PEDOT dispersion with a low power-of-law N

Abstract

The present invention relates to a dispersion comprising i) a dispersant; and ii) at least one polythiophene dispersed in the dispersant i). Т =Ky n The exponent n in the power law is in the range of 0.40 to 0.65, and in the formula, T θ is the shear stress, K is the flow viscosity constant, and Y is the shear rate dy / dt. The present invention also relates to a process for preparing a dispersion, the dispersion obtained by the process, a process for preparing a laminate, the laminate obtained by the process, and the use of the dispersion for forming a polymer outer layer in a capacitor.

Description

[Technical Field]

[0001] The present invention relates to a dispersion comprising a dispersant and at least one polythiophene dispersed in the dispersant, a process for preparing the dispersion, a dispersion obtained by the process, a process for preparing a laminate, a laminate obtained by the process, and the use of the dispersion for forming a polymer outer layer in a capacitor. [Background technology]

[0002] A typical electrolytic capacitor generally consists of a porous metal electrode, an oxide layer placed on the metal surface, a generally solid conductive material introduced into the porous structure, external electrodes (contacts) such as a silver layer, and other electrical contacts and encapsulants. One frequently used electrolytic capacitor is the tantalum electrolytic capacitor, where the anode electrode is made from valve metal tantalum, and a uniform dielectric layer of tantalum pentoxide is formed (also called "formed") on top of it by anodizing. A liquid or solid electrolyte forms the cathode of the capacitor. Aluminum capacitors are also frequently used, where the anode electrode is made from valve metal aluminum, and a uniform electrically insulating aluminum oxide layer is formed as the dielectric on top of it by anodizing. Here again, a liquid or solid electrolyte forms the cathode of the capacitor. Aluminum capacitors are generally embodied as wound capacitors or stacked capacitors.

[0003] Due to their high conductivity, π-conjugated polymers are particularly suitable as solid electrolytes in the above-mentioned capacitors. π-conjugated polymers are also called conductive polymers or synthetic metals. Compared to metals, polymers have advantages in terms of processing, weight, and the selective tuning of properties by chemical modification, and therefore conjugated polymers are gaining increasing commercial importance. Examples of known π-conjugated polymers include polypyrrole, polythiophene, polyaniline, polyacetylene, polyphenylene, and poly(p-phenylene-vinylene), with poly(3,4-ethylene-dioxythiophene) (PEDOT) being a particularly important polythiophene used technically due to its very high conductivity in its oxidized form.

[0004] Modern solid electrolytic capacitors require low equivalent series resistance (ESR), low leakage current, and good stability against external stresses. High mechanical stresses, which can significantly increase the leakage current of the capacitor anode, occur particularly during the manufacturing process when sealing the capacitor anode.

[0005] Such stability against stress, and therefore low leakage current, can be achieved primarily by an outer layer approximately 5-50 μm thick, made of a conductive polymer, on the capacitor anode. Such a layer is used as a mechanical buffer between the capacitor anode and the cathode electrode. This prevents the silver layer (contact) from directly contacting the dielectric or damaging it, thus preventing an increase in the capacitor's leakage current, for example, when mechanical stress is applied.

[0006] In the prior art, PEDOT / PSS dispersions have been used not only for forming a solid electrolyte layer but also for forming a polymer outer layer applied on top of the solid electrolyte layer. For example, German Patent Application Publication No. 102005033839(A) discloses the use of a dispersion comprising conductive polymer particles and a binder for forming a polymer outer layer, wherein the proportion of conductive polymer particles in the dispersion having a diameter of less than 700 nm forms at least 5% of the solid content by weight of the dispersion, and the dispersion further comprises solid particles having a diameter in the range of 0.7 to 20 μm.

[0007] However, the leakage current of electrolytic capacitors in which the polymer outer layer is prepared using a PEDOT / PSS-based dispersion, such as that disclosed in German Patent Application Publication No. 102005033839(A), has often been observed to be too high for certain applications.

[0008] The present invention relates to capacitors, preferably to solid electrolytic capacitors, and more preferably to capacitors known from the prior art that include a polymer outer layer on a solid electrolyte layer, and is based on the objective of overcoming the shortcomings arising from the prior art, wherein the polymer outer layer is based on a π-conjugated polymer such as PEDOT, and even more preferably to capacitors known from the prior art that include a polymer outer layer based on PEDOT / PSS.

[0009] In particular, the present invention is based on the objective of providing a dispersion containing at least one polythiophene, preferably a dispersion containing a polythiophene-polyanion complex, and more preferably a dispersion containing a PEDOT / PSS complex, which is particularly useful for preparing a polymer outer layer in a capacitor characterized by low leakage current.

[0010] Furthermore, an object of the present invention was to provide a process for preparing such advantageous dispersions. The process for preparing advantageous dispersions should be characterized by enabling the production of these dispersions in the simplest possible manner, and in particular, with the fewest possible process steps.

[0011] Furthermore, an object of the present invention was to provide a preparation process for a laminate, preferably an electrolytic capacitor, characterized by a reduction in leakage current compared to electrolytic capacitors known from the prior art. [Overview of the project]

[0012] Contributions to solving at least one, preferably two or more, of the above objectives are made by the independent claims. Dependent claims provide preferred embodiments that contribute to solving at least one of the objectives at least partially.

[0013] |1a| A contribution to solving at least one of the objectives of the present invention is, i) Dispersants (also called "dispersing agents"); ii) A dispersion comprising i) at least one polythiophene dispersed in a dispersant; Regarding dispersions, related to Ostwald de Waele.

[0014]

number

[0015]

number

[0016] As used in connection with the present invention, the term "dispersion" generally refers to any liquid composition in which polythiophene, for example, polythiophene as part of a complex containing polythiophene and polyanion, is distributed in some way in a homogeneous phase formed by liquid dispersant i) (dispersant i), and thus forms the liquid phase of the dispersion. Note that the transition between "dispersion" and "solution" can be fluid. Therefore, there is no distinction between the terms "dispersed" and "dissolved" below. Similarly, there is no distinction between "dispersion" and "solution" or between "dispersant" and "solvent." Rather, these terms are used synonymously.

[0017] |2a|According to a preferred embodiment of the dispersion according to the present invention, the dispersant i) comprises water. Preferably, in each case, the dispersant i) comprises water in an amount of at least 50% by weight, more preferably at least 65% by weight, even more preferably at least 70% by weight, and most preferably at least 80% by weight, based on the total weight of the dispersion. This preferred embodiment is a second embodiment of the dispersion according to the present invention, and is preferably dependent on the first embodiment.

[0018] |3a|According to a more preferred embodiment of the dispersion according to the present invention, at least one polythiophene ii) is an externally doped polythiophene such as a cationic polythiophene existing in the form of a polythiophene / polyanion complex, more preferably in the form of a PEDOT / PSS complex, a self-doped polythiophene such as poly(4-[(2,3-dihydrothieno-[3,4-b]-[1,4]dioxin-2-yl)methoxy]propane-1-sulfonic acid), poly(4-[(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy]butane-1-sulfonic acid)(PEDOT-S) or poly-(4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonic acid)), or a mixture thereof. This preferred embodiment is a third embodiment of the dispersion according to the present invention and is preferably dependent on the first or second embodiment.

[0019] |4a|According to a more preferred embodiment of the dispersion according to the present invention, at least one polythiophene ii) exists in the form of particles of a complex comprising at least one polythiophene ii) and a polyanion. This preferred embodiment is a fourth embodiment of the dispersion according to the present invention, and is preferably dependent on any of the first to third embodiments.

[0020] |5a|According to a more preferred embodiment of the dispersion according to the present invention, at least one polythiophene ii) exists in the form of particles of a complex comprising at least one polythiophene ii) and a polyanion, where the polythiophene is poly(3,4-ethylenedioxythiophene) and the polyanion is an anion of polystyrene sulfonic acid. Therefore, the complex of polythiophene and polyanion is preferably a PEDOT / PSS complex. This preferred embodiment is a fifth embodiment of the dispersion according to the present invention and is preferably dependent on any of the first to fourth embodiments.

[0021] |6a|According to a more preferred embodiment of the dispersion according to the present invention, at least one polythiophene ii) exists in the form of particles of a complex comprising at least one polythiophene ii) and a polyanion, preferably in the form of particles comprising PEDOT / PSS, and the dispersion contains the polyanion and polythiophene in a polyanion:polythiophene weight ratio in the range of 0.5:1 to 30:1, preferably in the range of 0.8:1 to 15:1, more preferably in the range of 1:1 to 10:1, even more preferably in the range of 1.2:1 to 8:1, and most preferably in the range of 1.4:1 to 4:1. The weight of polythiophene in this context corresponds to the weight of the thiophene monomer used in the preparation of the polythiophene, assuming that complete conversion occurs during polymerization. This preferred embodiment is a sixth embodiment of the dispersion according to the present invention, and is preferably dependent on any of the first to fifth embodiments.

[0022] |7a|According to a more preferred embodiment of the dispersion according to the present invention, at least one polythiophene ii) is present in the form of particles of a complex comprising at least one polythiophene ii) and a polyanion, preferably in the form of particles comprising PEDOT / PSS, and the weight-average diameter (d) of these particles is determined by ultracentrifugation measurement. 50The wavelength range is 10 nm to 500 nm, more preferably 20 nm to 400 nm, even more preferably 30 nm to 300 nm, and most preferably 40 nm to 300 nm. This preferred embodiment is a seventh embodiment of the dispersion according to the present invention, and is preferably dependent on any of the first to sixth embodiments.

[0023] |8a|According to a more preferred embodiment of the dispersion according to the present invention, at least one polythiophene ii) is present in the form of particles of a composite comprising at least one polythiophene ii) and a polyanion, preferably in the form of particles comprising PEDOT / PSS, and the dispersion has a diameter distribution of these particles determined by ultracentrifugation measurement at less than 1,000 nm, preferably less than 800 nm, more preferably less than 600 nm, and most preferably less than 500 nm. 90 It has a value. This preferred embodiment is an eighth embodiment of the dispersion according to the present invention, and is preferably dependent on any of the first to seventh embodiments.

[0024] |9a|According to a more preferred embodiment of the dispersion according to the present invention, at least one polythiophene ii) is present in the form of particles of a composite comprising at least one polythiophene ii) and a polyanion, preferably in the form of particles comprising PEDOT / PSS, and the dispersion has a diameter distribution of these particles determined by ultracentrifugation measurement of greater than 2 nm, preferably greater than 5 nm, more preferably greater than 10 nm, and most preferably greater than 20 nm. 10 It has a value. This preferred embodiment is a ninth embodiment of the dispersion according to the present invention, and is preferably dependent on any of the first to eighth embodiments.

[0025] |10a|According to a more preferred embodiment of the dispersion according to the present invention, the dispersion in each case has a solid content of at least 1% by weight, preferably at least 1.4% by weight, more preferably at least 1.6% by weight, even more preferably at least 1.8% by weight, and most preferably at least 2.0% by weight, based on the total weight of the dispersion. This preferred embodiment is a tenth embodiment of the dispersion according to the present invention, which is preferably dependent on any of the first to ninth embodiments.

[0026] |11a|According to a more preferred embodiment of the dispersion according to the present invention, the dispersion has a pH value (measured at 25°C) in the range of 1 to 8.0, preferably in the range of 1.5 to 7, and more preferably in the range of 2.5 to 6. This preferred embodiment is the 11th embodiment of the dispersion according to the present invention, and is preferably dependent on any of the 1st to 10th embodiments.

[0027] |12a|According to a more preferred embodiment of the dispersion according to the present invention, the conductive layer prepared from the dispersion has a conductivity of at least 10 S / cm, preferably at least 50 S / cm, more preferably at least 100 S / cm, and most preferably at least 200 S / cm, as determined by the test method disclosed herein (i.e., the test method for determining the conductivity of the conductive layer for a dispersion obtained after adding 1 g of DMSO to 19 g of the dispersion according to the present invention). This preferred embodiment is a twelfth embodiment of the dispersion according to the present invention, which preferably depends on any of the first to eleventh embodiments.

[0028] |13a|According to a more preferred embodiment of the dispersion according to the present invention, at least one polythiophene ii) is present in the form of particles of a complex comprising at least one polythiophene ii) and a polyanion, preferably in the form of particles comprising PEDOT / PSS, and the dispersion in each case contains a total amount of polythiophene and polyanion (i.e., amount of polythiophene + amount of polyanion) of at least 1% by weight, preferably at least 1.4% by weight, more preferably at least 1.6% by weight, even more preferably at least 1.7% by weight, and most preferably at least 1.8% by weight, based on the total weight of the dispersion. This preferred embodiment is a thirteenth embodiment of the dispersion according to the present invention, preferably dependent on any of the first to twelfth embodiments.

[0029] |14a|According to a more preferred embodiment of the dispersion according to the present invention, the dispersion is iii) further comprising at least one additive, the at least one of which is selected from the group consisting of binders, pH adjusters, crosslinking agents, adhesion promoters, conductivity enhancers, surfactants, stabilizers, and at least two combinations thereof.

[0030] This preferred embodiment is a 14th embodiment of the dispersion according to the present invention, and is preferably dependent on any of the 1st to 13th embodiments.

[0031] |15a|According to a more preferred embodiment of the dispersion according to the present invention, the dispersion includes, as an additive, iii) further comprising at least one organic binder, preferably selected from the group consisting of polyolefins, polyvinyl acetate, polycarbonate, polyvinyl butyral, polyacrylic acid esters, polyacrylamides, polymethacrylates, polymethacrylates, polystyrene, polyacrylonitrile, polyvinyl chloride, polyvinylpyrrolidone, polybutadiene, polyisoprene, polyethers, polyesters, polyurethanes, polyamides, polyimides, polysulfones, polysilicones, epoxy resins, styrene acrylates, vinyl acetate / acrylate and ethylene / vinyl acetate copolymers, polyvinyl alcohol or cellulose derivatives and mixtures thereof.

[0032] Preferably, the dispersion contains an organic binder in each case in an amount ranging from 0.1 to 20% by weight, preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight, and even more preferably 1 to 5% by weight, based on the total weight of the dispersion. This preferred embodiment is a 15th embodiment of the dispersion according to the present invention, and is preferably dependent on the 14th embodiment.

[0033] |16a|According to a more preferred embodiment of the dispersion according to the present invention, the dispersion has a viscosity in the range of 1 to 1000 mPa×s, preferably in the range of 5 to 750 mPa×s, more preferably in the range of 10 to 500 mPa×s, and most preferably in the range of 20 to 300 mPa×s (at 20°C and 100°S) -1 It has a shear rate (measured with a rheometer). This preferred embodiment is the 16th embodiment of the dispersion according to the present invention, and is preferably dependent on any of the 1st to 15th embodiments.

[0034] |1b| A contribution to solving at least one objective of the present invention is a process 1 for preparing a dispersion, I) i) Dispersant; ii) A dispersion comprising at least one polythiophene dispersed in a dispersant i), A step provided by polymerizing a thiophene monomer in the presence of a dispersant i), II) This is also done by a first embodiment of process 1 for preparing a dispersion, which includes the step of adjusting the power law exponent n in the dispersion provided in process step I) to be in the range of 0.40 to 0.65, preferably in the range of 0.41 to 0.64, more preferably in the range of 0.42 to 0.63, and even more preferably in the range of 0.45 to 0.60.

[0035] |2b|According to a preferred embodiment of Process 1 according to the present invention, the dispersant i) comprises water. Preferably, in each case, the dispersant i) comprises water in an amount of at least 50% by weight, more preferably at least 65% by weight, even more preferably at least 70% by weight, and most preferably at least 80% by weight, based on the total weight of the dispersion. This preferred embodiment is a second embodiment of Process 1 according to the present invention, and is preferably dependent on the first embodiment.

[0036] |3b|According to a more preferred embodiment of Process 1 according to the present invention, the thiophene monomer is polymerized in the presence of a dispersant i) and a polyanion to obtain a dispersion containing a polythiophene-polyanion complex. This preferred embodiment is a third embodiment of Process 1 according to the present invention and is preferably dependent on the first or second embodiment.

[0037] |4b|According to a more preferred embodiment of Process 1 according to the present invention, a thiophene monomer is polymerized in the presence of a dispersant i) and a polyanion to obtain a dispersion containing a polythiophene-polyanion complex, wherein the thiophene monomer is 3,4-ethylenedioxythiophene and the polyanion is an anion of polystyrene sulfonic acid. Therefore, the polythiophene-polyanion complex is preferably a PEDOT / PSS complex. This preferred embodiment is a fourth embodiment of Process 1 according to the present invention and is preferably dependent on any of the first to third embodiments.

[0038] |5b|According to a more preferred embodiment of process 1 according to the present invention, the adjustment of the power law exponent n in the dispersion provided in process step I) is performed in process step: IIb) In each case, based on the total weight of the dispersant i) in the dispersion provided in process step I), a step of removing 5 to 15% by weight, more preferably 6 to 13% by weight, and most preferably 7 to 11% by weight of the dispersant i) by ultrafiltration, IIc) This is achieved by a process comprising the step of heating the concentrated dispersion obtained in process step IIb) to a temperature in the range of 70 to 96°C for 30 to 120 minutes, preferably in the range of 80 to 94°C for 40 to 90 minutes, and more preferably in the range of 85 to 92°C for 50 to 70 minutes.

[0039] This preferred embodiment is a fifth embodiment of process 1 according to the present invention, and is preferably dependent on any one of the first to fourth embodiments.

[0040] |6b|According to a more preferred embodiment of process 1 according to the present invention, the adjustment of the power law exponent n in the dispersion provided in process step I) is performed in process step: IIa) Homogenizing the dispersion provided in process step I), preferably high-pressure homogenization, more preferably at a pressure of at least 1,000 bar, preferably at least 1,100 bar, more preferably at least 1,200 bar, more preferably at least 1,300 bar, most preferably at least 1,400 bar, and subjecting it to a series of high-pressure homogenization steps of at least 25, preferably at least 35, more preferably at least 45, more preferably at least 55, most preferably at least 65, carried out at a pressure of at least 1,400 bar. IIb) In each case, based on the total weight of the dispersant i) in the dispersion obtained in process step IIa), a step of removing 10-20% by weight, more preferably 12-18% by weight, and most preferably 14-16% by weight of the dispersant i) by ultrafiltration, IIc) This is achieved by a process comprising the step of heating the concentrated dispersion obtained in process step IIb) at a temperature in the range of 70 to 96°C for 2 to 6 hours, preferably at a temperature in the range of 80 to 95°C for 3 to 5 hours, and more preferably at a temperature in the range of 85 to 94°C for 3.5 to 4.5 hours.

[0041] This preferred embodiment is a sixth embodiment of process 1 according to the present invention, and is preferably dependent on any one of the first to fourth embodiments.

[0042] |1c| A contribution to solving at least one objective of the present invention is also made by a dispersion obtained by process 1 according to the present invention, preferably by process 1 according to any of the first to sixth embodiments thereof. Preferably, this dispersion has the same properties as the dispersion according to the present invention, preferably as defined in any of the first to sixteenth embodiments thereof.

[0043] |1d| A contribution to solving at least one of the objectives of the present invention is also made by a first embodiment of process 2 for the preparation of a laminate, the process comprising the following steps: A) The process of preparing the base material, B) A step of applying a dispersion according to the present invention, preferably a dispersion according to the present invention as defined in any of the first to sixteenth embodiments thereof, or a dispersion obtained by process 1 according to the present invention, preferably a dispersion obtained by process 1 as defined in any of the first to sixth embodiments thereof, to at least a portion of the surface of the substrate. C) The process includes a step of at least partially removing the dispersant i) in order to obtain a laminate having a conductive layer coated on at least a portion of the surface of the substrate.

[0044] |2d|According to a preferred embodiment of process 2 according to the present invention, the laminate is part of an electrolytic capacitor, the substrate is a porous electrode body made of an electrode material, the dielectric layer covers at least partially the surface of the electrode material, the solid electrolyte layer covers at least partially the surface of the dielectric layer, and the conductive layer is a polymer outer layer that covers at least partially the surface of the solid electrolyte layer. This preferred embodiment is a second embodiment of process 2 according to the present invention and is preferably dependent on the first embodiment.

[0045] |3d|According to a preferred embodiment of process 2 according to the present invention, the process is A) A step of preparing a porous electrode body made of an electrode material, wherein a dielectric layer covers at least partially the surface of the electrode material, and a solid electrolyte layer covers at least partially the surface of the dielectric layer. B) A step of applying a dispersion according to the present invention, preferably a dispersion according to the present invention as defined in any of the first to sixteenth embodiments thereof, or a dispersion that can be obtained by process 1 according to the present invention, preferably process 1 as defined in any of the first to sixth embodiments thereof, to at least a portion of the surface of the solid electrolyte layer. C) The process includes the step of at least partially removing the dispersant i) in order to form a polymer outer layer that at least partially covers the surface of the solid electrolyte layer.

[0046] This preferred embodiment is a third embodiment of process 2 according to the present invention, and is preferably dependent on the first or second embodiment.

[0047] |4d|According to a more preferred embodiment of Process 2 according to the present invention, the laminate is an aluminum capacitor or a tantalum capacitor. This preferred embodiment is a fourth embodiment of Process 2 according to the present invention, preferably dependent on any of the first to third embodiments thereof.

[0048] |1e| A contribution to solving at least one of the objectives of the present invention is also made by the laminate obtained by process 2 according to the present invention, preferably by process 2 according to any of the first to fourth embodiments thereof.

[0049] |1f| A contribution to solving at least one of the objectives of the present invention is also made by the use of a dispersion according to the present invention, preferably a dispersion according to the present invention as defined in any of its first to sixteenth embodiments, or a dispersion that can be obtained by process 1 according to the present invention, preferably process 1 as defined in any of its first to sixth embodiments, for the formation of a polymer outer layer in a capacitor.

[0050] |2f|According to a preferred embodiment of use according to the present invention, the capacitor is an aluminum capacitor or a tantalum capacitor. This preferred embodiment is a second embodiment of use according to the present invention and is preferably dependent on the first embodiment. [Modes for carrying out the invention]

[0051] Polythiophene The dispersion according to the present invention comprises a dispersant and at least one polythiophene dispersed in the dispersant.

[0052] Preferred polythiophenes are those having repeating units of general formula (I), general formula (II), general formula (III), or combinations thereof:

[0053] [ka] During the ceremony, A is an arbitrarily substituted C1-C5 alkylene group, R is independently substituted with C1-C in any linear or branched chain, with H. 18 - Alkyl alkyl groups, optionally substituted C5-C 12 -Cycloalkyl groups, optionally substituted C6-C 14-aryl group, optionally substituted C7~C 18 - Aralkyl group, optionally substituted C1-C4 hydroxyalkyl group or hydroxyl group, x is an integer between 0 and 8. If multiple R groups are bonded to A, they may be the same or different.

[0054] General formulas (I) and (II) should be understood as allowing x substituents R to bond to the alkylene group A.

[0055] Polythiophenes having repeating units of general formula (I) or (II), or repeating units of general formula (I) and (II), are particularly preferred, where A is an optionally substituted C2-C3 alkylene group and x is 0 or 1. Particularly preferred polythiophenes are optionally substituted poly(3,4-ethylenedioxythiophene) (PEDOT), such as poly(4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]propane-1-sulfonic acid), poly(4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-1-sulfonic acid) (PEDOT-S), or poly(4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonic acid).

[0056] In the context of the present invention, the prefix "poly" should be understood to mean that two or more identical or different repeating units are present in the polymer or polythiophene. The polythiophene contains a total of n repeating units of general formula (I) or general formula (II) or general formula (III), or general formula (I) and (II), or general formula (I) and (III), or general formula (II) and (III), or general formula (I), (II), and (III), where n is an integer from 2 to 2000, preferably from 2 to 100. The repeating units of general formula (I) or general formula (II) or general formula (III), or the repeating units of general formula (I) and (II), or the repeating units of general formula (I) and (III), or the repeating units of general formula (II) and (III), or the repeating units of general formula (I), (II), and (III) may each be the same or different within the polythiophene. In any case, polythiophenes having the same repeating units of general formula (I) or general formula (II) or general formula (III), or in any case having the same repeating units of general formula (I) and (II) or general formula (I) and (III) or general formula (II) and (III), or in any case having the same repeating units of general formula (I), (II), and (III) are preferred. In any case, polythiophenes having the same repeating units of general formula (I) or general formula (II), or in any case having the same repeating units of general formula (I) and (II) are particularly preferred. At the end groups, the polythiophene preferably each has H.

[0057] In the context of the present invention, the C1-C5-alkylene group A is preferably methylene, ethylene, n-propylene, n-butylene, or n-pentylene. C1-C 18-Alkyl R is preferably a linear or branched C1-C such as methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, or n-octadecyl. 18 -It is an alkyl group, C5~C 12 -The cycloalkyl group R is, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or cyclodecyl, C6-C 14 -The aryl group R is, for example, phenyl or naphthyl, and C7~C 18 -The aralkyl group R is, for example, benzyl, o-, m-, p-tolyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-xylyl, or mesityl. The above list is helpful in illustrating the present invention as an example and should not be considered exclusive.

[0058] In the context of the present invention, any further substituents of the A group and / or R group include a number of organic groups, such as alkyl, cycloalkyl, aryl, aralkyl, alkoxy, halogen, ether, thioether, disulfide, sulfoxide, sulfone, sulfonate, amino, aldehyde, keto, carboxylic acid ester, carboxylic acid, carbonate, carboxylate, cyano, alkylsilane and alkoxysilane groups, and carboxamide groups.

[0059] Polythiophenes may be uncharged or cationic. In preferred embodiments, they are cationic, and "cationic" refers only to the charge present in the main polythiophene chain. Due to substituents on the R group, polythiophenes can have positive and negative charges within their structural units, in which case the positive charge is on the main polythiophene chain, and the negative charge, if present, is on the R group substituted with a sulfonate or carboxylate group. The positive charge of the main polythiophene chain may be partially or completely saturated by anionic groups that may be present on the R group. Overall, polythiophenes in these cases may be cationic, uncharged, or anionic. Nevertheless, in the context of the present invention, the positive charge on the main polythiophene chain is important, so all are considered cationic polythiophenes. The positive charge is not shown in the formula because it is not possible to clearly state the exact number and location. However, the number of positive charges is at least 1 and at most n, where n is the total number of all repeating units (identical or different) in the polythiophene.

[0060] The positive charge of polythiophene can be balanced by sulfonate or carboxylate-substituted, and therefore negatively charged, R groups (so-called "self-doped polythiophene") or by counterions (so-called "externally doped polythiophene").

[0061] According to a first preferred embodiment of the polythiophene in dispersion according to the present invention, the polythiophene is a self-doped polythiophene containing repeating units of formula (IV) to preferably at least 50%, more preferably at least 75%, more preferably at least 95%, and most preferably at least 100%.

[0062] [ka] During the ceremony, X and Y are the same or different, O, S, NR 1 Show, R 1 is aryl, C1~C 18 - Represents alkyl or hydrogen, Z is an anionic functional group, preferably SO3. - It is an organic group having a group, and Z is -(CH2) m -CR 2 R 3 -(CH2) n - is particularly preferred, R 2 is hydrogen, -(CH2) s -O-(CR 4 2) p -SO3 - M + or -(CH2) p -SO3 - M + Show, R 3 is, -(CH2) s -O-(CR 4 2) p -SO3 - M + or -(CH2) p -SO3 - M + Show, M + This indicates a cation, m and n are integers between 0 and 3, and can be the same or different. R 4 is hydrogen or C1-C 10 The alkyl group, preferably a methyl group, s represents an integer between 0 and 10. p represents an integer between 1 and 18.

[0063] The percentage values ​​above are intended to represent the numerical content of units of structural formula (IV) in the total number of monomer units in the self-doped conductive polymer in this context.

[0064] Appropriate cation M + For example, H + Li + na + , K + , Rb + , Cs+ and NH4 + A particularly suitable cation is Na. + and K + That is the case.

[0065] The most preferred monomers for structural formula (IV) are as follows: X and Y indicate O. Z is -(CH2) m -CR 2 R 3 -(CH2) n - indicates, R 2 is hydrogen or -(CH2) s -O-(CH2) p -SO3 - M + ,-(CH2) p -SO3 - M + or -(CH2) s -O-(CH2) p -CHR 4 -SO3 - M + Show, R 3 is, -(CH2) s -O-(CH2) p -SO3 - M + ,-(CH2) p -SO3 - M + or -(CH2) s -O-(CH2) p -CHR 4 -SO3 - M + Show, M + This indicates a cation, m and n are integers between 0 and 3, and can be the same or different. R 4 This represents hydrogen, a methyl group, or an ethyl group. s represents an integer between 0 and 10. p represents an integer between 1 and 18.

[0066] The highly particularly preferred monomers of structural formula (IV) are as follows. X and Y represent O, Z is -(CH2)-CR 2 R 3 -(CH2) n - represents R 2 represents hydrogen, R 3 is -(CH2) s -O-(CH2) p -SO3 - M + 、-(CH2) p -SO3 - M + 、or -(CH2) s -O-(CH2) p -CH(CH3)-SO3 - M + or -(CH2) s -O-(CH2) p -CH(CH2CH3)-SO3 - M + represents M + is Na + or K + represents n represents 0 or 1, s represents 0 or 1, p represents 2, 3, 4, or 5.

[0067] Suitable examples of self-doped polymers are disclosed in International Publication No. WO 2014 / 048562 (A) and U.S. Patent Application Publication No. US 2015 / 0337061 (A). Specific examples of highly particularly preferred self-doped conductive polymers include poly(4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]propane-1-sulfonic acid), poly(4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-1-sulfonic acid) (PEDOT-S), poly(4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonic acid), or mixtures thereof.

[0068] According to a second preferred embodiment of the polythiophene in the dispersion according to the present invention, the polythiophene is preferably an externally doped polythiophene containing a polymer counterion for balancing the positive charge, the latter also referred to hereafter as "polyanion". Therefore, according to a preferred embodiment of the dispersion according to the present invention, the polythiophene is a cationic polythiophene containing a polyanion that functions as a counterion to the polythiophene.

[0069] Polyanions are preferred over monomer anions because they contribute to film formation and, due to their size, result in thermally more stable conductive films. Polyanions as used herein may be anions of polymeric carboxylic acids such as polyacrylic acid, polymethacrylic acid, or polymaleic acid, or polymeric sulfonic acids such as polystyrene sulfonic acid and polyvinyl sulfonic acid. These polycarboxylic acids and sulfonic acids may also be copolymers of vinyl carboxylic acids and vinyl sulfonic acids with other polymerizable monomers such as acrylic esters and styrene.

[0070] Preferred polyanions are anions of polymeric carboxylic acids or sulfonic acids. Particularly preferred polyanions are anions of polystyrene sulfonic acid (PSS) or its derivatives.

[0071] The molecular weight of the polyacid that yields the polyanion is preferably 1,000 to 2,000,000, more preferably 2,000 to 500,000. Polyacids or their alkali metal salts, such as polystyrene sulfonic acid and polyacrylic acid, are commercially available, or can otherwise be prepared by known methods (see, for example, Houben Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], vol. E 20 Makromolekulare Stoffe [Macromolecular Substances], part 2, (1987), p. 1141ff.).

[0072] A particularly preferred example of an externally doped polythiophene is the complex of poly(3,4-ethylenedioxythiophene) with the anion of polystyrene sulfonic acid (PEDOT / PSS).

[0073] Further additives According to a preferred embodiment of the dispersion according to the present invention, the dispersion further comprises at least one additive, the at least one additive being selected from the group consisting of binders, pH adjusters, crosslinking agents, adhesion promoters, conductivity enhancers, surfactants, stabilizers, and at least two combinations thereof.

[0074] Suitable binders include organic binders that are particularly soluble in organic solvents, such as polyolefins, polyvinyl acetate, polycarbonate, polyvinyl butyral, polyacrylic acid esters, polyacrylamides, polymethacrylates, polymethacrylates, polystyrene, polyacrylonitrile, polyvinyl chloride, polyvinylpyrrolidone, polybutadiene, polyisoprene, polyethers, polyesters, polyurethanes, polyamides, polyimides, polysulfones, polysilicones, epoxy resins, styrene-acrylates, vinyl acetate / acrylate and ethylene / vinyl acetate copolymers, polyvinyl alcohol, or cellulose derivatives, which can also be added to the composition. Copolymers of the above polymers are also suitable as binders. - Suitable pH adjusters include, for example, bases or acids described in International Publication No. 2010 / 003874(A2), page 4, lines 13-32. Additives that do not inhibit film formation of the dispersion, do not volatilize at relatively high temperatures, such as soldering temperatures, and remain in the solid electrolyte under these conditions are preferred. Compounds such as 2-dimethylaminoethanol, 2,2'-iminodiethanol, or 2,2',2''-nitrilotriethanol and polystyrene sulfonic acid are particularly suitable. - Suitable crosslinking agents include melamine compounds, capped isocyanates, functional silanes such as tetraethoxysilane, alkoxysilane hydrolysates based on tetraethoxysilane, or epoxysilanes such as 3-glycidoxypropyltrialkoxysilane. - Suitable adhesion promoters include organic functional silanes or their hydrolysates, such as 3-glycidoxypropyltrialkoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-methacrylicoxypropyltrimethoxysilane, vinyltrimethoxysilane, or octyltriethoxysilane. - Suitable conductivity enhancers include, for example, compounds such as tetrahydrofuran, lactone group-containing compounds such as butyrolactone and valerolactone, amide group-containing compounds or lactam group-containing compounds such as caprolactam, N-methylcaprolactam, N,N-dimethylacetamide, N-methylacetamide, N,N-dimethylformamide (DMF), N-methylformamide, N-methylformanilide, and N-methylpyrrolidone (NMP), pyrrolidone, sulfones and sulfoxides, such as sulfolane (tetramethylenesulfone) and dimethyl sulfoxide (DMSO), sugars or sugar derivatives, such as sucrose, glucose, fructose, and lactose, sugar-based surfactants, such as Tween or Span 60, sugar alcohols, such as sorbitol and mannitol, furan derivatives, such as 2-furanic acid and 3-furanic acid, and / or di- or polyalcohols, such as ethylene glycol, glycerol, or di- or triethylene glycol or polyglycerin. As conductivity enhancers, ethylene glycol, diethylene glycol, triethylene glycol, polyglycerin, dimethyl sulfoxide, or sorbitol are particularly preferred. Suitable surfactants include anionic surfactants, such as alkylbenzene sulfonic acids and salts, paraffin sulfonates, alcohol sulfonates, ether sulfonates, sulfosuccinates, phosphate esters, alkyl ether carboxylic acids or carboxylates; cationic surfactants, such as quaternary alkylammonium salts; and nonionic surfactants, particularly nonionic amphiphilic surfactants, such as linear or branched alcohol ethoxylates, oxo alcohol ethoxylates, alkylphenol ethoxylates or alkyl polyglucosides. Representative examples of suitable surfactants include fluorinated surfactants, such as ZONYL® surfactants, including ZONYL® FSN, ZONYL® FSO, ZONYL® FSA, ZONYL® FSH (DuPont Chemicals, Wilmington, Del.) and NOVEC® (3M, St. Paul, Minn.). Other exemplary surfactants include nonionic surfactants based on alkylphenol ethoxylates. Preferred surfactants include, for example, octylphenol ethoxylates such as TRITON®, and secondary alcohol ethoxylates such as TERGITOL® 15-S series (Dow Chemical Company, Midland Mich.). Further exemplary nonionic surfactants include acetylene-based surfactants, n-dodecyl β-D-maltoside, and alcohol ethoxylates, such as TERGITOL® TMN. - Suitable stabilizers are compounds mentioned in International Publication No. 2012 / 041507(A1), and aromatic compounds containing at least two OH groups and one further functional group having a heteroatom different from carbon are particularly preferred. Examples of preferred stabilizers include 3,4,5-trihydroxybenzoic acid and its derivatives such as 3,4,5-trihydroxybenzoic acid esters (gallic acid esters), more particularly alkyl esters, alkenyl esters, cycloalkyl esters, cycloalkenyl esters, and aryl esters, each preferably having 1 to 15 carbon atoms in the aryl or alkyl group of the ester. Particularly preferred are gallic acid and gallic acid esterified with sugars, which are often called tannins or gallotannins (see Rompp Chemie, 10th edition (1999), p. 4391). Suitable stabilizers include the "hydroxyl group-containing aromatic compounds" mentioned in paragraph

[0049] of European Patent Publication No. 1798259(A1), the "antioxidants" mentioned in paragraph

[0025] of European Patent Publication No. 1043720(A1), and the "sulfo group-excluded aromatic compounds containing at least two hydroxyl groups" mentioned on pages 10 and 11 of International Publication No. 2008 / 055834(A1).

[0075] Capacitor manufacturing process According to a preferred embodiment of the laminate preparation process of the present invention, the laminate is part of an electrolytic capacitor. In this case, the process is A) A step of preparing a porous electrode body made of an electrode material, wherein a dielectric layer covers at least partially the surface of the electrode material, and a solid electrolyte layer covers at least partially the surface of the dielectric layer. B) A step of applying a dispersion according to the present invention, preferably a dispersion according to the present invention as defined in any of the first to sixteenth embodiments thereof, or a dispersion that can be obtained by process 1 according to the present invention, preferably process 1 as defined in any of the first to sixth embodiments thereof, to at least a portion of the surface of the solid electrolyte layer. C) The process includes the step of at least partially removing the dispersant i) in order to form a polymer outer layer that at least partially covers the surface of the solid electrolyte layer.

[0076] Process step A): In process step A, a porous electrode body made of electrode material is provided, in which case the dielectric layer covers at least partially the surface of the electrode material, and the solid electrolyte layer covers at least partially the surface of the dielectric layer.

[0077] In principle, a porous electrode body can be manufactured by compressing and sintering valve metal powder having a large surface area to form the porous electrode body. In this regard, an electrical contact wire, preferably made from valve metal such as tantalum, is conventionally compressed into the porous electrode body. The porous electrode body is then coated with a dielectric, i.e., an oxide layer, for example, by electrochemical oxidation. Alternatively, to obtain an anode film having porous regions, a metal film can be etched and coated with a dielectric by electrochemical oxidation. In the case of a wound capacitor, the anode film and cathode film, which have porous regions forming the electrode body, are separated by a separator and wound together.

[0078] Within the scope of this invention, metals whose oxide coatings do not allow current to flow uniformly in both directions are understood as valve metals. When a voltage is applied to the anode, the oxide layer of the valve metal blocks the flow of current, while when a voltage is applied to the cathode, a large current is generated, potentially destroying the oxide layer. Examples of valve metals include Be, Mg, Al, Ge, Si, Sn, Sb, Bi, Ti, Zr, Hf, V, Nb, Ta, and W, as well as alloys or compounds of at least one of these metals with other elements. The most well-known representative examples of valve metals are Al, Ta, and Nb. Combinations of electrical properties equivalent to valve metals are those that have the conductivity of a metal, can be oxidized, and whose oxide layer provides the above properties. For example, NbO exhibits the conductivity of a metal but is generally not considered a valve metal. However, a layer of oxidized NbO exhibits typical properties of a valve metal oxide layer, and as a result, NbO or alloys or compounds of NbO are typical examples of compounds with electrical properties equivalent to valve metals. Electrode materials made of tantalum, aluminum, and niobium or niobium oxide are preferred. Tantalum is particularly preferred as the electrode material.

[0079] To manufacture porous electrode bodies, which often have porous regions, the valve metal can be sintered, for example, in powder form to provide a generally porous electrode body, or alternatively, the porous structure can be imprinted onto the metal body. The latter can be carried out, for example, by etching a film.

[0080] For brevity, a body containing porous regions is also referred to as a porous body. For example, an electrode body containing porous regions is also referred to as a porous electrode body. On the one hand, a porous body can be permeated by multiple channels and is therefore spongy. This is often the case when tantalum is used in capacitor structures. On the other hand, pores can exist only on the surface, and regions located beneath the surface pores can be formed in a solid state. This is often observed when aluminum is used in capacitor structures.

[0081] Next, the porous electrode body thus manufactured is oxidized by applying a voltage in a suitable electrolyte, such as phosphoric acid or an aqueous solution of ammonium adipate, to form a dielectric. The magnitude of this formation voltage depends on the thickness of the oxide layer to be achieved, or correspondingly, the operating voltage of the subsequent capacitor. Preferred formation voltages are in the range of 1 to 1000 V, particularly preferably in the range of 10 to 200 V, more preferably in the range of 15 to 100 V, and more preferably in the range of 20 to 50 V.

[0082] The porous electrode body used preferably has a porosity of 10-90%, preferably 30-80%, and particularly preferably 50-80%, and an average pore diameter of 10-10000nm, preferably 50-5000nm, and particularly preferably 100-3000nm.

[0083] According to a special embodiment of the process of the present invention, the electrolytic capacitor to be manufactured is an aluminum wound capacitor. In this case, in process step A), a porous aluminum film is formed on the anode as an electrode material, thereby forming an aluminum oxide coating as a dielectric. Then, a contact wire is provided on the aluminum film thus obtained (anode film) and it is wound, and a contact wire is also provided on a further porous aluminum film (cathode film), so that these two films are separated from each other by one or more separator papers, for example, based on cellulose, or preferably based on synthetic paper. After winding, the anode body thus obtained is fixed, for example, by adhesive tape. The separator paper can be carbonized by heating in an oven. A method for manufacturing an anode body for this aluminum wound capacitor is well known from the prior art, for example, described in U.S. Patent No. 7,497,879(B2).

[0084] To form a solid electrolyte layer that at least partially covers the surface of the dielectric layer, a conductive polymer is deposited on the dielectric chemically or electrochemically, for example, by oxidative polymerization. For this purpose, a precursor for preparing the conductive polymer, one or more oxidizing agents, and, if appropriate, counterions, are applied together or successively to the dielectric of the porous electrode body and polymerized chemically and oxidatively, or the precursor for producing the conductive polymer and counterions is polymerized on the dielectric of the porous electrode body by electrochemical polymerization.

[0085] Preferably, a dispersion containing a conductive polymer can be introduced into at least a portion of the provided porous electrode body to form a solid electrolyte layer that at least partially covers the surface of the dielectric layer, and the dispersant is then removed to at least partially form a solid electrolyte that at least partially covers the surface of the dielectric layer.

[0086] Examples of conductive polymers suitable for forming a solid electrolyte layer include polypyrrole, polythiophene, polyaniline, polyacetylene, polyphenylene, and poly(p-phenylene-vinylene), with polythiophene, and in particular, those already described above, being preferred as the polythiophene for the dispersion according to the present invention. Most preferred for forming a solid electrolyte layer is a dispersion containing cationic polythiophenes existing in the form of a polythiophene / polyanion complex, and more preferably in the form of a PEDOT / PSS complex, such as poly(4-[(2,3-dihydrothieno-[3,4-b]-[1,4]dioxin-2-yl)methoxy]propane-1-sulfonic acid), poly(4-[(2,3-dihydrothieno-[3,4-b][1,4]-dioxin-2-yl)methoxy]butane-1-sulfonic acid) (PEDOT-S), or poly-(4-[(2,3-dihydrothieno[3,4-b][1,4]-dioxin-2-yl)methoxy]butane-2-sulfonic acid), or mixtures thereof.

[0087] Such dispersions can be introduced into the porous region using known processes, such as immersion, immersion, pouring, dropping, injection, spraying, diffusion, coating, or printing such as inkjet printing, screen printing, or pad printing. Introduction is preferably carried out by immersing the porous electrode body in the dispersion, thereby impregnating it with the dispersion. Immersion or impregnation in the dispersion is preferably carried out for a duration ranging from 1 second to 120 minutes, particularly preferably from 10 seconds to 60 minutes, and most preferably from 30 seconds to 15 minutes. Introduction of the dispersion into the anode body can be facilitated, for example, by increasing or decreasing pressure, vibration, ultrasound, or heat.

[0088] After impregnating the porous electrode body with the above dispersion, the dispersant is removed at least partially to form a solid electrolyte layer that partially or completely covers the dielectric. In this regard, the coverage of the dielectric by the solid electrolyte layer is preferably at least 50%, particularly preferably at least 70%, and most preferably at least 80%, enabling the measurement of the capacitance of the capacitor under dry and wet conditions at 120°C to make determinations as described in German Patent Publication No. 102005043828(A).

[0089] The removal of the dispersant is preferably carried out by removing the porous electrode body from the dispersion and subsequently drying it, preferably at a temperature in the range of 20°C to 200°C, particularly preferably in the range of 50°C to 180°C, and more preferably in the range of 80°C to 150°C. The drying conditions (i.e., drying time, drying pressure, and drying temperature) are preferably adjusted to ensure that at least 50% by weight, more preferably at least 75% by weight, even more preferably at least 90% by weight, even more preferably at least 95% by weight, and most preferably at least 99% by weight of the total amount of dispersant is removed when forming the solid electrolyte layer. In a particularly preferred embodiment of the process according to the present invention, the drying conditions are adjusted to ensure that the dispersant is completely removed when forming the solid electrolyte layer.

[0090] Process steps B) and C): In process step B), the dispersion according to the present invention, preferably the dispersion according to the present invention as defined in any of its first to sixteenth embodiments, or the dispersion that can be obtained by process 1 according to the present invention, preferably process 1 as defined in any of its first to sixth embodiments, is applied to at least a portion of the surface of the solid electrolyte layer. Then, in process step C), the dispersant i) is at least partially removed to form a polymer outer layer that at least partially covers the surface of the solid electrolyte layer.

[0091] As used herein, the term “polymer outer layer” preferably refers to an outer layer that differs from the solid electrolyte layer in terms of properties such as chemical composition, conductivity, and / or hardness, surface roughness, and adhesive properties, although it may contain the exact same conductive polymer as the solid electrolyte layer. Typically having a thickness in the range of 5 to 50 μm, the polymer outer layer functions as a mechanical buffer between the capacitor anode and cathode-side contact area, preventing the cathode-side contact area from coming into contact with the dielectric under mechanical stresses that may occur during the manufacture of the capacitor.

[0092] Applying the dispersion according to the present invention to at least a portion of the surface of the solid electrolyte layer in process step B), and then removing the dispersant in process step C), can be achieved in the same manner as described above with respect to the application of the dispersion used to prepare the solid electrolyte layer.

[0093] Before applying the dispersion according to the present invention to at least a portion of the surface of the solid electrolyte layer in process step B), it may also be advantageous to apply a crosslinking agent to at least a portion of the surface of the solid electrolyte layer in order to improve the coverage of the capacitor anode by the polymer outer layer. Suitable crosslinking agents and processes for such applications are disclosed, for example, in German Patent Application Publication No. 10 2009 007 594(A1).

[0094] Encapsulation in process step D): After the polymer outer layer is applied, the electrolytic capacitor can be finished and, in particular, sealed in a manner known to those skilled in the art. In the case of a tantalum electrolytic capacitor, the capacitor body can be coated with a graphite layer and a silver layer, for example, as known from German Patent Publication No. 102005043828(A), and in the case of an aluminum wound capacitor corresponding to the teachings of U.S. Patent No. 7,497,879(B2), the capacitor body is constructed in an aluminum cup, provided with sealing rubber, and mechanically tightly closed by flanging.

[0095] Encapsulation is preferably achieved by sealing the capacitor body with a resin such as an epoxy resin or thermoplastic resin, as disclosed in European Patent Publication No. 0 447 165(A2). In the case of an aluminum electrolytic capacitor, encapsulation is preferably achieved by providing an aluminum cup to the porous electrode body obtained in process step e) and closing it with sealing rubber.

[0096] The features disclosed in the claims, specification, and drawings are likely essential, either individually or in any combination with each other, for the various embodiments of the invention described in the claims. [Brief explanation of the drawing]

[0097] The following schematic diagrams illustrate embodiments of the present invention to further enhance understanding of the invention in relation to several illustrative figures. [Figure 1] The layered structure according to the present invention, for example, the structure of a layer body 100 prepared by a general antistatic film preparation process, is shown. On the substrate surface of the substrate 101, there is a conductive layer 102 prepared with the composition according to the present invention, which is often a PE, PP, or PET layer in the case of an antistatic film. [Figure 2]This is a schematic cross-sectional view of a part of a capacitor obtained by a specific embodiment of the preparation process for a laminated structure according to the present invention. The capacitor includes a porous electrode body 101a containing pores 103, mainly made from a porous electrode material 101b such as aluminum. A dielectric layer 101c is formed in a thin layer on the surface of the electrode material 101b, forming a porous anode body including the electrode body 101a made of electrode material 101b and the dielectric layer 101c. A layer of solid electrolyte layer 101d is optionally followed by a further layer on the dielectric layer 101c, thereby forming a capacitor body including the electrode body 101a made of electrode material 101b, the dielectric layer 101c and the solid electrolyte layer 101d. At least a portion of the solid electrolyte layer 101d is covered by a polymer outer layer 102a (made using a dispersion according to the present invention).

[0098] Measurement method: Solids Weigh an empty measuring bottle with a cap (50 mm in diameter) using an analytical balance (weight A). Fill the empty measuring bottle with approximately 5 g of dispersion and weigh it using the cap (weight B). Transfer the opened measuring bottle and cap separately to a drying cabinet and dry at 100°C for 15-16 hours.

[0099] After drying, seal the measuring bottle directly with the cap and leave the cap on to cool to room temperature. Then, weigh the bottle using the cap. (Weight C) Repeat the second measurement with a new sample.

[0100] The solid content is calculated as follows: Weight % solids = (CA) × 100 / (BA)

[0101] The solids content is measured as two separate measurements. The two solids content measurements may differ by up to 0.03%. If the difference is greater, the measurement must be repeated.

[0102] The final value is the average of two single measurements.

[0103] conductivity To measure electrical conductivity, 19 g of the dispersion of the analyte is mixed with 1 g of DMSO in a beaker and stirred for 10 minutes. Electrical conductivity is the reciprocal of resistivity. Resistivity is calculated from the product of the surface resistance and thickness of the conductive polymer layer. Surface resistance is determined for conductive polymers according to DIN EN ISO 3915. The mixture of polymer dispersion and DMSO is applied as a homogeneous film to a completely cleaned 50 mm × 50 mm glass substrate by spin coating. The coating composition is applied to the substrate by pipette to completely cover the area and is directly spun off by spin coating. The spin conditions for the coating composition were approximately 1,000 rpm for 20 seconds in air. Subsequently, a drying process was performed on a hot plate (130°C in air for 15 minutes). A silver electrode 2.0 cm long and 2.0 cm apart is deposited onto the polymer layer via a shadow mask. Then, a square area of ​​the layer between the electrodes is electrically isolated from the rest of the layer by scratching two lines with a scalpel. Surface resistance is measured between Ag electrodes using a resistometer (Keithley 614). The thickness of the polymer layer is determined at the scraped area using a Stylus Profilometer (Dektac 150, Veeco).

[0104] Determination of the exponent n in a power law The power law exponent n is measured using a Rheometer Haake RV 1 with thermostat (supplied by Haake), a PC with Software Rheo Win Pro, and a cup and rotor for a double-gap cylinder system DG 43 (supplied by Haake).

[0105] The zero value is set once, the day before the first measurement. A dry, clean cup is placed in the rheometer and pressed into the unit using the palm of your hand. It is then secured using the locking lever. The rotor is secured to the top using the appropriate screws. The computer is started, and then the software "Rheo Win Jobmanager" is launched. The program point "Manual Use" is opened, and "Setting Zero Value" is opened. The zero value is then set automatically, and the "Manual Use" unit is closed.

[0106] The thermostat is set so that the temperature reader inside the rheometer reads 20.0°C. The temperature must be within the range of 20.0°C ± 0.2°C. The gap in the dry, clean cup is filled with 12.0 ± 0.3 mL of the dispersion of the analyte. The cylinder and rotor are fixed inside the rheometer. The program for determining the exponent n includes the following steps: 1) Rotation at 20.0℃, deviation + / -0.2℃, time 120 seconds, shear rate 20 1 / second 2) Rotating ramp at 20.0℃, from 20 1 / second to 1000 1 / second for no more than 100 seconds. 3) Regression of a rotating ramp using the Ostwald de Waele model selected in the Rheo Win job manager.

[0107] The value of the exponent n is recorded so that it is measured according to the regression using Rheo Win software.

[0108] Particle size (d 50 ) decision The particle size is determined as disclosed by HGMuller in Colloid Polym. Sci. 267, 1113-1116 (1989). The diameter distribution is d 50 The value is that 50% of the total weight of all conductive polymer particles in the dispersion is d 50 This indicates that it can be assigned to particles with a diameter less than or equal to the value.

[0109] Leakage current measurement Leakage current (DCL) was measured using a Keithley 199 multimeter after applying a 20V voltage for 3 minutes. The leakage current of five capacitors was measured, and the average leakage current (DCL) value was determined.

[0110] average Unless otherwise specified, the average corresponds to the arithmetic mean. [Examples]

[0111] Example 1 In a 3L stainless steel reactor equipped with a stirrer, vents, an upper material inlet, an internal thermometer, an UltraTurrax, a lower material outlet, and a temperature jacket connected to a thermostat, 1,925 g of deionized water and 660 g of aqueous polystyrene sulfonic acid (average molecular weight Mw 70,000 g / mol; 3.8 wt% solids; total PSS solids 25.1 g) were initially charged. The reaction temperature was maintained at 18°C. The mixture was flushed with nitrogen for 3 hours. The mixture was then evacuated to 33 hPa. 10.2 g of 3,4-ethylenedioxythiophene (71.8 mmol) was added with stirring and using Turrax. The solution was stirred for 30 minutes. Then, 0.06 g of iron(III) sulfate and 19.0 g of sodium persulfate (79.8 mmol) dissolved in 25 g of water were added, and the solution was stirred and dispersed under reduced pressure for a further 23 hours.

[0112] After the reaction was complete, the inorganic salts were removed using 200 mL of a strongly acidic cation exchanger (Lewatit S108H, Lanxess AG) and 500 mL of a weakly basic anion exchanger (Lewatit MP 62, Lanxess AG), and the solution was stirred for a further 2 hours. The ion exchanger was filtered off. The resulting dispersion is "Dispersion 1A".

[0113] A 2,000g dispersion (1A) was ultrafiltered using a Pall Membrane (Pall Microza Ultrafiltration Module SLP 1053). 200g of permeate was removed at a pressure of 0.8 bar. Then, 400g of the dispersion was placed in a 1L round-bottom flask and heated at 90°C for 1 hour.

[0114] The resulting "Dispersion 1B" exhibited the following characteristics: Solid content: 1.2% by weight

[0115] 80 g of dispersion 1B, 3 g of sulfopolyester (Eastek 1100, Eastman), and 4 g of dimethyl sulfoxide were vigorously mixed for 1 hour in a glass beaker equipped with a stirrer. The properties of "dispersion 1C" (according to the present invention) are summarized in Table 1.

[0116] Example 2 A 2,000 g dispersion, identical to dispersion 1A, was ultrafiltered using a Pall Membrane (Pall Microza Ultrafiltration Module SLP 1053). 620 g of permeate was removed at a pressure of 0.8 bar. The resulting 400 g dispersion was then placed in a 1 L round-bottom flask and heated at 90°C for 1 hour.

[0117] The resulting "dispersion 2B" exhibited the following characteristics: Solid content: 1.6% by weight

[0118] 80 g of dispersion 2B, 3 g of sulfopolyester (Eastek 1100, Eastman), and 4 g of dimethyl sulfoxide were vigorously mixed for 1 hour in a glass beaker equipped with a stirrer. The properties of "dispersion 2C" (not according to the present invention) are summarized in Table 1.

[0119] Example 3 A 2,000g dispersion identical to dispersion 1A was homogenized 10 times at 1,000 bar using a high-pressure homogenizer.

[0120] The resulting "dispersion 3B" exhibited the following characteristics: Solid content: 1.1% by weight

[0121] 80 g of dispersion 3B, 3 g of sulfopolyester (Eastek 1100, Eastman), and 4 g of dimethyl sulfoxide were vigorously mixed for 1 hour in a glass beaker equipped with a stirrer. The properties of "dispersion 3C" (not according to the present invention) are summarized in Table 1.

[0122] Example 4 400g of dispersion 3B was placed in a 1L round-bottom flask and heated at 90°C for 1 hour. The resulting dispersion 4B exhibited the following characteristics: Solid content: 1.1% by weight

[0123] 80 g of dispersion 4B, 3 g of sulfopolyester (Eastek 1100, Eastman), and 4 g of dimethyl sulfoxide were vigorously mixed for 1 hour in a glass beaker equipped with a stirrer.

[0124] The characteristics of "Dispersion 4C" (not according to the present invention) are summarized in Table 1.

[0125] Example 5 A 2,000g dispersion identical to dispersion 1A was homogenized 10 times at 1,000 bar. Then, 200g was removed by ultrafiltration using a Pall membrane. Next, 400g of the dispersion was placed in a 1L round-bottom flask and heated at 90°C for 4 hours.

[0126] The resulting "dispersion 5B" exhibited the following characteristics: Solid content: 1.2% by weight

[0127] 80 g of dispersion 5B, 3 g of sulfopolyester (Eastek 1100, Eastman), and 4 g of dimethyl sulfoxide were vigorously mixed for 1 hour in a glass beaker equipped with a stirrer. The properties of "dispersion 5C" (not according to the present invention) are summarized in Table 1.

[0128] Example 6 A 2,000g dispersion identical to dispersion 1A was homogenized 10 times at 1,000 bar. Then, 300g was removed by ultrafiltration using a Pall membrane. Next, 400g of the dispersion was placed in a 1L round-bottom flask and heated at 90°C for 4 hours.

[0129] The resulting "dispersion 6B" exhibited the following characteristics: Solid content: 1.3% by weight

[0130] 80 g of dispersion 6B, 3 g of sulfopolyester (Eastek 1100, Eastman), and 4 g of dimethyl sulfoxide were vigorously mixed for 1 hour in a glass beaker equipped with a stirrer. The properties of "dispersion 6C" (according to the present invention) are summarized in Table 1.

[0131] Example 7 A 2,000g dispersion identical to dispersion 1A was homogenized 10 times at 1,000 bar. Then, 620g was ultrafiltered using a Pall Membrane (Pall Microza ultrafiltration module SLP 1053). Next, 400g of the dispersion was placed in a 1L round-bottom flask and heated at 90°C for 4 hours.

[0132] The resulting "dispersion 7B" (not according to the present invention) exhibited the following characteristics: Solid content: 1.6% by weight

[0133] 80 g of dispersion 7B, 3 g of sulfopolyester (Eastek 1100, Eastman), and 4 g of dimethyl sulfoxide were vigorously mixed for 1 hour in a glass beaker equipped with a stirrer. The properties of dispersion 7C are summarized in Table 1.

[0134] Example 8 A dispersion identical to dispersion 1A was prepared. 2,000 g of the dispersion was ultrafiltered using a Pall Membrane (Pall Microza Ultrafiltration Module SLP 1053). 140 g of permeate was removed at a pressure of 0.8 bar. Then, 400 g of the dispersion was placed in a 1 L round-bottom flask and heated at 90°C for 1 hour.

[0135] The resulting "dispersion 8B" exhibited the following characteristics: Solid content: 1.2% by weight

[0136] 80 g of dispersion 8B, 3 g of sulfopolyester (Eastek 1100, Eastman), and 4 g of dimethyl sulfoxide were vigorously mixed for 1 hour in a glass beaker equipped with a stirrer. The properties of "dispersion 8C" (according to the present invention) are summarized in Table 1.

[0137] Table 1 summarizes the results of Examples 1 to 8.

[0138] [Table 1] i. = According to the present invention; ni = Not according to the present invention

[0139] Example 9 Capacitor preparation process Process step A): A tantalum powder having a specific capacitance of 70,000 CV / g was pressed into a pellet containing tantalum wire and sintered to form a porous electrode body with dimensions of 1.5 mm × 2.9 mm × 4.0 mm. The porous electrode body was anodized in a phosphate electrolyte at 30 V to form a dielectric and obtain a capacitor body.

[0140] The capacitor body in the process step was impregnated with an aqueous solution of poly(3,4-ethylenedioxythiophene) / polystyrene sulfonate (Clevios K Nano LV, Heraeus Deutschland) for 1 minute. Then, it was dried at 120°C for 10 minutes. The impregnation and drying process was repeated nine more times to obtain a solid electrolyte layer based on PEDOT / PSS.

[0141] Process steps B) and C): The outer polymer layer on the capacitor body was obtained by process steps B) and C). In process step B), the capacitor body from process step A) was impregnated with a crosslinking agent solution (Clevios K Primer W15, Heraeus Deutschland). After drying at 120°C for 10 minutes, the capacitor body was impregnated with dispersion 1C of Example 1. Then, in process step C), drying was carried out at 120°C for 10 minutes.

[0142] Next, to obtain the completed capacitor in this manner, the capacitor body from process step C) was covered with a graphite layer, and then covered with a silver layer.

[0143] Table 2 shows the average leakage current of the capacitor (according to the present invention).

[0144] Example 10 A capacitor was fabricated and evaluated in the same manner as in Example 9, except that in process step B), dispersion 2C from Example 2 was used instead of 1C from Example 1. The average leakage current of the capacitor (not according to the present invention) is shown in Table 2.

[0145] Example 11 A capacitor was fabricated and evaluated in the same manner as in Example 9, except that in process step B), dispersion 3C from Example 3 was used instead of 1C from Example 1. The average leakage current of the capacitor (not according to the present invention) is shown in Table 2.

[0146] Example 12 In process step B), a capacitor was fabricated and evaluated in the same manner as in Example 9, except that dispersion 4C from Example 4 was used instead of 1C from Example 1. The average leakage current of the capacitor (not according to the present invention) is shown in Table 2.

[0147] Example 13 A capacitor was fabricated and evaluated in the same manner as in Example 9, except that in process step B), dispersion 5C from Example 5 was used instead of 1C from Example 1. The average leakage current of the capacitor (not according to the present invention) is shown in Table 2.

[0148] Example 14 In process step B), the capacitor was manufactured and evaluated in the same manner as in Example 9, except that dispersion 6C from Example 6 was used instead of 1C from Example 1. The average leakage current of the capacitor (according to the present invention) is shown in Table 2.

[0149] Example 15 In process step B), a capacitor was fabricated and evaluated in the same manner as in Example 9, except that dispersion 7C from Example 7 was used instead of 1C from Example 1. The average leakage current of the capacitor (not according to the present invention) is shown in Table 2.

[0150] Example 16 In process step B), the capacitor was manufactured and evaluated in the same manner as in Example 9, except that dispersion 8C from Example 8 was used instead of 1C from Example 1. The average leakage current of the capacitor (according to the present invention) is shown in Table 2.

[0151] Table 2 summarizes the results of Examples 9-16.

[0152] [Table 2] i. = According to the present invention; ni = Not according to the present invention

[0153] Key for reference number 100-layer structure 101 Base material 101a Porous electrode body 101b Electrode material 10¹c dielectric 101d Solid electrolyte layer 102 Conductive layer 102a Polymer outer layer 103 Pores

Claims

1. i) Dispersant; ii) at least one polythiophene dispersed in the dispersant i); A dispersion containing, Regarding the aforementioned dispersion, Ostwald de Waele relationship [Math 1] The power law exponent n in this case is in the range of 0.40 to 0.65, τ is the shear stress, and K is the flow viscosity constant. [Math 2] A dispersion where the shear rate is dγ / dt.

2. The dispersion according to claim 1, wherein the power law exponent n is in the range of 0.42 to 0.

63.

3. The dispersion according to claim 12, wherein the power law exponent n is in the range of 0.45 to 0.

60.

4. The dispersion according to any one of claims 1 to 3, wherein the dispersant i) contains water.

5. The dispersion according to any one of claims 1 to 4, wherein the polythiophene exists in the form of particles of a complex containing the polythiophene and a polyanion.

6. The dispersion according to claim 5, wherein the polythiophene is poly(3,4-ethylenedioxythiophene) and the polyanion is an anion of polystyrene sulfonic acid.

7. Weight-average diameter (d) of particles in a composite containing polythiophene and polyanion ５０ The dispersion according to claim 5 or 6, wherein the wavelength is in the range of 10 nm to 500 nm.

8. The dispersion according to any one of claims 1 to 7, wherein the conductive layer prepared from the dispersion has an conductivity of at least 10 S / cm as determined by the test method disclosed herein.

9. The dispersion according to any one of claims 1 to 8, wherein the dispersion has a solid content of at least 1% by weight based on the total weight of the dispersion.

10. The dispersion has a viscosity in the range of 1 to 1000 mPa × s (at 20°C and 100°C). －１ A dispersion according to any one of claims 1 to 9, having a shear rate (measured with a rheometer).

11. A process for preparing a laminate (100), comprising the process steps: A) A step of preparing the base material (101), B) A step of applying the dispersion according to any one of claims 1 to 10 to at least a portion of the surface of the substrate (101), C) To obtain a laminate (100) including a conductive layer (102) coated on at least a portion of the surface of the substrate (101), the steps include removing at least a portion of the dispersant i), A process that includes this.

12. The process according to claim 11, wherein the laminate (100) is part of an electrolytic capacitor, the substrate (101) is a porous electrode body (101a) made of an electrode material (101b), a dielectric layer (101c) at least partially covers the surface of the electrode material (101b), a solid electrolyte layer (101d) at least partially covers the surface of the dielectric layer (101c), and the conductive layer (102) is a polymer outer layer (102a) that at least partially covers the surface of the solid electrolyte layer (101d).

13. The aforementioned process, A) A step of preparing a porous electrode body (101a) made of electrode material (101b), wherein a dielectric layer (101c) covers at least partially the surface of the electrode material (101b), and a solid electrolyte layer (101d) covers at least partially the surface of the dielectric layer (101c), B) A step of applying the dispersion according to any one of claims 1 to 10 to at least a portion of the solid electrolyte layer (101d), C) A step of at least partially removing the dispersant i) in order to form a polymer outer layer (102a) that at least partially covers the surface of the solid electrolyte layer (101d), The process according to claim 12, including the process described in claim 12.

14. A laminate obtained by the process described in any one of claims 11 to 13.

15. Use of the dispersion according to any one of claims 1 to 10 for forming a polymer outer layer in a capacitor.

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