JP2011057814A - Method for producing organic solvent system conductive polymer dispersion, and its application - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To easily produce an organic solvent system conductive polymer dispersion by easily performing conversion from an aqueous dispersion to an organic solvent system dispersion of a conductive polymer. <P>SOLUTION: The organic solvent system conductive polymer dispersion having ≤10 mass% water content is produced via a step (1) for synthesizing a conductive polymer by oxidatively polymerizing a thiophene or its derivative in water or aqueous liquid made of a mixture of water and a solvent which can be mixed with water in the presence of a polymer sulfonic acid to be a dopant to obtain an aqueous dispersion of the conductive polymer, a step (2) for supplying a non-aqueous amine to the aqueous dispersion of the conductive polymer to flocculate the conductive polymer, a step (3) for taking out flocculated product of the conductive polymer from water or the aqueous liquid and a step (4) for dispersing the flocculated product of the conductive polymer in an organic solvent. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an organic solvent-based conductive polymer dispersion and its application, that is, a conductive polymer obtained by drying the organic solvent-based conductive polymer dispersion, and the organic solvent-based conductive polymer dispersion. Organic solvent-based conductive polymer-containing resin composition dispersion obtained by mixing a binder resin and a conductive polymer-containing resin obtained by drying the organic solvent-based conductive polymer-containing resin composition dispersion Resin composition, antistatic film comprising conductive polymer-containing resin composition film obtained by drying organic solvent-based conductive polymer-containing resin composition dispersion, organic solvent-based conductive polymer-containing resin composition The antistatic sheet having the conductive polymer-containing resin composition film obtained by drying the product dispersion as a conductive layer on one or both sides of the base sheet, and the organic solvent-based conductive polymer dispersion is dried. Get Electrolytic capacitor using a conductive polymer as a solid electrolyte, and a solid electrolytic capacitor using a conductive polymer-containing resin composition obtained by drying the organic solvent-based conductive polymer-containing resin composition dispersion as a solid electrolyte , A method for producing a solid electrolytic capacitor comprising a solid electrolyte using the organic solvent-based conductive polymer dispersion, and a solid electrolyte comprising a solid electrolyte using the organic solvent-based conductive polymer-containing resin composition dispersion The present invention relates to a method for manufacturing a capacitor.

  Conductive polymers are used, for example, as solid electrolytes for antistatic films and solid electrolytic capacitors because of their high conductivity.

  As the conductive polymer in this application, for example, a polymer synthesized by oxidative polymerization of a polymerizable monomer such as thiophene or a derivative thereof is used.

  As a dopant when performing oxidative polymerization of a polymerizable monomer such as thiophene or a derivative thereof, particularly chemical oxidative polymerization, organic sulfonic acid is mainly used, and among them, aromatic sulfonic acid is said to be suitable. Transition metals are used as oxidants, among which ferric iron is said to be suitable. Usually, ferric salts of aromatic sulfonic acids are chemically oxidative polymerization of polymerizable monomers such as thiophene or its derivatives. It has been used as an oxidizing agent / dopant agent.

  And among the ferric salts of aromatic sulfonic acids, it is said that ferric salts of toluene sulfonic acid and ferric salts of methoxybenzene sulfonic acid are particularly useful, and conductive polymers using them. It can be synthesized by mixing those oxidizing agent / dopant with a polymerizable monomer such as thiophene or a derivative thereof, and is reported to be simple and suitable for industrialization (Patent Document 1, Patent Document) 2).

  However, the conductive polymer obtained using ferric toluenesulfonate as an oxidizing agent and dopant does not have sufficiently satisfactory characteristics in terms of initial resistance and heat resistance, and methoxybenzenesulfonic acid. The conductive polymer obtained using ferric salt as an oxidant and dopant has lower initial resistance and excellent heat resistance than the conductive polymer using ferric toluenesulfonate. Even so, satisfactory characteristics were not obtained.

  Therefore, the present inventors use a high molecular sulfonic acid such as polystyrene sulfonic acid, sulfonated polyester, and phenol sulfonic acid novolak resin as the organic sulfonic acid serving as a dopant, and has high conductivity and excellent heat resistance. Have developed patentable polymers and have already filed patent applications (PCT / JP2009 / 57241, PCT / JP2009 / 57242).

  However, in the case where the aromatic sulfonic acid is used as a dopant and the polymer sulfonic acid is used as a dopant, the oxidative polymerization of the polymerizable monomer is carried out in water or in an aqueous liquid composed of a mixture of water and a water-miscible solvent. Therefore, the conductive polymer is obtained in a state of being dispersed in water or an aqueous liquid.

  Therefore, when the antistatic film is formed from the conductive polymer obtained as described above and the binder resin is mixed with the aqueous dispersion of the conductive polymer, the binder resin is aggregated, and the conductive polymer is conductive. There was a problem that sufficient mixing of the functional polymer and the binder resin could not be performed within a short time,

  In addition, the obtained conductive polymer is often used in the construction of an organic conductive member of an electronic device, such as being used as a solid electrolyte of a solid electrolytic capacitor. Since the metal member of the electronic device is corroded and causes electric current leakage to cause power loss, the aqueous dispersion has a problem that careful handling must be taken.

  Therefore, attempts have been made to change the aqueous dispersion of the obtained conductive polymer to an organic solvent dispersion (Patent Documents 3 to 5).

  However, these methods described in Patent Documents 3 to 5 convert the conductive polymer dispersion liquid from an aqueous system to an organic solvent system through concentration, solvent replacement, and the like. Therefore, there was a problem that the cost was increased.

JP 2003-160647 A JP 2004-265927 A Japanese Patent No. 40386696 Japanese Patent No. 4225785 Japanese Patent Laid-Open No. 4208720

  In view of the above circumstances, the present invention provides a method capable of easily converting an aqueous dispersion of a conductive polymer from an aqueous dispersion of an electroconductive polymer to an organic solvent-based dispersion and easily producing an organic solvent-based conductive polymer dispersion. For the purpose.

  As a result of intensive studies to solve the above problems, the present inventor has found that when a non-aqueous amine is added to an aqueous dispersion of a conductive polymer, the conductive polymer aggregates. The present invention has been completed.

That is, the present invention
(1) Conduction is conducted by synthesizing a conductive polymer by oxidative polymerization of thiophene or a derivative thereof in water or an aqueous liquid composed of a mixture of water and a water-miscible solvent in the presence of a polymer sulfonic acid as a dopant. Obtaining an aqueous dispersion of a functional polymer;
(2) adding a non-aqueous amine to the aqueous dispersion of the conductive polymer to aggregate the conductive polymer;
(3) a step of taking out the aggregate of the conductive polymer from water or an aqueous liquid;
(4) An organic solvent-based conductive polymer dispersion having a water content of 10% by mass or less, wherein the conductive polymer aggregate is produced through a step of dispersing the aggregate of the conductive polymer in an organic solvent. It relates to a manufacturing method.

  The present invention also provides a conductive polymer obtained by drying the organic solvent-based conductive polymer dispersion, an organic solvent obtained by mixing the organic solvent-based conductive polymer dispersion and a binder resin. Conductive polymer-containing resin composition dispersion, conductive polymer-containing resin composition obtained by drying the organic solvent-based conductive polymer-containing resin composition dispersion, and organic solvent-based conductive polymer-containing Antistatic film comprising conductive polymer-containing resin composition film obtained by drying resin composition dispersion, conductive polymer obtained by drying organic solvent-based conductive polymer-containing resin composition dispersion An antistatic sheet having a resin composition film as a conductive layer on one or both sides of a base sheet, a solid having a conductive polymer obtained by drying the organic solvent-based conductive polymer dispersion as a solid electrolyte Electrolytic capacitor A solid electrolytic capacitor having a conductive polymer-containing resin composition obtained by drying the organic solvent-based conductive polymer-containing resin composition dispersion as a solid electrolyte, and the organic solvent-based conductive polymer dispersion described above. The present invention relates to a method for producing a solid electrolytic capacitor comprising a solid electrolyte and a method for producing a solid electrolytic capacitor comprising a solid electrolyte using the organic solvent-based conductive polymer-containing resin composition dispersion.

And as said non-aqueous amine, the amine represented by following General formula (1) is used suitably.
R ₁ —NH ₂ (1)
(In the formula, R ₁ is an alkyl group having 6 to 30 carbon atoms, and the alkyl group may be linear or branched. The alkyl group may contain an ether bond, an ester bond or a double bond, and the hydrogen atom may be optionally substituted with another atom)

The polymer sulfonic acid is preferably polystyrene sulfonic acid, sulfonated polyester, or phenol sulfonic acid novolak resin, and the phenol sulfonic acid novolak resin has a repeating unit represented by the following general formula (2). Those are preferred.

  According to the present invention, an organic solvent-based conductive polymer dispersion can be easily produced. That is, according to the present invention, the conductive polymer in the aqueous dispersion can be easily aggregated by adding the non-aqueous amine to the aqueous dispersion of the conductive polymer. This is because the non-aqueous amine is partially bonded to the polymer sulfonic acid that functions as a conductive polymer dopant, so that the conductive polymer becomes non-aqueous and conductive in water or aqueous liquid. It is considered that the polymer is easily aggregated. The aggregate can be easily taken out from water or an aqueous liquid by filtration or the like, and the aggregate can be easily dispersed in an organic solvent due to the presence of a non-aqueous amine. Therefore, according to the present invention, it is possible to easily convert an aqueous dispersion of a conductive polymer into an organic solvent-based dispersion, thereby easily manufacturing an organic solvent-based conductive polymer dispersion. it can.

  Further, the conductive polymer obtained by drying the organic solvent-based conductive polymer dispersion has high conductivity and excellent heat resistance. This is because the higher sulfonic acid used as the dopant in the synthesis of the conductive polymer also functions as an excellent dispersant during the synthesis of the conductive polymer, and thiophene or a derivative thereof as a polymerizable monomer or as required. The added catalyst is uniformly dispersed in water or aqueous liquid, and is incorporated into the synthesized polymer as a dopant, making the conductive polymer highly conductive and functioning as an excellent dispersant. This is considered to be a factor that makes the heat resistance excellent.

  Further, the organic solvent-based conductive polymer dispersion obtained by the present invention does not aggregate the binder resin when mixed with the non-aqueous binder resin. Can be sufficiently mixed in a short time, and an organic solvent-based conductive polymer-containing resin composition dispersion liquid in which the conductive polymer and the binder resin are sufficiently mixed can be easily obtained.

  Furthermore, since the organic solvent-based conductive polymer dispersion and the organic solvent-based conductive polymer-containing resin composition dispersion of the present invention are based on an organic solvent, they are used in organic devices such as the formation of solid electrolyte layers of solid electrolytic capacitors. In the configuration of the conductive member, there is no problem caused by water in the electronic device. That is, unlike the water-based conductive polymer dispersion, water does not corrode the metal member of the electronic device to cause a leakage current, thereby causing no power loss when driving the electronic device.

  In the present invention, by adding a non-aqueous amine to the aqueous dispersion of the conductive polymer, the conductive polymer is aggregated so that it can be separated from water. This will be explained from matters related to this.

  As described above, the amine added to the aqueous dispersion of the conductive polymer is preferably an amine represented by the general formula (1). Specific examples of the amine represented by the general formula (1) include For example, hexylamine, heptylamine, octylamine, decylamine, laurylamine, myristylamine, hexadecylamine, octadecylamine, N-methylhexylamine, 2-ethylhexylamine, di-2-ethylhexylamine, di-n-butylamine, Di-n-hexylamine, di-n-octylamine, 3- (2-ethylhexyloxy) propylamine, oleylamine and the like can be mentioned. Among them, 3- (2-ethylhexyloxy) propylamine, hexylamine, Heptylamine, octylamine, decylamine, lauryl Min are preferred, especially 3- (2-ethylhexyl oxy) propylamine are preferred. In other words, the non-aqueous primary amine and secondary amine can cause aggregation of the conductive polymer, but the primary amine has a stronger cohesion and is particularly familiar with water in the alkyl group. Since amines having substituents such as easy ether bonds have a stronger cohesive force, primary amines such as hexylamine, heptylamine, octylamine, decylamine, and laurylamine are mentioned as preferred amines as described above. Among them, 3- (2-ethylhexyl) propylamine having an ether bond in the alkyl group is particularly preferable. And if the alkyl group of the non-aqueous amine becomes too long, the amine tends to solidify at room temperature, and therefore the handling property of the amine in the process of aggregating the conductive polymer may be reduced. An amine having 20 or less is preferable, and an amine having 14 or less carbon atoms is particularly preferable.

  The concentration of the conductive polymer in the aqueous dispersion of the conductive polymer that causes aggregation by the addition of the non-aqueous amine is not particularly limited, but is preferably 0.1% by mass or more, 0.5 It is more preferably at least mass%, more preferably at least 25 mass%, and even more preferably at most 10 mass%.

  The addition rate of the non-aqueous amine for aggregating the conductive polymer in the aqueous dispersion is not particularly limited, but the amine is more uniformly diffused by slowly adding the dispersion while stirring. preferable. The temperature at the time of addition of a non-aqueous amine can be performed in the range of 0-100 degreeC, 5 degreeC or more is especially preferable, and 50 degreeC or less is preferable.

  As the addition amount of the non-aqueous amine, if the pH of the aqueous dispersion of the conductive polymer becomes 3 or more, the conductive polymer will aggregate, so an appropriate amount may be added. Even if the amount of water-based amine is increased and the pH is increased, there is no problem in the aggregation of the conductive polymer itself, but there is a possibility that the conductive polymer having a pH higher than 11 may be dedoped, so that the pH is 11 It is preferable to add in the following range.

  The conductive polymer aggregates can be easily removed from the water or aqueous liquid by, for example, separating the aggregates from the water or aqueous liquid by filtering through a mesh (sieve) having a diameter of 100 μm. Can be implemented. Although it is preferable that the conductive polymer aggregates are separated from water or an aqueous liquid as the remaining moisture is small, it is not necessary to completely separate the aggregate from the water. If some moisture remains in the agglomerate, there is also an aspect of faster dispersion in the next organic solvent, and depending on the intended use of the organic solvent-based conductive polymer dispersion finally obtained, Should be reduced.

  In other words, when the finally obtained organic solvent-based conductive polymer dispersion is used in applications where water is not required, the aggregate of the conductive polymer is subjected to pressure by applying pressure to the aggregate by centrifugation or a filter press. It may be taken out from water or an aqueous liquid while reducing the amount of water, and if it is necessary to further reduce the water content, the water content may be reduced by drying accordingly.

  Conductive polymer dispersion is dispersed by adding aggregate of conductive polymer taken out of water or aqueous liquid to organic solvent and dispersing with a dispersing machine such as SG (side grinder) or ultrasonic homogenizer. A liquid is obtained.

  Examples of the organic solvent used in the preparation of the organic solvent-based dispersion include n-methylpyrrolidone, dimethylformamide, dimethylacetamide, ethylene glycol, dimethylsiloxide, sulfolane, γ-butyrolactone, methyl ethyl ketone, and ethyl acetate. Among these, n-methylpyrrolidone, dimethylformamide, and dimethylacetamide are preferable, and n-methylpyrrolidone is particularly preferable.

  The organic solvent-based conductive polymer dispersion is mixed with a binder resin to produce an organic solvent-based conductive polymer-containing resin composition dispersion, for example, in the production of a conductive layer for an antistatic film or an antistatic sheet. However, in this case, even if some moisture is contained, the binder resin is not agglomerated, so the moisture content may be 10% by mass or less.

  The concentration of the conductive polymer in the organic solvent-based conductive polymer dispersion is not particularly limited, but from the viewpoint of obtaining a uniform dispersion, the concentration of the conductive polymer is 5% by mass or less. Is preferable, and 3% by mass or less is particularly preferable. In addition, if the concentration of the conductive polymer is too low, the working efficiency when using the organic solvent-based conductive polymer dispersion is deteriorated, so 0.2% by mass or more is preferable, particularly 0.5% by mass. % Or more is preferable.

  If the concentration of the conductive polymer in the organic solvent-based conductive polymer dispersion is the above level, the organic solvent-based conductive polymer dispersion looks almost transparent to the naked eye, and part of the conductive polymer is It is considered that it is dissolved in an organic solvent and dispersed in the organic solvent in a dissolved state.

  As described above, the aggregate of the conductive polymer is in water or an aqueous liquid (this water or aqueous liquid refers to water or aqueous liquid in a system in which oxidative polymerization of thiophene or a derivative thereof is performed. The agglomerates removed by filtration from thiophene or its derivatives are subjected to filtration in water or aqueous liquid), and have a dry solid content of about 65 to 75% by mass and contain moisture up to about 35%. However, the concentration of the conductive polymer in the finally obtained organic solvent-based conductive polymer dispersion is preferably up to about 5% by mass. In order to obtain such an organic solvent-based conductive polymer dispersion, Even if the agglomerates of the conductive polymer contain such a level of water, the water content of the organic solvent-based conductive polymer dispersion can be reduced to 10% by mass or less. Depending on the use of the dispersion, Since it is not pressing severe residual water content of aggregates in the polymer without causing high cost, it is possible to obtain an organic solvent-based conductive polymer-containing resin composition dispersion.

  However, in application to electronic devices, it is desirable that the amount of water is low, and it is suitable for use in the production of solid electrolytes for solid electrolytic capacitors by using organic solvent-based conductive polymer dispersions with low water content. Furthermore, it can be expected to be used as a conductivity improver for lithium ion batteries, a hole transport layer for organic EL, a device electrode, a conductive agent for non-aqueous conductive polymer paints, and the like.

  The aqueous dispersion of the conductive polymer serving as the base of the organic solvent-based conductive polymer dispersion is prepared in water or in an aqueous liquid in the presence of a polymeric monomer, thiophene or a derivative thereof, and a polymer sulfonic acid serving as a dopant. Examples of thiophene derivatives in thiophene or its derivatives include 3,4-ethylenedioxythiophene, 3-alkylthiophene, 3-alkoxythiophene, 3-alkyl-4-alkoxy. Examples thereof include thiophene, 3,4-alkylthiophene, and 3,4-alkoxythiophene. The alkyl group or alkoxy group preferably has 1 to 16 carbon atoms, but 3,4-ethylenedioxythiophene is particularly preferable. .

  As the polymer sulfonic acid serving as a dopant, polystyrene sulfonic acid sulfonated polyester and phenol sulfonic acid novolak resin are preferably used.

  Polymer sulfonic acids such as polystyrene sulfonic acid, sulfonated polyester, phenol sulfonic acid novolak resin and the like serve as dopants for the conductive polymer. As described above, these are used during the synthesis of the conductive polymer. , Which also functions as an excellent dispersant, uniformly disperse thiophene or its derivative as an oxidant or polymerizable monomer in water or an aqueous liquid, and is incorporated as a dopant in the synthesized polymer, resulting in conductivity Conductive polymer obtained by making the conductive polymer have high conductivity suitable for use as an antistatic film or a solid electrolyte of a solid electrolytic capacitor, and that the dopant functions as an excellent dispersant To have excellent heat resistance suitable for use as a solid electrolyte in solid electrolytic capacitors Was also believed to cause have high transparency suitable for use as antistatic film.

  As said polystyrene sulfonic acid, that whose weight average molecular weight is 10,000-1,000,000 is preferable.

  That is, when the weight average molecular weight of the polystyrene sulfonic acid is smaller than 10,000, the conductivity of the obtained conductive polymer is lowered and the transparency may be deteriorated. Moreover, when the weight average molecular weight of the said polystyrene sulfonic acid is larger than 1,000,000, the viscosity of the dispersion liquid of a conductive polymer will become high, and it will become difficult to use it in preparation of a solid electrolytic capacitor. The polystyrene sulfonic acid has a weight average molecular weight within the above range, preferably 20,000 or more, more preferably 40,000 or more, and preferably 800,000 or less. More preferable is 1,000 or less.

  The sulfonated polyester is a polycondensation polymer of dicarboxybenzenesulfonic acid diester such as sulfoisophthalic acid ester or sulfoterephthalic acid ester and alkylene glycol in the presence of a catalyst such as antimony oxide or zinc oxide. The sulfonated polyester preferably has a weight average molecular weight of 5,000 to 300,000.

  That is, when the weight average molecular weight of the sulfonated polyester is smaller than 5,000, the conductivity of the obtained conductive polymer is lowered and the transparency may be deteriorated. Further, when the weight average molecular weight of the sulfonated polyester is larger than 300,000, the viscosity of the conductive polymer dispersion becomes high, and it becomes difficult to use in the production of a solid electrolytic capacitor or the like. The water-soluble polyester preferably has a weight average molecular weight of 10,000 or more, more preferably 20,000 or more, and preferably 100,000 or less, within the above range. More preferable is 1,000 or less.

  Moreover, as a phenolsulfonic acid novolak resin, that whose weight average molecular weight is 5,000-500,000 is preferable.

  That is, when the weight average molecular weight of the phenolsulfonic acid novolak resin is less than 5,000, the conductivity of the obtained conductive polymer is lowered and the transparency may be deteriorated. In addition, when the weight average molecular weight of the phenolsulfonic acid novolak resin is larger than 500,000, the viscosity of the conductive polymer dispersion becomes high, which makes it difficult to use in the production of a solid electrolytic capacitor. The phenol sulfonic acid novolak resin has a weight average molecular weight within the above range, preferably 5,000 or more, more preferably 10,000 or more, and preferably 400,000 or less. 80,000 or less is more preferable.

  Polystyrene sulfonic acid, sulfonated polyester, and phenol sulfonic acid novolak resin as dopants are all soluble in aqueous liquids consisting of water or a mixture of water and water-miscible solvents. Can be carried out in water or in an aqueous liquid.

  Examples of the water-miscible solvent constituting the aqueous liquid include methanol, ethanol, propanol, acetone, acetonitrile, and the like. The mixing ratio of these water-miscible solvents with water is 50 in the entire aqueous liquid. The mass% or less is preferable.

  As the oxidative polymerization for synthesizing the conductive polymer, either chemical oxidative polymerization or electrolytic oxidative polymerization can be employed.

  For example, persulfate is used as an oxidizing agent in performing chemical oxidative polymerization. Examples of the persulfate include ammonium persulfate, sodium persulfate, potassium persulfate, calcium persulfate, and barium persulfate. Is used.

  In chemical oxidative polymerization, the amount of dopant, polymerizable monomer, and oxidizing agent used is not particularly limited. For example, polystyrene sulfonic acid is used as the dopant, and 3,4-ethylenedioxythiophene is used as the polymerizable monomer. When ammonium persulfate is used as an oxidizing agent, the use ratio thereof is preferably a mass ratio of dopant: polymerizable monomer: oxidant = 1: 0.1-10: 0.1-10, Dopant: polymerizable monomer: oxidizing agent = 1: 0.2-4: 0.2-4 are preferable. Such a use ratio is substantially the same even when other dopants, polymerizable monomers, and oxidizing agents are used. The temperature during chemical oxidative polymerization is preferably 5 to 95 ° C, more preferably 10 to 30 ° C, and the polymerization time is preferably 1 to 72 hours, more preferably 8 to 24 hours.

Electrolytic oxidation polymerization is be carried out even at a constant voltage at a constant current, for example, when performing electrolytic oxidation polymerization at a constant current, preferably 0.05mA ^/ cm ² ~10mA ^/ cm 2 as the current value, 0.2 mA / cm more preferably ^{2 ~4mA} / cm ^2, when performing electrolytic oxidation polymerization at a constant voltage, preferably 0.5V~10V as voltage, 1.5V to 5V is more preferable. The temperature during electrolytic oxidation polymerization is preferably 5 to 95 ° C, particularly preferably 10 to 30 ° C. The polymerization time is preferably 1 hour to 72 hours, more preferably 8 hours to 24 hours. In the electrolytic oxidation polymerization, ferrous sulfate or ferric sulfate may be added as a catalyst.

  The conductive polymer obtained as described above is obtained immediately after polymerization, in a state of being dispersed in water or an aqueous liquid, and includes a persulfate as an oxidizing agent, an iron sulfate used as a catalyst, or a decomposition product thereof. Contains. Therefore, the conductive polymer aqueous dispersion containing the impurity is dispersed in an dispersing machine such as an ultrasonic homogenizer or a planetary ball mill, and then the metal component is removed with a cation exchange resin. The particle size of the conductive polymer at this time is preferably 100 μm or less, and particularly preferably 10 μm or less. Thereafter, it is preferable to remove as much as possible the sulfuric acid produced by the decomposition of the oxidizing agent and the catalyst by an ethanol precipitation method, an ultrafiltration method, an anion exchange resin or the like.

  The conductive polymer obtained by drying the organic solvent-based conductive polymer dispersion of the present invention can be used as a solid electrolyte of a solid electrolytic capacitor, such as a tantalum solid electrolytic capacitor, a niobium solid electrolytic capacitor, and an aluminum solid electrolytic capacitor. Therefore, it is possible to provide a solid electrolytic capacitor that is suitably used as a solid electrolyte of a solid electrolytic capacitor such as the above, has low ESR, and high reliability under high temperature conditions.

  As described above, when the conductive polymer obtained by drying the organic solvent-based conductive polymer dispersion of the present invention is used as the solid electrolyte of the solid electrolytic capacitor, the organic solvent-based conductive polymer dispersion is dried. The conductive polymer can be used as it is, but it is used in the state of an organic solvent-based conductive polymer dispersion in which the conductive polymer is dispersed in an organic solvent, and then dried. It is more suitable to use the conductive polymer to be used as a solid electrolyte. At that time, in order to improve the adhesion between the conductive polymer and the capacitor element, it is preferable to add a binder resin to the dispersion of the conductive polymer.

  Examples of such binder resins include polyurethane, polyester, acrylic resin, polyamide, polyimide, epoxy resin, polyacrylonitrile resin, polymethacrylonitrile resin, polystyrene resin, novolac resin, silane coupling agent, etc. Polyester, polyurethane, acrylic resin and the like are preferable. Moreover, since the electroconductivity of a conductive polymer can be improved when the sulfone group is added like sulfonated polyallyl, sulfonated polyvinyl, and sulfonated polystyrene, it is more preferable.

  The above binder resins are all hydrophobic, and if the conductive polymer dispersion is aqueous, the binder resin aggregates upon addition, and the conductive polymer and the binder resin are uniform. In order to obtain such a mixture, it takes a long time to mix. However, according to the organic solvent-based conductive polymer dispersion of the present invention, the added binder resin does not cause aggregation. Uniform mixing of the polymer and the binder resin can be easily achieved, and a dispersion of the organic solvent-based conductive polymer-containing resin composition in which the conductive polymer and the binder resin are uniformly mixed can be easily obtained.

  An example of producing a solid electrolytic capacitor by forming a solid electrolyte of the solid electrolytic capacitor using the organic solvent-based conductive polymer dispersion or the organic solvent-based conductive polymer-containing resin composition dispersion of the present invention. Will be explained. However, since the organic solvent-based conductive polymer dispersion of the present invention can be used in the same manner when the organic solvent-based conductive polymer-containing resin composition dispersion is used, the organic solvent-based conductive polymer dispersion The liquid will be described as a representative.

  First, when producing a tantalum solid electrolytic capacitor, a niobium solid electrolytic capacitor, a laminated aluminum solid electrolytic capacitor, etc., an anode made of a porous body of a valve metal such as tantalum, niobium or aluminum, and a dielectric made of an oxide film of the valve metal. The capacitor element having the body layer is immersed in the organic solvent-based conductive polymer dispersion of the present invention, taken out, dried, and repeatedly immersed in this dispersion and dried to repeat the process of increasing the conductivity. After forming a solid electrolyte layer consisting of molecules, carbon paste and silver paste are applied and dried, then anode and cathode terminals are attached and covered with resin, so that tantalum solid electrolytic capacitor, niobium solid electrolytic capacitor, multilayer type An aluminum solid electrolytic capacitor or the like can be manufactured.

  Further, for example, using polystyrene sulfonic acid as a dispersant and dopant, the capacitor element is immersed in a liquid containing a polymerizable monomer and an oxidizing agent, taken out, then polymerized, immersed in water, taken out, and washed. Then, after the conductive polymers are synthesized by drying, the whole is immersed in the organic solvent-based conductive polymer dispersion of the present invention, taken out and dried to form a solid electrolyte layer. Also good.

  Then, after forming a solid electrolyte layer made of a conductive polymer on the capacitor element as described above, through a carbon paste or silver paste coating as described above, a tantalum solid electrolytic capacitor, a niobium solid electrolytic capacitor, A laminated aluminum solid electrolytic capacitor or the like can also be produced.

  In the case of producing a wound aluminum solid electrolytic capacitor, after etching the surface of the aluminum foil, a lead terminal is attached to the anode on which the dielectric layer is formed by performing a chemical conversion treatment, and a cathode made of aluminum foil. After attaching the lead terminal, the capacitor element produced by winding the anode and cathode with the lead terminal through a separator was immersed in the organic solvent-based conductive polymer dispersion of the present invention, taken out, dried, In order to remove the conductive polymer that does not enter the pores formed by etching the aluminum foil, it is immersed in an organic solvent, taken out, dried, and after repeating these operations, it is packaged with an exterior material, A wound aluminum solid electrolytic capacitor can be produced.

  In the above example, the case where the solid electrolytic capacitor is produced by the method of immersing the capacitor element in the organic solvent-based conductive polymer dispersion of the present invention has been described. Instead of immersing in a solid electrolytic capacitor, a solid electrolytic capacitor can also be produced by a method of applying a capacitor element to the organic solvent-based conductive polymer dispersion of the present invention.

  As described above, when a solid electrolytic capacitor is produced using the organic solvent-based conductive polymer dispersion of the present invention, since the dispersion is an organic solvent-based, it is easier to dry than the aqueous dispersion. The inconvenience of a solid electrolytic capacitor due to residual moisture as in the case of using an aqueous dispersion does not occur.

  In the production of an antistatic film or an antistatic sheet, an organic solvent-based conductive polymer-containing resin obtained by mixing a binder resin in an organic solvent-based conductive polymer dispersion rather than an organic solvent-based conductive polymer dispersion The composition dispersion is preferably used. For example, the organic solvent-based conductive polymer-containing resin composition dispersion of the present invention is applied to the base sheet, or the base sheet is used as the organic solvent-based conductive polymer-containing resin. After dipping in the composition dispersion, pulling up and drying, a film is formed, the film may be peeled from the base sheet, and used as an antistatic film, or one of the base sheets The film formed on this surface or both surfaces may be used as a conductive layer without peeling off from the base sheet, and the base sheet as a support material as an antistatic sheet.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited only to those illustrated in these examples. In the following examples and the like,% in the case of showing the concentration and the amount used is% based on mass unless otherwise specified.

Example 1
600 g of 4% aqueous solution of polystyrene sulfonic acid (manufactured by Teika Co., Ltd., weight average molecular weight 100,000) is put in a stainless steel container having an internal volume of 1 L, and 0.3 g of ferrous sulfate heptahydrate is added. 4 mL of 3,4-ethylenedioxythiophene was slowly added dropwise. A stainless steel mesh (diameter: 2 mm) measuring 3 cm wide x 20 cm long is placed in the container, and two of them are opposed to each other in a form that sandwiches a stirring bar from the lower end to the 5 cm vertical portion. Set in shape. The stainless steel mesh was attached with an anode and the other with a cathode, and electrolytic oxidation polymerization of 3,4-ethylenedioxythiophene was performed with stirring at a constant current of 1 mA / cm ² over 18 hours. After the electrolytic oxidation polymerization, it was diluted 6 times with water, and then subjected to a dispersion treatment for 30 minutes with an ultrasonic homogenizer (manufactured by Nippon Seiki Co., Ltd., US-T300). Thereafter, 100 g of Cation Exchange Resin Amberlite 120B (trade name) manufactured by Organo Corporation was added and stirred with a stirrer for 1 hour. Subsequently, filter paper No. manufactured by Toyo Filter Paper Co., Ltd. The mixture was filtered through 131, and the treatment with this cation exchange resin and filtration were repeated three times to remove all cation components such as iron ions in the liquid. The liquid was concentrated using an ultrafiltration device (Vivaflow 200 (trade name) manufactured by Sartorius, molecular weight fraction 50,000). The dry solid content concentration measured at 105 ° C. was 3.0%.

  While stirring the aqueous dispersion of the conductive polymer obtained as described above with a stirrer, 3- (2-ethylhexyloxy) propylamine as a non-aqueous amine was gradually added thereto, pH 3 The aggregation of the conductive polymer started gradually from the degree, and when the pH exceeded 4, the aggregation was completed, and a transparent liquid and an aggregate were separated. This liquid was passed through a stainless steel mesh having a diameter of 100 μm to separate agglomerates. When the dry solid content concentration of this aggregate was measured under the condition of 105 ° C., it was 68%.

  5 g of this agglomerate was put into 250 g of n-methylpyrrolidone and dispersed with an ultrasonic homogenizer (manufactured by Nippon Seiki Co., Ltd., US-T300) for 20 minutes. It filtered with 131 and the organic solvent type dispersion liquid of the conductive polymer was obtained. The dry solid content concentration of this dispersion measured at 150 ° C. under dry conditions was 1.4%. In addition, the moisture content measured by Karl Fischer was 0.6%. Even when this organic solvent-based conductive polymer dispersion was allowed to stand at 5 ° C. for 1 month, no aggregation was observed and the organic dispersion was stable.

Example 2
Instead of polystyrene sulfonic acid in Example 1, sulfonated polyester [Plus Coat Z-561 (trade name), weight average molecular weight 27,000, manufactured by Kyoyo Chemical Industry Co., Ltd.] was used, and ferrous sulfate with respect to 600 g of 5% aqueous solution thereof. -Except that the amount of heptahydrate was changed from 0.3 g in Example 1 to 0.05 g, the same operation as in Example 1 was carried out until the ultrafiltration operation, and water of the conductive polymer was obtained. A dispersion was obtained. The dry solid content concentration measured at 105 ° C. was 3.0%.

  While the aqueous dispersion of the conductive polymer obtained as described above was stirred with a stirrer, 3- (2-ethylhexyloxy) propylamine was gradually added thereto, and the pH was about 3.0. Aggregation of the conductive polymer gradually started, and when pH 4 was exceeded, the aggregation was completed, and a transparent liquid and an aggregate were separated. This liquid was passed through a stainless steel mesh having a diameter of 100 μm to separate agglomerates. When the dry solid content concentration of the aggregate was measured under the condition of 105 ° C., it was 71%.

  5 g of this agglomerate was put into 200 g of n-methylpyrrolidone and dispersed with an ultrasonic homogenizer (Nippon Seiki, US-T300) for 20 minutes. It filtered with 131 and the organic solvent type dispersion liquid of the conductive polymer was obtained. The dry solid content concentration of this dispersion measured at 150 ° C. under dry conditions was 1.8%. In addition, the water content measured by Karl Fischer was 0.8%. The organic solvent-based conductive polymer dispersion was stable with no aggregation observed even after standing for 1 month at 5 ° C.

Example 3
A phenolsulfonic acid novolak resin having a repeating unit represented by the general formula (2) instead of polystyrenesulfonic acid [LotEW00130 (trade name) manufactured by Konishi Chemical Industries, Ltd., weight average molecular weight 60,000, R is hydrogen] Except that was used, the same operation as in Example 1 was performed up to the ultrafiltration operation to obtain an aqueous dispersion of a conductive polymer. The dry solid content concentration measured at 105 ° C. was 3.0%.

  While stirring the aqueous dispersion of the conductive polymer with a stirrer, 3- (2-ethylhexyloxy) propylamine is gradually added to the dispersion. Aggregation started, and when pH 3 was exceeded, the aggregation was completed, and the solution became a liquid in which the transparent liquid and the aggregate were separated. This liquid was passed through a stainless steel mesh having a diameter of 100 μm to separate agglomerates. When the dry solid content concentration of the aggregate was measured under the condition of 105 ° C., it was 70%.

  5 g of this agglomerate was put into 350 g of n-methylpyrrolidone and dispersed with an ultrasonic homogenizer (Nippon Seiki Co., Ltd., US-T300) for 20 minutes. It filtered with 131 and the organic solvent type dispersion liquid of the conductive polymer was obtained. The dry solid content concentration of this dispersion measured at 150 ° C. under dry conditions was 1.0%. Further, the moisture content measured by Karl Fischer was 0.4%. The organic solvent-based conductive polymer dispersion was stable with no aggregation observed even after standing for 1 month at 5 ° C.

Example 4
The same operation as in Example 1 was performed except that hexylamine was used in place of 3- (2-ethylhexyloxy) propylamine, and the aggregate was taken out by a filter press. When the dry solid content concentration of the aggregate was measured at 105 ° C., it was 90%.

  5 g of this agglomerate was put into 250 g of n-methylpyrrolidone and dispersed with an ultrasonic homogenizer (manufactured by Nippon Seiki Co., Ltd., US-T300) for 20 minutes. It filtered with 131 and the organic solvent type dispersion liquid of the conductive polymer was obtained. The dry solid content concentration of this dispersion measured at 150 ° C. under dry conditions was 1.4%. Further, the moisture content measured by Karl Fischer was 0.2%. The organic solvent-based conductive polymer dispersion was stable with no aggregation observed even after standing for 1 month at 5 ° C.

Example 5
The same operation as in Example 1 was performed except that octylamine was used instead of 3- (2-ethylhexyloxy) propylamine, and the aggregate was taken out by a filter press. When the dry solid content concentration of the aggregate was measured at 105 ° C., it was 90%.

  5 g of this agglomerate was put into 250 g of n-methylpyrrolidone and dispersed with an ultrasonic homogenizer (manufactured by Nippon Seiki Co., Ltd., US-T300) for 20 minutes. It filtered with 131 and the organic solvent type dispersion liquid of the conductive polymer was obtained. The dry solid content concentration of this agglomerate when measured under a drying condition of 150 ° C. was 1.4%. Further, the moisture content measured by Karl Fischer was 0.2%. The organic solvent-based conductive polymer dispersion was stable with no aggregation observed even after standing for 1 month at 5 ° C.

Example 6
The same operation as in Example 1 was performed except that laurylamine was used in place of 3- (2-ethylhexyloxy) propylamine, and the aggregate was taken out by a filter press. When the dry solid content concentration of the aggregate was measured at 105 ° C., it was 90%.

  5 g of this agglomerate was put into 250 g of n-methylpyrrolidone and dispersed with an ultrasonic homogenizer (manufactured by Nippon Seiki Co., Ltd., US-T300) for 20 minutes. It filtered with 131 and the organic solvent type dispersion liquid of the conductive polymer was obtained. The dry solid content concentration of this dispersion measured at 150 ° C. under dry conditions was 1.4%. Further, the moisture content measured by Karl Fischer was 0.2%. The organic solvent-based conductive polymer dispersion was stable with no aggregation observed even after standing for 1 month at 5 ° C.

Comparative Example 1
The same operation as in Example 1 was performed until butylamine was gradually added instead of 3- (2-ethylhexyloxy) propylamine. However, even when butylamine was gradually added until pH 14 was reached, the conductive polymer did not aggregate.

Comparative Example 2
The same operation as in Example 1 was performed until 2-methylimidazole was gradually added instead of 3- (2-ethylhexyloxy) propylamine. However, the conductive polymer did not aggregate even when 2-methylimidazole was gradually added until the pH increase limit of 9 due to the addition of 2-methylimidazole was reached.

Comparative Example 3
The same operation as in Example 1 was performed until an aqueous dispersion of a conductive polymer having a concentration of 3% was obtained. 100 g of n-methylpyrrolidone was added to 50 g of this aqueous dispersion of conductive polymer, and the mixture was concentrated by distillation in a water bath at 40 ° C. under a vacuum degree of 20 hPa.

  However, when about 35 g of water flows out, agglomeration occurs and the conductive polymer is precipitated, and an organic solvent-based dispersion of the conductive polymer having a water content of 10% or less can be prepared. There wasn't.

Comparative Example 4
The same operation as in Example 1 was performed until an aqueous dispersion of a conductive polymer having a concentration of 3% was obtained. 200 g of ethylene glycol was added to 50 g of this aqueous dispersion of conductive polymer, and the mixture was concentrated by distillation in a water bath at 40 ° C. under a vacuum degree of 20 hPa.

  When about 30 g of water flowed out, concentration was stopped and the water content was measured by Karl Fischer. As a result, it was 9% and the solid content was 0.7%. However, when this organic solvent-based dispersion was allowed to stand for 1 day at 5 ° C., the conductive polymer aggregated, lacked stability, and was not practical.

[Evaluation as antistatic film]
Example 7
To 15 g of the organic solvent-based conductive polymer dispersion prepared in Example 1, 20 g of Acrydic A801 (trade name, acrylic resin manufactured by DIC), 30 g of methyl ethyl ketone and 20 g of isopropyl alcohol were added as a binder resin, and mixed by stirring. As a result, an organic solvent-based conductive polymer-containing resin composition dispersion was obtained without aggregation of the added binder resin. Then, 400 μL of the organic solvent-based conductive polymer-containing resin composition dispersion liquid was dropped on a 10 cm × 20 cm polyethylene sheet as a base sheet. After making it uniform with 12 bar coaters, it was dried at 150 ° C. for 2 minutes to produce an antistatic film comprising a film of a conductive polymer-containing resin composition.

Example 8
When 10 g of the organic solvent-based conductive polymer dispersion prepared in Example 2 is added as a binder resin, 20 g of Acrydic A801 (supra), 35 g of methyl ethyl ketone and 20 g of isopropyl alcohol are stirred and mixed, aggregation occurs. Thus, an organic solvent-based conductive polymer-containing resin composition dispersion was obtained. Then, 400 μL of the organic solvent-based conductive polymer-containing resin composition dispersion liquid was dropped on a 10 cm × 20 cm polyethylene sheet as a base sheet. After making it uniform with 12 bar coaters, it was dried at 150 ° C. for 2 minutes to produce an antistatic film comprising a film of a conductive polymer-containing resin composition.

Example 9
When 15 g of the organic solvent-based conductive polymer dispersion prepared in Example 3 is added as a binder resin, 20 g of Acrydic A801 (supra), 30 g of methyl ethyl ketone and 20 g of isopropyl alcohol are stirred and mixed, aggregation occurs. Thus, an organic solvent-based conductive polymer-containing resin composition dispersion was obtained. Then, 400 μL of the organic solvent-based conductive polymer-containing resin composition dispersion was dropped onto a 10 cm × 20 cm polyethylene sheet as a base sheet, After making it uniform with 12 bar coaters, it was dried at 150 ° C. for 2 minutes to produce an antistatic film comprising a film of a conductive polymer-containing resin composition.

Comparative Example 5
The same operation as in Example 1 was carried out until a 30% conductive polymer aqueous dispersion was obtained, and Acrydic A801 was used as a binder resin with respect to 25 g of the conductive polymer aqueous dispersion thus obtained. (Above) When 20 g, 30 g of methyl ethyl ketone and 30 g of isopropyl alcohol were added and stirred and mixed, immediately after mixing, agglomeration of Acrydic A801, a resin for binder, occurred, and a uniform organic solvent-based conductive polymer-containing resin composition dispersion liquid As a result, a film could not be formed.

  The surface resistance of the obtained antistatic films of Examples 7 to 9 was measured at room temperature (about 25 ° C.) according to JIS K 7194, a four-probe conductivity meter [MCP-T600 (trade name, manufactured by Mitsubishi Chemical Corporation). )] And the visible light transmittance at a wavelength of 400 nm to 700 nm was measured by UV-VIS-NIR RECORDING SPECTROTOPOMETER [UV3100 (trade name) manufactured by Shimadzu Corporation]. It shows in Table 1 with the kind of organic-solvent type conductive polymer dispersion using the result. In addition, measurement is performed for each sample for five points, and the numerical values shown in Table 1 are obtained by calculating an average value of the five points and rounding off the decimals.

[Evaluation with a wound aluminum solid electrolytic capacitor]
Example 10
After etching the surface of the aluminum foil, a lead terminal is attached to the anode on which the dielectric layer is formed by performing a chemical conversion treatment, and the lead terminal is attached to the cathode made of aluminum foil. Was wound through a separator to produce a capacitor element.

  The capacitor element was immersed in the organic solvent-based conductive polymer dispersion obtained in Example 1, taken out after 120 seconds, and dried at 180 ° C. for 30 minutes. This operation was repeated 4 times, and then allowed to stand at 200 ° C. for 30 minutes to form a solid electrolyte layer made of a conductive polymer. Then, it was put in an aluminum outer case and sealed to produce a wound aluminum solid electrolytic capacitor.

Example 11
The same operation as in Example 10 was performed except that the organic solvent-based conductive polymer dispersion obtained in Example 5 was used instead of the organic solvent-based conductive polymer dispersion obtained in Example 1. A wound aluminum solid electrolytic capacitor was produced.

Comparative Example 6
The same operation as in Example 1 was performed until a 3% conductive polymer aqueous dispersion was obtained, and the conductive polymer aqueous dispersion obtained thereby was obtained as the organic solvent obtained in Example 1. A wound aluminum solid electrolytic capacitor was produced in the same manner as in Example 10 except that the conductive polymer dispersion was used instead of the conductive polymer dispersion.

  For the wound aluminum solid electrolytic capacitors of Examples 10 and 11 and Comparative Example 6 produced as described above, their ESR (equivalent series resistance), capacitance and leakage current were measured. The results are shown in Table 2. In addition, the measuring method of ESR, an electrostatic capacitance, and a leakage current is as showing below. The ESR is measured using an LCR meter (4284A) manufactured by HEWLETT PACKARD at 25 ° C. and 100 kHz, and the capacitance is measured using an LCR meter (4284A) manufactured by HEWLETT PACKARD at 25 ° C. The electrostatic capacity was measured at 120 Hz. The leakage current was measured by applying a rated voltage of 25 ° C. and 25 V for 60 seconds, and then measuring the leakage current with a digital oscilloscope. Each sample was measured for 10 samples, and the ESR value, capacitance value, and leakage current value shown in Table 2 were obtained by calculating the average of those 10 values and rounding off the decimals. It is.

  As shown in Table 2, the wound aluminum solid electrolytic capacitors of Example 10 and Example 11 had a leakage current two orders of magnitude lower than that of the wound aluminum solid electrolytic capacitor of Comparative Example 6. This is because the wound aluminum solid electrolytic capacitor of Comparative Example 6 uses an aqueous dispersion of a conductive polymer for its production, and therefore the surface of the oxide film constituting the dielectric layer is corroded with water. it is conceivable that.

  As described above, the wound aluminum solid electrolytic capacitors of Example 10 and Example 11 have lower leakage current and less power loss as a capacitor than the wound aluminum solid electrolytic capacitor of Comparative Example 6. In addition to this, the ESR was small, the capacitance was large, and no deterioration in characteristics due to the use of the conductive polymer as an organic solvent-based dispersion was observed.

Claims (12)

(1) Conduction is conducted by synthesizing a conductive polymer by oxidative polymerization of thiophene or a derivative thereof in water or an aqueous liquid composed of a mixture of water and a water-miscible solvent in the presence of a polymer sulfonic acid as a dopant. Obtaining an aqueous dispersion of a functional polymer;
(2) adding a non-aqueous amine to the aqueous dispersion of the conductive polymer to aggregate the conductive polymer;
(3) a step of taking out the aggregate of the conductive polymer from water or an aqueous liquid;
(4) An organic solvent-based conductive polymer dispersion having a water content of 10% by mass or less, wherein the conductive polymer aggregate is produced through a step of dispersing the aggregate of the conductive polymer in an organic solvent. Production method. The method for producing an organic solvent-based conductive polymer dispersion according to claim 1, wherein the non-aqueous amine is an amine represented by the following general formula (1).
R ₁ —NH ₂ (1)
(In the formula, R ₁ is an alkyl group having 6 to 30 carbon atoms, and the alkyl group may be linear or branched. The alkyl group may contain an ether bond, an ester bond or a double bond in the molecular chain, and the hydrogen atom may be substituted with another atom)   The method for producing an organic solvent-based conductive polymer dispersion according to claim 1, wherein the polymer sulfonic acid is at least one selected from the group consisting of polystyrene sulfonic acid, sulfonated polyester, and phenolsulfonic acid novolak resin.   A conductive polymer obtained by drying the organic solvent-based conductive polymer dispersion according to claim 1.   An organic solvent-based conductive polymer-containing resin composition dispersion obtained by mixing the organic solvent-based conductive polymer dispersion according to any one of claims 1 to 3 and a binder resin. .   A conductive polymer-containing resin composition obtained by drying the organic solvent-based conductive polymer-containing resin dispersion according to claim 5.   An antistatic film comprising a conductive polymer-containing resin composition film obtained by drying the organic solvent-based conductive polymer-containing resin composition dispersion according to claim 5.   The conductive polymer-containing resin composition film obtained by drying the organic solvent-based conductive polymer-containing resin composition dispersion according to claim 5 is used as a conductive layer on one or both sides of the base sheet. An antistatic sheet characterized by the above.   A solid electrolytic capacitor, wherein the conductive polymer obtained by drying the organic solvent-based conductive polymer dispersion according to claim 1 is used as a solid electrolyte.   A solid electrolytic capacitor comprising a conductive polymer-containing resin composition obtained by drying the organic solvent-based conductive polymer-containing resin composition dispersion according to claim 5 as a solid electrolyte.   In manufacturing a solid electrolytic capacitor having an anode made of a porous body of valve metal such as tantalum, niobium or aluminum, a dielectric layer made of an oxide film of the valve metal, and a solid electrolyte, any one of claims 1 to 3. A capacitor element is immersed in the organic solvent-based conductive polymer dispersion liquid or obtained by applying the organic solvent-based conductive polymer dispersion liquid according to claim 1 to the capacitor element and drying. A method for producing a solid electrolytic capacitor, wherein the conductive polymer used is a solid electrolyte. 6. An organic solvent-based conductive material according to claim 5, in manufacturing a solid electrolytic capacitor having an anode made of a porous body of valve metal such as tantalum, niobium or aluminum, a dielectric layer made of an oxide film of the valve metal, and a solid electrolyte. A capacitor element is immersed in the polymer-containing resin composition dispersion, or the organic solvent-based conductive polymer-containing resin composition dispersion according to claim 5 is applied to the capacitor element and dried. A method for producing a solid electrolytic capacitor, wherein the molecule-containing resin composition is used as a solid electrolyte.