JP4507653B2 - Method for forming conductive polymer and method for producing electrolytic capacitor - Google Patents

Description

  The present invention relates to a method for forming a conductive polymer, and a method for manufacturing an electrolytic capacitor using the method for forming a conductive polymer.

  In recent years, electrolytic capacitors are mounted on various electronic devices as one of electronic components suitable for high-frequency applications. With regard to this electrolytic capacitor, for example, in a situation where the digitization, downsizing and speeding up of electronic devices are accelerating, there is a demand for large capacity and low impedance, as well as operational stability and operation. There is also a demand for ensuring reliability and extending the service life.

  An electrolytic capacitor has, for example, an anode made of a valve metal, a dielectric layer made of an oxide film formed by anodizing the surface layer of the anode, an electrolyte layer, and a cathode in this order. Have a structure.

  This electrolytic capacitor is mainly divided into two types according to the type of the electrolyte layer. That is, a liquid electrolytic capacitor having an electrolyte layer (electrolytic solution) made of a liquid material and having a conductive mechanism mainly utilizing ion conductivity, and an electrolyte layer made of a solid material such as a complex salt or a conductive polymer A solid electrolytic capacitor having a (solid electrolyte layer) and having a conductive mechanism mainly utilizing electronic conductivity. When these two types of electrolytic capacitors are compared in terms of stability of operating characteristics, for example, in liquid electrolytic capacitors, the operating characteristics may deteriorate over time due to leakage or evaporation of the electrolytic solution. As the electrolytic capacitors that can become the mainstream in the future are recently being actively researched and developed for solid electrolytic capacitors instead of liquid electrolytic capacitors, the deterioration of the operating characteristics due to leakage and evaporation of the liquid cannot occur with solid electrolytic capacitors. ing. In this research process on solid electrolytic capacitors, for example, considering the series of operating characteristics such as leakage current characteristics, impedance characteristics, and heat resistance characteristics, the main part of the solid electrolyte layer is composed of manganese dioxide or complex salts and conjugated conductive polymers. Is moving rapidly.

  The conductive polymer constituting the solid electrolyte layer is generated, for example, by chemically oxidatively polymerizing a monomer using an oxidizing agent. When this conductive polymer is produced, for example, in order to increase the conductivity of the conductive polymer, the conductive polymer contains (dope) an electron donating or electron accepting substance (dopant). ing.

  In the production process of a solid electrolytic capacitor, for example, a conductive polymer is generated through a chemical oxidative polymerization reaction, and then the unpolymerized monomer contained in the conductive polymer is not doped into the conductive polymer. In order to remove excessive dopant or used oxidizing agent, the conductive polymer is cleaned using a cleaning liquid such as water or alcohol. If the unpolymerized monomer, excess dopant, or used oxidizer remains, the conductivity of the conductive polymer can deteriorate. The polymer washing process is important.

Several techniques are already known for cleaning the conductive polymer constituting the solid electrolyte layer. Specifically, for example, as a general cleaning example, a technique of cleaning a conductive polymer using a cleaning liquid and then drying the conductive polymer is known (see, for example, Patent Document 1). ). For example, a technique using shower cleaning is known as a method for cleaning a conductive polymer (see, for example, Patent Document 2). Furthermore, for example, a technique is known in which the conductive polymer is washed while applying a voltage in a solution containing an electrolyte to adjust the iron concentration of the conductive polymer to 100 ppm or less (for example, Patent Documents). 3).
JP 2002-313684 A JP 2002-158144 A JP 2002-167981 A

In addition, in relation to the cleaning treatment of the conductive polymer constituting the solid electrolyte layer, other treatments other than the cleaning treatment applied to the conductive polymer include, for example, a conductive material containing a first proton acid. After producing the polymer, the conductive polymer is immersed in a solution containing the second protonic acid (a protonic acid having a higher heat resistance than the first protonic acid), thereby bringing the first protonic acid into the second protonic acid. A technique for exchanging with a protonic acid is known (for example, see Patent Document 4).
JP 2003-142343 A

For reference, in fields other than solid electrolytic capacitors, for example, in the field of CRT (Cathode Ray Tube) development, a technology for cleaning conductive polymers for suppressing an AC electric field using an ethanol solution is known ( For example, see Patent Document 5.)
JP-T-2002-514 566

  By the way, in order to ensure the operating characteristics of the solid electrolytic capacitor, for example, in order to improve the conductivity of the solid electrolyte layer as stably as possible, the doping rate of the dopant contained in the conductive polymer is stabilized. There is a need to improve. However, in the solid electrolytic capacitor manufactured using the above-described conventional method of manufacturing a solid electrolytic capacitor, the doping rate is likely to decrease over time in a high temperature environment. Since it tends to decrease, there is still room for improvement in terms of stably improving the conductivity of the solid electrolyte layer. In particular, if the conductivity of the solid electrolyte layer decreases, the equivalent series resistance (ESR) increases or the capacitance decreases in the solid electrolytic capacitor. In consideration of supply, there is an urgent need to establish a technique capable of improving the conductivity of the solid electrolyte layer as stably as possible. In this case, it is also important to realize the above-described stability improvement of the conductivity as easily as possible, especially considering the mass productivity of the solid electrolytic capacitor.

  The present invention has been made in view of such problems, and a first object thereof is to provide a method for forming a conductive polymer capable of improving the conductivity of the conductive polymer as stably and easily as possible. It is to provide.

  The second object of the present invention is to produce an electrolytic capacitor capable of improving the conductivity of the solid electrolyte layer as stably and easily as possible by using the method for forming a conductive polymer of the present invention. It is to provide a method.

In the method for forming a conductive polymer according to the present invention, a first dopant is added to a monomer and polymerized to generate a conductive polymer precursor doped with the first dopant . When the conductive polymer precursor is formed by cleaning the conductive polymer precursor using a cleaning liquid containing a second dopant different from the first dopant, and the conductive polymer precursor is cleaned, The removal treatment of the first dopant not doped in the unpolymerized monomer and the conductive polymer precursor and the additional doping treatment of the second dopant are performed at the same time .

In the method for forming a conductive polymer according to the present invention, after a conductive polymer precursor doped with the first dopant is generated, a cleaning liquid containing a second dopant different from the first dopant is used. Then, the conductive polymer precursor is washed to form a conductive polymer. When this conductive polymer precursor is washed, the removal of the first dopant not doped in the unpolymerized monomer and the conductive polymer precursor, and the additional doping treatment of the second dopant, Are performed simultaneously. Based on the cleaning process using this cleaning solution, the dopant fixing property to the conductive polymer precursor is improved, so that the conventional conductive polymer forming method in which the doping rate is likely to decrease over time without performing the cleaning process. In contrast, the doping rate of the conductive polymer is stably improved. In addition, since the fixability of the dopant to the conductive polymer precursor can be improved by diverting the cleaning treatment, the doping rate of the conductive polymer can be easily improved.

Method of manufacturing an electrolytic capacitor according to the present invention is a method for producing an electrolytic capacitor having a solid electrolyte layer, by polymerizing by adding first dopant to the monomer, the first dopant is doped After generating the conductive polymer precursor, by the first dopant to form a conductive polymer by washing the conducting polymer precursors by using a cleaning solution containing different second dopant , the conductive polymer to form a including solid-solid electrolyte layer, when cleaning the conductive polymer precursor, the first that has not been doped monomer and the conductive polymer precursor unpolymerized The dopant removal process and the second dopant additional doping process are performed simultaneously .

  In the method for producing an electrolytic capacitor according to the present invention, since the solid electrolyte layer is formed using the method for forming a conductive polymer of the present invention, the doping rate of the solid electrolyte layer is stably and easily improved.

The method for forming a conductive polymer according to the present invention, when generating a conductive polymer precursor by oxidative polymerization of monomers using an acid agent, conductive high using a cleaning solution By washing the molecular precursor, the used oxidizing agent is further removed.

In the method for forming a conductive polymer according to the present invention, water containing the second dopant or alcohol containing the second dopant may be used as the cleaning liquid .

  According to the method for forming a conductive polymer according to the present invention, the conductive polymer precursor containing the first dopant is cleaned by using the cleaning liquid containing the second dopant, thereby doping the conductive polymer. Since the rate is improved stably and easily, the conductivity of the conductive polymer can be improved as stably and easily as possible. As a result, in particular, the conductivity of the conductive polymer can be maintained as much as possible even in a high temperature environment.

  According to the method for manufacturing an electrolytic capacitor according to the present invention, the solid electrolyte layer is formed using the method for forming a conductive polymer of the present invention, so that the doping rate of the solid electrolyte layer is stable and easy. Therefore, the conductivity of the solid electrolyte layer can be improved as stably and easily as possible, and in particular, the conductivity of the solid electrolyte layer can be maintained as much as possible even in a high temperature environment.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

  First, with reference to FIG. 1, the conductive polymer formed using the formation method of the conductive polymer which concerns on one embodiment of this invention is demonstrated easily. FIG. 1 shows a cross-sectional configuration of the conductive polymer 1.

  The conductive polymer 1 includes, for example, an electrolytic capacitor, a battery, an electrode, a transistor, an ultraviolet shielding material, an antistatic agent, a capacitor, a diode, an electrochromic element, an electroluminescence (EL) element, a solar cell, A part of electronic components typified by an optical recording medium or various sensors can be configured. For example, as shown in FIG. 1, the conductive polymer 1 is formed on a predetermined substrate 2, that is, formed into a film on the substrate 2.

  In particular, the conductive polymer 1 is formed by cleaning the conductive polymer precursor 1Z using a cleaning liquid to be described later, and is doped with a dopant for increasing conductivity. . The conductive polymer precursor 1Z is generated by adding a dopant to a monomer and polymerizing the precursor as a precursor for forming the conductive polymer 1. The substrate 2 is a support used for forming the conductive polymer 1 into a film. The materials of the conductive polymer 1 and the base 2 will be described later.

  Next, a method for forming the conductive polymer 1 shown in FIG. 1 will be described with reference to FIGS. FIG. 2 is for explaining the flow of the method for forming the conductive polymer 1, and FIG. 3 shows the composition of a series of solutions (monomer solution, cleaning solution) used in the process of forming the conductive polymer 1. It is for explaining.

  When forming the conductive polymer 1, after preparing the substrate 2, first, the monomer solution shown in FIG. 3 is prepared (FIG. 2; step S101). In preparing this monomer solution, a monomer for producing the conductive polymer precursor 1Z and a main dopant (first first) for increasing the conductivity of the conductive polymer precursor 1Z. Dopant) and a solvent for dispersing these monomers and the main dopant. In particular, when preparing the monomer solution, for example, together with the above-described monomer, main dopant and solvent, an oxidizing agent for oxidative polymerization of the monomer is included.

  The material used when preparing a monomer solution is as follows, for example.

  That is, examples of the monomer include aniline, pyrrole, thiophene, furan, thiophene vinylene, isothianaphthene, acetylene, p-phenylene, phenylene vinylene, methoxy vinylene, methoxy phenylene, phenylene sulfide, phenylene oxide, anthracene, naphthalene. , Pyrene, azulene, selenophene, tellurophene and at least one of the group comprising these derivatives, preferably at least one of the group comprising aniline, pyrrole, thiophene, furan and their derivatives is used. .

As the main dopant, for example, either a donor-type or an acceptor-type dopant can be used, and at least one of a group including the following series of materials is used. Examples of the donor-type dopant include alkali metals such as lithium (Li), sodium (Na), and potassium (K), and alkaline earth metals such as calcium (Ca). On the other hand, examples of acceptor-type dopants include halogens such as chlorine (Cl ₂ ), bromine (Br ₂ ), and iodine (I ₂ ), phosphorus fluoride (PF ₃ ), arsenic fluoride (AsF ₅ ), and fluorine. Lewis acids such as boron fluoride (BF ₃ ), hydrogen fluoride (HF), hydrogen chloride (HCl), nitric acid (HNO ₃ ), sulfuric acid (H ₂ SO ₄ ), phosphoric acid (H ₃ PO ₄ ) or perchlorine Protic acids such as acids (HClO ₄ ), alkylbenzene sulfonic acids (eg, paratoluene sulfonic acid), alkyl naphthalene sulfonic acids or salts thereof (eg, sodium paratoluene sulfonate or sodium alkyl naphthalene sulfonate), iron chloride (FeCl _3), perchlorate (FeOCl _2), a transition such as titanium chloride (TiCl ₄₎ or tungsten chloride (WCl ₃₎ And group compound, chlorine ion (Cl ^-), bromine ion (Br ^-), iodide ion (I ^-), perchlorate ion (ClO ₄ ^-), fluoride phosphorus (PF ₃ ^-), boron fluoride ions (BF ₃ ⁻ ) or electrolyte anions such as arsenic fluoride ion (AsF ₃ ⁻ ).

  As the solvent, for example, water or an organic solvent such as butanol is used.

Examples of the oxidizing agent include halogens such as iodine or bromine, metal halides such as silicon pentafluoride (SiF ₅ ), protonic acids such as sulfuric acid, oxygen compounds such as sulfur trioxide (SO ₃ ), Sulfates such as cerium sulfate (Ce (SO ₄ ) ₂ ), persulfates such as sodium persulfate (Na ₂ S ₂ O ₈ ), peroxides such as hydrogen peroxide (H ₂ O ₂ ), An alkylbenzene sulfonate (for example, iron paratoluene sulfonate) is used.

  The monomer solution may further contain various additives in addition to the above-described monomer, main dopant, solvent, and oxidizing agent. Examples of the “additive” include an antioxidant (for example, nitrophenol).

  As the substrate 2, for example, glass, ceramic, stainless steel, metal, resin, cotton cloth or fiber is used. Among these series of materials, for example, the metal includes aluminum, and the resin includes acrylic, polycarbonate, polyethylene terephthalate (PET), and the like. For example, when the conductive polymer 1 is used as a solid electrolyte layer of an electrolytic capacitor, the valve action of aluminum, titanium, tantalum, niobium or the like is used as the substrate 2. A metal foil or a valve action metal sintered body is used. As these valve action metal foil or valve action metal sintered body, for example, the surface enlargement process is performed in advance and the surface uneven structure is formed, and similarly, the chemical conversion process is performed in advance to form the dielectric layer. It is preferable to use what is formed. For example, when the conductive polymer 1 is used as an EL element (for example, a hole injection layer), a transparent electrode such as indium tin oxide (ITO) is used as the substrate 2.

  Subsequently, for example, by applying a monomer solution to the substrate 2 using a coating method typified by a spray method, a roller method, a spin coating method, a dip method or the like (FIG. 2; step S102), the substrate 2. Supply the monomer solution on one side. When supplying the monomer solution to one surface of the substrate 2, for example, an immersion method is used instead of using the above-described coating method, that is, the substrate 2 is simply immersed in the monomer solution. May be.

  Subsequently, the monomer in the monomer solution supplied to one surface of the substrate 2 is polymerized to generate the conductive polymer precursor 1Z containing the main dopant, that is, so that the main dopant is doped. (FIG. 2; step S103). Thereby, one surface of the base 2 is covered with the conductive polymer precursor 1Z. When this conductive polymer precursor 1Z is produced, for example, by heating the monomer solution using a heating device such as a dryer, the oxidizing agent contained in the monomer solution is changed. Used to oxidatively polymerize the monomer. At this time, the heating temperature can be appropriately set in consideration of the heat-resistant temperature of the substrate 2 and the like, for example, about 40 to 180 ° C. In this case, in particular, if the heating temperature is too high, the main dopant doped in the conductive polymer precursor 1Z is desorbed, or the conductive polymer precursor 1Z itself is oxidized and deteriorated to cause the conductivity. Therefore, the heating temperature is preferably about 40 ° C. to 150 ° C. in order to prevent this decrease in conductivity. The heating time can be appropriately set in consideration of the reactivity of the monomer (polymerizability), the reactivity of the oxidant (oxidizing power), and the like, and is, for example, about 5 minutes to 24 hours.

  The conductive polymer precursor 1Z produced through this oxidative polymerization reaction is, for example, polyaniline, polypyrrole, polythiophene, polyfuran, polythiophene vinylene, polyisothianaphthene, polyacetylene, poly-p-phenylene, polyphenylene vinylene, polymethoxy vinylene. , Polymethoxyphenylene, polyphenylene sulfide, polyphenylene oxide, polyanthracene, polynaphthalene, polypyrene, polyazulene, polyselenophene, polytellurophene and at least one of these derivatives. As the conductive polymer precursor 1Z, for example, a conjugated polymer having a one-dimensional chain in the polymer skeleton and having an electron donating function or an electron accepting function (so-called dopamine function) is preferable. Among these, considering the ease of production using an oxidative polymerization reaction, for example, at least one selected from the group comprising polyaniline, polypyrrole, polythiophene, polyfuran and derivatives thereof is preferable. Specifically, this type of conductive polymer precursor 1Z is, for example, a polythiophene derivative, which can be produced by oxidative polymerization of 3,4-ethylenedioxythiophene as a monomer. Thiophene is mentioned.

  Subsequently, the cleaning liquid shown in FIG. 3 is prepared (FIG. 2; step S104). When preparing this cleaning liquid, it contains a subdopant (second dopant) for supplementing the conductivity of the conductive polymer precursor 1Z and a solvent for dispersing the subdopant, The concentration of the secondary dopant is about 0.1% to 5.0%. As the sub-dopant, for example, at least one of the above-described series of materials can be used as the main dopant. In particular, the same material as the main dopant may be used, or Different ones may be used. Any solvent can be used as long as the subdopant can be dispersed. For example, water or alcohol is used. In particular, when water is used as the solvent, it is preferable to use warm water (hot water), for example, in order to increase the cleaning ability of the cleaning liquid. In preparing the cleaning liquid, the cleaning liquid does not necessarily have to be prepared after the production of the conductive polymer precursor 1Z. For example, the cleaning liquid may be prepared together with the monomer solution in advance. Good.

  Finally, after cleaning the conductive polymer precursor 1Z using the cleaning liquid (FIG. 2; step S105), the conductive polymer precursor 1Z after the cleaning is dried (FIG. 2; step S106). The conductive polymer 1 shown in FIG. 1 is completed (FIG. 2; step S107). When the conductive polymer precursor 1Z is cleaned using the cleaning liquid, for example, the conductive polymer precursor 1Z is shower-cleaned by spraying the cleaning liquid using a shower cleaning machine, or in the cleaning liquid. By immersing the conductive polymer precursor 1Z into the unpolymerized monomer contained in the conductive polymer precursor 1Z, an excess main dopant not doped in the conductive polymer precursor 1Z, In addition, the used oxidizing agent is washed away. At this time, as the cleaning conditions, for example, the temperature of the cleaning liquid = about 20 to 80 ° C., and the cleaning time = about 1 to 20 minutes. By this washing treatment, the unpolymerized monomer, excess main dopant and used oxidizing agent are removed, and the sub-dopant in the washing solution is additionally supplied to the conductive polymer precursor 1Z (additional dope). Therefore, the conductive polymer 1 is formed so as to include both the main dopant and the sub-dopant, that is, the doping amount of the conductive polymer 1 is increased by the amount of additional doping of the sub-dopant.

  In particular, when the conductive polymer 1 is formed, the timing of doping the conductive polymer precursor 1Z is different between the main dopant and the sub-dopant, that is, the conductivity in which the main dopant is doped in advance. Since the sub-dopant is additionally doped afterwards into the polymer precursor 1Z, in the conductive polymer 1, for example, the main dopant is fixed in the deep part and its vicinity in the polymer structure, It is presumed that the subdopant is fixed on the surface portion in the polymer structure and in the vicinity thereof, that is, the main dopant and the subdopant are distributed so as to form a two-layer structure in the polymer structure. . In the description up to the confirmation, the “subdopant” is a name given to distinguish it from the “main dopant”. That is, there is no functional superiority or inferiority between the “main dopant” and the “subdopant”, and these “main dopant” and “subdopant” function equally in the conductive polymer 1. is there.

  In addition, when the conductive polymer precursor 1Z is cleaned using the cleaning liquid, strictly, for example, under the influence of the cleaning process, not only the above-described unpolymerized monomers, but also in advance It is considered that even a part of the main dopant doped in the conductive polymer precursor 1Z may be unintentionally washed away and removed. However, when the removal amount D1 of the unintended main dopant during cleaning and the additional doping amount D2 of the sub-dopant are compared, the additional doping amount D2 greatly exceeds the removal amount D1 (D2 >> D1). It is assumed that the doping amount of the polymer 1 increases without decreasing. As a support for the phenomenon that the doping amount of the conductive polymer 1 increases, when the doping rate of the conductive polymer 1 is examined as described later (see FIG. 8), the conductivity increases as the doping amount increases. Since it is confirmed that the doping rate of the molecule 1 is improved, the sub-dopant in the cleaning liquid becomes a conductive polymer precursor as described above by the cleaning treatment of the conductive polymer precursor 1Z using the cleaning liquid. It is assumed that the outflow (desorption) of the main dopant doped in advance to 1Z and previously doped in the conductive polymer precursor 1Z is suppressed.

  In the method for forming the conductive polymer according to the present embodiment, after the conductive polymer precursor 1Z is generated so as to include the main dopant, the conductive polymer precursor pair 1Z is formed using the cleaning liquid containing the sub-dopant. Since the conductive polymer 1 is formed by washing, as described above, the sub-dopant in the washing liquid is additionally doped to the conductive polymer precursor 1Z by the washing treatment, and as a result, the conductive polymer precursor is obtained. In addition to the main dopant previously doped in the body 1Z, the conductive polymer 1 is formed so as to include a subdopant additionally doped in the conductive polymer precursor 1Z. In addition, during the cleaning process, the outflow (desorption) of the main dopant previously doped in the conductive polymer precursor 1Z is suppressed based on the fact that the sub-dopant is included in the cleaning liquid. In this case, since the fixability of the dopant (main dopant, sub-dopant) to the conductive polymer 1 is increased, the doping rate is increased without cleaning the conductive polymer precursor 1Z using the cleaning liquid containing the sub-dopant. Unlike the conventional method for forming a conductive polymer that tends to decrease with time, the doping rate of the conductive polymer 1 is stably improved. Therefore, in the present embodiment, the conductivity of the conductive polymer 1 can be improved as stably as possible. As a result, in particular, the conductivity of the conductive polymer 1 can be maintained as much as possible even in a high temperature environment.

  Here, to supplement the method for forming the conductive polymer according to the present embodiment, the cleaning process, which is a feature of the method for forming the conductive polymer, is substantially completed to form the conductive polymer 1. Before the time point, that is, before the conductive polymer 1 is completed by washing and drying the conductive polymer precursor 1Z for the purpose of removing unpolymerized monomers and the like. As a result, a remarkable effect is brought about with respect to the improvement in the stability of the conductivity of the conductive polymer 1, which is after the substantial completion of the formation of the conductive polymer 1, that is, the conductive polymer precursor 1 </ b> Z. When the conductive polymer 1 is completed after being washed and dried, it does not produce a significant effect on the stability improvement of the conductivity of the conductive polymer 1. This is because when the cleaning treatment is performed before the completion of the formation of the conductive polymer 1, the polymer structure of the conductive polymer precursor 1Z before drying is still in a non-equilibrium state. The sub-dopant is easily doped into the conductive polymer precursor 1Z. However, when the cleaning treatment is performed after the completion of the formation of the conductive polymer 1, the dried conductive polymer precursor 1Z (that is, the conductive polymer precursor 1Z). This is because the sub-dopant in the cleaning liquid is not easily doped into the conductive polymer precursor 1Z because the polymer structure of the conductive polymer 1) is already in an equilibrium state. In particular, the cleaning treatment of the method for forming a conductive polymer according to the present embodiment is to additionally dope a sub-dopant by diverting a cleaning operation for the purpose of removing unpolymerized monomers, that is, It is characterized in that the removal process of unpolymerized monomers and the like, which is the original purpose, and the additional doping process of the sub-dopant are simultaneously performed in a single process.

  In particular, in the present embodiment, by removing the conductive polymer precursor 1Z using a cleaning liquid containing a sub-dopant, as described above, the removal process of unreacted monomers and the like in a single step. And additional doping treatment of the sub-dopant is performed, and after removing the unpolymerized monomer and the like using the cleaning liquid not containing the sub-dopant, the sub-dopant using the solution containing the sub-dopant is used. The additional dope treatment is separately performed, that is, the unpolymerized monomer and the like are compared with the case where the removal treatment of the unpolymerized monomer and the additional dope treatment of the sub-dopant are performed in two steps. Therefore, the number of processes required for performing the removal process and the additional doping process of the sub-dopant is reduced, and the process contents are simplified. Therefore, in the present embodiment, the conductivity of the conductive polymer 1 can be improved as easily as possible.

  In the present embodiment, when the conductive polymer precursor 1Z is generated, a single solution (monomer solution) containing the monomer, the main dopant, and the oxidizing agent in a lump is used. However, the present invention is not necessarily limited to this. For example, instead of the single solution described above, two or more kinds of solutions containing a monomer, a main dopant, and an oxidizing agent in any combination may be used. Also good. Specifically, for example, two types of a solution containing a monomer and a main dopant (monomer solution) and a solution containing an oxidant (oxidant solution) may be used. Also in this case, since the conductive polymer precursor 1Z can be generated on the substrate 2 by using the above-described two kinds of solutions in order, the same effect as in the above embodiment can be obtained.

  In the present embodiment, the conductive polymer precursor 1Z is generated in a liquid phase system using a solution (monomer solution) containing a monomer, a main dopant, and an oxidizing agent. However, the conductive polymer precursor 1Z may be generated in a gas phase system instead of the liquid phase system. In this case, for example, a solution containing an oxidant and main dopant (oxidant and main dopant solution) is prepared, and the oxidant and main dopant solution is applied to one surface of the substrate 2 and then in the monomer vapor. The conductive polymer precursor 1Z can be formed on one surface of the substrate 2 by subjecting the substrate 2 to exposure to oxidative polymerization of the monomer using an oxidizing agent in the same manner as in the liquid phase system. It is. Even in this case, the same effect as the above-described embodiment can be obtained.

  Above, the description regarding the formation method of the conductive polymer which concerns on one embodiment of this invention is complete | finished.

  Next, with reference to FIG. 4 and FIG. 5, the structure of the electrolytic capacitor manufactured using the electrolytic capacitor manufacturing method according to the embodiment of the present invention will be briefly described. 4 and 5 show the configuration of the main part (capacitor element 10) of the electrolytic capacitor, FIG. 4 shows the external configuration, and FIG. 5 is an enlarged cross-sectional configuration along the line V-V shown in FIG. As shown.

  In this electrolytic capacitor, an anode lead and a cathode lead (both not shown) are connected to the capacitor element 10 shown in FIGS. 4 and 5 so that both the anode lead and the cathode lead are partially exposed. The capacitor element 10 has a structure in which the periphery is covered with a mold resin (not shown). The capacitor element 10 generates an electrical reaction as a main part of the electrolytic capacitor. For example, as shown in FIGS. 4 and 5, the anode 11 and the periphery (one end) of the anode 11 are partially provided. A dielectric layer 12 provided to cover the dielectric layer 12, a solid electrolyte layer 13 provided to cover the periphery of the dielectric layer 12, and a cathode 14 provided to cover the periphery of the solid electrolyte layer 13. In other words, the anode 1, the dielectric layer 12, the solid electrolyte layer 13 and the cathode 14 are laminated in this order.

  The anode 11 has an uneven surface (or roughened) surface uneven structure, for example, a valve metal such as aluminum (Al), titanium (Ti), tantalum (Ta), or niobium (Nb). It is comprised by. Specifically, the anode 11 is a metal foil such as aluminum or titanium, or a metal sintered body such as tantalum or niobium. The details of the surface uneven structure of the anode 11 that has been enlarged will be described later (see FIG. 6).

The dielectric layer 12 is an oxide film formed by, for example, anodizing the surface layer of the anode 11 made of a valve metal. For example, when the anode 11 is made of aluminum, the dielectric layer 12 is made of aluminum oxide (Al ₂ O ₃ ; hereinafter simply referred to as “alumina”).

  The solid electrolyte layer 13 includes the conductive polymer 1 described in the above embodiment. Since the conductive polymer 1 and the material of the dopant (main dopant, subdopant) doped in the conductive polymer 1 have already been described in detail, the description thereof is omitted. The capacitor element 10 provided with the solid electrolyte layer 13 is a so-called solid electrolytic capacitor element.

  The cathode 14 has, for example, a laminated structure in which a carbon (graphite) layer 14A and a silver (Ag) layer 14B are laminated. However, the anode 14 does not necessarily have a laminated structure, and may have, for example, a single layer structure.

  For reference, both the anode lead and the cathode lead are, for example, metals such as iron (Fe) or copper (Cu), and plating treatment (for example, tin (Sn) plating or tin lead (SnPb)) on these metals. It is made of a plated metal subjected to plating, and is connected to the anode 11 and the cathode 14 of the capacitor element 10, respectively. The mold resin is made of an insulating resin such as an epoxy resin, for example.

  Next, a detailed configuration of the capacitor element 10 will be described with reference to FIG. FIG. 6 shows a partially enlarged cross-sectional configuration of the capacitor element 10 shown in FIG.

  In the capacitor element 10, for example, as shown in FIG. 6, a dielectric layer 12, a solid electrolyte layer 13, and a cathode 14 (carbon layer 14A, silver layer 14B) are laminated in this order so as to cover the anode 11. In the capacitor element 10, as described above, in order to realize a high capacity by increasing the surface area of the anode 11, the anode 11 is subjected to a surface enlargement process (or a surface roughening process). That is, the anode 11 has a fine surface uneven structure. Accordingly, the dielectric layer 12 formed so as to cover the anode 11 has a fine uneven structure, and the solid electrolyte layer covers the dielectric layer 12 having this fine uneven structure. 13 is provided. In particular, the dielectric layer 12 constitutes a plurality of pores 12H as recesses in the concavo-convex structure, and the solid electrolyte layer 13 partially enters the plurality of pores 12H constituted by the dielectric layer 12. It is out.

  Next, with reference to FIGS. 4-7, the manufacturing method of the electrolytic capacitor provided with the capacitor | condenser element 10 shown in FIGS. 4-6 is demonstrated. FIG. 7 is a diagram for explaining the flow of a method for manufacturing an electrolytic capacitor.

  When manufacturing an electrolytic capacitor, first, the capacitor element 10 shown in FIGS. 4 to 6 is formed. That is, first, a valve action metal foil (for example, an aluminum foil or a titanium foil) is prepared as a material for forming the anode 11, and then the valve action metal foil is subjected to a surface enlargement process using chemical or electrochemical etching. Thus, the anode 11 having a fine surface uneven structure is formed (FIG. 7; step S201). As a material for forming the anode 11, for example, a valve metal sintered body such as tantalum or niobium can be used instead of the valve metal foil described above. When forming the anode 11, for example, after preparing an untreated valve metal foil that has not been subjected to a surface expansion treatment as described above, a surface expansion treatment is separately performed on the valve metal foil. Instead of applying, a processed valve action metal foil or a valve action metal sintered body that has been subjected to the surface enlargement process in advance may be used in order to save the effort required for the surface enlargement process.

  Subsequently, the surface layer of the anode 11 is anodized to form a dielectric layer 12 made of an oxide film so as to partially cover the periphery of the anode 11 (FIG. 7; step S202). The dielectric layer 12 has a concavo-convex structure corresponding to the surface concavo-convex structure of the anode 11, and constitutes a plurality of pores 12H as concave portions in the concavo-convex structure. As the dielectric layer 12, for example, when an aluminum-enlarged foil is used as a material for forming the anode 11, the dielectric layer 12 can be formed so as to be composed of alumina. When the dielectric layer 12 is formed, for example, after the anode 11 is immersed in the chemical conversion solution, a voltage is applied to the anode 12 to advance the anodic oxidation reaction. As this chemical conversion solution, for example, a buffer solution containing ammonium borate, ammonium phosphate, or organic acid ammonium is used, and preferably an aqueous solution containing ammonium adipate as the organic acid ammonium is used. The voltage applied to the anode 11 can be freely set within a range of several V to several hundred V, for example, depending on the formation thickness of the dielectric layer 12.

  Subsequently, the conductive polymer 1 is formed by forming the conductive polymer 1 doped with the dopant (main dopant, sub-dopant) using the method for forming the conductive polymer described in the above embodiment. The solid electrolyte layer 13 is formed so as to include (FIG. 7; step S203). Since the method for forming the conductive polymer 1 has already been described in detail in the above embodiment, the description thereof is omitted.

  Subsequently, the cathode 14 is formed so as to cover the periphery of the solid electrolyte layer 13 (FIG. 7; step S204). When the cathode 14 is formed, for example, a carbon paste is applied around the solid electrolyte layer 13 and dried to form the carbon layer 14A, and then a silver paste is further applied onto the carbon layer 14A. The silver layer 14B is formed by drying, and the cathode 14 is formed so as to have a laminated structure in which the carbon layer 14A and the silver layer 14B are laminated in this order. Thereby, the capacitor element 10 having a laminated structure in which the anode 11, the dielectric layer 12, the solid electrolyte layer 13, and the cathode 14 are laminated in this order is completed (see FIGS. 4 to 6).

  After the capacitor element 10 is formed, an electrolytic capacitor is assembled using the capacitor element 10. That is, for example, after connecting the anode lead to the anode 11 of the capacitor element 10 and connecting the cathode lead to the cathode 14 (FIG. 7; step S205), both the anode lead and the cathode lead are partially exposed. Thus, the periphery of the capacitor element 10 is covered with a mold resin (FIG. 7; step S206). Thereby, the anode lead and the cathode lead are connected to the capacitor element 10, and the capacitor element 10 has a structure in which the periphery of the capacitor element 10 is covered with the mold resin so that both the anode lead and the cathode lead are partially exposed. Is completed. In addition, when connecting the anode lead and the cathode lead to the capacitor element 10, for example, the capacitor element 10 may be directly connected using a welding process or a caulking process, or a conductive adhesive is used. You may make it connect indirectly.

  In this electrolytic capacitor manufacturing method, since the solid electrolyte layer 13 is formed by forming the conductive polymer 1 using the method for forming a conductive polymer of the present invention, the operation described in the above embodiment is used. In addition, the conductivity of the solid electrolyte layer 13 is stably improved, and the formation process of the solid electrolyte layer 13 is simplified. Therefore, the conductivity of the solid electrolyte layer 13 can be improved as stably and easily as possible, and in particular, the conductivity of the solid electrolyte layer 13 can be maintained as much as possible even in a high temperature environment.

  The other procedures, actions, and modifications of the electrolytic capacitor manufacturing method are the same as in the above embodiment.

  Next, specific examples of the present invention will be described.

Example 1
Using the conductive polymer forming method described in the above embodiment, the conductive polymer was formed in a liquid phase system. That is, first, a glass substrate (26 mm × 76 mm × 1 mm) as a substrate was ultrasonically cleaned with a neutral detergent solution, and then rinsed thoroughly with double distilled water, and then the substrate was put into a drier and dried. . Subsequently, 3,4-ethylenedioxythiophene (Baytron M (trade name) manufactured by Bayer Co., Ltd.) as a monomer, and iron (III) paratoluenesulfonate 50% butanol solution (Bayer Co., Ltd.) as a main dopant and oxidizing agent After sufficiently cooling Baytron C (trade name) made with ice water, 0.867 g and 10.4 g of these monomers and main dopant / oxidizer were weighed and mixed with a magnetic stirrer while cooling with ice water. -A monomer solution was prepared by stirring. Subsequently, the monomer solution was applied to one surface of the substrate using a spin coating method. At this time, the spin coating conditions were such that the number of rotations was 2000 rpm and the rotation time was 2 minutes. Subsequently, after leaving the substrate coated with the monomer solution at room temperature for about 1 hour, the substrate is heated and the monomer is oxidatively polymerized using an oxidant to form one surface of the substrate. Polyethylenedioxythiophene was produced as a conductive polymer precursor doped with the main dopant. At this time, the heating conditions were heating temperature = 100 ° C. and heating time = 15 minutes. Subsequently, the conductive polymer precursor is washed using a 1% aqueous solution of sodium paratoluenesulfonate as a cleaning liquid containing the subdopant, and then the conductive polymer precursor is dried, so that the subdopant is combined with the main dopant. A conductive polymer doped with is formed. At this time, the cleaning conditions were cleaning liquid temperature = 25 ° C. and cleaning time = 15 minutes.

(Example 2)
The same procedure as in Example 1 except that the conductive polymer precursor was cleaned using a 1% aqueous solution of sodium alkylnaphthalene sulfonate instead of the 1% aqueous solution of sodium paratoluenesulfonate as the cleaning liquid containing the sub-dopant. After that, a conductive polymer was formed.

(Comparative Example 1)
A conductive polymer is formed through the same procedure as in Example 1 except that the conductive polymer precursor is cleaned using a cleaning liquid (water) that does not contain a sub-dopant instead of the cleaning liquid that contains a sub-dopant. did.

(Comparative Example 2)
The conductive polymer precursor is not cleaned using the cleaning liquid, and the conductive polymer precursor is subjected to the same procedure as in Example 1 except that the uncleaned conductive polymer precursor is directly used as the conductive polymer. A polymer was formed.

(Comparative Example 3)
As a cleaning liquid containing a sub-dopant, a 1% aqueous solution of sodium paratoluenesulfonate is used in the same manner as in Example 1, and a cleaning liquid is used as described in the above embodiment as a modified example of the method for forming a conductive polymer. The conductive polymer was formed through the same procedure as in Example 1 except that the cleaning treatment was performed after the completion of the formation of the conductive polymer.

Example 4
As a cleaning liquid containing a sub-dopant, a 1% aqueous solution of sodium alkylnaphthalene sulfonate is used in the same manner as in Example 2, and a cleaning liquid is used as described in the above embodiment as a modification of the method for forming a conductive polymer. The conductive polymer was formed through the same procedure as in Example 1 except that the cleaning treatment was performed after the completion of the formation of the conductive polymer.

(Comparative Example 5)
As in Comparative Example 1, the cleaning liquid (water) containing no sub-dopant was used, and the cleaning process using the cleaning liquid was conducted as described in the above embodiment as a modification of the method for forming the conductive polymer. A conductive polymer was formed through the same procedure as in Comparative Example 1 except that the process was performed after the completion of the formation of the conductive polymer.

  When the various characteristics of the conductive polymers of Examples 1 and 2 and Comparative Examples 1 to 5 were examined, the following results were obtained.

  First, when the doping rates of the conductive polymers of Examples 1 and 2 and Comparative Example 1 were examined, the results shown in FIG. 8 were obtained. FIG. 8 shows changes in light absorption characteristics of the conductive polymer, where the “horizontal axis” indicates the wavelength (nm) and the “vertical axis” indicates the absorbance. “8A (solid line (thin line))”, “8B (solid line (thick line))” and “8C (dashed line)” in FIG. 8 indicate the results regarding Example 1, Example 2, and Comparative Example 1, respectively. . When examining the change in light absorption characteristics of the conductive polymer, a spectrophotometer (UV-3101PC) manufactured by Shimadzu Corporation was used, and the ultraviolet-visible spectral absorption in the wavelength range of 300 nm to 1800 nm for the conductive polymer. The spectrum was measured.

Regarding the doping rate of the dopant doped in the conductive polymer, it is possible to grasp the doping rate based on the spectrum measurement result by measuring the ultraviolet-visible spectral absorption spectrum of the conductive polymer. is there. That is, with respect to the doping rate of the conductive polymer, it is generally known that when the doping rate increases, the light absorption tendency in the near-infrared region increases in the spectrum measurement result. The phase difference between the doping rate and the spectrum measurement result has already been confirmed for a system in which, for example, polythiophene as a conductive polymer is doped with boron fluoride ion (BF ₄ ⁻ ) as a dopant. This phenomenon is considered to be caused by the formation of a kind of band based on the generation of polaron or bipolaron between the valence band and the conduction band of the conductive polymer.

  As can be seen from the results shown in FIG. 8, Examples 1 (8A) and 2 (8B) in which the conductive polymer precursor was cleaned using a cleaning liquid containing a subdopant and a cleaning liquid not containing a subdopant were used. When the spectrum measurement results were compared with Comparative Example 1 (8C) in which the conductive polymer precursor was washed, the near-infrared region (wavelength region of about 750 nm to about 1800 nm in Example 1 and 2 than Comparative Example 1) ) Increased, that is, the tendency to absorb light increased. From this, it was confirmed that in Examples 1 and 2, the doping rate of the conductive polymer was increased as compared with Comparative Example 1. In this case, in particular, when the spectrum measurement results are compared between Examples 1 and 2, the light absorption tendency is higher in Example 2 than in Example 1, so that the doping rate of the conductive polymer is improved. It was also confirmed that sodium alkylnaphthalene sulfonate was more effective as a sub-dopant than sodium paratoluene sulfonate.

  In addition, although it does not explain after showing data concretely, when other dopants other than sodium paratoluenesulfonate and sodium alkylnaphthalenesulfonate are used as a sub-dopant regarding the conductive polymers of Examples 1 and 2. In FIG. 8, the same result as that shown in FIG. 8 was obtained. From this, it was confirmed that when the conductive polymer precursor was cleaned using a cleaning liquid containing a subdopant, the doping rate of the conductive polymer increased regardless of the type of the subdopant.

  Subsequently, when the stability of the conductivity of the conductive polymers of Examples 1 and 2 and Comparative Examples 1 and 2 was examined, the result shown in FIG. 9 was obtained. FIG. 9 shows changes in resistance characteristics of the conductive polymer, where the “horizontal axis” represents the standing time (hours) and the “vertical axis” represents the resistance (kΩ). "9A (▲; solid line (thin line))", "9B (●; solid line (thick line))", "9C (■; broken line (thin line))" and "9D (x; broken line (thick line))" in FIG. "Shows the results for Example 1, Example 2, Comparative Example 1 and Comparative Example 2, respectively. When investigating the stability of the conductivity of the conductive polymer, each conductive polymer was left in a high temperature environment of 125 ° C. in an unloaded state (non-energized state) for about 800 hours. The resistance change was tracked by measuring the resistance during standing as needed.

  As can be seen from the results shown in FIG. 9, Examples 1 (9A) and 2 (9B) in which the conductive polymer precursor was cleaned using the cleaning liquid containing the sub-dopant, and the cleaning liquid not containing the sub-dopant were used. In any case of Comparative Example 1 (9C) where the conductive polymer precursor was washed, the resistance gradually increased with the passage of the standing time. However, when the resistance change was compared between Examples 1 and 2 and Comparative Example 1, the resistance change was smaller in Examples 1 and 2 than in Comparative Example 1. Specifically, in Comparative Example 1, the resistance reached about 35000 kΩ after being left for about 800 hours, whereas in Examples 1 and 2, the resistance remained at about 1300 kΩ to 1900 kΩ after being left for about 800 hours. From this, in consideration of the result derived from FIG. 8, the doping rate increases in Examples 1 and 2 as compared with Comparative Example 1. Therefore, in Examples 1 and 2, the conductive polymer in a high temperature environment is used. It was confirmed that the change in resistance of the conductive polymer was small, that is, the conductivity of the conductive polymer was stably improved. In this case, in particular, when the resistance after being left for about 800 hours between Examples 1 and 2 is compared, the resistance is about 1700 kΩ to 1900 kΩ in Example 1, and the resistance is about 1300 kΩ to 1400 kΩ in Example 2. Similar to the results derived from No. 8, it was also confirmed that sodium alkylnaphthalene sulfonate was more effective as a sub-dopant than sodium paratoluene sulfonate in improving the conductivity of the conductive polymer stably.

  In addition, it was resistance between the comparative example 1 (9C) which wash | cleaned the conductive polymer precursor using the washing | cleaning liquid which does not contain a subdopant, and the comparative example 2 (9D) which did not wash | clean the conductive polymer precursor. When the changes were compared, the resistance change was smaller in Comparative Example 1 than in Comparative Example 2. This is because, in Comparative Example 2, the unpolymerized monomer and the like are not removed and remain excessively in the conductive polymer, and therefore the conductive polymer is caused by the presence of the excessive residual component. In Comparative Example 1, since the unpolymerized monomer and the like are removed and do not remain excessively in the conductive polymer, Comparative Example 2 It is considered that the resistance of the conductive polymer is less likely to change with time in a high temperature environment as compared with the above.

  Finally, for reference, the stability of the conductivity of the conductive polymers of Comparative Examples 3 to 5 was examined, and the results shown in FIG. 10 were obtained. FIG. 10 shows the change in resistance characteristics of the conductive polymer as in FIG. In FIG. 10, “10A (▲; solid line (thin line))”, “10B (●; solid line (thick line))” and “10C (■; broken line)” are Comparative Example 3, Comparative Example 4 and Comparative Example 5, respectively. Results are shown. Note that the experimental conditions when examining the change in resistance characteristics of the conductive polymer are the same as those described with reference to FIG.

  As can be seen from the results shown in FIG. 10, Comparative Examples 3 (10A) and 4 (10B) in which the cleaning treatment was performed after the completion of the formation of the conductive polymer using the cleaning liquid containing the subdopant and the subdopant were not included. In any case of Comparative Example 5 (10C) in which the cleaning treatment was performed after the formation of the conductive polymer using the cleaning liquid, the resistance gradually increased with the passage of the standing time. However, when the resistance change was compared between Comparative Examples 3 and 4 and Comparative Example 5, the resistance change was smaller in Examples 3 and 4 than in Comparative Example 5. Specifically, in Comparative Example 5, the resistance reached about 35000 kΩ after being left for about 800 hours, while in Comparative Examples 3 and 4, the resistance remained at about 14000 kΩ to 26000 kΩ after being left for about 800 hours. In this case, in particular, the resistance after being left for about 800 hours between Comparative Examples 3 and 4 was about 22000 kΩ to 26000 kΩ in Comparative Example 3, and about 14000 kΩ to 15000 kΩ in Comparative Example 4. From this, it is confirmed that in Comparative Examples 3 and 4, the doping rate is increased as compared with Comparative Example 5, so that in Comparative Examples 3 and 4, the resistance change of the conductive polymer in a high temperature environment is reduced. It was.

  However, referring to FIG. 9 and FIG. 10, using the cleaning liquid containing the sub-dopant and Examples 1 and 2 in which the cleaning process was performed before the completion of the formation of the conductive polymer using the cleaning liquid containing the sub-dopant. When the resistance after being left for about 800 hours is compared with Comparative Examples 3 and 4 in which the cleaning treatment is performed after the formation of the conductive polymer is completed, the resistance change is more remarkable in Examples 1 and 2 than in Comparative Examples 3 and 4. It has become smaller. When repeated until confirmation, the resistance after standing for about 800 hours is about 1700 kΩ to 1900 kΩ in Example 1, about 1300 kΩ to 1400 kΩ in Example 2, about 22000 kΩ to 26000 kΩ in Comparative Example 3, and about 14000 kΩ to 15000 kΩ in Comparative Example 4. there were. From this, it was confirmed in Examples 1 and 2 that the resistance change of the conductive polymer in a high temperature environment was remarkably reduced, that is, the conductivity of the conductive polymer was improved as stably as possible.

  Although the present invention has been described with reference to the embodiments and examples, the present invention is not limited to these embodiments and examples, and various modifications can be made. Specifically, in the above-described embodiments and examples, the method for forming a conductive polymer has been described, and the method for forming the conductive polymer has been specifically described as an application example of the method for forming the conductive polymer. However, the present invention is not necessarily limited thereto, and the method for forming a conductive polymer of the present invention can also be applied to a method for manufacturing electronic components other than electrolytic capacitors. As described above, the “other electronic component” includes, for example, a battery, an electrode, a transistor, an ultraviolet shielding material, an antistatic agent, a capacitor, a diode, an electrochromic element, an EL element, a solar cell, an optical recording medium, or Examples include various sensors. Even when the method for forming a conductive polymer of the present invention is applied to these other electronic component manufacturing methods, the same effects as those of the above-described embodiment and examples can be obtained.

  The method for forming a conductive polymer according to the present invention can be applied to a manufacturing process of various electronic parts represented by an electrolytic capacitor in which a main part that generates an electrical reaction is composed of a solid material (conductive polymer). Is possible.

It is sectional drawing showing the cross-sectional structure of the conductive polymer formed using the formation method of the conductive polymer which concerns on one embodiment of this invention. It is a flowchart for demonstrating the flow of the formation process regarding the formation method of the conductive polymer which concerns on one embodiment of this invention. It is a figure for demonstrating a composition of a series of solutions (monomer solution, washing | cleaning liquid) used in the formation process of the conductive polymer shown in FIG. It is an external view showing the external appearance structure of the capacitor | condenser element manufactured using the manufacturing method of the electrolytic capacitor of this invention. FIG. 5 is an enlarged cross-sectional view illustrating a cross-sectional configuration along the line VV of the capacitor element illustrated in FIG. 4. FIG. 6 is a cross-sectional view illustrating a partially enlarged cross-sectional configuration of the capacitor element illustrated in FIG. 5. It is a flowchart for demonstrating the flow of the manufacturing process regarding the manufacturing method of an electrolytic capacitor. It is a figure showing the light absorption characteristic change of a conductive polymer. It is a figure showing the resistance characteristic change of a conductive polymer. It is a figure showing the other resistance characteristic change of a conductive polymer.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Conductive polymer, 1Z ... Conductive polymer precursor, 2 ... Base | substrate, 10 ... Capacitor element, 11 ... Anode, 12 ... Dielectric layer, 12H ... Fine pore, 13 ... Solid electrolyte layer, 14 ... Cathode, 14A ... carbon layer, 14B ... silver layer.

Claims (8)

After the first dopant is added to the monomer and polymerized, a conductive polymer precursor doped with the first dopant is generated, and then a second dopant different from the first dopant is added. Forming the conductive polymer by cleaning the conductive polymer precursor using a cleaning liquid containing ,
When the conductive polymer precursor is washed, the unpolymerized monomer and the first dopant not doped in the conductive polymer precursor are removed and the second dopant is additionally doped. A method for forming a conductive polymer, wherein the treatment is performed simultaneously . As the cleaning solution, the water containing the second dopant or the method for forming a conductive polymer of claim 1 Symbol placement, characterized by using an alcohol containing a second dopant. The method for forming a conductive polymer according to claim 1 or 2 , wherein the conductive polymer precursor is generated by oxidative polymerization of the monomer using an oxidant. The method for forming a conductive polymer according to claim 3 , wherein the used oxidizing agent is further removed by cleaning the conductive polymer precursor using the cleaning liquid. The method for forming a conductive polymer according to any one of claims 1 to 4 , wherein the conductive polymer is formed on a predetermined substrate. As the conductive polymer precursor, polyaniline, polypyrrole, polythiophene, and polyfuran and any one of claims 1 to 5, characterized in that to generate at least one of the group comprising these derivatives The formation method of the conductive polymer of description. The first and second dopants are at least one selected from the group consisting of alkylbenzene sulfonic acid and its salt, alkyl naphthalene sulfonic acid and its salt, and phosphoric acid. Item 7. A method for forming a conductive polymer according to any one of Items 6 to 7. A method of manufacturing an electrolytic capacitor having a solid electrolyte layer,
After the first dopant is added to the monomer and polymerized, a conductive polymer precursor doped with the first dopant is generated, and then a second dopant different from the first dopant is added. by forming a conductive polymer by washing the conducting polymer precursors by using a cleaning solution containing, the conductive polymer to form a including pre Symbol solid electrolyte layer,
When the conductive polymer precursor is washed, the unpolymerized monomer and the first dopant not doped in the conductive polymer precursor are removed and the second dopant is additionally doped. A method for producing an electrolytic capacitor, wherein the treatment is performed simultaneously .

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