TWI322436B - Electroconductive polymer solution, electroconductive film, condenser and method for producing the same - Google Patents

Description

IX. Description of the Invention: [Technical Field] The present invention relates to a conductive horse molecule solution containing 7 conjugated conjugated conductive material from the octagonal singular 77, and used to impart electrical conductivity to electronic parts or packaging materials. Conductive coating. Also, regarding aluminum electrolytic capacitors and planers. The face is as a... % listen to capacitors such as electric pirates, tantalum electrolytic capacitors and their manufacturing methods. [Prior Art]; Common: Conductive polymer, used for electronic parts, general-purpose anti-electric materials, and (4) anti-static packaging materials for electronic parts. ▼寺电子成 The conjugated conductive polymer has a medium-sized, so-called insoluble c-solvent that decomposes before reaching the dazzle. Therefore, in order to make the film easy to form, it is difficult to dissolve the conductive polymer in the solvent, such as adding it.吏2 = a component of a sexual molecule that is soluble. [beta], "For example, Patent Document 1 proposes: by the polymerization of benzene in the presence of a polyanion, dispersing the base, etc. in appearance and performance, _ and: =:=, etc.: Liquid, suitable for use as a conductive material for water-soluble polymers', so by mixing the water-soluble polymer, the performance of the antistatic material can be obtained, and the product has excellent performance. In recent years, with the digital position of the electronic machine. It is required to reduce the impedance of capacitors used in electronic equipment in the high-frequency field. Since it has been used, it has used so-called functional capacitors, which are made of aluminum and a metal oxide film of a valve metal. 1. A light-based conductive polymer is used as a cathode. The surface of the surface is formed as a "common: functional capacitor", as shown in Patent Reading 2, generally two: two anodes made of porous metal, the anode surface Oxygen: the electric layer, which is a solid electrolyte layer, a carbon layer, and a cathode formed on the dielectric layer. The solid electrolyte layer of the capacitor is a light conductive polymer. τ conjugate, conductivity high The method of forming the film of the sub-organ is known as an electrochemical polymerization method and a chemical oxidation polymerization method. The electrochemical polymerization method described in Patent Document 3 and the like is a method in which a manganese oxide is formed on the surface of the intermetallic porous body in advance. After the conductive layer, it is used as an electrode for electrochemical polymerization... 匕, the problem is: when the conductive layer is formed, and the conductivity of the oxidized oxide is low, resulting in high conductivity τ conjugate conductivity Further, the chemical oxidation polymerization method described in Patent Document 4 has a long polymerization time and requires repeated polymerization in order to secure the thickness of the film, so that the production efficiency of the capacitor is low, and the conductivity is also higher than that of the electricity. In addition, since the solution in the chemical oxidative polymerization method exhibits extremely strong acidity due to the oxidizing agent, it causes 'corrosion of the dielectric layer of the oxide film' and leads to an increase in equivalent series resistance. In the case of an aluminum electrolytic capacitor, the problem is that it is impossible to use a separator made of cellulose as a raw material, which is hindered by the cellulose in the 8 1322436 plate. The method of forming a π-conjugated conductive polymer film other than the electrochemical polymerization method and the chemical oxidative polymerization method, Φ has been proposed to coexist with a polyanion having a base or a slow base. The aniline is subjected to chemical oxidative polymerization to prepare a water-soluble polyaniline, and the polyaniline aqueous solution is applied and dried to form a coating film (see Patent Document 1).

A polyanion and a solution of a specific organic compound form a coating film (see Patent Document 5). The π-conjugated conductive polymer is coated and dried, and is disclosed in Japanese Laid-Open Patent Publication No. Hei 7-105718. Patent Document 2: Japanese Patent Publication No. 2〇〇3·37〇24. Patent Document 3: JP-A-63-158829. Patent Document 4: 曰本特开昭63·1733π. Patent Document 5: Japanese Patent No. 2916〇98.

L 货明Ν暮J 斑; 'And the use of the polyaniline-containing liquid described in Patent Document i for the contact of the conductive sub-parts will cause metal corrosion and cause contact with the electrical polymer solution. Disadvantages of discoloration of items (eg, food, etc.). Although the method described in the document U can be used to simplify the film of the "electrothermal conductivity", the problem of the dielectric layer is not solved. Therefore, the equivalent series resistance of the capacitor cannot be reduced. The invention is contrary to the above-mentioned situation, and the object thereof is to provide a conductive polymer solution which can prevent a metal rot or a contact film from providing a low capacitance and a color change thereof, and a conductive type coating can be prevented. Dielectric layer corrosion and equivalent series resistance method. The results of investigation of metal corrosion and contact discoloration by Yue Ren et al. found that the reason is that the π-conjugated inter-guided knife/liquid is low and the conductivity is low. A polymer solution and a conductive coating film. The polymer solution is characterized in that it contains an I anion and a solvent, and the temperature is 2 5 , that is, the conductive π-conjugated conductive polymer of the present invention has a pH of 3 Preferably, the conductive polymer solution of the present invention is further contained in the conductive polymer solution of the present invention. Further, it is preferable that the conductive polymer solution of the present invention contains: Molecular hydroxyl group A compound of a glycidyl group or an amine group formed by a polymer solution. The capacitor of the present invention is characterized in that: an anode 'anode surface composed of a porous body is formed by oxidation: and is formed in the medium a cathode having a solid electrolyte layer on the electric layer, and the m-electrolyte layer of the cathode contains a π-co-leap, a polyanion, and a solvent, and is coated with a conductive polymer, and is electrically high- The conductive polymer solution is adjusted to a temperature H (4) of 3 to 13 Η. In the capacitor of the present invention, it is preferred to add a base to the conductive f-molecule solution to adjust the pH to the above range. In the case of the capacitor of the present invention, the conductive polymer solution preferably contains a radical, a glycidyl group or an amine group in the molecule. More than one compound. The method for manufacturing a valve capacitor of the present invention is characterized in that it has a one-by-one process in a capacitor intermediate (an anode having a porous metal body and a surface of the anode) In the dielectric layer formed by oxidation, the surface of the layer is coated with a conductive polymer solution (containing 2 molecules, polyanions, and solvents, and the pH of the temperature has been adjusted to 3 to 13). .) and carry out the drying process. The conductive polymer solution of the present invention can not only sufficiently ensure the solubility of the electric property to the molecules, but also prevent the metal rotten rice or the contact article. Therefore, it can be applied to a cathode material of a functional capacitor or an electronic component such as an electric component or a food packaging material. The conductive JJ of the present invention can be used to prevent metal corrosion and discoloration of contact articles. Further, the thunderstorm of the present invention can prevent the corrosion of the dielectric layer, so that the series effect resistance of the temple is low. Therefore, i: The capacitor of the present invention can prevent the dielectric layer from being corroded, so that the leakage current is small and the capacitance is high. By the invention of the thunder and #0. . The morphological shifting method prevents corrosion of the dielectric layer and low equivalent series resistance of the thief. [Embodiment] Hereinafter, an embodiment of the conductive polymer solution and the conductive coating film of the present invention and the production thereof will be described. <Electrically conductive polymer solution Μπ-general conductive polymer) A versatile light-based conductive south molecule, and an organic polymer of ρ φ ^ can be used. For example, a total of light structure, polyacetylene, polyphenylene, polyphenylene phenylene, polythiophene, polyacene CDQ1 X soil_vinyl, polyaniline-polymer ΐν , Polyporide vinyl building, and these four materials. From the standpoint of the ease of polymerization, the air, the concentration of the air, the concentration of the air, and the polyaniline are preferred. In the π-conjugated conductive polymer, sufficient conductivity is obtained, and the original state can be used as a base, a sulfhydryl group, or an electric group. Preferably, the κ alkoxy group and the hydroxyl group are burned. A conjugated conductive polymer such as a cyano group. s This group introduces π. The π-conjugated system has high conductivity, and 綮W ^ ' can be, for example, polypyrid (N.methyl) or poly(3-methyl'pyrrole' 1 (3-ethyl octyl) h base. ^), poly (3. butyl), poly (3 octyl), poly (3-癸 base), poly ( & (3_ t (3,4_ dimethyl^ each) ), poly (3,4-dibutyl), ethyl oxime) dir 竣 base), poly (3·methyl + hydroxy group (3 - fluorenyl-4- decyl butyl) )), 〇 〇 0 0 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ )' Polyporphin, poly(3_poly(3-ethylthiophene), poly(3·propylthiophene dirule (3·butylthiophene), 12 1322436 poly(3-hexylthiophene), poly(3- Heptylthiophene), poly(3-octyl porphin), poly(3-mercaptothiophene), poly(3-dodecylthiophene), poly(3·8-yard thiophene), poly(3- Bromothiophene) poly(3_ylthiophene), poly(3-iodothiophene), poly(3.cyanothiophene), poly(3-phenylthiophene), poly(3,4-didecyl) Thiophene), poly(3,4-dibutylthiophene) , poly(3 hydroxy singer 0), water (3-methoxy porphin), poly(3-ethoxy ose phenanthene), poly(3-butoxythiophene), poly(3-hexyloxy) Thiophene), poly(3heptyloxythiophene), poly(3-octyloxythiophene), poly(3-methoxythiophene), poly(3-dodecyloxythiophene), poly(3_18 Alkoxythiophene), poly(3,4-dihydroxythiophene), poly(3,4-dimethoxythiophene)' poly(3,4-diethoxythiophene), poly(3,4-dipropene) Oxythiophene), poly(3,4·dibutylidenethiophene), poly(3,4-dihexyloxythiophene), poly(3,4-diheptyloxythiophene), poly(3,4-difluorene) Oxythiophene), poly(3,4•bisdodecyloxythiophene), poly(3,4-ethylenedioxythiophene), poly(3,4-propanedioxythiophene), poly(3, 4-butyldioxythiophene), poly(3-methyl-4-methoxythiophene), poly(3-mercapto-4-ethoxythiophene), poly(3-carboxythiophene), poly(3) · Methyl-4-carboxythiophene), poly(3-methyl-4-carboxyethylthiophene), poly(3-methyl-4-carboxybutylthiophene), polyaniline, polymethylaniline, poly(3) -isobutylaniline 'poly(2·aniline sulfonic acid), poly(3-aniline sulfonic acid), etc. Among them, from the viewpoint of resistance value and reactivity, it is preferred to use a compound selected from the group consisting of polypyrrole, polythiophene, and poly(Ν· (co-pyridyl), poly(3-methylthiophene), poly(3-methoxythiophene), poly(3,4-diethoxythiophene) or two (co)polymers Furthermore, the conductivity can be improved, and 13

From the viewpoint of improving heat resistance, H Hoxythiophene is more preferable. IC 3,4-B, and 'poly(N-methyl-), poly(3-methyl porphin), etc., because of its solvent cross-linking J, compatibility, when adding hydrophobic resin The nature and dispersion can be improved, and its Φ is better. Further, in the group of the alkyl-substituted compound, in the middle, in order to prevent a decrease in conductivity, a methyl group is preferred. The π-co-electricity is removed from the factory in a solvent, and a suitable oxidizing agent (3) and an arsenic having an anionic group are formed in a solvent. In the presence of a knives, it is easy to chemically oxidize and polymerize the body's early body's role as a conjugated agent in the molecule. The polymer 卩 卩. ^ ^ , , /, also forms a 7 conjugate in the main chain. Department. For example, u ratio. Various types of moons and their organisms, thiophenes and their derivatives, anilines and their bamboo organisms. Specific examples of the pre-latch monomer include, for example, nN_m, 3 methyl groups, 4 3-ethylpyrrole, 3-n-propylpyrrole, butylpyrrole, octyl °, and 3 癸 晚, 3·12 yards, 3,4· dimethyl phloilos, 3,4-dibutylpyrrole, 3 carboxypyrrole, 3·fluorenyl | carboxypyrrole, 3-methyl _4_ The ethyl group 0 is a specific one, 3 - fluorenyl 4- butyl butyl. Bilo '3-ethoxyl pyrrole, 3-butoxypyrrole, 3-hexyloxypyrrole, 3_fluorenyl-4 hexyloxypyrrole, thiophene, 3-methylthiophene, 3-ethyl Thiophene, propyl thiophene, hong butyl thiophene, 3-hexyl porphin, 3. heptyl sin, 3 octyl porphin, 3 fluorenyl porphin, 3 _ 12 decyl porphin, 3- Octadecyl porphin, 3_ phenanthrene, % chloro phenyl, 3-iodothiophene, 3-cyanothiophene, 3-phenylthiophene, 3,4-dimethylthiophene, 1322436 3, 4-dibutyl porphin, 3- thiophene, 3-methoxy thiol, 3 ethoxy thiophene, 3-butoxythiophene, 3-hexyloxythiophene, 3-heptyloxy Thiophene, 3-octyloxythiophene, 3-methoxyoxythiophene, 3-dodecyloxyporphin, 3-octadecyloxy. Cerebral, 3,4-di-based "• semaphate, 3,4-dimethoxycarcinoma, 3,4-diethoxy thiophene, 3,4-dipropoxy sin, 3 , 4 - dibutoxy ° pheno, 3,4-dihexyloxythiophene, 3,4-diheptyloxy porphin, 3,4-dimethoxyoxyl thiophene, 3,4_double二院氧°e, 3,4-ethanedioxy^e, 3,4-propanedioxyseptene, 3,4-butadioxy-septene, 3-methyl-4- Alkoxy. Cephthophene, 3-methyl-4-ethoxyphenthiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3-methyl-4-carboxyethyl thiophene, 3-methyl- 4-renylbutyl η cephene, aniline, 2-methylaniline, 3-isobutylaniline, 2-aniline sulfonic acid ' 3-aniline sulfonic acid, and the like. - The solvent to be used in the production of the conductive polymer is not particularly limited as long as the precursor monomer can be dissolved or dispersed, and the oxidizing power of the oxidizing agent can be maintained. For example, water, hydrazine-mercapto-2-pyrrolidone, hydrazine, hydrazine-dimethyl decylamine hydrazine, hydrazine-dimercaptoacetamide, dimercaptoarylene, hexamethylenephosphonium Polar solvents such as amine, acetonitrile and benzonitrile; phenols such as indophenol, phenol, xylenol; alcohols such as decyl alcohol, ethanol, propanol and butanol; ketones such as acetone and acetophenone; Hydrocarbons such as benzene and toluene; carboxylic acids such as formic acid and acetic acid; carbonate compounds such as ethylene carbonate and propylene carbonate; ether compounds such as dioxane and diethyl ether; ethylene glycol dialkyl ether and propylene glycol dialkyl ether; a chain ether such as polyethylene glycol dialkyl ether or polypropylene glycol dialkyl ether; a heterocyclic compound such as 3_fluorenyl-2-oxazolidinone; acetonitrile 'glutaronitrile, methoxyacetonitrile, propionitrile , benzonitrile and other guessing compounds. These solvents may be used singly or in combination of two or more kinds of 15 1322436 or a mixture with other solvents. The oxidizing agent may be one which can oxidize the precursor monomer and obtain a τ conjugated conductive polymer, and examples thereof include ammonium peroxydisulfate (ammonium persulfate) and sodium peroxodisulfate. Peroxodisulfate such as sodium sulphate or potassium peroxydisulfate (potassium persulfate); transition metal compounds such as iron oxide, iron sulfate, iron nitrate, and copper chloride; metalloids such as boron trifluoride and aluminum hydride a metal oxide such as silver oxide or ruthenium oxide; a peroxide such as hydrogen peroxide or ozone; an organic peroxide such as benzamidine peroxide; and oxygen. (polyanion) polyanion's substituted or unsubstituted polyalkylene, substituted or unsubstituted polyalkenyiene, substituted or unsubstituted polyimine, substituted or unsubstituted polyamine, substituted or not The substituted polyester and the copolymer of the 'including an anionic group may also comprise a constituent unit having no anionic group. The anion group of the polyanion has a function as a dopant for the π-conjugated conductive polymer, and improves the conductivity and heat resistance of the π-conjugated conductive polymer. The term "polyalkylene" refers to a polymer composed of a repeating methylene group in the main chain. The polypyrazole may, for example, be polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyvinyl alcohol, polyvinylphenol, poly(3,3,3-trifluoropropene), polyacrylonitrile, Polyacrylate, polystyrene, and the like. The term "polyalkylene" refers to a polymer in which the main chain is a constituent unit containing one or more unsaturated bonds (vinyl groups). Specific examples of the polyalkylene support include, for example, a propylene support, a fluorene-based propylene support, a butyl propylene support, a 1322436 decyl propylene building, a κ cyano propylene building, a phenyl propylene building, and an i ray. Base two-thickness, 1·butyl sulphate, i•methyl xiaodinglou, i•ethyl xiaodinglou, (· 辛基-1-丁料, 丨_15th county Xiaoding (four), 2m• Dingshuanglou, 2 ethyl-1-butadiene, 2-butyl q•butene, 2_hexyl+butene, 2·octyl-1-butane, 2-mercaptobutyl Floor, 2_12-base small m phenyl-1-butane, 2-butaline, i•methyl_2•butadiene, i-ethyl·sweet, 1-octyl- 2-丁浠Support, i•15 burning base_2_丁妇撑, 2_methyl_2 丁稀楼, 2-ethyl-2-2butene floor, 2_ butyl·2 butyl support, 2 _Hexyl_2_丁浠撑, 2-octyl-2-butene floor, 2_癸基_2_丁丁撑, 2·12-decylbutene, 2-phenyl·2_butylene, 2_丙妇苯_2•丁稀楼,3_甲美2-丁稀撑,3·乙_2_丁稀礼,3_butyl_2_丁稀#,3. 己基·ζ·丁Fine support, 3-octyl-2-butane selection, 3_mercapto·2_·, 3_12 dazzle base _ 2_ Ding women standard, 3-phenyl _ 2_butene floor, 3·propanyl bromide_2_ 丁稀楼, 2•戍=Support, heart propyl-2-decene, 4-butyl·2_pentane, 4·... Propylene, 4-cyano-2-pentene, 3_methyl_2_pentamidine, 4_ethyl-2·pentene, --2-pental #, 4 • 戍, a polymer of at least a constituent unit of hexene shot. Among them, the unsaturated bond 靼π it ±<=4 $ bond 7Γ conjugated conductive polymer may be used, and It is preferred that the substituted or unsubstituted dibutyl dichloride is used as the starting material, so that it is preferably substituted or unsubstituted butene. The polyimine may, for example, benephrine dianhydride or biphenyl tetracarboxylate. Acid di wild, - ketone ketone four acid, two needles, 2,2,3,3_tetrazolyldiphenyl fluorene dioxan, 2,2_:,4-(dicarboxyphenyl) phenyl]propane a sour acid such as di-hepatic acid, and a polyamine 13 1322436 imine derived from a diamine such as hydroxydiamine, p-phenylenediamine, m-phenylenediamine or diphenyl f-diamine. Polyamines, for example, polyamines 6, Polyamine 6,6, polyamidamine 6] oxime, etc. 'Poly vinegar, for example, polyethylene terephthalate vinegar, polytrimethylene terephthalate g, etc. When the polyanion has a substituent, the substituent may, for example, be an alkyl group, a hydroxyl group, an amine group, a carboxyl group, a cyano group, a phenyl group, a phenol group, an ester group or an alkoxy group. Solubility, heat resistance, compatibility with a resin, etc., etc., preferably an alkyl group, a hydroxyl group, a phenol group, an ester group, etc. The solubility and dispersibility of a base to a polar solvent or a nonpolar solvent The compatibility with the resin and the dispersibility of the resin; the hydroxyl group easily forms a hydrogen bond with other hydrogen atoms, and the solubility in an organic solvent, the bathing property of the resin, the dispersibility, and the adhesion property can be improved. Further, the cyano group and the hydroxyphenyl group can improve the compatibility and solubility of the resin, and can also improve the heat resistance. Among the above substituents, an alkyl group, a hydroxyl group, an ester group, and a cyano group are preferred. ^ The alkyl group may, for example, be a chain alkyl group such as a mercapto group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group or a dodecyl group; a cycloalkyl group such as a cyclopropyl group, a cyclopentyl group or a cyclohexyl group. In view of solubility in an organic solvent, dispersibility to a resin, steric hindrance, and the like, a hospital base having a carbon number of 1 to 12 is preferred. The far-reaching base may, for example, be a hydroxyl group directly bonded to a polyanion main chain or a hydroxyl group bonded through another functional group. The other functional group may, for example, be a carbon group having 1 to 7 carbon atoms, a burning group having 2 to 7 carbon atoms, a mercapto group or an imido group. Substituting a base to the end or in the functional groups. Among these, the 18-pair resin and the solubility in the organic solvent are preferably a hydroxyl group bonded to the alkyl group terminal having 1 to 6 carbon atoms bonded to the main chain. The amine group may, for example, be an amine group directly bonded to a polyanion main chain or an amine group bonded through another functional group. The other functional group may, for example, be an alkyl group having 1 to 7 carbon atoms, an alkylene group having 2 to 7 carbon atoms, a decylamino group or an imido group. The amine group is substituted to the end or in the functional groups. The phenol group may, for example, be a phenol group directly bonded to a polyanion main chain or a phenol group bonded through another functional group. The other functional group may, for example, be an alkyl group having 1 to 7 carbon atoms, an alkylene group having a carbon number of 2 to 7 and an imido group. The phenolic group is substituted to the end or in the functional groups. The ester group may, for example, be an alkyl ester group directly bonded to a polyanion main chain, an aromatic ester group, an alkyl ester group which is transmitted through another functional group, or an aromatic ester group. The cyano group may, for example, be a cyano group directly bonded to a polyanion main chain, a cyano group bonded to a terminal of a carbon number of 1 to 7 (bonded to a polyanion main chain), and bonded to a carbon number of 2 to 2 The alkyl group of 7 (bonded to the polyanion backbone) at the end of the cyano group. The anion group of the polyanion may be a functional group which can cause chemical oxidation doping of the conjugated conductive polymer, but it is a monosubstituted sulfate from the viewpoints of ease of manufacture and virginity. A base, a monosubstituted phosphate group, a phosphate group, a carboxyl group, a sulfo group and the like are preferred. Further, from the viewpoint of the doping effect of the functional group on the 7 fluorene-based conductive polymer, a sulfo group, a monosubstituted sulfate group or a carboxyl group is preferred. Specific examples of the polyanion include, for example, polyvinylsulfonic acid, polystyrene 1322436 sulfonic acid, polyallylsulfonic acid, polyacrylic acid ethanesulfonic acid, polyacrylic acid butanesulfonic acid, polypropylenesulfonic acid, polymethylacrylic acid. Sulfonic acid, poly(2-propenylamine 2 -methylpropanesulfonic acid), polyisoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, poly A propylene carboxylic acid, a polymethacryl carboxylic acid, a poly(2-propenyl decyl -2-methylpropane carboxylic acid), a polyisoprene carboxylic acid, a polyacrylic acid, or the like. These may be such a single polymer or a copolymer of two or more kinds. Among these, polystyrenesulfonic acid, polyisoprenesulfonic acid, polyacrylic acid, ethyl peracetic acid, and polyacrylic acid are preferred. These polyanions can alleviate the thermal decomposition of the π-conjugated conductive polymer. The degree of polymerization of the polyanion is preferably in the range of 1 〇 to 1 单体 of the monomer unit. If the solvent solubility and conductivity are considered, the range of 5 () to cholesteric is preferred. . The method of taking a column ion into a polymer having no anionic group, and the method of sulfonating a δ-containing substance having no anionic group with a sulfonating agent is a polymerization of an anionic group-containing polymerizable monomer. The method of manufacture. dry

: A method for producing by polymerizing an anionic polymerizable monomer, for example, in the presence of an anion and/or a polymeric contact enzyme, in the presence of an oxidizing agent, which is too oxidized to form a polymer or a free radical. Aggregate the method of & Specifically, the anion-containing polymerizable single I* in the mouthpiece and the solution A 卞丨i is dissolved in the agent and kept at the _ mouthpiece! • Dissolve a predetermined amount of oxidizing agent in the early-early agent and add the pre-dissolved time. The reaction was obtained by the reaction of the bis-contact enzyme: solution. In the production method, the refrigerant is also adjusted to be sufficiently concentrated; and the 3 anionic polymerizable monomer copolymerizes the monomer having no 20 anionic polymerizable monomer. Oxygen used in the polymerization of anionic group-containing polysaccharide seedlings

The solvent ' is the same as the user when π is formed. When the polymer is a polyanionic salt, it is preferred to modify it to form a poly-polymer. The method of mass-forming an anion acid may, for example, be an ion exchange method using an ion exchange resin, a dialysis method, a super-transition method, etc., among which, from the viewpoint of ease of work, '

蜕., in the loss, the ultrafiltration method is better. The polymerizable monomer having an anionic group is early, and a part of the precursor is taken as a monosulfate group, a carboxyl group, a sulfo group or the like, and examples thereof include a substituted or unsubstituted vinylsulfonic acid compound, and a substituted hydrazine~ Substituted ethylenesulfonic acid compound, substituted or unsubstituted propylene, non-substituted N 碲 I sa phthalic acid compound, substituted or unsubstituted methacrylate acid-reducting compound, substituted or unsubstituted a propylene-based phthalic acid cross-acid compound, a substituted or a compound; a # a 〜 乂 取代 substituted cyclic vinyl sulfonic acid compound, a substituted or unsubstituted succinic acid compound, a bucket a; a substituted or unsubstituted vinyl aromatic A compound of a cross-acid.

Specific examples include, for example, ethylene acid and salts thereof, dilute citric acid and salts thereof, methyl propyl acid and salts thereof, and acetic acid and methyl propyl groups. Benzene acid and its salts, allyl benzoic acid and its salts, α-mercapto styrene sulfonic acid and its salts, propenyl decylamine - tert-butyl = acid and its salts, 2-propenyl decylamine 2-methylpropane sulfonic acid and its salts, cyclobutene-3-sulfonic acid and its salts, isoprene sulfonic acid and its salts, ι3 And its salts, i•methyl_u·butadiene·2·supply acid and its salts 7 1-methyl-M-butadiene·4-sulfonic acid and its salts, acetyl sulfonic acid 21 1322436 (ch2ch-coo-(ch2)2-so3h) and its salts, acrylic acid (ch2ch-co〇-(ch2)3-so3h) and its salts, butyl succinate ( Ch2ch-coo-c(ch3)2ch2-so3h) and its salts, n-butyl acrylate sulfonic acid (CH2CH-C00-(CH2)4-S03H) and its salts, propyl sulfonic acid CH2CH ch2-coo-(ch2)2-so3h) and its salts, dimethyl succinic acid (ch2ch CH2-COO-C(CH3)2CH2-S03H) and its salts, 4-pentenoic acid Ethane sulfonic acid (ch2ch (ch 2) 2-coo-(ch2)2-so3h) and its salts, 4-pentenoic acid propanesulfonic acid (ch2ch (ch2)2-coo-(CH2)3-S03H) and its salts, 4-pentyl Benzene n-butanesulfonic acid (CH2CH(ch2)2-coo-(ch2)4-so3h) and its salts, 4-pentenoic acid tert-butyric acid (CH2CH(ch2)2-coo-c(ch3) 2ch2-so3h) and its salts, 4-pentenoic acid benzenesulfonic acid (ch2ch (ch2)2-coo-c6h4-so3h) and its salts, 4-pentenoic acid naphthalenesulfonic acid (CH2CH (ch2)2 -coo-c 丨.h8-so3h) and its salts, methacrylic acid ethanesulfonic acid (ch2c (ch3) -coo- (ch2)2-so3h) and its salts, methacrylic acid propane sulfonic acid (ch2c ( Ch3) -coo-(ch2)3-so3h) and its salts, butyl methacrylate methacrylate (ch2c (ch3) -coo- c(ch3)2ch2-so3h) and its salts, methacrylic acid Butanesulfonic acid (CH2C (CH3) -C00-(CH2)4-S03H) and its salts, phenyl sulfonic acid benzoic acid (ch2c (ch3) -coo-c6h4-so3h) and its salts, methacrylic acid Naphthalenesulfonic acid (ch2c (CH3) -CO〇-C10H8-SO3H) and its salts, polyethylene retinoic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polypropylene carboxylic acid, polydecyl propylene Carboxylic acid, poly-2-propenyl decylamine-2-mercaptopropyl ketone Two rebel dilute acid, polyacrylic acid and the like. Further, it may be a copolymer containing two or more of these. 22 132243b A polymerizable monomer which is not an anion group, and examples thereof include ethylene, propylene, butene, 2-butene, pentene, 2-pentene, decylene, 2 hexene, styrene, and p-. Methylstyrene, p-butylstyrene, 2,4,6-trimethylstyrene, p-methoxyphenyridinium alpha-methylstyrene, 2-vinylnaphthalene, 6-mercapto-2-_2 Vinyl naphthalene, 1-vinylimidazole, vinyl pyridine, vinyl acetate, acrolein, acrylonitrile, fluorene-vinyl-2-pyrrolidone, oxime vinylamine Ν•vinylamine, Ν•乙稀米嗤, acrylamide, hydrazine, hydrazine-dimercapto acrylamide, acrylic acid, bismuth acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid Third butyl ester, isooctyl acrylate, isodecyl acrylate, lauryl acrylate, allyl acrylate, stearyl acrylate, isobonyl acrylate, cyclohexyl acrylate, propylene Benzyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, hydroxyethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate Methoxybutyl acrylate, methacrylic acid, decyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, thiol 2- Ethylhexyl ester, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid 2-hydroxypropyl ester, propylene morpholine, vinylamine, N,N-dimethylvinylamine, N,N-diethylvinylamine, N,N-dibutylvinylamine, N-di-tertiary Vinylamine, N,N-diphenylvinylamine, N-vinylcarbazole, vinyl alcohol, vaporized ethylene, fluorinated ethylene, methyl vinyl ether, ethyl vinyl ether, cyclopropene, cyclobutene, cyclopentane Alkene, cyclohexene, cycloheptene, cyclooctene, 2-methylcyclohexene, vinylphenol '1,3-butadiene, 1-methyl·1,3·butadiene, 2-mercapto -1,3- 23 Upper W2436 Butadiene, 1,4-Dimethyl_U_ Butadiene, Bismuth 2_ Dibutyl, Dioctyl, U.S., Ding, 1, J-Ding Two suspected butadiene, Bu Phenyl-U-butadiene, 2-phenyl-butane, 2-octyl-13·1'3-butadiene, 2-hydroxy-1,3-butadiene, and the like. The olefin, the hydrazine-hydroxy group _ is copolymerized by the polymerizable property of the anionic group-free polymerizable solvent, and the ratio of the comonous anion in the conductive polymer solution is preferably a polyanion _ = Molecule and poly-based conductive polymer are 1 〇〇〇 mass part 1 redundant hT conjugate molecule is not full! In the case of a mass, the conductivity is insufficient, and the conductivity is high _ mass parts, and there is a tendency for the solvent solubility to be insufficient: 'Μ exceeds (dopant). The conductive polymer solution has high conductivity of the polyanion. In addition, the π-conjugated system of the molecule may contain a poly-ion ion X % 'but in the conductive polymer solution, it is also: a foreign matter (hereinafter referred to as another dopant). In the original case, the second conjugated conductive polymer may be oxidized, and may be a donor or an acceptor. [Dosing body dopant] The donor dopant can be, for example, sodium, oblique, etc., metallurgical soil, four money, four money, four propyl records, four butyl records, methyl = acetamidine a 4-grade amine compound such as -methyldiethylammonium. [Receptor dopant] * Body! 4 impurities, can be used such as dentate compound, Lewis acid, proton S-organic compound, organometallic compound, laughter thin (_(10) small 24 hydrogen fumarate, fish 惫# #rolling flurene, carboxy Acetolene, sulfonate, etc. Among them, the compound is exemplified by gas (cl2), desert (牝), : 2) gasified hydrazine (IC1), desertified bismuth (IBr), fluorinated Moth (if) and so on. PFs . AsFs ^ SbFs^ BFs ^ BCl5^ BBr5, S03, etc. Organic cyanide. As the substance, a compound having two or more cyano groups in the conjugated bond can be used. For example, tetracyanoethylene, tetracyanoethylene oxide, tetracyanobenzene, : gas dicyanoquinone, benzene... DQ), tetracyanoquinone, tetracyanoqulnodimethane, tetracyanoporphyrin

Itetracyanoazanaphthalene) et al. Examples of the protic acid include inorganic acids, organic acids, and inorganic acids such as hydrochloric acid, sulfuric acid m acid, (tetra)hydrogen acid, hydrogen fluoride = chloric acid, and the like. Further, examples of the organic acid include organic money, organic sulfonic acid, and the like. Human organic acid retardation, can be used in aliphatic, aromatic, cyclic aliphatic, etc.: one or two bases. For example, formic acid, acetic acid, oxalic acid, : methyl phthalate, phthalic acid, maleic acid, fumaric acid, tartaric acid, citric acid, ritual, acesulfonic acid, mono-acetic acid, di-acetic acid, trichloroacetic acid, nitrate Acetic acid, triphenylacetic acid, and the like. As the organic acid, it is possible to use a polymer having one or more sulfo groups or a sulfo group in an aliphatic 'aromatic, cyclic aliphatic or the like. The one containing a sulfo group may, for example, be methanesulfonic acid, ethanesulfonic acid, 1 propanesulfonic acid, 1-butyric acid, hydrazine, hexanic acid, hydrazine, and acid; 2 25 1322436 1 - Sustained acid, 1 - 12 rhodamine, 1 - 14 burning acid, 1 - 15 burning acid, 2 - > Smelly acid, 3 - gas - 2 - branch Propionate acid, dioxin acid, acenaphthoric acid, colistin methanesulfonic acid, 2-acrylic acid decylamine-2-methylpropane sulfonic acid, amine fluorite, 1-amino -2-Prepared 4-acid acid, 2-amino-5-- -7-supply acid, 3-aminopropionic acid, N-cyclohexyl-3-aminopropionic acid, benzoic acid , benzoic acid, p-toluene acid, diphenylbenzene acid, ethyl benzene acid, propyl benzoic acid, butyl benzene sulfonic acid, pentyl benzene sulfonic acid, hexyl benzene sulfonic acid, heptyl benzene Sulfonic acid, octylbenzene acid, decyl benzene acid, decyl benzoic acid, hydrazine-based benzene acid, ruthenium-based benzene acid, fifteen-based benzene acid, hexadecane Benzene acid, 2,4-dimethylbenzenesulfonic acid, dipropylbenzenesulfonic acid, 4-aminobenzenesulfonic acid, o-aminophthalic acid, m-aminobenzoic acid, 4-amino group- 2-gas toluene_5_ Acid, 4-amino-3-methylbenzene-1 -hemeic acid, 4-amino-5-indolyl-2-mercaptobenzoic acid, 2-amino-5-methylbenzene- 1-sulfonic acid, 4-amino-2-mercaptobenzene-1-sulfonic acid, 5-amino-2-methyl-n-sulfonic acid, 4-amino-3-methylbenzene-1- Sulfonic acid, 4-acetamide-3-chlorobenzenesulfonic acid, 4-chloro-3-nitrophenyl acid, p-benzoic acid, naphthalene acid, methylnaphthalene acid, propylnaphthalenesulfonic acid, Butylnaphthalenesulfonic acid, amyl naphthalenesulfonic acid, 4-amino-1-naphthalene® sulfonic acid, 8-chloronaphthalene-1 -sulfonic acid, naphthalenesulfonic acid formaldehyde liquid polycondensate, melamine sulfonic acid formaldehyde liquid polycondensate, Onion sulfonic acid, sulfonic acid, etc. Further, these metal salts can also be used. Examples of the compound containing two or more sulfonic groups include ethanedisulfonic acid, succinic acid, glutaric acid, sulfonium disulfonic acid, phthalic acid, isophthalic acid, and p-benzoic acid. Toluene dihydro acid, xylene dibasic acid, gas phthalic acid, benzodiazepine, dimethylbenzene succinic acid, diethyl benzoic acid, aniline-2,4-dihydro acid, Aniline-2,5-disulfonic acid, 3,4-hydroxy-1,3-benzenedisulfonic acid, naphthalene disulfonic acid, 26 1322436 methylnaphthalene disulfonic acid, ethylnaphthalene disulfonic acid, pentadecyl Naphthalene disulfonic acid, 3-amino-5-yl-based-2,7-naphthalene dibasic acid, 1·ethinamine·8_transcarbyl_3,6-naphthalene-2-amino-1,4- Benzene disulfonic acid, 1-amino-3,8-naphthalene disulfonic acid, 3 amine, i 5 naphthalene disulfonic acid, 8-amino-1-naphthol_3,6-disulfonic acid, 4_ Amine·5·naphthol·2′,7_disulfonic acid, 4·acetamidine-4′-isocyanato acid smile_2,2,·disulfonic acid, 4•acetamidine-4′- Maleic anhydride imidazolium-2,2'-disulfonic acid 'naphthalene trisulfonic acid, dinaphthyl anthracene disulfonic acid, onion disulfonic acid, onion sulfonic acid and the like. Further, these metal salts can also be used. (Solvent) The solvent contained in the conductive polymer solution is preferably such that the solubility parameter (SP value) is 10 or more. SP value Λ] 0 α μ 、, - square, in case of horse 10 or more solvent, for example, water, methanol, ethanol, ethylene glycol, two r - nightmare s yizhizhi, such as yeast, succinic anhydride, maleic anhydride, etc. Fatty acid, N-methylmethyl hydrazine * methamine, methyl acetamide, acetonitrile and other nitrogen compounds, ethylene carbonate, magnetic bismuth acrylate. The solvent may be one type or two or more types. Also, > 谷剂' is particularly good, in:

At the same time as dissolving the polyanion and the precursor monomer, the oxidizing agent is dissolved and pushed. The polymerization of the monomer of the precursor. (ρ Η of the conductive polymer solution) The conductive polymer solution has a pH of 3 to 13, preferably 5 to 13 when the temperature is 25 ° C, and the gas is 7 Ί main rain 7 ~11. If the pH is less than 3, the metal rot and the contact change cannot be prevented from being changed by the double bar, and if the right is over 13, the polyanion will be detached and the conductivity will be insufficient. The method of adjusting the pH is a method of forming a salt by mixing a polymer with a polyanion, for example, a method of forming a salt by mixing an aqueous solution (referred to as a composite 27 2322436 aqueous solution under a 7 conjugated conductivity). A method of esterification, a method of alanating an acid group, and the like. The base to be used in the mixing of the base is not particularly limited, and a known inorganic base or organic base can be used. The inorganic base may, for example, be sodium hydroxide, potassium hydroxide, calcium hydroxide or aqueous ammonia. Further, the organic base may, for example, be an aliphatic amine or an aniline such as diethylamine or diethylamine 'methylethylamine' triethylamine. Aromatic amines such as argonamine, pyrrole, imidazole, and pyridine, and derivatives thereof; sodium alkoxides such as pyrrole, sodium methoxide, and sodium ethoxide; metal alkoxides such as potassium alkoxide and calcium alkoxide. Among these, aliphatic amines, aromatic amines and metal alkoxides of a weak base are preferred. Further, as the organic base, a nitrogen-containing aromatic cyclic compound can be used. The nitrogen-containing aromatic cyclic compound not only prevents the detachment of the polyanion but also improves the electrical conductivity. Here, the term "nitrogen-containing aromatic cyclic compound" means an aromatic ring having at least one nitrogen atom, and the nitrogen atom of the aromatic ring t is kept in a conjugated relationship with other atoms in the aromatic ring. In order to form a conjugate relationship, the nitrogen atom forms an unsaturated bond with other atomic systems. Alternatively, if the nitrogen atom does not directly form an unsaturated bond with other atoms, it may be adjacent to other atoms forming an unsaturated bond. It is a non-shared electron pair existing on a nitrogen atom and can form a similar conjugation relationship with unsaturated bonds formed by other atoms. In each of the nitrogen-aromatic cyclic compounds, it is preferred to have a nitrogen atom having a conjugated relationship with other atoms and a nitrogen atom adjacent to another atom forming an unsaturated bond. 28 1322436 Such a nitrogen-containing aromatic cyclic compound may, for example, contain one gas atom...and derivatives thereof, (four) and hair derivatives containing two nitrogen atoms, (iv) and (iv) biological ... Its derivatives contain three kinds: the original: diazines and their derivatives. From the viewpoint of solvent solubility, A 'pyridine and its derivatives 'imidazoles and derivatives thereof, pyrimidines and derivatives thereof are preferred. Further, the nitrogen-containing aromatic cyclic compound may be one in which an alkyl group, a carboxyl group, a carboxyl group, a cyano 'phenyl group, a phenol group, a hydroxy group, an alkoxy group 'carbon group, or the like is introduced into the ring. Is not imported. X, the ring can also be multi-ring. In the substituent, the alkyl group may, for example, be an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a tert-butyl 'pentyl group, a hexyl group, an octyl group, a decyl group or a tetradentyl group. a cycloalkyl group such as a cyclopropyl group, a cyclopentyl group or a cyclohexyl group. However, it is preferable to use a hospital base having a carbon number of 1 to 12 in consideration of solubility in an organic solvent, dispersibility to a resin, steric hindrance, and the like. The base group may, for example, be a hydroxyl group, a fluorenyl hydroxy group, an ethylene hydroxy group, a trimethylene hydroxy group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a hexamethylene group, a propylene group, a propylene group or a butyl group. An alkylene group such as an alkyl group or an ethyl methylene group such as an alkyl group, a propylene group, a butene group or a pentene group. The carboxyl group may, for example, be a carboxyl group, a methylene carboxyl group, an ethylene carboxyl group, a triethylene carboxyl group, a propylene carboxyl group, a tetramethylene carboxyl group, a penta methylene carboxyl group, a hexamethylene carboxyl group, a heptamethyl carboxyl group or an ethyl group. An alkylene group such as an alkylene carboxyl group such as a methylene carboxyl group or a phenylethylene carboxyl group, an isoprene carboxyl group, an propylene carboxyl group, a butylene carboxyl group or a pentene carboxyl group. 29

The murine group may, for example, be a cyano group, a methylene cyano group, an ethylene cyano group, a trimethylene cyano group, a tetra-β 备 I I, a methylene sulfonyl group, a methylene cyano group, a hexamethylene cyanyl group, An alkylene cyano group such as a cyanocyano group, a propylene cyano group, a butenyl cyano group or an ethyl sulfonium cyano group such as an alkylene cyanopropyl cyano group, a butene cyano group or a fluorene cyano group. Examples of the phenol group include alkylphenol groups such as phenol, cresol, ethylphenol, and butanol, methylene ethene phenol, trimethylene methyl, tetramethylene cresol, pentaerythritol, and hexamethylene cresol. An alkylene phenol group or the like. The phenyl group may, for example, be a phenyl group such as a phenyl group, a tolyl 'butylphenyl group, an octylphenyl group or a xylyl group, a decylphenyl group, an ethenylene group, a trimethylenephenyl group or a tetramethylene group. And an alkylene group such as a phenylene group, a hexamethylene phenyl group or a heptaylene group, a phenylene group such as a phenylene group, a propylene phenyl group, a butylene group or a pentene group. The alkoxy group may, for example, be a methoxy group, an ethoxy group, a butoxy group or a phenoxy group. Specific examples of the pyridines and derivatives thereof include pyridine and 2-methyl 0 ratio. Fixed, 3-methyl. Specific bite, 4-mercapto group 0 to 0, 4-ethyl group 0 bite, 2,4-dimethyl 0 ratio, 2,4,6-trimethyl group ratio bite, 3- gas group- 5-methyl 0 ratio. Fixed, 2-° ratio of biting acid, 6-mercapto-2-pyridinecarboxylic acid, 2,6-pyridinedicarboxylic acid, 4-pyridinecarboxyaldehyde, 4-aminopyridine, 2,3-dicyanopyridine , 2,6-dicyanopyridine, 2,6-dicyano-4-indolylpyridine, 4-hydroxypyridine, 2,6-dihydroxypyridine, methyl 6-hydroxynicotinic acid, 2-hydroxy- 5-pyridinemethanol, ethyl 6-hydroxynicotinate, 4-pyridinemethanol, 4-pyridineethanol, 2-phenylpyridine, 3-mercaptoquinoline, 3-ethylquinoline, quinolinol, 2, 3-cyclopentenepyridine, 2,3-cyclohexenepyridine, 1,2-bis(4-pyridyl)ethyl pit, 1,2-di(4-D ratio), 2-° ratio Chiral base chain, 2-η ratio, 30 酉夂, 2-pyridine pyridine, 2,3 pyridine dicarboxyl-M^, pyridyl-carboxylic acid, 2,5·pyridinium, 6·° pyridine Dicarboxylic acid, 3-pyridinesulfonate, and the like. Specific imidazoles of imidazoles and derivatives thereof, such as imidazole, 2-mercapto group, "2-epylene alkyl saliva, 2-phenyl mer. sitting, hydrazine-methyl carbazole, 1-(2) Hydroxyethyl) odor, 2· 廿, 0丞·4·methylimidazole, 1 2-dimethylimidazole, 1-pentyl-2-methylimidazole, 丨-pentyl, Λ? ^ , Han 丞2_benzimidazole, 1-cyanoethylidene-2-methylimidazole, guanidinium-cyanoethyl-2-epoxide, quinone f, thiol saliva, 2-phenyl-4,5-: one rice , B-flavored saliva, 4,5·imidinic acid, 4,5-flavored dimethyl phthalate, benzoquinone σ sitting, 幷4 4 & amine basic imidazole, 2-amino group Benzene 2 (2 = fluorenyl small methyl stupid (tetra) saliva, 2, phenyl hydrazine (tetra) ' (2-pyridyl) abbreviated imidazole, etc.: Specific examples of bitings and derivatives thereof can be exemplified, for example, 2_ Amino-4 Methyl t-but, 2•Amino·6_Chloro_4_methoxy oxime]•Amino group _4,6•Two gas mouth ^2, Amino group · 4,6_Two Base spray, 2, amine _4,6-dimethyl phenidine, 2 amino-4,6-dimethoxy (tetra), 2-amino group, 2, _4_methyl (4) , 4,6-di-based, chlorinated, 2,4,-di-based dimethyl carboxylic acid, 2,4,6•triamino-xylidine 2,4-dimethoxypyrimidine, 2'4,5-trihydroxypyrimidine, 2,4-pyrimidinol, etc. Specific examples of the lottery and its derivatives include, for example, pyridinium, 2·methylhydrazine Call, 2,5-dimethyl. Ratio. Qin, than sputum acid, 2,3_0 than sputum acid, % methazine pyrazine, pyrazinium, 5-methylpyrazinium, Indole cyanopyrazine, aminopyrazine, 3-aminopyrazine-2-carboxylic acid, 2-ethyl-3-methylpyrazine, 2 3 monomethyl 0, 2,3 -diethyl Specific examples of the triazines and derivatives thereof include, for example, 1 3 =azine, 2-amino group, 3,5-triazine, 3-amino-1>2, and three-heart noise. , 2 winter diamine, phenyl 31 triazine, 2,4,6 · triamine], 3 5 • triterpene, 2, 4, 6 tris (three gas: 3, 5 · triazine, 2 ,4,6_三三嗓,定)5 6 bis(4'phenylsulfonic acid)]2 4 -矣^)_5j6' i 24 , )· ', · 二嗓二纳, 3-(2" than lamp 5,6•Diphenyl·,,-diazine, 3-(2-pyridyl)-5,6-diphenyldi-nano, W gas-cutting, three-noise, etc. “...acid electricity:: nitrogenous aromatic It is easy for a nitrogen atom in a cyclic compound to have a substituent or a proton on a non-coordinated nitrogen atom. Bit or bond. There is a substituent on the atom or a proton field ion meter m纟.w, there is a positive relationship on the gas atom,: difficult to 1 place, because the nitrogen atom and other atoms have a cation away from the atom ^ The charge generated by the coordination or bonding substituent or proton will diffuse in the nitrogen-containing aromatic ring, and will be contained in the stable form. Substituents to form a nitrogen-containing aromatic cyclic compound cation. See also 'can also be combined to form a salt with non-cationic nitrogen. Even if it is salt. The niobium 3 nitrogen-based aromatic cyclic compound is similar in effect, and the substituted soil introduced on the nitrogen atom of the nitrogen-aromatic cyclic compound may, for example, be chlorine, stunned, and western, and its p ^8 group, Mercapto, cyano, phenyl, phenyl, decyl, alkoxy, carbon, and the like. The third one may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group or an isobutyl group, and an alkyl group such as a pentyl group, a hexyl group, an octyl group, a decyl group or a dodecyl group; a cyclohexyl group or the like. In view of organic glutinability, dispersibility to resin, steric hindrance, etc., it is preferred to use a carbon group of 32 1322436 1 to 12. The base group may, for example, be a hydroxyl group, a fluorenyl hydroxy group, an ethylene hydroxy group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptaylene group or a propylene group. An alkene-hydroxyl group such as a butylene-hydroxyl group or an ethyl-methylene-hydroxyl group, such as an alkylene group, a propylene group, a butene group, a pentene group or a hydroxy group. The buffer group may, for example, be a 'carboxy group, a methylene carboxyl group, an ethylene carboxyl group, a triethylene suspending group, a propylene carboxyl group, a tetradecylene carboxyl group, a penta-quinonecarboxy group, a hexamethylene group or a hepta-carboxy group. An alkylene group such as an ethyl sulfonium carboxyl group or a phenylethylene carboxyl group, an alkylene carboxyl group, an isoprene carboxyl group, an propylene carboxyl group, a butylene carboxyl group or a pentene carboxyl group. The cyano group may, for example, be a cyano group, a fluorenyl cyano group, an ethylene cyano group, a trianthylene cyano group, a tetramethylene cyano group, a methylene cyano group, a hexamethylene cyanyl group or a hepta cyano cyano group. An alkylene cyano group such as an alkyl cyano group such as an acryl cyano group, a butenyl cyano group or an ethyl sulfonium cyano group; an acryl phenyl group, a butylene cyano group or a pentene cyano group. The phenolic group may, for example, be an alkylphenol group such as phenol, cresol, ethylphenol or butanol, methylene cresol, ethylene phenol, tridecyl phenol, tetramethylene cresol, pentacresol, hexamethylene phenol An alkylene phenol group or the like. The phenyl group may, for example, be an alkylphenyl group such as a phenyl group, a tolyl group, a butylphenyl group, an octylphenyl group or a xylyl group, an anthranylene group, an ethylenephenyl group, a trimethylenephenyl group or a tetraammine. An alkylene group such as a phenyl group, a pentaphenylene group, a hexamethylene group or a heptaylene group; an phenylene group such as an alkylene group such as a phenylene group or a phenylene group; The oxyoxy group may, for example, be an anthracenyloxy group, an ethoxy group, a butoxy group or a phenoxy group 33 1322436. The method of esterifying or hydrating an acid group can be, for example, 'adding a compound having a functional group forming an acid group and an ester bond in an aqueous solution of a complex (a compound having an intramolecular radical, having an intramolecular glycidyl group) a compound) or a compound having a functional group forming a guanamine bond (a compound having an intramolecular glycidyl group) to cause a reaction. Examples of the compound having a molecular intracellular group include aliphatic alcohols such as methanol, ethanol, propanol, diethanol, difluoroethanol, hydroxyethyl acrylate, and hydroxyethyl acrylamide, and alcohols, phenols, and phenols. An aromatic alcohol such as benzenediol, pyrogallol, resorcin or catechol, a compound containing a phenolic hydroxyl group, an amino alcohol such as ethanolamine, diethanolamine or triethanolamine. As described above, when a compound having an intramolecular hydroxyl group is added, the acid group can be acetated. Examples of the compound having an intramolecular glycidyl group include ethyl glycidyl ether, butyl glycidyl ether, tert-butyl glycidyl ether, allyl glycidyl ether, benzyl glycidyl ether, and glycidyl phenyl ether. a glycidyl compound such as bisphenol A, diglycidyl ether or glycidyl methacrylate. As described above, when a compound having an intramolecular glycidyl group is added, an acid group can also be esterified. Examples of the compound having an intramolecular amine group include the above-mentioned amino alcohols, ethylamine, aniline, and the like. An amine compound such as an amine. When a compound having an intramolecular amine group is added, the acid group can also be acetated. In the case of Xuan et al, the conductivity of the π-conjugated conductive polymer can be improved, and an aliphatic alcohol or a compound containing a phenolic hydroxyl group is preferred. In addition, compounds containing abundance are particularly good because they have the function of preventing oxidation and are also characterized by heat and long-term female nature. Further, the ethyl propylene-derived amine or a compound having an acryl group such as ethacrylic acid vine can be used to crosslink the 7r-based conductive polymer by the first or the initiator. Thermal properties and mechanical properties are preferred. (Manufacturing method of conductive polymer solution): A method for producing electric H and a knife/liquid, for example, first dispersing polyanion in water or a solvent, and adding a total of W to the solution prepared thereby

Lt!: polymer precursor monomer and if necessary, add dopants, fully "diluted human oxidant to polymerize precursor monomer 4 conjugated conductive polymer, with % _ π solvent solubility . Next, after the completion of the polymerization, the oxidizing agent and the residual monomer are removed and purified, and the conductive polymer solution is obtained by the above-mentioned adjustment method = 3 to 13'. ΡΗAdjusting the conductive polymer solution into/described, because ΡΗ is adjusted to 3 to U, so '...' is "born" to prevent corrosion when in contact with metal, and to discolor when in contact with the contact... due to polyanion Charge: The second is protected against π (four) conductive polymer, so conductivity can be ensured. ', / miscellaneous < conductive coating film> The conductive coating film of the present invention is formed by coating. The coating method of the conductive polymer coating, the electric coating, the coating, the light coating, the gravure printing, and the like. For example, a -cracking, electrocardiographic conductive coating film, specifically, is formed in an electronic component such as an antistatic material such as an antistatic packaging material, a liquid crystal surface, and an electric device: 35 1322436 electromagnetic wave shielding material of the screen Electronic camera parts such as printing tape, developing roller, charging roller, transfer roller, optical information recording such as CD and DVD. When the electronic component or packaging material of a weak acid is formed, the effect of the present invention can be particularly exerted. That is, even when a conductive coating film is formed on an electronic component, the corrosion of the metal or metal compound constituting the electronic component is prevented. Specifically, 'the second layer of functional capacitance of a dielectric layer composed of an oxide composed of a valve metal such as a group or a group, which is formed by oxidation of the oxide obtained by the casting:::...corrosion, therefore, can be reduced The leakage current of the capacitor. Further, when the conductive coating film of the present invention is formed on the packaged plastic knee film, discoloration of the packaged (contact) is prevented. state. The following describes the capacitor of the present invention and the method for manufacturing the same. Fig. 1 shows a capacitor 10 of the present embodiment, which is a schematic configuration. 5 hai electric anode ", anode u 矣... The surface of the ruthenium 11 formed by the porous body (4) is shaped to form the cathode 13 on the dielectric layer 12.曰2 and shape <Anode> The valve metal constituting the anode U may, for example, be zirconium, zirconium, zinc, crane, ruthenium or osmium. Among them - Ming, titanium, 铪, aiming m ^ aluminum, button, 铌 is better. Specific examples of 11 include, for example, those in which the surface is subjected to oxidation treatment to increase the surface of the sintered body to be oxidized. The surface of the 36 is formed with irregularities via the processors. <Dielectric Layer> The dielectric layer 12 is similarly formed by anodizing the surface of the group and the electrolyte in an electrolytic solution such as an aqueous solution of ammonium adipate. s tl_ , m ] ^ - „θ a hurricane. Therefore, if the mouth 1 is not the same as the anode u, the convex surface. The surface of the cymbal 2 is also formed with a concave <cathode> cathode 13 having: M tm 1, U~, turtle solution layer 13a, formed in solid state electricity, a • Lu foil and other cathode metal layer 13b, solid-state electricity # f _ guide: 糸 conductive polymer, polyanion, and solvent with high conductivity The formation of the molecular solution. With the one (71 a total of conductive polymer), 71, a total of Lee's conductive polymer, σ ii yoke system can not be the main chain The copolymerized phenotype π molecule can be used. For example, poly-[, polyaniline type II: class 1 benzene building class, poly-phenylene-extended ethylene group, this class of t and stupid, double Daling B suspect; ^ disk „ \基呍乙埤Supporting, and the like, and the use of polypyrroles, polythiophenes, and polyanilines for the consideration of the ease of production of the polymerization, the sufficiency of the six gas, and the hardness of the work. Preferably, the ~π-conjugated conductive polymer 'is in an unsubstituted original state, and sufficient conductivity is also known, and Υ & τ is used to judge the chargeability, but to be more conductive, preferably, a functional group such as an alkyl group, a fluorenyl group, a thiol group, a thiol group, a hydrazine group, or a gas group is introduced into the ruthenium-based roll-type conductive polymer. Specific examples of the π-conjugated conductive polymer include the above. Among them, from the viewpoint of resistance value and reactivity, it is preferred to use 37 selected from polypyrrole, polythiophene, poly(N-methyl kecan, tibe), poly(3-methylthiophene), a (co)polymer composed of one or two of poly(3-methoxythiophene) and poly(3 _ hexyl thiophene). Further, the polycondensation is 0, and the poly (3, 4) -Ethylenedioxythiophene) is more preferable because it can further improve conductivity and improve heat resistance. Further, poly(Ν-methylpyrrole), polyη田#軚(3·methylthiophene), etc. The alkyl-substituted compound has better solvent solubility and better compatibility with dispersibility when added to the hydrophobic resin, and is more preferable. Further, in the alkyl group of the alkyl group-substituted compound, conductivity is prevented from decreasing. It is preferable that a methyl group is used. =4« a conductive polymer can be used to dissolve the first four-region monomer of the four conductive polymer in the presence of a suitable oxidizing agent and a polymer having an anionic group, which will be described later.仃Chemical gasification and polymerization are easy. The former boat monomer has a molecular system. When it is polymerized by appropriate oxidation: its main bond is also formed. The conjugated system can be exemplified by a specific example of the precursor monomer, for example, the above-mentioned pirate-based conjugated system, benzoic acid and derivatives thereof, aniline and derivatives thereof, and the like. The solvent used in the production of the conductive polymer is not particularly limited as long as the precursor can be used. The monomer may be dissolved or dispersed, and the oxidizing power of the oxime I may be maintained. Specific examples of the solvent include the above-mentioned solvents, and may be used singly or in combination of two or more kinds; A mixture with another solvent is used. ^ The sulfonating agent may be one which oxidizes the precursor monomer to obtain a π-conjugated conductive arsenic. Specific examples of the oxidizing agent include the above. 38 1322436 ( Polyanion) polyanion's substituted or unsubstituted polyalkylene, substituted or unsubstituted polythene, substituted or unsubstituted polyimine, substituted or unsubstituted polydecylamine, substituted or unsubstituted polyester And the copolymers of these may contain a constituent unit having no anionic group except for the constituent unit having an anionic group. The anionic group of the polyanion has a function as a dopant for the π-conjugated conductive polymer. The conductivity and heat resistance of the π-conjugated conductive polymer are improved. The term "polyalkylene" refers to a polymer composed of a repeating methylene group in the main chain. Specific examples of the polypyramidation include the above. The term "polyalkylene" refers to a polymer in which the main chain is a constituent unit containing one or more unsaturated bonds (vinyl groups). The specific example of the polycrystalline building is as described above, wherein the unsaturated bond interacts with the π-coaxial conductive polymer, and the substituted or unsubstituted butylene is easily used as a starting material, so that it is easy to synthesize It is better to replace or replace the Dinglou. Specific examples of the polyimine, polyamine, and polyester are as described above. When the polyanion has a substituent, the substituent may, for example, be an alkyl group, a hydroxyl group, an amine group, a carboxyl group, a cyano group, a phenyl 'phenol group, an ester group or an alkoxy group. When considering the solubility in a solvent, the heat retention property, the compatibility with a resin, etc., it is preferable to use a base, a base, a base, and g. The base can improve the solubility and dispersibility of the polar solvent or the non-polar solvent, compatibility with the resin, and dispersibility. The hydroxyl group can easily form hydrogen bonds with other hydrogen atoms, and can improve the organic solvent. A VIII, the solubility of the mixture, the compatibility with the tree 39 grease, dispersibility, and adhesion. Further, the cyano group and the hydroxyphenyl group can improve the compatibility and solubility of the resin, and can also improve the heat resistance. Among the above substituents, an alkyl group, a hydroxyl group, an ester group or a cyano group is preferred. ^The alkyl group may, for example, be a chain alkyl group such as methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, decyl, hexyl, octyl, decyl or dodecyl. a cycloalkyl group such as a cyclopropyl group, a cyclopentyl group or a decyl group. In view of solubility in an organic catalyzing agent, dispersibility to a resin, steric hindrance, and the like, a burning group having a hindrance of 1 to 12 is preferred. The hydroxyl group may, for example, be a hydroxyl group directly bonded to a polyanion main chain or a permeation group bonded through another functional group. The other functional group may, for example, be a carbon group having 1 to 7 carbon atoms, a carbonic acid group having 2 to 7 carbon atoms, a mercapto group or an imido group. The indenyl group is substituted to the end or in the functional groups. Among these, a hydroxyl group bonded to the alkyl group having 1 to 6 carbon atoms bonded to the main chain bonded to the main chain is preferred because of compatibility with the resin and solubility in the organic solvent. The amine group may, for example, be an amine group directly bonded to the polyanion main chain or an amine group bonded through another g sulfhydryl group. The other functional group may, for example, be an alkyl group having 1 to 7 carbon atoms, an alkylene group having a carbon number of 2 to 7 and an imido group. The amine group is substituted to the end or in the functional groups. The phenol group may, for example, be a phenol group directly bonded to a polyanionic backbone or a phenol group bonded through another functional group. The other functional group may, for example, be an alkyl group of carbon number 7, an alkylene group having 2 to 7 carbon atoms, a mercapto group or an imido group. The phenolic group is substituted to the end or in the functional groups. The ester group may, for example, be an alkyl ester group directly bonded to a polyanion main chain, an aromatic ester group, an alkyl ester group bonded through another functional group, 40 1322436 or an aromatic ester group. The cyano group may, for example, be a cyano group directly bonded to a polyanion main chain, a cyano group bonded to an alkyl group having 1 to 7 carbon atoms (bonded to a polyanion main chain), and a bond "". A murine group at the end of the alkyl group of 2 to 7 (bonded to the polyanionic backbone).

The anion group of the polyanion may be a functional group which can cause chemical oxidation doping of the π-conjugated conductive polymer, but it is considered to be a mono-substituted sulfate sulphate from the viewpoint of easiness of production and stability. Take one: Fill the acid vinegar base, phosphate base, slow base, and base. Further, from the viewpoint of the compatibility of the functional group with the 7 fluorene-based conductive polymer, it is preferred to use a base group, a monosubstituted sulfate group or a carboxyl group. Specific examples of the polyanion may be, for example, the above-mentioned monomers, or may be two or more kinds of copolymers. Among the ruthenium and the like, polystyrene acid, polyisoprene crude acid, polyacrylic acid, and polyacrylic acid diced acid are preferred. These polyanions can alleviate the thermal decomposition of the π-conjugated conductive polymer. The degree of polymerization of the polyanion is preferably in the range of 1 Å to 单体, and is preferably in the range of from the viewpoint of solvent solubility and conductivity. 'A method of producing an anionic group using an acid and an anionic group-polymerizable monomer having no anionic group, and a method for producing a polyanion, for example, a method of introducing a polymer into a polymer having no anionic group as a sulfonating agent The method of sulfonation, the method by which the polymerization is carried out. Polymerization by anion-containing polymerizable monomer 41 436 For example, in an solvent, an anionic group-containing polymerizable monomer is used in the presence of an oxidizing agent and/or a polymeric contact enzyme by oxidative polymerization or radical polymerization. The method of manufacture. I body and r, so that a quantitative amount of the anionic polymerizable monomer is dissolved in a solvent, and it is kept at a certain temperature, and a solution of a predetermined amount of the oxidizing agent and/or a polymeric contact enzyme in a solvent = solution is added. The polymer obtained by reacting the reaction between 疋 and s is adjusted to a certain degree of solubility with a solvent. In the production method, the anionic group-containing polymerizable monomer may be copolymerized with an anionic polymerizable monomer. The oxidizing agent or solvent used in the polymerization of the anionic polymerizable monomer is the same as that used in the case of forming a conductive polymer. When the early diterpene is a polyanion salt, the method of changing it into a polyanion can be used to form an anion acid, for example, an ion exchange method using an ion parent, a dialysis method, Exceeding the method of sputum, etc., in the basin, it is preferable to use the ultrafiltration method from the viewpoint of ease of operation. The polymerizable monomer containing an anion group is a mono-substituted sulfate group, a carboxyl group, a sulfo group, etc. Substituent, ^ ^ rm ^ m ^ For example, substituted or unsubstituted ethylene stone page I compound, hydrazine, ^ W t present vinyl sulfonic acid compound, substituted or unsubstituted acrylate sulfonate yada IAP ^ 〇 , substituted or unsubstituted methacryl oxime sulfonic acid compound 'sulfonic acid compound, substituted * 心 上 本 本 未 未 未 未 未 烯 烯 烯 烯 烯 烯 烯 烯 烯 烯 烯 烯 烯An unsubstituted butadiene-acid compound, a substituted or a sulfonic acid compound. Specifically, the above-mentioned J horse contains the above-mentioned two kinds of copolymers of 42 1322436 or more. The polymerizable monomer based on the above may be, for example, the above Solvent solubility can be controlled by copolymerizing these anionic group-free polymerizable monomers. :Electric!·In the kiln cold liquid, the ratio of the π-conjugated conductive polymer to the poly- The material 'is a part of the polyanion (10) f, and the π total 糸 conductive polymer is 1 to 1 〇〇〇皙 Α Α υϋ〇 υϋ〇 。 。. If the π conjugated high conductivity knife is less than 1 part by mass, then There is a tendency that the conductivity of the 1λλλ#曰100 is insufficient, and if it exceeds the mass, the solubility of the solvent tends to be insufficient. (Doping) Conductivity: The polyelectron solution in the electropolymer solution has... It is a function of a molecular dopant, but a conductive substance other than a polyanion (hereinafter referred to as a different dopant) is also included in the conductive polymer solution. ^ The π-conjugated iridium conductive polymer is oxidized. - It can be either a donor or an acceptor. [Applicator Doping] The donor dopant can be an alkaline earth metal such as steel or potassium, or the like. Recorded, B, Ethyl Ammonium, Tetrapropylammonium, Tetrabutylammonium, Methyl Triethyl, Methyldiethyl, etc. Compounds, etc. - [Receptor dopants] Receptor dopants, such as ruthenium compound acid, organic cyano compound, organic metal & you can enter the "standard olefin, gas. (4) metal compounds, Fleurene, hydrogenated Fleur, fried, straight, Fu, welding, «Fu_, rhyme, and so on. The dentate compound 'for example, gas (α2), filled (ΒΓ2), 43 iodine (etc., vaporized iodine (IC1), iodine bromide (IBr), fluorinated iodine)

The IF Lewis acid may, for example, be PF5, AsF5, SbF5 'BFs' BCl5, BBr5, s〇3 or the like. As the organic cyanide compound, a compound having two or more cyano groups in the conjugated bond can be used. For example, four-episo-ethylene, tetra-ethene ethylene oxide, tetra-ocrylic benzene, gas dicyano-p-benzophenone (DDQ), tetracyano-p-tetramethyl-phenyl-quinoline (tetracyan〇quin〇dimethane), tetracyano quinoline

Ctetracyanoazanaphthalene) and so on. Examples of the protic acid include inorganic acids, organic acids, inorganic acids, hydrochloric acid, sulfuric acid, nitric acid, dish acid 1, hydrogen fluoride, fluorinated gases, and m-chlorous acid. Further, an organic acid, an organic sulfonic acid or the like. "Arrows such as organic carboxylic acids, phenols, and organic m acids" may be ones having one or two or more carboxyl groups, such as an aliphatic group, a right aromatic group, or a cyclic aliphatic group. 〇« △ J such as citric acid, acetic acid, hydrazine酴, Benthic acid, benzoic acid, maleic acid, lactic acid, 诫 舻 田. Tian Ma 驮, tartaric acid, citric acid, ritual-yi amber @文,一轧 acetic acid, two negative 7 舻ί〇ί «. Acetic acid, di-acetic acid, trifluoroacetic acid, nitroacetic acid, triphenylacetic acid, etc.. Ordinary organic sulfonic acid, aliphatic, ^ one or more bases, such as Fangxiangzhi, bad aliphatic, etc. Chinese person seven or a polymer containing a continuation base. 3 There is a performance base, and the ancient _ can also use these metal salts. ~ One base is as described above, and (solvent) conductive polymer solution The respective agents to be contained may, for example, be water and/or organic 44: an organic solvent, and are not particularly limited, and examples thereof include N-methyl-2-pyridyl::, hydrazine, hydrazine dimethylformamide, (10) · Dimethyl acetamide, dimethyl ', methylene phase diamine, N · ethyl ketone, ν · Ethylene, f, N · ethyl acetamide Solvents nu benzene and other sources: members, alcohols such as alcohol, ethanol, propanol, butanol, ethylene glycol, diethylene glycol, alcohol-propanol, -propylene glycol, 1,3-butanediol, l, 4-butanediol, ...-glycerol, D-grape*, 〇glucanol, isoprene glycol, oxime alcohol 1,5·pentanol 'I6·hexadiol' 1,9-nonanediol 'New pentanediol, sulphuric acid alcohol, acetone, methyl ethyl ketone and other ketones, hexane, benzene, methyl abundance, thyroxine and other acid retardation, ethylene carbonate vinegar, propylene carbonate vinegar, etc. 2 S" An ether compound such as a hydrazine compound, a dioxane or a diethyl ether; a chain ether such as a glycol dialkyl condensate, a propylene glycol dialkyl group, a polyethylene glycol dialkyl group, or a polypropylene glycol disaccharide, 3_ a heterocyclic compound such as methyloxazolidinone, a nitrile compound such as acetamidine, methoxyacetonitrile, propionitrile or benzoquinone. The "loose agent" may be used singly or in combination of two or more kinds thereof, or a mixture with other solvents may be used. + The organic solvent may interact with the π-conjugated conductive polymer and the polyanthracene*. In order to improve the electrical conductivity of the solid electrolyte, it is preferably included in the conductive polymer solution. The solvent contained in the conductive polymer solution can be directly used to produce a polyanion or a π-conjugated conductive polymer. The solvent to be used may be re-added. Since the polyanion is mostly water-soluble, it is preferable to use a solvent which can be mixed with water in the organic solvent, and it is possible to have a high conductivity of 45 molecules and agglomerate. The anion is more intersecting with π π to create an interaction' and the thunder conductivity of the solid electrolyte becomes more ancient. The electrolysis of the electrolyzed shell... 'There is Ν-methyl-2·pyrrolidine _, ΝΝ-dimethyl ketone醯amine, Ν, Ν.-甲Α & Τ 甲基 - methyl acetamide, dimethyl sulfoxide, Ν vinyl slip 夂 ps, methylene hydrazine, alkanone, hydrazine - vinyl Indoleamine, isopolar solvent, multi-component 醢^ d Preferably, the chain-like ether is preferred. (pH of the conductive polymer solution) The conductive polymer solution is (4) at a temperature of 3 to 13, preferably 5 to 13, more preferably 7 to u: • If the two changes and & + prt is less than 3', the acidity is too strong, and the dielectric layer 12 cannot be prevented. From the A1, the right 拽 is only the layer 13b, and the right is over 13, the polyanion will D1 is separated from 'the conductivity of the solid electrolyte is insufficient." The method of adjusting the pH of the electric shell layer 13a can be carried out, for example, in the case of the π-conjugated derivative and the polyanion complex. Keep the electricity to A knife, the following liquid, called the complex aqueous solution). Add the alkali to form the acid fish gizzard, the current method, the method of esterifying the acid group of the polyanion, and the acid amide The method of adding, etc. can be shaped as long as it can be shaped _ _ ^ ^, 丽, g, 醯 amine, the method and order of alkali treatment is not particularly limited. + 疋曰 when no other additives are added, only add the test To the high conductivity, early, goods, production + „, the annual electricity can be easily adjusted to the pH of the knife solution. 'There are /^· plus other adding force 0 drowning test*, ^寺' can be adjusted by adding other additives to adjust the pH, adding the other additives with the base w W i pH, and simultaneously using the alkali Adjust pH and add other additives. Here, the method of adjusting the pH after adding other additives can be adjusted with high precision and can be easily adjusted to a predetermined pH. In the method of adjusting the pH with alkali and then adding other additives to the compound, it is possible to easily change the conductive high-porosity conductivity of the molecular electrical material due to pH adjustment by adding other additives. Adjusting and guiding at the same time with alkali adjustment # Λ The operation can be easily carried out. Ρ 〃 Add other additives, age when alkali is added, and organic base. & Μ ', the temple is not limited, you can use the well-known inorganic base and organic test. Inorganic base, 峨 Λ, . ^ + For example, sodium bismuth oxide, potassium hydroxide, calcium hydroxide, hydrazine, and the like. In addition, the ancient breast milk? face 7 organic base, such as ethylamine, diethylamine, methyl ethylamine, diethylamine and other aliphatic amines, (four) and other aromatic amines and their derivatives read, material " rice saliva , « ^ Ν _ methyl · 2 _ pyrrolidone, hydrazine, hydrazine - dimethyl ketoamine, ] & m methyl acetamide, hexamethylene phosphonium triamine, Ν · 乙 ° ° Nitrogen-containing compounds such as ketones, phthalocyanines, oximes, ketones, acetophenes, acetophenones, acetophenones, and the like, such as sodium alkoxides such as sodium alkoxide and sodium ethoxide, potassium salt, and dimethyl sulfoxide. Alkoxides such as salt and about fermented salt: good grades, etc. - amines, aromatic amines, tender gas, and organic tests, nitrogen-containing aromatic cyclic compounds can be used. The gas-containing aromatic cyclic compound not only prevents the detachment of the polyanion but also improves the electrical conductivity. Here, the nitrogen-containing aromatic cyclic compound means an aromatic ring having at least one nitrogen atom, and the other atom in the aromatic ring of the nitrogen atom in the aromatic ring is kept in a common (four) system. In order to form a common (four) system, the disordered atoms form unsaturated bonds with other atomic systems. Alternatively, if the nitrogen atom does not directly form an unsaturated bond with other atoms, it may be adjacent to other atoms forming an unsaturated bond. It is due to the fact that the unshared electrons present on the nitrogen atom 47 1322436 form a similar light-weight relationship with the unsaturated bonds that can be formed with other atoms. In the nitrogen-containing aromatic cyclic compound, it is preferred to have a nitrogen atom having a conjugated relationship with other atoms and a nitrogen atom adjacent to another atom forming an unsaturated bond. Such a nitrogen-containing aromatic cyclic compound may, for example, be a pyridine having a nitrogen atom and a derivative thereof, a azole having two nitrogen atoms, a living organism thereof, a pyrimidine or a derivative thereof, or a pyrazine. Classes and derivatives thereof, diazines containing three nitrogen atoms and derivatives thereof. From the viewpoint of solvent solubility, it is preferred to use money and its derivatives, (4) and its derivatives, (4) and its derivatives. Further, the nitrogen-containing aromatic cyclic compound may be one in which a substituent such as an alkyl group, a thiol group, a slow group, a cyano group, a phenyl group, a phenyl group, a acetoxy group, an anthracene group or a carbon group is introduced into the ring. Can be unimported. Also, the ring may be a multi-ring. In the substituent, the alkyl group may, for example, be an alkyl group such as a methyl group, an ethyl group, a propyl 'butyl group, an isobutyl group, a pentyl group, a pentyl group, a hexyl group, an octyl group, a decyl group or a dodecyl group. a cycloalkyl group such as a C, a cyclopentyl group or a cyclohexyl group. Among them, in view of solubility in an organic solvent, dispersibility to a resin, steric hindrance, and the like, an alkyl group having 1 to 12 carbon atoms is preferred. Specific examples of the soap group, the thiol group, the cyano group, the phenyl group, the phenyl group and the oxime group include the above. . Specific examples of the biting type, the snail type, the squirting type, the bismuth, the triterpenoid, and the derivatives may be, for example, the above. Since the nitrogen atom in the nitrogen-containing aromatic cyclic compound has a non-co-electron pair of electrons, the argon atom is substituted for the argon atom to facilitate coordination or bonding. When there are substituents or protons on the milk atom, Ό%, there is a tendency for the nitrogen atom to have a positive scorpion. Here, r, 〇W歹, and 虱 are conjugated with other atoms, so the 离子-ion charge generated by the substitution of the + @ substituent or proton by the coordination of the nitrogen atom on the nitrogen atom will occur. The nitrogen-containing aromatic milk tube is diffused and exists in a stable form. Therefore, the nitrogen-containing aromatic cyclic compound may be a substituent on the nitrogen atom to form a nitrogen-containing aromatic cyclic compound cation. Further, it is also possible to combine (iv) ions and anions to form a salt. Even if it is a ruthenium, it can also have the same effect as a nitrogen-containing aromatic cyclic compound which is not a cation. The substituent 'imported on the nitrogen atom of the nitrogen-containing aromatic cyclic compound' may, for example, be an argon 'alkyl group, a hydroxyl group, a carboxyl group, a cyano group, a phenyl group, a phenol group' ester group, an alkoxy group, a carbon group or the like. . The earth alkyl group may, for example, be an alkyl group such as a mercapto group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a first butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group or a dodecyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group. It is preferable to use a hospital base having a carbon number of 1 to 12 in consideration of the solubility of the machine, the dispersibility of the resin, and the steric hindrance. Specific examples of the group, the carboxyl group, the cyano group, the phenol group, the phenyl group and the alkoxy group include the above. When the base is contained in the conductive polymer solution, the electrical conductivity of the solid electrolyte layer 13a (which is formed by coating the conductive polymer solution) can be improved. When the capacitor 10 is used in an electrical circuit, a sufficiently low equivalent is required.

Series resistance (ESR). The ESR of Leikong A is often subject to various factors such as the electrical conductivity of the solid electrolyte sound 13a, the area occupied by the thunder shell electrode, and the compactness of the solid electrolyte layer. The abdomen of the electric 10 is at least necessary to make the influence of the solidification large, and the solid electrolyte layer 13a is made high in order to lower the capacitor. Therefore, the solid-state electrolysis has been "4". The electrical conductivity of the U-boiled shell layer 13a is preferably ls/cm or more, more preferably 10 S/cm or more, and more preferably 50 s/cm or more. The electric conductivity of the solid electrolyte layer 13a is increased by ns/cm, for example, in a conductive polymer solution, a method of adding a test to carry out the method, or a method of adding a hydroxyl group, a glycidyl group, or A method in which the amine is more than one kind, and the compound is used. Further, as a method for improving the conductivity of the solid electrolytic ice, it is also possible to use a method in which the conductive polymer contains the organic solvent in the liquid mixture. The compound having a meridine group may, for example, be methanol, ethanol, propylene, acetophenone, dioxin, sulfur, oxime ethyl acrylate, hydroxyethyl propylene, lie 4 aliphatic alcohol, quinone phenol, bisphenol Phenol, pyrogallol, m-benzene =-, phthalic acid aromatic alcohol, or compound containing (iv) thiol, hexanol face - adding I' diol amine, triethanolamine and other amine alcohols, etc. When adding a compound of a hydroxyl group in the molecule, the acid group can be esterified. Glycerol 1 has glycidol The compound of the group may, for example, be ethyl shrinkage 7, butyl glycidol, third butyl glycidol, dipropyl glyceryl ether, benzyl glycidyl ether, glycidyl phenyl ether, bisphenol A. The K-g' can be obtained by adding a glycidyl group such as ether or glycidyl methacrylate to a compound having an intramolecular glycidyl group, and the acid 50 1322436 s can also be used. The compound may, for example, be an amine compound such as the above-described amino alcohol, ethylamine, aniline or benzylamine, etc. When a compound having an amine group in the molecule is added, the acid group may be esterified. It is preferable to increase the conductivity of the 7-inch conductive polymer, and it is preferable to use an aliphatic alcohol or a compound containing a phenolic hydroxyl group. Further, the compound containing a phenolic hydroxyl group has a function of preventing oxidation and can also enhance the financial property. Thermal and long-term stability is particularly good. In addition, a compound having an propylene group such as ethyl propylamine or hydroxyethyl acrylate can be used to induce conjugated conductivity by using light or a starter. Cross-linking of macromolecules The thermal characteristics and the mechanical properties are preferred. The capacitor 1〇 described above has a solid electrolyte layer of the cathode 13 coated with a conductive polymer solution, and the conductive polymer solution contains a high conductivity of 7Γ. ^ s ^ Knife, dopant, and nitrogen-containing aromatic 1 flaky compound, and the pH has been adjusted to ° 3 to 13. That is, the solid electrolyte is increased by 1 3 a ' because the acid is extinguished The road ^ " 巳 weakened conductive polymer solution is formed, two: stop the dielectric layer 12 of the rot, and can reduce the equivalent series resistance. In addition, the :3 conductive polymer solution can be treated to improve the electrical conductivity of the solid electrolyte ^, so it can be improved. Moreover, the capacitor 1 〇 is formed by the tunnel + electrolyte drawer to form the solid-purity layer 13a from the 4 conductive polymer solution, thereby preventing the stagnation of the dielectric charge capacitor, and thus the leakage current is small and (Manufacturing Method of Capacitor) The manufacturing method of the electric capacitor of the present invention is described in the following description. 51 1322436 The manufacturing method of the present invention is based on a capacitor intermediate (having a porous body of metal) On the side of the dielectric layer on the anode and the dielectric layer of the oxide film formed on the surface of the anode, the conductive polymer solution having a pH of 3 to 13 is applied to form a solid electrolyte layer. The coating method of the solution may, for example, be a coating method, a dipping method, or a known method of drying the method, and a known method such as hot air drying may be mentioned.

After the solid electrolyte is formed, a carbon paste or a silver paste may be applied to form a cathode or a silver paste to form a cathode. Need to make the electrolyte penetrate, and secondly. Further, the separator may be impregnated with a carbon paste separator, and a single- or hybrid nonwoven fabric such as cellulose fibers, glass fibers, polypropylene fibers, polyi fibers, polyamide fibers, or the like, and carbonized nonwoven fabrics may be used. In the above method for producing a capacitor, a conductive polymer solution (adjusted at a pH of 25 ° C to 3 to 13) is applied to the surface of the dielectric layer to form a solid electrolyte layer, so that corrosion of the dielectric layer can be prevented. The knot reduces the equivalent series resistance of the capacitor. [Examples] <Conductive Southern Molecular Solution and Conductive Coating Film> (Example 1) (1) Preparation of Polystyrene Vinsulfonic Acid Solution 50 g of sodium styrenesulfonate was dissolved in 5 ml of water and added to polymerization. The initiator was 0.15 g of ammonium persulfate, which was polymerized at 7 Torr for 5 hours. After the completion of the polymerization, a 30% aqueous sulfuric acid solution of 3 〇g' was added and water i5 〇〇〇m was added to concentrate to 300 ml by ultrafiltration 52 1322436 to prepare a polystyrene sulfonic acid solution. (2) The conductive polymer solution was prepared in 1 μg of the polystyrene sulfonic acid solution prepared in (1), and 30 g of 3,4-ethylenedioxythiophene was added thereto, and cooled to 1 (TC stirring) An oxidizing agent solution obtained by dissolving 250 g of gasified iron in 1250 ml of water, kept at i〇cc and dropped into the above-prepared solution in 2 hours, and continuously stirred for 2 hours to polymerize 3.4-ethylenedioxythiophene. After the completion of the polymerization, the obtained reaction solution was subjected to ultrafiltration to remove the oxidized β residue, the unreacted monomer, and the oligomer (〇Ug〇mer) component to prepare a solution having a concentration of 1 lb.%. The solid content of the solution is 质量(), and 1 〇〇 part by mass of 2-methylimidazole is added, and the conductive polymer solution is prepared by stirring for a few hours. The conductive polymer solution obtained is determined according to the following. The surface resistance, pH, and metal corrosion were measured for evaluation. The evaluation results are shown in Table 1. U) Surface resistance The conductive polymer solution thus prepared was applied to PET having a thickness of 丨〇〇μηι. Squeezing and drying, forming a conductive coating film of thickness, Dyer instrument (DIA INSTRUMENTS) manufactured by Great Hailei Si (Hiresta) measured surface resistance of the coating film.

(b) pH

In the constant temperature room of 25 C, the pH of the prepared conductive polymer solution was measured by a commercially available pH meter (pH 6 F-22 manufactured by Horiba, Ltd.). Chemical acid (stock) phthalic acid pH 53 standard solution (pH 4 · 〇 1 borax salt pH standard solution (c) metal humification pH 6.86), neutral citrate p Η standard solution (pH 9.18) get on. Properties: The conductive coating film formed during the surface resistance measurement is Tang 0 5 plate (thickness (M—, u is set to 85 〇/Rh ^ m of iron and placed in pure water to adjust the environment to 85 ° C , , , , θ in 100 hours. Receiver, visually confirm the corrosion of the iron plate after 100 hours.

Environmental test sample of 85/0RH (Example 2) A conductive polymer solution was obtained in the same manner as in the Example except that imidazole-substituted 2·methyl oxazole was added. Next, evaluation was performed in the same manner as in Example i. The evaluation results are shown in 纟. (Example 3) A conductive polymer solution was obtained in the same manner as in Example 添加 except that hydroxyethyl acrylate was used in place of 2, methylimidazole, and then I was refluxed at 1 Torr C for 1 hour. Next, evaluation was carried out in the same manner as in Example 。. The evaluation results are shown in Table 1. (Example 4) (1) Preparation of polyacrylic acid solution 50 g of sodium benzoate was dissolved in 5 ml of water, 0.15 g of persulfate of a polymerization initiator was added, and polymerization was carried out at 70 ° C for 5 hours. After the end of the polymerization, a solution of 3 〇g of 30% aqueous sulfuric acid was added, and 15 〇〇〇 ml of water was added thereto, and a polyacrylic acid solution was prepared by ultra-transition concentration to 300 m. (2) The conductive polymer solution was prepared in (1) the obtained polyacrylic acid solution 10 g, and 3 g of 3,4-ethylenedithiothiophene was added, and the mixture was stirred for 1 hour while cooling to 1 〇〇c. . 25 〇g of ferric chloride was dissolved in 1250 ml of water to obtain an oxidizing agent solution, kept at 1 〇〇c and dropped into the above prepared solution in 2 hours, and stirring was continued for 12 hours to polymerize 3.4 _ ethylene oxide Thiophene.

After the end of I, the spleen print * 4 "V CT rfc ultra-filtration of the reaction solution to remove the oxidizer residue" is not reversed, the early body, and oligomer components, made a concentration of 1% by mass Solution. Next, the crucible &gt; was added in an amount of 100 parts by mass to 1 part by mass of the solid content of the bath. The conductive high molecular solution was prepared by refluxing at 100 C for 1 hour. (Example 5) The same procedure as in Example 1 was carried out in the same manner as in Example 1 except that diethylamine was added in the same manner as in Example 1 to carry out the reaction: (Comparative Example 1) The results of the ° ° S parity are shown in Table 1. In Example 1, the concentration i liquid obtained by the filtration was evaluated without pH adjustment, and the obtained reaction solution was supercharged after the completion of the polymerization. The conductive polymer film formed in the range of 3 to 13 in the same manner as in Example 1 except that the conductive polymer was dissolved as a conductive polymer, and the conductivity of the polymer solution of *5 was The surface electric P is not damaged, and the metal rot is excellent in the property of 55 1322436. On the other hand, the conductive coating film formed by the conductive polymer solution of the comparative example having a pH of less than 3, and the iron plate in contact therewith Red rust is generated. &lt;Capacitor and its manufacture&gt; (Example 6) (1) Preparation of conductive polymer solution 14.2 g (〇.im〇i) of 3,4·ethylenedioxythiophene' 27 5g (〇.15mol) polystyrenesulfonic acid (molecular weight about ι5〇〇〇〇) dissolved in 2〇〇〇mi ion exchange The solution of water was mixed at 20 ° C. The mixed solution thus obtained was kept at 20 ° C, and while stirring, 29.64 g (〇_13 mol) of persulfate was added, and 8.0 g (〇.〇2 mol) was added. The ferric sulfate solution is dissolved in 200 ml of an ion-exchanged water oxidizing catalyst solution and allowed to react for 3 hours to carry out the reaction. The obtained reaction solution is subjected to dialysis to remove unreacted monomers and oxidizing agents to obtain a mixture containing about 1.5% by mass. A solution of poly(3,4-ethylenedioxythiophene) was doped with styrenesulfonic acid, and then 2.79 g of a solution was dissolved in 1 ml of the solution to obtain a conductive polymer solution having a pH of 8.1. Further, the measurement of the pH was carried out at 25 ° C (the same applies to the following examples). In order to evaluate the performance of the π-conjugated conductive polymer, the obtained conductive polymer solution was applied onto the glass at 120 The conductive film was dried in a hot air dryer at °C to form a conductive film having a thickness of 2 μm, and the electrical conductivity was measured by a Rolls-Royce (made by Daihatsu Instruments). The results are shown in Table 2. 56 1322436

(2) Manufacturing of capacitor After the anode lead terminal was connected to an etched aluminum foil (anode foil), it was 10 mass% in ammonium adipic acid. A capacitor intermediate is prepared by chemical treatment (oxidation treatment) in an aqueous solution to form a dielectric layer on the surface of the junction. The human-man's laminated aluminum foil with a cathode lead terminal is laminated on the anode foil of the capacitor intermediate through a separator made of cellulose, and wound up to form a capacitor element. 57 1322436 The separator is immersed in the (1) prepared conductive surface molecular solution under reduced pressure, and then dried in a process of drying for 1 minute by a hot air dryer (TC) for 5 times. A solid electrolyte layer is formed on the side surface of the dielectric layer of the capacitor intermediate. Next, in the aluminum case, the capacitor element forming the solid electrolyte layer is sealed with a sealing glue to form a capacitor. For the obtained capacitor, an LCZ meter is used. 2345 (NF circuit design public system), measuring the capacitance of 12 Hz, the starting value of the equivalent series resistance (ESR) of 100 Hz '15 (Tc 'ESR after 1000 hours. (Example 7) • Acrylic acid 2.38 g of hydroxyethyl ester, which was substituted for 2.79 g of the imidazole in Example 6, and added to a solution containing about h5 mass% of polystyrenesulfonic acid-doped poly(3,4-ethylenedioxythiophene) to prepare ρΗ 5 4. Conductive polymer solution of 4. Then, a capacitor was fabricated in the same manner as in Example 6. For the obtained capacitor, the capacitance of 12 、 was measured, and the equivalent of one • of the connected resistance (ESR) was measured. The initial value, i50°c, ESR after 1 hour. The results are shown in Table 2. (Example 8) 2-Ethylamine 2-52 g, instead of the imidazole 2 79 g in Example 6, was added to a polystyrenesulfonic acid doped poly(3〆2) containing about 1.5% by mass. In a solution of oxythiophene), a conductive polymer solution of pH 12 4 was obtained by refluxing for 10 hours at rc. Then, a capacitor was fabricated in the same manner as in Example 6. 58 1322436 For the device, measure the capacitance of 12 Hz, the starting value of the equivalent series electric M (ESR) of ι〇〇Ηζ, and 15 (TC, ESR after 1000 hours. The results of these measurements are shown in Table 2. (Comparative Example 2) A capacitor was produced in the same manner as in Example 6 except that the conductive polymer solution was prepared in the same manner as in Example 6, and the pH of the conductive polymer solution was 1.2. The obtained capacitor was measured for the capacitance of 120 Hz, the electrical conductivity of the conductive film, the initial value of the equivalent series resistance (ESR) of 100 Hz, and the ESJ of 1000 hours later. The results of these measurements are shown in Table 2. Example 9) A solution containing poly(3,4-ethylenedioxy porphin) doped with polystyrene sulfonic acid, a U)g &lt; N_f base·2_D is a conductive polymer solution having a pH of 7.5 after adding copper water to the copper. - The conductive polymer solution obtained is spurred in the same manner as in the sixth embodiment. The conductivity was changed, and the capacitor 2 was produced using the obtained conductive polymer solution, and evaluated in the same manner as in Example 6. The results are shown in Table a. (Example 1 〇) ^Including the polymerization in Example 6 A solution of poly(3,4-ethylenedihydrate f-thin) is doped with hexene sulfonic acid, and after adding 1 gg of dimethyl (tetra), ammonia water is added to prepare a conductive polymer solution of pH 7.5. The conductive polymer solution thus obtained was measured for electrical conductivity in the same manner as in the examples, and a capacitor was produced using the obtained conductive polymer solution, and evaluated in the same manner as in Example 6. The results are shown in Table 2. 59 (Example 11) - a solution containing polystyrenesulfonic acid doped poly(3, an acetophene thiophene) in Example 6, added with 乙烯g of N ethylene acetamide, added Ammonia water's a conductive polymer solution of pH 7.5. The conductive polymer solution thus obtained was evaluated in the same manner as in Example 6 except that the conductive polymer solution was prepared in the same manner as in Example 6 except that the obtained conductive polymer solution was used. The results are shown in Table (Example 12). The solution containing polystyrenesulfonic acid-doped poly(3,4-diylthiophene) in Example 6 was added after adding 6 g of ethylene glycol. Ammonia water, a conductive polymer solution of PH 7.5. The conductive polymer solution thus obtained was set to have electrical conductivity in the same manner as in Example 6, and a capacitor was produced using the obtained conductive polymer solution, and evaluated in the same manner as in Example 6. The results are shown in Table 2. (Example 1 3) The solution containing polystyrenesulfonic acid-doped poly(3,4·ethanedithiolthiophene) in Example 6 was added, and after adding 6 g of glycerin, ammonia water was added to obtain a conductive layer having a pH of 7.5. Polymer solution. The conductive polymer solution thus obtained was subjected to electrical conductivity in the same manner as in Example 6, and an electric grid was prepared using the obtained conductive polymer solution, and evaluated in the same manner as in Example 6. The results are shown in Table 2. (Example 1 4) A solution containing polystyrenesulfonic acid doped poly(3,4-ethylenedithiothiophene) in Example 6 was added, and after adding 1 g of cresol, ammonia water was added to prepare 60. A highly conductive, bifurcated solution of pH 7.5. The conductive polymer solution thus obtained was subjected to electrical conductivity in the same manner as in Example 6, and a capacitor was produced using the obtained conductive polymer solution, and evaluated in the same manner as in Example 6. The results are shown in Table 2. (Example 1 5) A conductive polymer solution of pH 7.5 was obtained by substituting the addition of ammonia water in Example 1 to add a taste. The conductive polymer solution obtained was prepared in the same manner as in Example 6 in the same manner as in Example 6, and a capacitor was produced using the obtained conductive polymer solution, and evaluated in the same manner as in Example 6. The results are shown in Table 2. (Example 16) Instead of adding ammonia water to the crucible of Example 1, diethylamine was added to prepare a conductive polymer solution having a pH of 7.5. The electrical conductivity of the obtained conductive polymer solution was determined in the same manner as in Example 6, and a capacitor was produced using the obtained conductive polymer solution, and evaluated in the same manner as in Example 6. The results are shown in Table 2 (Example 17). The solution containing polystyrenesulfonic acid doped poly(-ethylidenethiophene) in Example 6 was added with ammonia water to prepare a solution of ρΗ 7 4 - g Ν,Ν-dimercaptoacetamide (DMAc) was added to the solution to prepare a conductive polymer solution of ^ ^ PH 6.9. The electrical conductivity was measured, and the obtained conductive polymer capacitor was used and evaluated in the same manner as in Example 6. The results are shown in Table 61 ^ 22436 (Example 18). 4 g of 20% aqueous ammonia in Example 17 was mixed with N,N•dimercaptoacetamide to obtain a mixed solution. This mixed solution was added to a solution containing polystyrenesulfonic acid-doped poly(3,4-ethylenedioxythiophene) to prepare a conductive polymer solution having a pH of 6.3. (Comparative examples 3 ~ 8)

The capacitors of Comparative Examples 3 to 8 were prepared in the same manner as in Examples 9 to 14 except that the conductive polymer solution of Examples 9 to 14 was prepared without adding ammonia. These capacitors were evaluated in the same manner as in Example 6. The capacitors of Examples 6 to 18 having a solid electrolyte layer formed by a conductive polymer solution having a pH adjusted to 3 to 13 at the cathode can prevent corrosion of the dielectric layer, and since the solid electrolyte has high electrical conductivity, Esr is low. After another 疋15 0 C, the E S R after 1 hour is low. And the capacitance is also high. On the other hand, the capacitors of Comparative Examples 2 to 8 in which the solid electrolyte layer formed of the conductive molecular solution whose pH was not adjusted to 3 to 13 at the cathode could not prevent corrosion of the dielectric layer and could not lower the ESR. Further, in Comparative Example 3: the capacitor, when the solid electrolyte layer was formed, since the conductive polymer solution containing ~! was used, the electrical conductivity was high, but since the corrosion of the electric layer was not prevented, the esr could not be lowered. . BRIEF DESCRIPTION OF THE DRAWINGS Fig. 2 shows a cross section of an embodiment of a capacitor of the present invention. 62 1322436 [Explanation of main component symbols] 10 Capacitor 11 Anode 12 Dielectric layer 13 Cathode 13a Solid electrolyte layer

63

Claims (1)

U22436 Take the year l·I announcement S _〇 6734 patent application, apply for the patent scope for the month ή曰 repair L, ” original +, the scope of application patent: 八i A conductive polymer solution containing π conjugated molecules The polyanion and the solvent are characterized in that the conductive polymer solution is at a temperature of 25. (The time is 5.4 to 12 5, and the ratio of the π-co-light-based conductive polymer to the polyanion in the conductive polymer solution is (10) parts by mass relative to the polyanion, and the π-covalent conductive polymer is 2. (10) 2. The conductive polymer solution of the scope of the patent item further contains a nitrogen-containing aromatic cyclic compound. 3. The conductive polymer solution according to the scope of the patent application, The step further comprises a compound having at least one of a glycidyl group and an amine group in the molecule. ::: A conductive coating film is characterized in that it is a coating application patent ranging from brother 1 to brother 3 The conductive polymer solution is formed by the galvanic: one: the capacitor s which has a dielectric layer formed by oxidizing the surface of the (N) pole formed by the porous body of the ruthenium metal The cathode having the solid electrolyte layer is characterized in that the solid cathode of the far cathode is «.. . . . ^ . The conductive polymer solution is formed, and the conductive polymer solution contains the sputum molecule and the polyanion. And solvent And, &quot;electricity south, and the conductivity...sub-C is adjusted to a ratio of polyanion to polyanion (10) mass f, and two: conductive polymer is 1 to 1000 parts by mass. Yoke 糸 6 · As in the patent application range 5th valley state, the base is added to the conductive 64 polymer solution to adjust its pH at the temperature of 2 generations to 5.4 ~ 12.5. 〃 7. Such as the patent scope The capacitor of the sixth aspect, wherein the test is a nitrogen-containing aromatic cyclic compound. The capacitor according to any one of claims 5 to 7, wherein the conductive polymer solution is contained in a molecule a compound having at least one of a thiol group, a glycidyl group and an amine group. 9. A method for producing a capacitor, which has the following: a dielectric layer side surface of a capacitor intermediate (4) a material high-cutting liquid And performing the dry process; the capacitor intermediate has a dielectric layer of a porous body of a valve metal and a dielectric layer formed by oxidation of the surface of the anode; the conductive:: sub-cold liquid containing 胄π conjugated conductive Polymer, polyanion, ^valid' At the temperature of 2 rc, the lanthanum is adjusted to 5.4 to 125. The electrical polymer, Yidas. The ratio of the conductive polymer and the polyanion is proportional to the polyanion. Quantities, π total light system = 1~1000 mass parts. The knife between the axe is XI, the pattern: as the next page 65