Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C309/41—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
  • C07C309/42—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton having the sulfo groups bound to carbon atoms of non-condensed six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0091—Complexes with metal-heteroatom-bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/41—Compounds containing sulfur bound to oxygen
  • C08K5/42—Sulfonic acids; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
  • H01G9/0029—Processes of manufacture
  • H01G9/0036—Formation of the solid electrolyte layer
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
  • H01G9/004—Details
  • H01G9/022—Electrolytes; Absorbents
  • H01G9/025—Solid electrolytes
  • H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/10—Definition of the polymer structure
  • C08G2261/14—Side-groups
  • C08G2261/142—Side-chains containing oxygen
  • C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/70—Post-treatment
  • C08G2261/79—Post-treatment doping
  • C08G2261/792—Post-treatment doping with low-molecular weight dopants
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/02—Polyamines
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
  • H01G9/15—Solid electrolytic capacitors

Definitions

• the present invention relates to a reaction accelerator used for synthesizing a conductive polymer, a conductive polymer produced by using the reaction accelerator, and a solid electrolytic capacitor including the conductive polymer as a solid electrolyte.
• the solid electrolytic capacitor using the conductive polymer as a solid electrolyte is less likely to ignite and has a low ESR (equivalent series resistance), compared with conventional solid electrolytic capacitors using manganese dioxide, a solid electrolyte.
• ESR equivalent series resistance
• Patent document 1 Japanese Laid Open Patent Publication No. 10-50558, and
• Patent document 2 Japanese Laid Open Patent Publication 2000-106331.
• the present invention has been accomplished in view of the above problems of the conventional technology. It promotes the synthetic reaction of a conductive polymer.
• a conductive polymer obtained by using the reaction accelerator is also provided.
• the inventors of the present invention have researched in order to solve the objectives and found a reaction accelerator for preparing a conductive polymer.
• the reaction accelerator includes a salt of an anion derived from a sulfonic acid having a skeleton of benzene or naphthalene having at least one OH group, and at least one divalent or more cation other than a transition metal cation.
• a conductive polymer is polymerized. It promotes the polymerization reaction of the monomers for the conductive polymer, thereby resulting in efficient production of a conductive polymer with a good electric conductivity.
• the conductive polymer is used as a solid electrolyte to obtain a solid electrolytic capacitor which is reliable over a long period of time.
• the reaction accelerator for the conductive polymer composition of the present invention is characterized in that it includes a salt of an anion derived from a sulfonic acid having a skeleton of benzene or naphthalene having at least one OH group, and at least one divalent or more cation other than a transition metal cation.
• the conductive polymer of the present invention is characterized in that it includes a salt of an anion derived from a sulfonic acid having a skeleton of benzene or naphthalene having at least one OH group, and at least one divalent or more cation other than a transition metal cation in a matrix of the conductive polymer.
• the solid electrolytic capacitor of the present invention is characterized in that it includes the conductive polymer of the present invention as a solid electrolyte.
• a reaction accelerator in which the polymerization reaction of the monomer can be promoted in the process of preparing a conductive polymer.
• the electric conductivity of the conductive polymer can be maintained high.
• the solid electrolytic capacitor can be reliable over a long period of time.
• a specific salt is used as a reaction accelerator for obtaining a conductive polymer.
• the reaction accelerator does not include a transition metal (transition metal cation) which causes acceleration of the degradation of the conductive polymer.
• the salt concerned in the reaction accelerator is incorporated into the conductive polymer, thereby improving the electric conductivity, while efficiently polymerizing monomers.
• a conductive polymer can be produced, which has a electric conductivity and an excellent heat resistance.
• a solid electrolytic capacitor reliable over a long period of time compared with conventional ones.
• the conductive polymer of the present invention has a high electric conductivity and does not include a transition metal salt. Thus, a rapid degradation caused by the transition metal salt does not occur in the present invention, though it was observed in conventional conductive polymers. Therefore, it can be mainly used as a solid electrolyte of a solid electrolytic capacitor. Other than that, it can be also used as e.g., a cathode active material for batteries, an electrification prevention sheet, an electrification prevention paint, an electrification prevention agent such as an electrification prevention resin, and a corrosive proof agent such as a corrosion proof paint, in light of the advantageous properties.
• the anion derived from a sulfonic acid having a skeleton of benzene having at least one OH group is an anion in which “H” (hydrogen) of a sulfonate group of a sulfonic acid having a skeleton of benzene having at least one OH group is eliminated.
• the anion derived from a sulfonic acid having a skeleton of naphthalene having at least one OH group is an anion in which “H” (hydrogen) of a sulfonate group of a sulfonic acid having a skeleton of naphthalene having at least one OH group is eliminated.
• the anion derived from a sulfonic acid having a benzene or naphthalene skeleton having at least one OH group can include ones derived from acids selected from the group consisting of phenol sulfonic acid, phenol disulfonic acid, cresol sulfonic acid, catechol sulfonic acid, dodecyl phenol sulfonic acid, sulfosalicylic acid, naphthol sulfonic acid, naphthol disulfonic acid, and naphthol trisulfonic acid.
• an anion derived from phenol sulfonic acid or an anion derived from cresol sulfonic acid can be used in particular.
• the salt of the reaction accelerator of the present invention includes the anion as stated above and at least one divalent or more cation (other than a transition metal cation).
• the divalent or more cation is one which is divalent or more, including various inorganic cations and organic cations other than transition metals.
• the above-mentioned inorganic cation can include magnesium ion (Mg 2+ ), calcium ion (Ca 2+ ), strontium ion (Sr 2+ ), barium ion (Ba 2+ ), radium ion (Ra 2+ ), aluminum ion (Al 3+ ), etc.
• calcium ion, strontium ion, barium ion and aluminum ion can be used.
• the organic cation can include e.g., ethylenediamine ion ( + H 3 NCH 2 CH 2 NH 3 + ), 1,3-propyldiamine ion ( + H 3 NCH 2 CH 2 CH 2 NH 3 + ), and 1,2-propyldiamine ion [ + H 3 NCH 2 CH(NH 3 + )CH 3 ].
• ethylenediamine ion can be used.
• the salt of the reaction accelerator is composed of the anion and the cation. There is no specific limination of the combination of the anion and the cation.
• the reaction accelerator can include a single salt, or a combination of two or more salts.
• phenolsulfonates such as calcium phenolsulfonate, strontium phenolsulfonate, barium phenolsulfonate, aluminum phenolsulfonate, ethylenediamine phenolsulfonate
• cresolsulfonates such as calcium cresolsulfonate, strontium cresolsulfonate, barium cresolsulfonate, aluminum cresolsulfonate, ethylenediamine cresolsulfonate can be particularly used.
• the reaction accelerator of the present invention can be in particular in a form of an aqueous solution in which the above-mentioned salt dissolves in water. Moreover, in order to improve permeability, a small amount of an alcohol or a surface active agent can be added. In addition, the concentration of the above-mentioned salt can be 0.1 mol/l or more, or in particular, 0.5 mol/l or more, in case of a solution of the reaction accelerator. While mentioned later in detail, when preparing a conductive polymer using the reaction accelerator of the present invention, the above-mentioned salt regarding the reaction accelerator is in advance applied to the surface of a base material (capacitor element etc.) in order to form a conductive polymer.
• a base material capacitor element etc.
• a base material (or a base material to which a monomer and/or an oxidizer has been applied) can be immersed into the reaction accelerator in the form of a solution.
• the reaction accelerator of the present invention when the reaction accelerator of the present invention is provided in a solution having the above-mentioned concentration, the operation as described above can apply the salt in a sufficient quantity, thereby improving the productivity of the conductive polymer.
• the upper limit of the concentration of the salt in the solution can be usually about 1 mol/l in view of the solubility of the salt.
• the method for preparing the salt is not particularly limited.
• an aqueous solution including a sulfonic acid having a benzene or naphthalene skeleton having at least one OH group can be neutralized with an alkali including a divalent or more cation other than a transition metal cation and an anion.
• a reaction accelerator can be prepared directly in the form of an aqueous solution.
• the reaction accelerator obtained as an aqueous solution form by the process above can be subjected to a process such as spray dry so as to isolate the salt, which can be then dissolved in water again to form a reaction accelerator solution in the form of an aqueous solution. According to this process, the concentration of the salt in the aqueous solution of the reaction accelerator can be more accurately adjusted.
• the reaction accelerator in a state of an aqueous solution at a concentration of 5 mass % can be in a condition with a pH value of 1 or more, and in particular, of 4 or more.
• the reaction accelerator is an aqueous solution having a pH value as explained above at the concentration of 5 mass %, it can be particularly used in the production of a conductive polymer for aluminum solid electrolytic capacitors.
• the reaction accelerator in a state of an aqueous solution at a concentration of 5 mass % can be in a condition of a pH of 10 or less, or in particular, of 8 or less.
• the amounts of the acid and alkali added can be adjusted in order to meet the pH value of the aqueous solution of the obtained salts at the concentration of 5 mass %.
• the anion of the salt is required to have at least one OH group. This is because OH group is considered to promote the polymerization reaction of the monomers as well as contribute the improvement of the conductivity of the obtained conductive polymer. The reason is not be proved, but it is considered that proton of the OH group promptly proceeds with the polymerization reaction and is made easy to be incorporated in the conductive polymer. Also, the reason why the anion of the salt is required to have a benzene or naphthalene skeleton is because it can improve the heat resistance of the obtained conductive polymer when the salt is incorporated therein.
• the reaction accelerator of the present invention can promote the polymerization reaction of the monomer, and can improve the productivity of the conductive polymer.
• the salt for the reaction accelerator can be incorporated into the produced conductive polymer as acid form to be served as a dopant. If it remains in the conductive polymer as salt form, it can contribute to the improvement of the electric conductivity of the conductive polymer.
• the reaction accelerator of the present invention does not include a transition metal. Thus, it does not affect the conductive polymer. Rather, the salt is incorporated into a conductive polymer, thereby improving the heat resistance of the conductive polymer as explained above. Therefore, the conductive polymer obtained by using the reaction accelerator of the present invention become excellent in conductivity and heat resistance.
• the conductive polymer of the present invention includes the salt regarding the reaction accelerator in the matrix of the conductive polymer. It can be particularly obtained by performing a chemical oxidation polymerization of monomers using the reaction accelerator and a persulfate as an oxidizer.
• the derivatives of thiophenes can include 3,4-ethylenedioxythiophene, 3-alkylthiophene, 3-alkoxythiophene, 3-alkyl-4-alkoxythiophene, 3,4-alkylthiophene, 3,4-alkoxythiophene.
• the derivatives of pyrroles can include 3,4-alkylpyrrole, and 3,4-alkoxypyrrole.
• the derivatives of anilines can include 2-alkylaniline, and 2-alkoxyaniline.
• the carbon number of the derivatives of the alkyl group or the alkoxy group in the derivatives of the thiophenes, the pyrroles and the anilines can be in particular 1 to 16.
• a conductive polymer is formed by carrying out Process (A), Process (B), Process (C), and Process (D).
• Process (A), Process (B), Process (C) and Process (D), respectively, can be carried out once to form a conductive polymer. However, note that each of these processes can be repeated several times to form a conductive polymer. Moreover, the order of Process (A), Process (B) and Process (C) can be changed arbitrarily.
• a base material of a ceramic board and a glass board can be used instead of a capacitor element.
• the procedures similar to Process (A), Process (B), Process (C) and Process (D) can be performed to form a conductive polymer on the surface of the base material. Then, the conductive polymer can be removed from the base material.
• persulfate imidazole (or imidazole derivatives) can include ones same as the “imidazole salt of a sulfonic acid having a benzene or naphthalene skeletone having at least one OH group and at least one sulfonate group” as mentioned later.
• the alkylamines constituting the alkylamine salts of the sulfonic acid having a benzene or naphthalene skeletone can include an alkyl group having a carbon number of 1 to 12. Examples thereof can be methylamine, ethylamine, propylamine, butylamine, octylamine, dodecylamine, 3-ethoxypropylamine, 3-(2-ethylhexyloxy)propylamine, etc.
• an aqueous solution can be which includes an organic solvent with a water affinity, such as ethanol, at an concentration of around 50 volume % or less.
• the mixing ratio of a persulfate with an alkylamine salt or imidazole salt of a sulfonic acid having a benzene or naphthalene skeletone having at least one OH group and at least one sulfonate group in the oxidizer dopant solution can be as follows: Per 1 mole of the alkylamine salt or imidazole salt of a sulfonic acid having a benzene or naphthalene skeletone having at least one OH group and at least one sulfonate group, the persulfate can be added at 0.3 mol or more, and in particular, 0.4 mol or more, but 2.0 mol or less, and in particular, 1.5 mol or less.
• the mixing ratio of the persulfate is more than the above range, the ratio of the alkylamine salt or imidazole salt of the specific organic sulfonic acid is decreased. As a result, the amount of the sulfuric acid ion as dopant is increased, thereby adversely affecting the improvement of the electric conductivity of the conductive polymer by the oxidizer dopant solution. On the contrary, the mixing ratio of the persulfate is less than the range as described above, it may become difficult to produce a conductive polymer.
• the content of the cation derived from the salt regarding the reaction accelerator (that is, a divalent or more cation other than a transition metal cation) in the entire conductive polymer can be 10 ppm or more, and in particular, 20 ppm or more, and more in particular, 50 ppm or more.
• the conductive polymer includes the divalent or more cation at the content stated above, better heat resistance can be obtained.
• the upper limit of the divalent or more cation in the conductive polymer is not limited, but usually, it can be about 5000 ppm, and in particular, 1000 ppm, and more in particular, 500 ppm, and yet more in particular, 300 ppm or less.
• the content of the divalent or more cation in the entire conductive polymer can be 10 ppm or more, and in particular, 20 ppm or more, and more in particular, 50 ppm or more, but 1000 ppm or less, and in particular, 500 ppm or less, and more in particular, 300 ppm or less.
• the content of the divalent or more cation in the conductive polymer can be measured by the method shown explained later.
• the present invention is described in detail hereafter based on examples. However, the following description of the examples does not restrict the present invention. Without departing from the scope inferred in the context, a modification is included in the present invention.
• the term “%” for the concentration of a solution, diluted solution, or dispersion solution, etc. means “mass %” unless otherwise stated.
• barium hydroxide was added in the same manner as Synthesis Example 1 so as to produce barium phenolsulfonate. A solution thereof having a concentration of 0.5 mol/l was obtained.
• a cresol sulfonic acid solution was used in the same manner as Synthesis Example 1 so as to produce calcium cresolsulfonate. A solution thereof having a concentration of the 0.5 mol/l was obtained.
• ethylenediamine was added in the same manner as Synthesis Example 1 so as to produce ethylenediamine phenolsulfonate. A solution thereof having a concentration of 0.5 mol/l was obtained.
• a heat-resistant tape (2 mm in width) was stuck on a ceramic plate (40 mm in length and 3.3 mm in the width) in the transverse direction thereof such that the heat-resistant tape divides into a portion having 30 mm in size from one end of the lengthwise direction and another portion having a size of 10 mm from the other end of the lengthwise direction. Then, the portion having 30 mm in size extending from the one end of the lengthwise direction of the ceramic plate to the heat-resistant tape (29 mm ⁇ 3.3 mm) was immersed into the 0.5 mol/l calcium phenolsulfonate solution (pH 6.0) prepared in Synthesis Example 1 for 1 minute. Then, the ceramic plate was taken out to place it into a drier at a temperature of 100° C.
• a solution (pH 1.5 when diluted into a concentration of 5%), in which 0.5 mol/l of ethylenediamine phenolsulfonate was dissolved into 20% ethylenediamine polystyrene phenolsulfonate aqueous solution as prepared in Synthesis Example 7, was used and the aqueous solution was kept at 60° C.
• the same procedures as Example 1 were performed so as to obtain a conductive polymer film formed on the surface of the ceramic plate.
• an oxidizer dopant solution in which 40% ammonium persulfate was mixed with 70% 2-methylimidazole phenolsulfonate aqueous solution (pH 5.0) at a volume ratio of 1:1 with further addition of decyldimethylamineoxide at a concentraton of 0.2% was used.
• the same procedures as Example 1 were performed so as to obtain a conductive polymer film formed on the surface of the ceramic plate.
• an oxidizer dopant solution in which 40% ammonium persulfate was mixed with 70% 4-methylimidazole phenolsulfonate aqueous solution (pH 5.0) at a volume ratio of 1:1 with further addition of decyldimethylamineoxide at a concentraton of 0.2% was used.
• the same procedures as Example 1 were performed so as to obtain a conductive polymer film formed on the surface of the ceramic plate.
• Example 1 0.5 mol/l calcium phenolsulfonate aqueous solution, 0.5 mol/l sodium phenolsulfonate aqueous solution (pH 6.0) was used. Instead of repeating the polymerization process four times, the polymerization was repeated six times. Other than the differences, the same procedures as Example 1 were performed so as to obtain a conductive polymer film formed on the surface of the ceramic plate.
• Example 1 0.5 mol/l calcium phenolsulfonate aqueous solution, 0.5 mol/l ammonium phenolsulfonate aqueous solution (pH 6.0) was used. Instead of repeating the polymerization process four times, the polymerization was repeated six times. Other than the differences, the same procedures as Example 1 were performed so as to obtain a conductive polymer film formed on the surface of the ceramic plate.
• Example 1 0.5 mol/l calcium phenolsulfonate aqueous solution, 0.5 mol/l calcium m-xylenesulfonate aqueous solution (pH 6.0) was used. Instead of repeating the polymerization process four times, the polymerization was repeated six times. Other than the differences, the same procedures as Example 1 were performed so as to obtain a conductive polymer film formed on the surface of the ceramic plate.
• Example 1 0.5 mol/l calcium phenolsulfonate aqueous solution, 0.5 mol/l sodium m-xylenesulfonate aqueous solution (pH 6.0) was used. Instead of repeating the polymerization process four times, the polymerization was repeated six times. Other than the differences, the same procedures as Example 1 were performed so as to obtain a conductive polymer film formed on the surface of the ceramic plate.
• Example 1 0.5 mol/l calcium phenolsulfonate aqueous solution, 0.5 mol/l sodium butylnaphthalenesulfonate aqueous solution (pH 6.0) was used. Instead of repeating the polymerization process four times, the polymerization was repeated six times. Other than the differences, the same procedures as Example 1 were performed so as to obtain a conductive polymer film formed on the surface of the ceramic plate.
• the conductive polymer film on the ceramic plate was kept in a constant temperature bath at 150° C. for 100 hours, and then taken out. Then, the electric conductivity of the conductive polymer film was measured in the same way as described above. The results are listed in Table 1 as “Electric Conductivity after 100 Hour Storage at 150° C.”
• Comparative Examples 1 to 5 the polymerization process was repeated four times at first. However, since a conductive polymer was not formed on the given portion of the ceramic plate, the polymerization was further repeated two times. As results, a conductive polymer film was finally formed entirely at the given portions of the ceramic plate in Comparative Examples 1 to 4. However, a conductive polymer film still could not be formed in Comparative Example 5. On the contrary, fewer repetition of the polymerization process could form good conductive polymer films in Examples 1 to 10.
• Example 1 the conductive polymer film of Example 1 was removed from the ceramic plate, 100 mg of which was put into a 50 ml vial with an airtight stopper. Then, 2 ml of sulfuric acid was added in it and kept at 50° C. for one day. Then, it diluted with water and was subjected to filtering. ICP measurement was performed to the solution. The amount of calcium ions in the conductive polymer was measured by using a calibration curve. It was measured as 103 ppm.
• the amount of ions in the conductive polymers of the conductive polymer films produced in accordance with Examples 2, 5, and 8 and Comparative Examples 1 and 3 was measured.
• Strontium ion was 68 ppm in Example 2; ethylenediamine ion was 60 ppm in Example 5; calcium ion was 65 ppm in Example 8; sodium ion was 4 ppm in Comparative Example 1; and calcium ion was 100 ppm in Comparative Examples 3.
• the same procedure as Example 1 was performed to prepare a solution to measure ammonium ion by ion chromatography, using the calibration curve. The concentration was 2 ppm.
• the conductive polymer of Example 1 was different from that of Comparative Example 3 only in the anions concerning the reaction accelerators. It is considered that the results listed in Table 1 show that the anion concerning the reaction accelerator, derived from a sulfonic acid having a benzene skeleton containing at least one OH group, contributed to improve the initial characteristic (initial electric conductivity) and the heat-resistant (electric conductivity after storage) of the conductive polymer.
• An aluminum etched foil having a size of 10 mm in length and 3.3 mm in width was provided.
• a polyimide solution was applied to the transverse direction of the above-mentioned foil to have a width of 1 mm in such a way that a portion with 4 mm in size extended from one end of the lengthwise direction was divided from another portion with 5 mm in size extended from the other end.
• the foil was dried.
• a silver wire was attached as a positive electrode at the portion to have a size of 2 mm spaced from the end, which is located in said portion with 5 mm in size from the other end.
• the portion with 4 mm in size from one end of the lengthwise direction (4 mm ⁇ 3.3 mm) was immersed into 10% adipic acid ammonium aqueous solution, while applying a voltage of 13V for chemical conversion treatment to form a dielectric coating so as to produce a capacitor element.
• Example 11 Instead of using 0.5 mol/l calcium phenolsulfonate aqueous solution in Example 11, 0.5 mol/l sodium phenolsulfonate aqueous solution (pH 6.0) was used. Other than that, the same procedure used in Example 11 was used to produce an aluminum solid electrolyte capacitor in this example.
• Example 11 Instead of using 0.5 mol/l calcium phenolsulfonate aqueous solution in Example 11, 0.5 mol/1 magnesium butylnaphthalenesulfonate aqueous solution (pH 6.0) was used. Other than that, the same procedure used in Example 11 was used to produce an aluminum solid electrolyte capacitor in this example.
• the tantalum sintered material was immersed for 5 seconds, and then it was taken out to keep it at room temperature for 30 minutes to form a conductive polymer layer. Then, the tantalum sintered material having its surface covered with conductive polymer layer was immersed into pure water for 30 minutes, and then it was taken out to dry it at 70° C. for 30 minutes.
• an oxidizer dopant solution in which 40% ammonium persulfate was mixed with 70% 2-methylimidazole phenolsulfonate aqueous solution (pH 5.0) at a volume ratio of 1:1 was used, and the number of repeating the polymerization process was decreased from 16 times to 10 times.
• the same procedure used in Example 15 was used to produce a tantalum solid electrolyte capacitor in this example.
• an oxidizer dopant solution in which 40% ammonium persulfate was mixed with 70% 2-methylimidazole phenolsulfonate aqueous solution (pH 5.0) at a volume ratio of 1:1 with further addition of decyldimethylamineoxide at a concentration of 0.2% was used, and the number of repeating the polymerization process was decreased from 16 times to 10 times.
• the same procedure used in Example 15 was used to produce a tantalum solid electrolyte capacitor in this example.
• an oxidizer dopant solution in which 40% ammonium persulfate was mixed with 70% 4-methylimidazole phenolsulfonate aqueous solution (pH 5.0) at a volume ratio of 1:1 with further addition of decyldimethylamineoxide at a concentration of 0.2% was used, and the number of repeating the polymerization process was decreased from 16 times to 10 times.
• the same procedure used in Example 15 was used to produce a tantalum solid electrolyte capacitor in this example.
• a tantalum sintered material was prepared in the same manner as Example 15 so as to form a dielectric coating. Then, it was immersed into 35% 3,4-ethylenedioxythiophene ethanol solution for 1 minute, and then it was taken out to keep it at room temperature for 5 minutes. Then, into the same oxidizer dopant solution used in Example 23, the tantalum sintered material was immersed for 5 seconds, and then taken out to keep it for 5 minutes. Then, into the 0.5% calcium phenolsulfonate aqueous solution (pH 6.0) prepared in accordance with Synthesis Example 1, the tantalum sintered material was immersed for 5 seconds, and then it was taken out to dry it at room temperature for 30 minutes to form a conductive polymer layer. Then, the tantalum sintered material having its surface covered with conductive polymer layer was immersed into pure water for 30 minutes, and then it was taken out to dry it at 70° C. for 30 minutes.
• a series of processes from the step of immersing the tantalum sintered material into the 3,4-ethylenedioxythiophene ethanol solution to the step of drying it at 70° C. for 30 minutes was repeated ten times. Then, the conductive polymer layer was covered with a carbon paste and a silver paste to prepare a tantalum solid electrolyte capacitor.
• an oxidizer dopant solution in which 40% ammonium persulfate was mixed with 70% 2-methylimidazole phenolsulfonate aqueous solution (pH 5.0) at a volume ratio of 1:1 was used, and the number of repeating the polymerization process was reduced from 16 times to 10 times.
• the same procedure used in Example 20 was used to produce a tantalum solid electrolyte capacitor in this example.
• an oxidizer dopant solution in which 40% ammonium persulfate was mixed with 70% 2-methylimidazole phenolsulfonate aqueous solution (pH 5.0) at a volume ratio of 1:1 was used, and the number of repeating the polymerization process was reduced from 16 times to 10 times.
• the same procedure used in Example 21 was used to produce a tantalum solid electrolyte capacitor in this example.
• Example 15 Instead of using 0.5 mol/l calcium phenolsulfonate aqueous solution in Example 15, 0.5 mol/l ammonium phenolsulfonate aqueous solution (pH 6.0) was used. Other than that, the same procedure used in Example 15 was used to produce a tantalum solid electrolyte capacitor in this example.
• Example 15 Instead of using 0.5 mol/l calcium phenolsulfonate aqueous solution in Example 15, 0.5 mol/l calcium m-xylenesulfonate aqueous solution (pH 6.0) was used. Other than that, the same procedure used in Example 15 was used to produce a tantalum solid electrolyte capacitor in this example.
• Example 15 Instead of using 0.5 mol/l calcium phenolsulfonate aqueous solution in Example 15, 0.5 mol/1 magnesium m-xylenesulfonate aqueous solution (pH 6.0) was used. Other than that, the same procedure used in Example 15 was used to produce a tantalum solid electrolyte capacitor in this example.
• the sequential process from the step of immersing the tantalum sintered material into the mixture of the ferric p-toluenesulfonate butanol solution and 3,4-ethylenedioxythiophene to the step of drying at 50° C. for 30 minutes was repeated five times to form a conductive polymer layer on the surface of the tantalum sintered material. Then, the conductive polymer layer was covered with a carbon paste and a silver paste to prepare a tantalum solid electrolyte capacitor.

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