preparation of polymer mixtures A first preferred method for preparing a polymer mixture includes the following steps: - A step to prepare an aqueous dispersion of the first polymer, -By adding a second polymer dissolved in a low-boiling point solvent to a dispersion of the first polymer, A step of forming a polymer mixture, and - A step to remove a low-boiling point solvent from a polymer mixture.

[0069] A second preferred method for preparing a polymer mixture includes the following steps: - A step of preparing a first polymer dissolved or dispersed in a first low-boiling point solvent, - A step of forming a polymer mixture by adding a second polymer dissolved in a second low-boiling point solvent to a solution or dispersion of a first polymer, and - The step of adding water to a polymer mixture, and - A step of removing the first and second low-boiling point solvents from the polymer mixture.

[0070] The first and second low-boiling point solvents mentioned above may be different from each other, or they may be the same. Preferably, the first and second low-boiling point solvents are the same, for example, with respect to better reuse of organic solvents.

[0071] The removal of low-boiling point solvents is preferably carried out by evaporation.

[0072] In this specification, a low-boiling point solvent may be either a water-miscible solvent or a water-immiscible solvent. The boiling point of a low-boiling point solvent is less than 100°C, or the solvent forms an azeotropic mixture with water, the boiling point of which is less than 100°C.

[0073] Examples of aqueous-soluble low-boiling point solvents include ethanol, 2-propanol, and acetone.

[0074] The low-boiling point solvent is preferably a water-immiscible solvent, i.e., its solubility in water at 20°C is less than 10% by volume.

[0075] Examples of water-immiscible low-boiling point solvents include ethyl acetate, isopropyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, sec-amyl acetate, n-amyl acetate, sec-amyl acetate, methylene chloride, chloroform, carbon tetrachloride, amyl chloride, cyclohexane, methylcyclohexane, isopropyl ether, diethyl carbonate, methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, cyclohexanone, benzene, toluene, xylene, ligroin, nitromethane, and mixtures thereof.

[0076] Suitable low-boiling solvents are ethyl acetate, methylene chloride, and mixtures thereof.

[0077] A low-boiling point solvent is preferable as it can swell the primary polymer. If a low-boiling solvent can swell the first polymer, the second polymer can penetrate the first polymer and form a homogeneous polymer mixture. If the low-boiling solvent does not completely swell the first polymer, or if polymer mobility is limited, a core-shell or so-called "loaded" polymer may be formed.

[0078] Depending on the application in which the conductive polymer dispersion is used, additional components can be added to the conductive polymer dispersion to form a conductive polymer formulation optimized for that application. As will be described in more detail below, for some applications, it may be advantageous that the majority of the dispersion medium in the conductive polymer formulation is non-aqueous. In such cases, the secondary polymer can be added as a solution or dispersion of a high-boiling point solvent, i.e., a solvent with a boiling point greater than 100°C, and this high-boiling point solvent is water-pivot. Such high-boiling point solvents typically remain in the conductive polymer formulation. Examples of such solvents include diethylene glycol, 1,2-dipropylene glycol, glycerol, 1,2-propanediol, 1,3-propanediol, or ethylene glycol.

[0079] conductive polymer Suitable conductive polymers are disclosed, for example, in "Conducting Polymers, Fundamentals and Applications: A Practical Approach" (Prasanna Chandrasekhar); "Conducting Polymers: A New Era in Electrochemistry" (Gyoergy Inzelt); "Handbook of Organic Conductive Molecules and Polymers: Conductive polymers: synthesis and electrical properties" (Hari Singh Nalwa); "Conjugated Polymers: Theory, Synthesis, Properties, and Characterization" (Terje A. Skotheim, John Reynolds); and "PEDOT: Principles and Applications of an Intrinsically Conductive Polymer" (Andreas Elschner et al.).

[0080] Examples of such conductive polymers include polythiophene, polyaniline, polypyrrole, and polyacetylene.

[0081] The conductive polymer according to the present invention is preferably a polymer or copolymer of substituted or unsubstituted thiophene.

[0082] Such polythiophenes typically have a positive charge, which is distributed along the polymer backbone. The positive charge is preferably at least partially offset by anions.

[0083] When anions are covalently bonded to a polymer, that polymer is often referred to as a self-doped polymer or an internally conductive polymer. The monomers used to create such self-doped polymers, i.e., polymers containing anionic groups, are also called self-doped monomers.

[0084] When the anion is a separate compound, the polymer is typically referred to as a doped polymer or an externally conductive polymer. The anion added as a separate compound is preferably one of the polyanions described below.

[0085] Suitable alternative doped polythiophenes are disclosed in EP-A440957, page 2, line 46 to page 3, line 14.

[0086] Particularly suitable external conductive polymers are polymers or copolymers represented by the following formula I: [ka] During the ceremony, n is an integer between 2 and 100, preferably between 3 and 50, and more preferably between 4 and 25. R1 and R2 independently represent hydrogen, a substituted or unsubstituted C1-C4 alkyl group, or together R1 and R2 form a substituted or unsubstituted C1-C4 alkylene group or a substituted or unsubstituted C3-C10 cycloalkylene group.

[0087] More preferably, R1 and R2 independently represent a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted 1,3-propylene group, or a substituted or unsubstituted 1,2-cyclohexylene group.

[0088] A preferred polythiophene is a homopolymer or copolymer of 3,4-dialkoxythiophene, wherein the two alkoxy groups of 3,4-dialkoxythiophene together form an oxyalkylene-oxycrosslink, and the 3,4-dialkoxythiophene is selected from the group consisting of substituted or unsubstituted 3,4-methylenedioxythiophene; substituted or unsubstituted 3,4-ethylenedioxythiophene; substituted or unsubstituted 3,4-propylenedioxythiophene; substituted or unsubstituted 3,4-butylenedioxythiophene; and derivatives thereof.

[0089] A particularly suitable external conductive polymer is poly(3,4-ethylenedioxythiophene) (PEDOT).

[0090] A suitable internally conductive polythiophene is a homopolymer or copolymer of monomers according to the following formula II: [ka] During the ceremony A represents a substituted or unsubstituted C1-C5 alkylene bridge with at least one additional functional group, wherein at least one functional group is selected from the group consisting of sulfonic acid or its salt, phosphonic acid or its salt, phosphate ester or its salt, sulfate ester or its salt, and carboxylic acid or its salt.

[0091] In formula II, A preferably represents a C2-alkylene bridge.

[0092] A more suitable internally conductive polythiophene is a homopolymer or copolymer of monomers according to the following formula III: [ka] During the ceremony L1 represents a divalent linking group having 1 to 15 carbon atoms, and C represents a functional group selected from the group consisting of sulfonic acid or its salt, phosphonic acid or its salt, phosphate ester or its salt, sulfuric acid ester or its salt, and carboxylic acid or its salt.

[0093] C preferably represents a sulfonic acid or a salt thereof.

[0094] Particularly preferred internal conductive polymers are thiophene homopolymers or copolymers containing monomer units according to the following formula IV: [ka] During the ceremony L2 represents a divalent linking group having 10 or fewer carbon atoms. M represents a counterion that cancels out the negative charge of hydrogen or a sulfonate group.

[0095] The conductive composition according to the present invention may include both the internally conductive polythiophene and the externally conductive polythiophene described above.

[0096] Preparation of conductive polymers The polythiophene conductive polymer is preferably prepared by oxidative polymerization of the thiophene monomer described above. More preferably, the conductive polymer is prepared by oxidative polymerization of the thiophene monomer described above in an aqueous medium.

[0097] In the case of externally conductive polythiophene, oxidative polymerization is preferably carried out in the presence of the polyanions described below.

[0098] The concentration of thiophene monomer in the aqueous phase medium is preferably in the range of 0.1 to 25% by weight, and more preferably in the range of 0.5 to 10% by weight, all of which are relative to the total weight of the aqueous reaction medium.

[0099] Suitable oxidizing agents include iron(III) salts such as FeCl3, iron(III) salts of aromatic and aliphatic sulfonic acids; H2O2; K2Cr2O7; KMnO4; alkali metal perborates; alkali metal persulfates or ammonium persulfates; and mixtures thereof.

[0100] Further suitable oxidizing agents can be found, for example, in Handbook of Conducting Polymers (Ed. Skotheim, TA, Marcel Dekker: New York, 1986, Vol. 1, pages 46-57).

[0101] Particularly preferred oxidizing agents are peroxodisulfates, especially K2S2O8, Na2S2O8; iron(III) salts, especially iron(III) chloride; or combinations thereof.

[0102] A mixture of a peroxodisulfate and at least one further compound that catalyzes the cleavage of the peroxodisulfate, such as an Fe(III) salt, is particularly preferred.

[0103] In a particularly preferred embodiment, the oxidizing agent is a mixture of Fe2(SO4)3 and Na2S2O8.

[0104] There are various methods for preparing aqueous reaction media. One method is to dissolve or disperse thiophene monomers in an aqueous reaction medium, followed by the addition of oxidizing agents, which can also be dissolved or dispersed in the aqueous phase. Alternatively, one can first dissolve or disperse oxidizing agents in an aqueous reaction medium, followed by the addition of thiophene monomers, which can also be dissolved or dispersed in the aqueous phase.

[0105] If more than one oxidizing agent is used, for example, a mixture of Fe2(SO4)3 and Na2S2O8, it is further possible to first mix one of these components with the thiophene monomer in an aqueous reaction medium, and then add the second oxidizing agent.

[0106] Oxidative polymerization is preferably carried out under an inert atmosphere as disclosed in EP-11453877 (Agfa Gevaert). When an oxidizing agent, such as peroxodisulfate, is added to the reaction medium, the oxygen content in the reaction medium is preferably less than 3 mg / liter, more preferably less than 1.5 mg / liter, and most preferably less than 0.5 mg / liter.

[0107] The oxygen concentration in the reaction medium can be adjusted by any means, such as freeze-thaw techniques, prolonged injection of an inert gas such as argon, nitrogen, or helium into the reaction medium, or consumption of oxygen by a sacrificial reaction under an inert gas atmosphere (blanket). Preferably, the inert gas is injected into the reaction medium until polymerization is complete, thereby maintaining the oxygen concentration below 3 mg / l.

[0108] Oxidative polymerization is preferably carried out at a low pH, as disclosed in EP-A 1384739 (Heraeus). The pH is preferably 1.5 or less, more preferably 1.00 or less.

[0109] To adjust the pH, an acid can be used, which is preferably selected from the group consisting of water-soluble inorganic acids and water-soluble organic acids. Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Examples of organic acids include p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid.

[0110] The temperature of the reaction mixture is preferably 0 to 100°C, more preferably 0 to 50°C, and most preferably 5 to 30°C.

[0111] The amounts of thiophene monomer and polyanion in the reaction mixture are selected such that a stable polythiophene / polyanion dispersion is obtained, and the solid content of this dispersion is preferably 0.05 to 25% by weight, more preferably 0.1 to 10% by weight, and most preferably 0.8 to 2% by weight.

[0112] After the polymerization reaction is complete, the liquid composition can be further purified, for example, by filtration, particularly by ultrafiltration, and / or by treatment with an ion exchanger, particularly by treatment with an anion exchanger and a cation exchanger.

[0113] After the purification process, the conductive polymer dispersion can be further optimized for its intended application. For example, when used in the preparation of an antistatic layer, the following liquid formulations can be prepared from the conductive polymer dispersion.

[0114] Various homogenization techniques can be used during the preparation of conductive polymers. The following homogenization techniques can be selected: -Ultrasonic homogenization technique; - Pressurized homogenization technique; and -Mechanical homogenization techniques.

[0115] Suitable mechanical homogenizers are rotor-stator homogenizers and blade-type homogenizers. Another mechanical homogenization technique is the use of a spinning disk reactor.

[0116] Suitable high-pressure homogenizers, such as Gaulin homogenizers or Ariete homogenizers, force a dispersion through a very narrow channel or orifice under pressure. Another suitable high-pressure homogenizer is a microfluidizer.

[0117] Two or more homogenizers can be used in combination, preferably in a continuous configuration.

[0118] Homogenization techniques can be used before, during, and after polymerization reactions. These homogenization techniques can also be used during the preparation of the liquid formulations described below.

[0119] Polyanion When the conductive polymer is an externally conductive polythiophene, the conductive polymer dispersion preferably contains a polyanion. The polyanion is preferably a polymer-type polyanion.

[0120] The conductive polymer dispersion contains polymer-type polyanions, wherein at least 75 mol%, more preferably at least 80 mol%, more preferably at least 90 mol%, and most preferably at least 99 mol%, of the monomer units of the polyanions contain substituents selected from the group consisting of: sulfonic acid or a salt thereof, phosphonic acid or a salt thereof, phosphate ester or a salt thereof, sulfuric acid ester or a salt thereof, and carboxylic acid or a salt thereof.

[0121] The functional group is preferably a sulfonic acid or a salt thereof.

[0122] Polymer-type polyanions can be copolymers of different monomers, but homopolymers are preferred.

[0123] In particularly preferred embodiments, the polymer-type polyanion is styrene-based.

[0124] In a particularly preferred embodiment, the polyanion is poly(4-styrenesulfonic acid) or a salt thereof.

[0125] These polyacids or their alkali salts are available commercially, or they can be prepared according to known methods, such as those described, for example, in Houben-Weyl, Methoden der Organische Chemie, Bd. E20 Makromolekulare Stoffe, Teil 2, (1987), pp.1141.

[0126] The weight-average molecular weight (Mw) of the polymer-type anion is not particularly limited, but is preferably 1 The range is 000 to 1,000,000 Da, more preferably 50,000 to 500,000 Da, and most preferably 100,000 to 300,000 Da.

[0127] Conductive polymers and polyanions combine to typically form particles. The median diameter (d) of polythiophene / polyanion particles. 50) is preferably 1 to 100 nm, more preferably 2 to 75 nm, most preferably 5 to 50 nm, and particularly preferably 10 to 40 nm. d 50 Particle size is preferably measured by liquid-phase centrifugal sedimentation particle size analysis.

[0128] conductive polymer formulations Depending on the application in which the conductive polymer dispersion is used, additional components can be added to the conductive polymer dispersion, thereby forming a conductive polymer formulation optimized for that application.

[0129] All or part of the additional components listed below may be added to what is referred to above as the conductive polymer dispersion.

[0130] Examples of such additional components include surfactants, adhesion promoters, crosslinking agents, additional binders, conductivity-enhancing compounds, thermal and moisture stability-enhancing compounds, acidic compounds, or alkaline compounds.

[0131] The following surfactant compounds are possible: - Anionic surfactants, such as alkylbenzene sulfonic acid and salts, paraffin sulfonates, alcohol sulfonates, ether sulfonates, sulfosuccinates, phosphate esters, alkyl ether carboxylic acids, or carboxylates; - Cationic surfactants, such as quaternary alkylammonium salts; - Nonionic surfactants, such as linear alcohol ethoxylates, oxo alcohol ethoxylates, alkylphenol ethoxylates, or alkyl polyglucosides; and - Zwitterionic surfactants, for example, compounds having both a carboxylic acid group and a quaternary ammonium group (e.g., lauryl-N,N-(dimethylammonio)butyrate and lauryl-N,N-(dimethyl)-glycine betaine, etc.), compounds having both a sulfate group and a quaternary ammonium group (e.g., 3-[(3-colamidopropyl)dimethylammonio]-1-propanesulfonate, 3-(4-tert-butyl-1-pyridinio)-1-propanesulfonate, 3-(1-pyridinio)-1-propanesulfonate, and 3-(benzyldimethylammonio)propanesulfonate, etc.), compounds having both a phosphate group and a quaternary ammonium group (e.g., those having hexadecylphosphocholine), compounds having a quaternary ammonium group with a hydroxyl group added (e.g., lauryldimethylammonio) A phospholipid comprising a quaternary ammonium head (such as N-oxide) coupled with two hydrophobic fatty acids via a phosphate group and glycerol.

[0132] Particularly suitable surfactants are commercially available surfactants under the trademarks Dynol® and Zonyl®.

[0133] Suitable adhesion promoters include organic functional silanes or their hydrolysates, such as 3-glycidoxypropyltrialkoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-methacrylateoxypropyltrimethoxysilane, vinyltrimethoxysilane, or octyltriethoxysilane.

[0134] Suitable crosslinking agents are selected from the group consisting of melamine compounds, epoxysilanes, silane hydrolysis products, and blocked isocyanates. A suitable epoxysilane is 3-glycidoxypropyltrialkoxysilane. Suitable silane hydrolysis products are those disclosed in EP-A 564911 (AGFA GEVAERT NV), such as hydrolysis products of tetraethoxysilane or tetramethoxysilane.

[0135] Suitable conductivity-improving compounds are as follows: - Compounds having an ether group, such as tetrahydrofuran; - Compounds having a lactone group, such as γ-butyrolactone or γ-valerolactone; - Compounds having an amide group or lactam group, such as caprolactam, N-methylcaprolactam, N,N-dimethylacetamide, N-methylacetamide, formamide, N,N-dimethylformamide (DMF), N-methylformamide, N-methylformanilide, N-methyl-2-pyrrolidone (NMP), N-octylpyrrolidone, 2-pyrrolidone, N-butylpyrrolidone, and N-hydroxyethylpyrrolidone; -Sulfones and sulfoxides, for example, sulfolanes (tetramethylene sulfone) or dimethyl sulfoxide (DMSO), etc.; - Sugars or sugar derivatives, such as arabinose, saccharose, glucose, fructose, or lactose; - Dialcohols or polyalcohols, such as sorbitol, xylitol, mannitol, mannose, galactose, sorbose, gluconic acid or ethylene glycol, di or tri(ethylene glycol), 1,1,1-trimethylolpropane, 1,3-propanediol, 1-,2-propanediol, 1,5-pentanediol, 1,2,3-propanetriol, 1,2,4-butanetriol, or 1,2,6-hexanetriol, aromatic di or polyalcohols, such as resorcinol. Particularly preferred conductivity-improving compounds are selected from the group consisting of N-methylpyrrolidinone, N-butylpyrrolidone, N-hydroxyethylpyrrolidone, DMSO, ethylene glycol, and diethylene glycol.

[0136] Suitable thermal and moisture stability improving compounds are specified in WO2008 / 055834 (AGFA). The aromatic compounds are those having at least two hydroxyl groups, as disclosed on page 10, line 15 to page 11, line 10 of GEVAERT NV. Particularly preferred compounds are selected from the group consisting of pyrogallol, gallic acid esters, and polyhydroxybenzoic acid.

[0137] To adjust the pH, a base or acid as described on page 4, lines 13-32 of WO2010 / 003874 is preferably used. These compounds do not impair film formation of the polymer capacitor formulation and do not volatilize even at high temperatures such as soldering temperatures. Suitable compounds are 2-dimethylaminoethanol, 2,2'-iminodiethanol, or 2,2',2''-nitrilotriethanol as bases, and polystyrene sulfoethanol as an acid. It is acid.

[0138] For certain applications, it may be advantageous for the majority of the dispersion medium of a conductive polymer formulation to be non-aqueous, for example, to improve the surface wettability of the conductive polymer formulation or to improve the drying properties of coatings / prints prepared from such formulations. Diluting a conductive polymer dispersion with an organic solvent reduces the weight percent concentration of the conductive polymer; however, instead of simply doing so, it is often preferable to add the organic solvent to the conductive polymer composition and then remove at least some of the water, as disclosed, for example, in EP-A 1453878 (AGFA GEVEAERT NV). The water is typically removed by evaporation. The water content is preferably reduced by at least 65% by weight. The organic solvent used to prepare such formulations is preferably selected from the group consisting of 1,2-propanediol, propylene glycol, diethylene glycol, N-methylpyrrolidone, and carbitol acetate.

[0139] The conductive polymer dispersion or formulation according to the present invention can be applied to a substrate by any suitable method, such as coating, printing, jet spraying, or atomizing.

[0140] The aqueous conductive dispersion according to the present invention is preferably used as a conductive printing ink, such as a conductive screen printing ink, gravure printing ink, conductive flexographic printing ink, inkjet printing ink, or offset printing ink. The conductive polymer compound according to the present invention is most preferably used as a screen printing ink.

[0141] The suitability of an aqueous conductive dispersion for a particular printing process is largely determined by the viscosity of the formulation.

[0142] The viscosity of gravure printing inks and flexographic printing inks is approximately 15 mPa·s during printing.

[0143] The viscosity of screen printing inks depends on the screen mesh used and the printing speed. Typical viscosity during printing is for high-speed processes (shear rate = approximately 100 seconds). -1 In the case of ), it is 0.5~5 Pa·s, and for low-speed processes (shear rate = approximately 1 second -1 ) in the case of 8-50 Pa·s, and while stopped (shear rate = approximately 10 -2 seconds -1 ) is 50-800 Pa·s.

[0144] Inkjet inks typically have a viscosity of 2–20 mPa·s under printing conditions.

[0145] Viscosity can be adjusted, for example, by adding appropriate rheological modifiers as further additives.

[0146] The solids content of the conductive polymer formulation is preferably 0.01 to 20% by weight, more preferably 0.1 to 15% by weight, and most preferably 0.25 to 10% by weight, in each case based on the total weight of the formulation.

[0147] Purpose The aqueous conductive dispersion according to the present invention is preferably used as a conductive printing ink, and more preferably as a conductive screen printing ink.

[0148] Screen printing inks are preferably used in applications such as home appliances, automobiles, energy production, and medical applications.

[0149] Screen printing inks can be applied to soft and hard substrates, such as polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), polyimide (PI), and glass.

[0150] Screen printing inks can be used to manufacture electrodes for EL lamps, transparent heating elements, capacitive touch sensors, membrane switches, fingerprint sensors, conductive biocompatible layers, medical sensors, printed displays including signs, labels, displays, or energy level matching layers. [Examples]

[0151] material Unless otherwise noted, all materials used in the following examples were readily available from standard suppliers, such as ALDRICH CHEMICAL Co. (Belgium) and ACROS (Belgium). Deionized water was used.

[0152] Carbopol Aqua 30 is an aqueous emulsion of acrylate / acrylic acid copolymer, manufactured by Lubrizol.

[0153] Dynacoll 7150 is made of polyester and is sold by Evonik.

[0154] EDOT is 3,4-ethylenedioxythiophene, sold by Heraeus.

[0155] Lewatit® MonoPlus M600 is a basic gel-type anion exchange resin, sold by Lanxess AG.

[0156] Lewatit® MonoPlus S 108 H is an acidic gel-type cation exchange resin, sold by Lanxess AG.

[0157] PSS is an aqueous solution of polystyrene sulfonic acid having Mw300kDa, and is prepared according to the method disclosed in Houben-Weyl, Methoden der organischen Chemie, Vol. E 20, Makromolekulaire Stoffe, Teil 2 (1987), page 1141).

[0158] Silwet L-7607 is a silicone / poly(ethylene oxide) copolymer, manufactured by Momentive Performance Materials.

[0159] Vondic 1980NE and Vondic 2220 are polyurethane resins dispersed in water, both sold by SunChemical.

[0160] MELINEX® ST507 (125μm) is a polyester substrate, sold by DuPont-Teijin.

[0161] PET rough (175 μm) is a polyester substrate prepared in-house without the use of primers.

[0162] method Surface resistance measurement The surface resistance SER was measured at room temperature using the two-terminal method.

[0163] Adhesion measurement The adhesion of screen-printed films onto different substrates was determined using a Cross Hatch Cutter Elcometer 1542 in accordance with ISO 2409:2020. Tesa 4104 tape (25 mm) was used. The measurement results were scored from 0 to 5, depending on whether the adhesion was high (0) or low (5).

[0164] Screen printing PEDOT / PSS screen printing ink was printed onto a substrate using a polyester screen P77 / 55 (77 wires / cm of 55μm diameter) with a flatbed screen printer. The printer was fitted with a Ulano Vision 35 capillary film with a 14μm EOM. A flat bar was used at an angle of 110°. A squeegee with a hardness of 80 shore was used at an angle of 80° and a speed of 300 mm / sec. After printing, the ink was dried in a belt conveyor dryer using hot air at 130°C for 3 minutes.

[0165] Example 1: Preparation of PEDOT / PSS In a reaction vessel, 73.3 g of PSS, 325 mL of deionized water, and 4.3 g of nitric acid (48.3 mmol) were mixed. 0.16 g of iron(III) sulfate and 3.16 g of sodium persulfate (13.3 mmol) were added. The reaction mixture was stirred under a nitrogen stream and cooled to 5°C. The oxygen level was less than 30 ppb.

[0166] EDOT (1.71 g, 12.1 mmol) was added to the reaction mixture and the mixture was stirred at 5°C for 20 hours.

[0167] Next, the reaction mixture was treated with an ion exchanger (110g of Lewatit® MonoPlus M600 + 60g of Lewatit® MonoPlus S 108 H, filtered and washed with 50 mL x 2 of water, and this process was repeated). The resulting viscous mixture was subjected to high-shear homogenization (Lab Gaulin, 4 x 600 bar).

[0168] After the vacuum concentration step, a blue 1.12 wt% PEDOT / PSS-1 aqueous dispersion (a) was obtained.

[0169] Example 2: Preparation of PEDOT / PSS-based formulations In a reaction vessel, the PEDOT / PSS (47.98 g) obtained in Example 1, 1,2-dipropylene glycol (69.12 g), and diethylene glycol (6.98 g) were added and stirred. Then, under reduced pressure at 48°C, water was removed from the mixture until the water content was less than 8% by weight.

[0170] After the reaction mixture was cooled to room temperature, (3-glycidyloxypropyl)trimethoxysilane (0.208 g), Silwet L-7607 (0.184 g), and Carbopol Aqua30 (2.58 g) were added, and the mixture was stirred.

[0171] Example 3: Preparation of the screen ink of the present invention Preparation of INV-01 Dissolve 1 g of Dynacoll 7150 in ethyl acetate (3 g) and add it to Vondic 1980NE (6.59 g) in a reaction vessel. Disperse the mixture using a Disperlux homogenizer at 3000 rpm. Then add deionized water (3 g) and remove the ethyl acetate by rotary evaporation. Dilute the resulting dispersion to a concentration of 40% by weight. The PEDOT / PSS-based formulation of Example 2 (3.9712 g) is subjected to high-shear homogenization (Lab Gaulin, 3 × 600 bar). Then, while stirring at 2500 rpm, Vondic 1980NE / Dynacoll 7150 Add the dispersion (0.288g). Add the dihydroxybenzoic acid (0.288g). After stirring for 30 minutes, neutralize the mixture to pH 2.61 with N,N-dimethylethylamine.

[0172] Preparation of INV-02 The experiment was carried out in the same manner as described in Example 1, except that 4.4 g of Vondic 1980NE was used. The mixture was neutralized to pH 2.71.

[0173] Example 4: Preparation of comparative screen inks Preparation of COMP-01 The PEDOT / PSS base formulation obtained in Manufacturing Example 2 was added to a container and stirred. Vondic 1980NE (0.576 g) was added and dispersed in a Disperlux homogenizer for 30 minutes. 12.8 g of the resulting mixture was further subjected to high-shear homogenization (Lab Gaulin, 3 × 600 bar). Dihydroxybenzoic acid (0.0922 g) was added. After stirring for 30 minutes, the formulation was neutralized to pH 2.78 with N,N-dimethylethylamine.

[0174] Preparation of COMP-02 The experiment was carried out in the same manner as described in Example 2, except that 0.0576 g of Vondic 2200 was used instead of Vondic 1980 NE. The mixture was neutralized to pH 2.50.

[0175] Example 3 The SER and adhesion properties of films screen-printed with the above-described screen ink and comparative screen ink on different substrates were measured as described above and are shown in Table 1 below. [Table 1]

[0176] As is clear from the results in Table 1, the adhesion of the screen-printed inks (INV-01 and INV-02) containing the polymer mixture according to the present invention as a binder is superior to that of the screen-printed ink (COMP-01) containing a different type of polymer binder and not containing NMP. The adhesion is also good, and is comparable to that of screen-printed ink (COMP-02) containing NMP, which includes different types of polymer binders.

Claims

1. A conductive polymer composition, the following: - Conductive polymers and, - Polymer binder and, The polymer binder comprises an aqueous dispersion of a polymer mixture, and the polymer mixture comprises a first polymer that is water-dispersible and a second polymer that is water-insoluble. The conductive polymer composition.

2. The conductive polymer composition according to claim 1, wherein the water-insoluble polymer is water-dispersible or non-dispersible.

3. The conductive polymer composition according to claim 1 or 2, wherein the first polymer and the second polymer are selected from the group consisting of polyurethane, polyester, and polyacrylate.

4. The conductive polymer composition according to any one of the prior claims, wherein the first polymer is polyurethane and the second polymer is polyester.

5. The conductive polymer composition according to any one of the prior claims, wherein the conductive polymer is polythiophene.

6. Furthermore, the conductive polymer composition according to any one of the prior claims, further containing a polyanion.

7. The polythiophene and polyanion exist as polythiophene / polyanion particles, and the particle size is measured by liquid-phase centrifugal sedimentation particle size analysis, with the median particle diameter (d ５０ The conductive polymer composition according to claim 6, wherein the length is 5 to 40 nm.

8. The conductive polymer composition according to claim 6 or 7, wherein the polyanion is polystyrene sulfonic acid or a salt thereof.

9. The conductive polymer composition according to any one of claims 6 to 8, wherein the weight-average molecular weight (Mw) of the polyanion is 50 to 500 kDa.

10. A conductive polymer compound comprising a conductive polymer composition as defined in any one of the prior claims.

11. The conductive polymer formulation according to claim 10, further comprising a conductivity-enhancing compound selected from the group consisting of N-methylpyrrolidinone, N-butylpyrrolidone, N-hydroxyethylpyrrolidone, DMSO, ethylene glycol, and diethylene glycol.

12. Furthermore, the conductive polymer compound according to claim 10 or 11 comprises a crosslinking agent selected from the group consisting of epoxysilane, hydrolysis products of silane, and blocked isocyanates.

13. Use of a conductive polymer formulation according to any one of claims 10 to 12 as a conductive screen printing ink.

14. Use of a conductive polymer composition according to any one of claims 1 to 9 or a conductive polymer compound according to any one of claims 11 to 12 for preparing a conductive layer for electronic equipment.

15. The use according to claim 14, wherein the electronic device is selected from photoconductive cells, photoresistors, photoswitches, phototransistors, photocells, IR detectors, photovoltaics, solar cells, coating materials for memory storage devices, field-effect resistors, antistatic films, biosensors, electrochromic devices, solid electrolyte capacitors, hybrid capacitors, supercapacitors, energy storage devices, batteries, and electromagnetic shielding.

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