CN101302340A - Conductive composite body, conductive polymer composition and electronic component using the conductive polymer composition - Google Patents
Conductive composite body, conductive polymer composition and electronic component using the conductive polymer composition Download PDFInfo
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Abstract
The invention provides a conducting complex which is combined by a conducting polymer A and a compound B except for the conducting polymer, and also can comprise polyanion, wherein, the compound B is polyethylene and derivates thereof, polyvinyl ether and derivates thereof, polyacrylamide and derivates thereof, polyacrylic acid and derivates thereof, etc. The conducting complex improves clinging property and filming property for matrix, and can maintain low specific resistance in a high-temperature environment. A conducting polymer composition comprises the conducting complex, has reduced specific resistance, and can maintain low specific resistance in a high-temperature environment. The invention also provides an electronic element with excellent performance through using a coating of the conducting complex and the conducting polymer composition. The coating of the conducting complex or the conducting polymer composition can be used in a solid electrolytic capacitor, a solar cell, an organic light emitting diode, an electroluminance, a display, an electrostatic copying part, a transfer printing part, a battery, epaper, a touch panel, an organic thin-filmtransistor, a field emission display (FED) and so on.
Description
Technical field
The present invention relates to conductive composite body, conductive polymer composition relates to and is used for electronic component.
Background technology
The conductive polymer composition that comprises electric conductive polymer is expected to be applied to: the purposes that the needs electricity is led, electrically conducting coating, antistatic agent, electromagnetic shielding material, the electro-conductive material of the transparency, battery material, capacitor material, transmitter, electronic material, semiconductive material, solar cell, Organic Light Emitting Diode, field emission type display (FED), touch-screen, EL sheet (Electroluminance), OTFT (Organic thin-film transistor), electrostatic duplicating parts, transfer member, Electronic Paper (epaper), electrofax material etc.
Particularly in recent years, along with the digitizing of electronic machine, require to reduce of the impedance of employed electrical condenser gradually at high-frequency region.For adapting to this requirement, used gradually and had for example by aluminium, tantalum (Ta), the anode that the porous insert of the metal of niobium valve actions such as (Nb) constitutes, the dielectric oxide film that constitutes by the oxide film of the metal of described valve action, on this oxide film, form electric conductive polymer layer then as solid electrolyte, carbon-coating, and the negative electrode that silver layer forms obtains.
As the electric conductive polymer layer of the solid electrolyte of this functional electric container, use the pyrroles, thiophene, aniline etc. are as monomer.When the conductive polymers that forms as described electrical condenser solid electrolyte, the main chemical oxidative polymerization method that uses, this method is by adding oxygenant and doping agent in conductive polymers, form conductive polymer coating (referring to patent documentation 1, for example Japanese Unexamined Patent Application publication spy opens flat 05-166681) thereby on the oxide film of metal porous body, induce reaction.
On the other hand, also use following technology, on the oxide film of metal porous body, do not carry out polymerization, but by preparing the soluble conductive polymers soln independently, flood this polymers soln and enter metal porous body, be dried to then and film, thereby on oxide film, form conductive polymer coating (referring to patent documentation 2, for example Japanese Unexamined Patent Application discloses 2001-023437).
In the technology of patent documentation 2, the molecular weight of soluble conductive polymkeric substance is with in the technology of patent documentation 2, the molecular weight of soluble conductive polymkeric substance enters porous insert inside with it perviousness is generally inverse relation, and the resistance of filming and the molecular weight of conductive polymers then tend to proportional.Therefore, if only form the solid electrolyte of electrical condenser with the soluble conductive polymers soln, then the ESR of electrical condenser and electric capacity have both and select one relation, so the example of this type of use is seldom.
In fact, usually so use the soluble conductive polymers soln:
(1) although its perviousness that enters porous insert is low, the soluble polymer that molecular weight is big is used to prepare and can forms the soluble polymer solution with low-resistance polymer layer, thereby is combined near the conductive polymer coating that forms big thickness the outermost surface of porous insert with chemical oxidative polymerization method.
(2) although its resistance height, the soluble polymer that molecular weight is little is used to prepare even also can promote in porous insert inside the soluble polymer solution of conductive polymer coating formation, thereby combines polymer layer as the matrix in the electrolytic polymerization with the electrolytic polymerization method.
3,4-ethylene dioxythiophene (below be called " EDOT) is oneself monomer through beginning to be used widely, and the big characteristics of one can obtain the low resistance conductive polymers exactly, therefore; when EDOT is used for the soluble conductive polymkeric substance, the normal using method that is similar to (1) of using.Now, when using the method for similar (1), compare with the conductive polymers that only forms by chemical oxidising polymerisation, the conductive polymers that is formed by the soluble conductive polymers soln can only form has several times to 100 times or the polymer layer of high resistivity more, in addition, its stability at high temperature is also poor, and resistance can raise at short notice, is a problem in solid electrolytic capacitor is used.
Usually, so-called electric conductive polymer is the polypyrrole class, polythiophene class, and the polyacetylene class, poly-inferior benzene class, polyphenylene 1, the inferior vinyl of 2-, polyaniline compound, the metaldehyde class, poly-vinylene thiophene-based, and these multipolymer etc.These electric conductive polymers can be by chemical oxidative polymerization and the preparation of solid electrolytic polymerization.
In the solid electrolytic polymerization, but in the solid electrolyte mixing solutions that monomer and doping agent by electric conductive polymer constitute, add preformed electrode materials, on electrode, electric conductive polymer is formed film like.Therefore, be difficult to preparation in large quantities.
In contrast to this, in chemical oxidative polymerization, do not have such restriction, the monomer of electric conductive polymer, suitable oxygenant and catalyzer, can be in solution a large amount of electric conductive polymer of polymerization.But, in chemical oxidative polymerization, along with the growth of electric conductive polymer main chain, for the solvability reduction of organic solvent.Therefore, what obtain mostly is insoluble solid shape powder, therefore, is difficult to use with this state.
For addressing this is that, such scheme has been proposed: by importing suitable substituting group or using the polyanion based compound to carry out solubilize to organic solvent.As the example of soluble conductive polymkeric substance, the Baytron-P of H.C.Starck-V TECH Ltd. production etc. is arranged on market.Yet, this polymkeric substance have high resistance and under high-temperature resistance enlarge markedly.
Summary of the invention
The present invention is for solving the high resistance problem of electric conductive polymer, and resistance enlarges markedly problem under high-temperature, and problem such as solvability.And the performance of the electronic component of the electric conductive polymer after the solution use polymerization, and the performance that solves under the hot environment is hanged down inferior problem.
The present invention provides a kind of conductive composite body, and this conductive composite body is to have the close property of enhancing to base material, the system film, and under hot environment, also can keep low-resistivity.This conductive composite body is by pyroles and derivative thereof, thiophene-based and derivative thereof, aniline and derivative thereof, metaldehyde class and derivative thereof, poly-1,2-vinylidene thiophene-based and derivative thereof, and the electric conductive polymer A of formation such as the multipolymer of these compounds and the compd B beyond this electric conductive polymer in conjunction with and form.
The present invention also provides a kind of conductive polymer composition, and this conductive polymer composition is to have the resistivity that reduces, and also can keep low-resistivity under hot environment.This conductive polymer composition comprises conductive composite body.
Another object of the present invention is by using filming of above-mentioned conductive composite body or conductive polymer composition, a kind of electronic component with excellent properties being provided.For example: solid electrolytic capacitor, solar cell, Organic Light Emitting Diode, EL sheet (Electroluminance), indicating meter, electrostatic duplicating parts, transfer member, battery, Electronic Paper (epaper), touch-screen (touch panel), OTFT (Organicthin-film transistor), field emission type display (FED) etc.
Conductive composite body of the present invention is by pyroles and derivative thereof, thiophene-based and derivative thereof, aniline and derivative thereof, metaldehyde class and derivative thereof, poly-1,2-vinylidene thiophene-based and derivative thereof, and the electric conductive polymer A that constitutes such as the multipolymer of these compounds and by replacing or unsubstituted polyethylene kind and derivative thereof, replace or unsubstituted glymes and derivative thereof, replace or unsubstituted polyacrylamide and derivative thereof, replace or unsubstituted polyacrylic and derivative thereof, replace or unsubstituted poly-phthalimide class and derivative thereof, replace or unsubstituted poly-phthalein amine and derivative thereof, replace or unsubstituted polyvinyl alcohol and derivative thereof, replace or unsubstituted poly-vinegar class and derivative thereof, replace or unsubstituted polyethylene glycols and derivative thereof, replace or unsubstituted poly-fluorochemical class and derivative thereof siliceous class and derivative thereof, and the compd B of these formation such as copolymerization combination and forming.
Compd B preferably contains carboxyl, amino, and-oxyl, carbonyl, sulfonic group, amide group, the fat-oxyl, ester group, ether, epoxy group(ing), aryl, aromatic series contains halogen, and is silica-based, fluorine-based, and electronics supplies and property base, electron attractivity base etc.
Conductive polymer composition of the present invention contains conductive composite body at least, can also contain polyanion, doping agent, and electroconductibility is adjusted wedding agent, resinous principle, conductive particle etc.
Conductive polymer composition of the present invention and conductive composite body can use the electrical conductor at electronic component.
Conductive composite body in the present invention and conductive polymer composition can obtain having the close property of enhancing to base material, system film, bridge formation, the excellent in stability of the relative outside atmosphere of specific conductivity, and thermotolerance, permanent stability etc.
Filming of conductive composite body of the present invention or conductive polymer composition can obtain excellent properties when being applied to electronic component.The solid electrolytic capacitor of using, the solid electrolytic capacitor that can obtain having excellent ESR property.And under hot environment, also can keep the performance of solid electrolytic capacitor.
Embodiment
Below, preference of the present invention is described.But the present invention is not limited to following each example.For example, the integrant of these examples and mode correspondence or appropriate combination mutually to each other.
Conductive composite body of the present invention is by pyroles and derivative thereof, thiophene-based and derivative thereof, aniline and derivative thereof, metaldehyde class and derivative thereof, poly-1,2-vinylidene thiophene-based and derivative thereof, and the electric conductive polymer A that constitutes such as the multipolymer of these compounds and by replacing or unsubstituted polyethylene kind and derivative thereof, replace or unsubstituted glymes and derivative thereof, replace or unsubstituted polyacrylamide and derivative thereof, replace or unsubstituted polyacrylic and derivative thereof, replace or unsubstituted poly-phthalimide class and derivative thereof, replace or unsubstituted poly-phthalein amine and derivative thereof, replace or unsubstituted polyvinyl alcoholization and derivative thereof, replace or unsubstituted poly-vinegar class and derivative thereof, replace or unsubstituted polyethylene glycols and derivative thereof, replace or unsubstituted poly-fluorochemical class and derivative thereof siliceous class and derivative thereof, and the compd B of these formation such as copolymerization combination and forming.
Conductive polymer composition of the present invention can also contain conductive composite body and polyanion, doping agent, and electroconductibility is adjusted wedding agent, resinous principle, conductive particle etc.
(conductive composite body)
Conductive composite body of the present invention is that user's chemical oxidative polymerization is synthetic, after by oxygenant or catalyzer polymerisable electric conductive polymer free oxygen being changed into electric conductive polymer, in the presence of oxygenant or catalyzer, obtain with the polymer reaction of reactive compounds B or reactive compounds B.When the growth step of reaction of electric conductive polymer is added reactive compounds B, generation association reaction between electric conductive polymer and the reactive compounds B and the conductive composite body that forms.
(electric conductive polymer)
In conductive composite body of the present invention, so long as main chain is got final product by the organic polymer that common rail system constitutes, there is not particular restriction as electric conductive polymer.For example can enumerate: polypyrrole class and derivative thereof, polythiophene class and derivative thereof, polyacetylene class and derivative thereof, poly-inferior benzene class and derivative thereof, polyphenylene 1, inferior vinyl of 2-and derivative thereof, polyaniline compound and derivative thereof, metaldehyde class and derivative thereof, poly-1,2-vinylidene thiophene-based and derivative thereof, and these multipolymer etc.Especially from chemical stabilization under air atmosphere, the good aspect of operability is considered, preferably uses the polypyrrole class,, polythiophene class, polyphenylene 1, the inferior vinyl of 2-, polyaniline compound.
Object lesson as the electric conductive polymer of preferred use can be enumerated: polypyrrole, poly-(3-methyl) pyrroles, poly-(3-ethyl) pyrroles, poly-(3-carboxyl) pyrroles, poly-(3-methyl-4-carboxyl) pyrroles, poly-(3-methyl-4-propyloic) pyrroles, poly-(3-hydroxyl) pyrroles, poly-(3-methoxyl group) pyrroles, poly-(3-oxyethyl group) pyrroles, poly-(3-butoxy) pyrroles, poly-(3-hexyloxy) pyrroles, poly-(3-methyl-4-hexyloxy) pyrroles waits the polypyrrole class; Polythiophene, poly-(3-methyl) thiophene, poly-(3-hexyl) thiophene, poly-(3-decyl) thiophene, poly-(3-phenyl) thiophene, poly-(3-dodecyl) thiophene, poly-(3, the 4-dimethyl) thiophene, poly-(3-hydroxyl) thiophene, poly-(3-methoxyl group) thiophene, poly-(3-oxyethyl group) thiophene, poly-(3-butoxy) thiophene, poly-(3-hexyloxy) thiophene, poly-(3-octyloxy) thiophene, poly-(3-oxygen in last of the ten Heavenly stems base) thiophene, poly-(3-dodecyloxy) thiophene, poly-(3, the 4-dihydroxyl) thiophene, poly-(3, the 4-dimethoxy) thiophene, poly-(3, the 4-diethoxy) thiophene, poly-(3,4-two hexyloxy) thiophene, poly-(3,4-oxygen base in two heptan) thiophene, poly-(3,4-two octyloxies) thiophene, poly-(3,4-didecyl oxygen base) thiophene, poly-(3,4-docosane oxygen base) thiophene, poly-(3, the 4-ethylenedioxy) thiophene, poly-(3, the inferior third dioxy base of 4-) thiophene, poly-(3,4-butylene dihydroxyl) thiophene, poly-(3-methyl-4-methoxyl group) thiophene, poly-(3,4-ethylene dioxy base) thiophene, polythiophene class and polyanilines such as poly-(3,4-butylene dioxy base) thiophene, poly-(2-aniline sulfonic acid), poly-polyaniline compounds such as (3-aniline sulfonic acid) etc.
These electric conductive polymers can prepare by chemical oxidative polymerization.Under the condition that has oxygenant or catalyzer, change into electric conductive polymer from polymerisable electric conductive polymer free oxygen.As long as having more than 2, the polymeric unit of electric conductive polymer can obtain good electrical conductivity.
The monomeric object lesson of polymerisable electric conductive polymer as preferred use can be enumerated: pyrroles, 3-methylpyrrole, 3-N-ethyl pyrrole N-, the 3-carboxy pyrrole, 3-methyl-4-carboxy pyrrole, 3-methyl-4-propyloic pyrroles, 3-hydroxyl pyrroles, 3-methoxyl group pyrroles, 3-oxyethyl group pyrroles, 3-butoxy pyrroles 3-hexyloxy pyrroles, 3-methyl-4-hexyloxy pyrroles, thiophene, 3 methyl thiophene, 3-hexyl thiophene, 3-decylthiophene, 3-phenyl thiophene, 3-dodecyl thiophene, 3, the 4-thioxene, 3-hydroxyl thiophene, 3-methoxythiophene, 3-oxyethyl group thiophene, 3-butoxy thiophene, 3-hexyloxy thiophene, 3-octyloxy thiophene, 3-oxygen in last of the ten Heavenly stems base thiophene, 3-dodecyloxy thiophene, 3,4-dihydroxyl thiophene, 3, the 4-dimethoxy-thiophene, 3,4-diethoxy thiophene, 3,4-two hexyloxy thiophene, 3,4-oxygen base in two heptan thiophene, 3,4-two octyloxy thiophene, 3,4-didecyl oxygen base thiophene, 3,4-docosane oxygen base thiophene, 3, the 4-Ethylenedioxy Thiophene, 3, the inferior third dioxy base thiophene of 4-, 3,4-butylene dihydroxyl thiophene, 3-methyl-4-methoxythiophene, 3, the 4-ethylene dioxythiophene, 3,4-butylene dioxy base thiophene, aniline, 2-aniline sulfonic acid, 3-aniline sulfonic acid etc.
Can use peroxydisulfate such as ammonium peroxydisulfate, Sodium persulfate, Potassium Persulfate as oxygenant, iron(ic) chloride, ferric sulfate, cupric chloride, transistion metal compounds such as tosic acid iron, silver suboxide, Cs2O metal oxides such as (se), hydrogen peroxide, superoxide such as ozone, organo-peroxides such as peroxidation benzene first phthalein, oxygen etc.
As the solvent of chemical oxidising polymerisation,, for example can enumerate: water, N-Methyl pyrrolidone (NMP) so long as the solvent of solubilized or dispersion oxygenant or oxypolymerization catalyzer gets final product, N, N '-dimethyl methyl phthalein amine (DMF), N, N '-dimethyl second phthalein amine (DMAc), dimethyl sulfoxide (DMSO) (DMSO), methylphenol, phenol, xylenol, methyl alcohol, ethanol, propyl alcohol, butanols, acetone, methyl ethyl ketone, hexane, benzene, toluene, formic acid, acetate, ethylene carbonate vinegar, propylene carbonate vinegar, dioxane, diethyl ether, dialkyl ether ethylene glycol vinegar, dialkyl ether propylene glycol vinegar, poly-dialkyl ether ethylene glycol vinegar, poly-dialkyl ether propylene glycol vinegar, second eyeball, methoxyl group second eyeball, propionitrile, benzene eyeball, glycol, glycerine, triethylene glycol butyl ether triethylene glycol butyl ether, triethylene glycol butyl ether, the triethylene glycol monobutyl ether, triglycol butyl ether, butoxy triethylene glycol ether etc.As required, these solvents can be independent, two or more mixing, or mix use with other organic solvents.
As polymerization temperature, as long as, be preferable over 0-130 ℃-30-200 ℃ scope.
Conductive composite body of the present invention is in the presence of oxygenant or catalyzer, behind the polymerization electric conductive polymer, in the presence of oxygenant or catalyzer, obtains with the polymer reaction of reactive compounds B or reactive compounds B.As required, can in the presence of doping agent and polyanion, carry out oxypolymerization.
(compd B)
In conductive composite body of the present invention, as compd B so long as can and electric conductive polymer be reacted into complex body and get final product, do not have particular restriction.For example can enumerate: by replacing or unsubstituted polyethylene kind and derivative (alkylene) thereof, replace or unsubstituted glymes and derivative thereof, replace or unsubstituted polyacrylamide and derivative (Acrylamide) thereof, replace or unsubstituted polyacrylic and derivative (Acryl) thereof, replace or unsubstituted poly-phthalimide class and derivative thereof, replace or unsubstituted poly-phthalein amine-phthalimide and derivative thereof, replace or unsubstituted poly-phthalein amine and derivative thereof, replace or unsubstituted polyvinyl alcohol and derivative thereof, replace or unsubstituted poly-vinegar class and derivative thereof, replace or unsubstituted polyethylene glycols and derivative thereof, replace or unsubstituted glycerols and derivative thereof, replace or unsubstituted poly-fluorochemical class and derivative thereof, siliceous class and derivative thereof, and these copolymerization etc.
There is not particular restriction as substituting group.Be preferably: alkyl, carboxyl (COOR), amino (NH),-oxyl (HO), carbonyl (CO), sulfonic group (SO3H), amide group (CONRR), fat-oxyl (alkoxyl), ester group (ester), ether (ether), epoxy group(ing), silica-based, fluorine-based, aryl, electronics supplies and property base, electron attractivity base etc.
Compd B is preferably: polyethylene kind and derivative thereof, glymes and derivative thereof, polyacrylamide and derivative thereof (Acrylamide), polyacrylic and derivative thereof (Acryl), polyvinyl alcohol and derivative thereof, poly-vinegar class and derivative thereof, polyethylene glycols and derivative thereof, Polyglycerine class and derivative thereof, poly-fluorochemical class and derivative thereof, and these copolymerization etc.The polymkeric substance of these compounds is in the presence of oxygenant or catalyzer, and the reactive compounds of these compounds reacts and obtains.For example can enumerate as the preferred reactive compound: ethene, propylene, divinyl, vinylbenzene (SM), 2, the 3-dichloropropylene, 1, the 3-dichloropropylene, vinylcarbinol, acrylate chloride, the ethene imidazoles, V-Pyrol RC, the ethene dimethyl sulfoxide (DMSO), divinylsulfone, iso-butylene, diallyl amine, the N-vinyl carbazole, the ethene triazole, vinylpyridine, the ethene pyrazoles, vinyl cyanide (AN), vinyl acetate between to for plastic (VAM), acrylamide (AM), Methacrylamide (MAM), N-alkyl acrylamide, N hydroxymethyl acrylamide (N-MAM), acrylic acid amides, vinylformic acid hydroxyl phthalein amine (HEAA), vinylformic acid (AA), methacrylic acid (MAA), methyl acrylate (MA), methyl methacrylate (MMA), ethyl propenoate (EA), Jia Jibingxisuanyizhi (EMA), butyl acrylate (BA), butyl methacrylate, Isooctyl acrylate monomer (2-EHA), propylene phthalein amine, N, N-dimethyl second phthalein amine (DMA), N,N-DMAA, N, N '-methylene-bisacrylamide (DMAM), ethene methyl first phthalein amine, n-methylolacrylamide, the hydroxyethyl acrylamide, N, N-dioctyl acrylamide, methene base bisacrylamide, Hydroxyethyl acrylate (HEA), hydroxyethyl methylacrylate (HEMA), Propylene glycol monoacrylate (HPA), Rocryl 410, Rocryl 410 (HPMA), vinylformic acid hydroxy butyl ester (HBA), n-BMA (nBMA), Propenoic acid, 2-methyl, isobutyl ester (IBMA), Isooctyl methacrylate (EHMA), isobornyl methacrylate (IBOMA), glycidyl methacrylate (GMA), cyclohexyl methacrylate (CHMA), tri (propylene glycol) diacrylate (TPGDA), 1,4 butanediol diacrylate (BDDA), Ethylene glycol dimethacrylate (EGDMA), neopentylglycol diacrylate (NPGDA), Viscoat 295 (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), methylmaleic acid, lauryl methacrylate(LMA) (LMA), vinyl sulfonic acid and vinyl sulfonate, styrene sulfonic acid and styrene sulfonate, vinylformic acid vinyl sulfonic acid and vinylformic acid vinyl sulfonate, first for allyl sulfonic acid and first for allyl sulfonate, methyl allyloxy Phenylsulfonic acid and methyl allyloxy benzene sulfonate, vinylidenefluoride, R 1216 etc.
As oxygenant, catalyzer can use oxygenant recited above and catalyzer, also can use the photopolymerization catalyzer.
As the temperature of reaction of compd B, so long as-scope of 30-200 ℃ gets final product, and preferred 0-130 ℃, more preferably 20-90 ℃.
In this conductive composite body, the mass ratio of electric conductive polymer and compd B (electric conductive polymer: compd B) preferred 95: 5-1: 99, more preferably 80: 20-5: 95.As long as in this scope, then electroconductibility and solvent solubility are all high, but when compd B is lower than this scope, the inadequate tendency of solvent solubility and close property are arranged then.When being higher than this scope, then can not obtain sufficient electroconductibility sometimes.
(polyanion)
In conductive composite body of the present invention, except that compd B and electric conductive polymer, can also contain polyanion, when containing polyanion, conductive composite body can obtain good solubility and electroconductibility.
So long as side chain has the carboxylic acid group, sulfonic polymer can use as polyanion.For example can enumerate as main chain: the polyalkylene compound that main chain is made of repeatedly methylene radical, main chain contain the poly-alkenylene compound of the component unit formation of vinyl, poly-vinegar resin, poly-phthalein polyimide resin, poly-phthalimide resin, fluoro-resin, ethenoid resin, Resins, epoxy, xylene resin, the aramid resin, polyurethane is a resin, melmac, phenolic resin, polyethers, acrylic resin and these compositions such as copolymer resins.Polyanion can be that polymerizable monomer and carboxylic acid are that polymerizable monomer obtains with polymerization by sulfonic acid, also can get multipolymer with other polymerizable monomers as required.Can enumerate as concrete example: replace or unsubstituted vinyl sulfonic acid compound, replace or unsubstituted styrene sulfonic acid compound, replace or unsubstituted heterocycle sulfoacid compound, replace or unsubstituted propylene phthalein amine sulfoacid compound, replace or the inferior vinyl sulfonic acid compound of unsubstituted ring, replace or unsubstituted vinyl aromatic sulfoacid compound replacement or unsubstituted vinylformic acid etc.Can enumerate as other polymerizable monomers: replace or unsubstituted vinyl compound, the substitutional crylic acid compound, replace or unsubstituted vinylbenzene, replace or unsubstituted vinyl-amine, the heterogeneous ring compound that contains unsaturated group, replace or unsubstituted propylene phthalein amine compound, replace or unsubstituted ring vinylidene compound, replace or unsubstituted adiene cpd, replace or unsubstituted vinyl aromatic compound, replace or unsubstituted divinyl benzene compound substituted ethylene base oxybenzene compound, replace silyl vinylbenzene arbitrarily, arbitrarily 5-substituted phenol compounds etc.
Can use peroxydisulfate such as ammonium peroxydisulfate, Sodium persulfate, Potassium Persulfate as polymerizing catalyst and oxygenant, iron(ic) chloride, ferric sulfate, cupric chloride, transistion metal compounds such as tosic acid iron, silver suboxide, metal oxides such as Cs2O, hydrogen peroxide, superoxide such as ozone, organo-peroxides such as peroxidation benzene first phthalein, oxygen, photopolymerization catalyzer etc.
The object lesson of poly-sulfonic acid can be enumerated: polyvinyl sulfonic acid with and salt, polystyrolsulfon acid with and salt, the polyacrylic acid vinyl sulfonic acid with and salt, poly-first for allyl sulfonic acid with and salt, poly-methyl allyloxy Phenylsulfonic acid with and salt, poly-sulfonic acid vinegar resin with and salt, poly-sulfonic acid phthalimide resin with and salt etc.
The molecular-weight average of poly-sulfonic acid is so long as 1,000-1, and 000,000 scope gets final product, and preferable range is 5,000-500,000.
As the positively charged ion of polysulfonate for example: tetramethyl ammonium, tetraethyl-ammonium salt, tetrapropyl ammonium salt, 4-butyl ammonium, tetrahexyl ammonium salt, trimethylammonium ethyl ammonium salt, trimethylphenyl ammonium salt, triethyl phenyl ammonium salt, Three methyl Benzene idol phthalein ammonium salt, 4 grades of ammonium salts such as trimethylammonium octyl group ammonium salt, metal cation salt, imidazole-like ionic salt, pyridines ion salt etc.
In this conduction complex body, the mass ratio of poly-sulfonic acid and electric conductive polymer (poly-sulfonic acid: electric conductive polymer) preferred 99: 1-1: 99, more preferably 95: 5-10: 90, most preferably 80: 20-30: 70.As long as in this scope, then electroconductibility and solvent solubility are all high, but when poly-sulfonic acid is lower than this scope, the inadequate tendency of solvent solubility are arranged then.When being higher than this scope, then can not obtain sufficient electroconductibility sometimes.
(doping agent and electroconductibility are adjusted wedding agent)
Can mixing and doping agent and electroconductibility adjustment wedding agent in order to improve its electroconductibility of described electric conductive polymer.Electroconductibility is adjusted the performance that wedding agent is adjusted film-forming properties in addition.
As long as can produce redox reaction with electric conductive polymer, do not limit electron acceptor or electronics and supply and body as doping agent.For example: halogen compound, Lewis acid, protonic acid etc.Can enumerate chlorine, iodine, iodine chloride, fuorine iodine etc. as halogen compound.In addition, can enumerate phosphorus pentafluoride (PF5), arsenic pentafluoride (AsF5), boron trifluoride (BF3), boron trichloride (BC13) etc. as Lewis acid.In addition, can enumerate as protonic acid: hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, fluoroboric acid, mineral acids such as hydrofluoric acid, organic carboxyl acid, organic acids such as organic sulfonic acid, organic cyanogen compound etc.
Can use in aliphatics as organic carboxyl acid, aromatic series contains one or more carboxylic acid groups' material on the annular aliphatic etc.For example can enumerate: formic acid, acetate, oxalic acid, M-nitro benzoic acid, phthalic acid, toxilic acid, fumaric acid, propanedioic acid, tartrate, citric acid, lactic acid, Monochloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA), trifluoroacetic acid, nitroacetic acid, triphenylacetic acid etc.Also can use these amine salt, metal-salt.
Can use in aliphatics as organic sulfonic acid, aromatic series, annular aliphatics etc. are gone up in conjunction with one or more sulfonic materials.Can enumerate as organic sulfonic acid: methylsulphonic acid, ethylsulfonic acid, trifluoromethane sulfonic acid, Phenylsulfonic acid, tosic acid, xylene monosulfonic acid, ethyl phenenyl azochlorosulfonate acid, 2, the 4-acid dimethyl, the dipropyl Phenylsulfonic acid, 4-aniline sulfonic acid, p-chlorobenzenesulfonic acid, naphthene sulfonic acid, methyl naphthalene sulfonic acid, naphthalene sulfonic acid formaldehyde condensation polymer, the green onion disulfonic acid, butyl green onion disulfonic acid, 1-second phthalein oxygen base-3,6,8-trisulfonic acid, 7-amino-1,3,6-naphthalene trisulfonic acid, o-sulfobenzoic acid, 3,5-disulfonic acid phenylformic acid, sulfophthalic acid, sulfo group pure terephthalic acid, cysteic acid, 5-sulphosalicylic acid etc.Also can use these ammonium salt, metal-salt.
In this conductive polymer composition, be the mol ratio (doping agent: electric conductive polymer) preferred 0.1: 1-10: 1, more preferably 0.5: 1-7: 1 of electric conductive polymer as the content of doping agent.When the content of doping agent is lower than this scope, then can not obtain sufficient electroconductibility sometimes.When being higher than this scope, then can not obtain sufficient electroconductibility sometimes.
Adjust wedding agent as electroconductibility and can use at hydroxy-containing compounds, carboxylated compound (organic acid) (COOH) contains aminocompound, the amino-contained aromatics contains carbonyl (CO) compound, contains the acetify compound, contain ammonia vinegar based compound, contain ether compound, amide compound contains imide compound, contain acrylic compound, contain epoxy compounds, silicon-containing compound, fluorochemicals etc.For example can enumerate: N-N-methyl-2-2-pyrrolidone N-, N, N '-dimethyl methyl phthalein amine, N, N ' dimethyl second phthalein amine, dimethyl sulfoxide (DMSO), triethylene glycol butyl ether triethylene glycol butyl ether, triethylene glycol butyl ether, the triethylene glycol monobutyl ether, triglycol butyl ether, butoxy triethylene glycol ether, oxeye alcohol, arabitol, 3-amino-1, the 2-propylene glycol, N.F,USP MANNITOL, glycol, glycol ether, triethylene glycol, poly-glycol, glycerine, Glycerol dimer, Polyglycerine, sorbyl alcohol, tetramethylolmethane, dipentaerythritol, 3-methoxyl group-1,2-propylene glycol, allitol, Xylitol, melampyrum, semi-lactosi, pectinose, glucose, monose, disaccharides, polysaccharide, galacturonic acid, glyconic acid, DL-hydroxy-butanedioic acid, glutinous acid, gulonic acid, different VC acid, oxalic acid, oxysuccinic acid, diacid ammonium, vitamin c class, tartrate, D-dibenzoyl tartaric acid, heptonic acid and these hydrochlorate, glucosamine, dioxane, diethyl ether, dialkyl ether ethylene glycol vinegar, dialkyl ether propylene glycol vinegar, poly-dialkyl ether ethylene glycol vinegar, poly-dialkyl ether propylene glycol vinegar, imidazoles, m-phthalic acid, SO 3 sulfonated m-phthalic acid, sour methyl esters, aforesaid compound B etc.
Can use stiffening agent in order to improve higher film-forming properties.Can use known method and known stiffening agent as curing condition and stiffening agent, not have particular restriction.For example: photochemical reaction, ionic reaction etc.Stiffening agent can be enumerated: aromatic ketone, methyl phenyl ketone, benzophenone, Octabenzone, platinum, ammonium peroxydisulfate, Sodium persulfate, peroxydisulfate such as Potassium Persulfate, iron(ic) chloride, ferric sulfate, cupric chloride, transistion metal compounds such as tosic acid iron, silver suboxide, metal oxides such as Cs2O, hydrogen peroxide, superoxide such as ozone, organo-peroxides such as peroxidation benzene first phthalein, oxygen etc.
In this electrically conductive composition, electroconductibility is adjusted mass ratio (the electroconductibility adjustment wedding agent: the complex body of electric conductive polymer-compd B) preferred 1: 99-99: 1 of the complex body of wedding agent and electric conductive polymer-compd B, more preferably 20: 80-95: 5, most preferably 30: 70-80: 20.As long as in this scope, then electroconductibility and solvent solubility are all high, but when electroconductibility adjustment wedding agent is lower than this scope, then can not obtain the tendency of sufficient electroconductibility and film-forming properties sometimes.When being higher than this scope, then can not obtain sufficient electroconductibility sometimes.
(resinous principle)
Electrically conductive composition of the present invention also can contain other compositions as required.
For example to adjust film-forming properties, film toughness etc. are purpose, can use other organic resins and other additives simultaneously.As organic resin, as long as electrically conductive composition is held concurrently molten or blending dispersion can be used any thermosetting resin, thermoplastic resin, photo-curable resin relatively.
Resin can be used as its object lesson, for example can enumerate: poly-vinegar resin, poly-phthalimide resin, poly-phthalein polyimide resin, poly-fluoro-resin, polyvinyl resin, Resins, epoxy, xylene resin, polyoxyethylene glycol, aramid resin, polyurethane is a resin, poly-vein system resin, melmac, phenolic resin, polyethers, the copolymer resins of acrylic resin and these materials, siliceous copolymer resins, aforesaid compd B, aforesaid electroconductibility is adjusted the part of wedding agent etc.
Can add resinous principle arbitrarily in the conductive composition of the present invention as required, add content and also be not particularly limited.
As other additives so long as can and conductive polymer composition is held concurrently molten or blending dispersion can be used any defoamer, neutralizing agent, oxidation inhibitor, tensio-active agent, coupling agent, conductive fillers etc. do not have particular restriction.
For example can enumerate as conductive filler: particle diameter is the carbon particles of 5-5000nm, graphite particle and copper, and nickel, silver, gold, tin, metallicss such as iron, staple length is that 10-10000nm and line directly are the carbon fiber of 1-1000nm, carbon nanotube etc.Wherein preferred use is added can improve electroconductibility on a small quantity, and the carbon fiber of favorable dispersity, graphite particle, carbon nanotube.
In addition, carbon particles, graphite particle, carbon fiber, the such carbon material of carbon nanotube has reductive action, has the effect of the electric conductive polymer deterioration that anti-block causes, so preferred.
In this conductive polymer composition, the mass ratio of the complex body of conductive filler and electric conductive polymer-compd B (conductive filler: the complex body of electric conductive polymer-compd B) preferred 1: 99-90: 10, more preferably 20: 80-80: 20.
Conductive composite body of the present invention is to form because carry out association reaction between electric conductive polymer and the reactive compounds B.So as mentioned above, can obtain having the close property of enhancing to base material, the system film, and have good electrical conductivity polymer compositions such as high conductance, permanent stability.
Another object of the present invention is by using filming of above-mentioned conductive composite body or conductive polymer composition, a kind of electronic component with excellent properties being provided.For example: solid electrolytic capacitor, solar cell, Organic Light Emitting Diode, EL sheet (Electroluminance), indicating meter, electrostatic duplicating parts, transfer member, battery, Electronic Paper (epaper), touch-screen (touch panel), OTFT (Organicthin-film transistor), field emission type display (FED) etc.
Be that example describes with the solid electrolytic capacitor to electronic component of the present invention below.
It has solid electrolytic capacitor of the present invention: the anode bodies of being made by the porous insert of the metal of valve action, be formed at the medium layer that the oxide film on the metallic surface of described valve acting constitutes, medium layer that oxide film constitutes and the solid electrolyte layer between the cathode, and cathode, in the described solid electrolyte layer, comprise at least: the complex body of electric conductive polymer-compd B.
Here, as long as include the solid electrolyte layer that the complex body of electric conductive polymer-compd B is led between medium layer and the cathode, structure, thickness, additives etc. all are not particularly limited.
When solid electrolytic capacitor of the present invention is wound capacitor, possesses electrolytic paper is arranged.Electrolytic paper is located between medium layer and cathode that the oxide film on the metallic surface of described valve acting constitutes.
(anode bodies)
At this, can enumerate as the metal of valve action: aluminium (Al), tantalum (Ta), niobium (Nb), titanium (Ti), bell (Hf), zirconium (Zr) etc., wherein as the preferred aluminium of the metal of the employed valve action of capacitor anode, tantalum, niobium.The preparation method of the medium layer that constitutes as the oxide film on the metallic surface of valve action: can use aluminium foil is carried out after etching and processing increases its surface-area, its surface be carried out the method for oxide treatment; And to the tantalum particle, the sintered compact surface of niobium particle is carried out oxide treatment and is made the known methods such as method of its powdered.
(solid electrolyte layer)
The solid electrolyte layer of solid electrolytic capacitor of the present invention, on the medium layer of solid electrolytic capacitor, use pickling process, method such as spraying method or print process coating electrically conducting coating, then with solvent seasoning, on the medium layer surface, form the solid electrolyte layer that contains conductive composite body, after forming negative electrode on the solid electrolyte layer, obtain solid electrolytic capacitor.
When solid electrolytic capacitor of the present invention is wound capacitor, possesses electrolytic paper is arranged.Electrolytic paper is located between medium layer and cathode that the oxide film on the described valve acting metallic surface constitutes.Solid electrolyte layer with solvent seasoning, forms the solid electrolyte layer that contains conductive composite body behind the solid electrolyte solution dipping, obtains solid electrolytic capacitor.
As the electrical conductor of solid electrolyte layer, can use the complex body and the conductive polymer composition of aforesaid electric conductive polymer-compd B.In the aforesaid solid electrolyte layer, can also contain the ionic conductivity compound.As long as the ionic conductivity compound ionic conductivity is arranged, does not have particular restriction.The ionogen of known solid electrolytic capacitor and polymer electrolyte all can use.Preferably contain carboxylic compound, sulfonic group compound, ionic liquid, poly-glycol, poly-phthalein amine, poly-carboxylic compound, poly-sulfoacid compound, polyvinyl alcohol, polyvinyl ether etc.
(cathode)
As the cathode of solid electrolytic capacitor of the present invention, can use electric conductive polymer, carbon, silver, aluminium, copper etc.The preparation method can prepare with electrical conductor paper tinsel or coating, does not have particular restriction.
(solid electrolytic paper)
As the electrolytic paper of solid electrolytic capacitor of the present invention, can use the electrolytic paper of known solid electrolytic capacitor not have particular restriction.
Another object of the present invention is by using filming of above-mentioned conductive polymer composition, a kind of heavy body that has is provided, the solid electrolytic capacitor of excellent properties such as low ESR.And under hot environment, also can keep the performance of solid electrolytic capacitor.
Beneficial effect
Conductive composite body in the present invention and conductive polymer composition can obtain having the close property of enhancing to base material, system film, bridge formation, the excellent in stability of the relative outside atmosphere of specific conductivity, and thermotolerance, permanent stability etc.And provide a conductive composite body that solvent solubility is higher.
Filming of conductive composite body of the present invention or conductive polymer composition can obtain excellent properties when being applied to electronic component.The solid electrolytic capacitor of using can obtain having heavy body, the solid electrolytic capacitor of excellent properties such as low ESR.And under hot environment, also can keep the performance of solid electrolytic capacitor.
Embodiment
Preparation object lesson to conductive polymer composition of the present invention and solid electrolytic capacitor describes below.The present invention is not only limited to this object lesson.
(synthetic polystyrene sulfonic acid)
The Sodium styrene sulfonate of 30g is dissolved in the 300ml water, adds the Sodium Persulfate of 0.2g, heated and stirred 3 hours.
Put cold after, spent ion exchange resin cationic exchange after, be modulated to the polystyrolsulfon acid aqueous solution of 3wt% with ion exchanged water.
Embodiment 1
With 3 of 3g, the 4-ethylene dioxythiophene, the polystyrolsulfon acid aqueous solution of the 3wt% of 300g, the Sodium Persulfate of 6g, the ferric sulfate of 1g and the pure water of 500ml stirred 3 hours after mixing.After adding the vinylformic acid (AA) and 4g Hydroxyethyl acrylate (HEA) of 2g in this reaction solution, heated and stirred 3 hours.
Put cold after, spent ion exchange resin is removed the residual ion in the solution, the aqueous solution that obtains the polystyrolsulfon acid of mazarine 1.5wt%-poly-(3,4-ethylene dioxy base) thiophene and poly acrylic acid-poly Hydroxyethyl acrylate is (to call in the following text: the aqueous solution 1).
After the mixing of the ethanol of the aqueous solution 1 of 1g and 9g, obtain the mixed ethanol aqueous solution 1.After being applied to aqueous ethanolic solution 1 on the polyester film, in 120 ℃ of baking ovens after dry 30 minutes, the electroconductibility thin coating film that obtains.Estimate the resistivity of electroconductibility thin coating film, its result is as shown in table 1.
Embodiment 2
With 3 of 3g, the 4-ethylene dioxythiophene, the polystyrolsulfon acid aqueous solution of the 3wt% of 300g, the Sodium Persulfate of 6g, the ferric sulfate of 1g and the pure water of 500ml stirred 3 hours after mixing, and obtained reaction solution 1.
With the pyrroles of 1.5g, the polystyrolsulfon acid aqueous solution of the 3wt% of 100g, the Sodium Persulfate of 5g, the ferric sulfate of 1g and the pure water of 500ml stirred 30 minutes after mixing, and obtained reaction solution 2.
Add the vinylformic acid hydroxyl phthalein amine of 2g and the Sodium styrene sulfonate of 6g in reaction solution 1, heated and stirred was added aforesaid reaction solution 2 after 1 hour in this reaction solution, continue to stir 1 hour.
Put cold after, spent ion exchange resin is removed the residual ion in the solution, the aqueous solution that obtains the polystyrolsulfon acid of black-and-blue 1.5wt%-poly-(3,4-ethylene dioxy base) thiophene-polypyrrole and polyacrylic acid-Hydroxyethyl acrylate is (to call in the following text: the aqueous solution 2).
Method is similarly to Example 1 made the electroconductibility thin coating film, estimates the resistivity of electroconductibility thin coating film, and its result is as shown in table 1.
Embodiment 3
Method similarly to Example 1, except that the vinylformic acid of 2g (AA) and 4g Hydroxyethyl acrylate (HEA) being changed into the hydroxyethyl acrylamide of 6g, all the same with embodiment 1 polystyrolsulfon acid-poly-(3, the 4-ethylene dioxy base) thiophene-poly-hydroxyethyl acrylamide of 1.5wt% that obtains is (to call in the following text: the aqueous solution 3).
Method is similarly to Example 1 made the electroconductibility thin coating film, estimates the resistivity of electroconductibility thin coating film, and its result is as shown in table 1.
Embodiment 4
Except that add the dimethyl sulfoxide (DMSO) of 0.15g toward 1 li of the aqueous ethanolic solution of embodiment 1, method similarly to Example 1, the electroconductibility thin coating film that obtains.Estimate the resistivity of electroconductibility thin coating film, its result is as shown in table 1.
Embodiment 5
Except that add the N-vinylcarbazole of 0.05g toward 1 li of the aqueous ethanolic solution of embodiment 1, method similarly to Example 1, the electroconductibility thin coating film that obtains.Estimate the resistivity of electroconductibility thin coating film, its result is as shown in table 1.
Embodiment 6
Except that the poly-sulfonic acid vinegar mixed with resin of the 25wt% of N-vinylcarbazole of adding 0.05g toward 1 li of the aqueous ethanolic solution of embodiment 1 and 0.2g stirs the back, method similarly to Example 1, the electroconductibility thin coating film that obtains.Estimate the resistivity of electroconductibility thin coating film, its result is as shown in table 1.
Embodiment 7
With 3 of 3g, the 4-ethylene dioxythiophene, the polystyrolsulfon acid aqueous solution of the 3wt% of 300g, the Sodium Persulfate of 6g, 50% the sulfophthalic acid aqueous solution of 12g, the ferric sulfate of 1g and the pure water of 500ml stirred 3 hours after mixing.Then, add vinylformic acid (AA) and the 4g Hydroxyethyl acrylate (HEA) of 2g in this reaction solution, heated and stirred 3 hours.
Put cold after, spent ion exchange resin is removed the residual ion in the solution, the aqueous solution that obtains the polystyrolsulfon acid of mazarine 1.5wt%-poly-(3,4-ethylene dioxy base) thiophene and polyacrylic acid-Hydroxyethyl acrylate is (to call in the following text: the aqueous solution 4).
After the mixing of the ethanol of the aforesaid aqueous solution of 1g and 9g, obtain the mixed ethanol aqueous solution.After being applied to this aqueous ethanolic solution on the polyester film, in 120 ℃ of baking ovens after dry 30 minutes, the electroconductibility thin coating film that obtains.Estimate the resistivity of electroconductibility thin coating film, its result is as shown in table 1.
Embodiment 8
With 3 of 3g, the 4-ethylene dioxythiophene, the Sodium Persulfate of 6g, 50% the sulfophthalic acid aqueous solution of 12g, the ferric sulfate of 1g and the pure water of 500ml stirred 3 hours after mixing, and obtained reaction solution 1.
With Sodium styrene sulfonate and the 4g Hydroxyethyl acrylate (HEA) of 6g, the vinylformic acid of 2g (AA), after the Sodium Persulfate of 0.05g and the pure water of 100ml mixed, heated and stirred 20 minutes obtained reaction solution 2.
Reaction solution 1 is with after reaction solution 2 mixes, heated and stirred 3 hours.
Put cold after, spent ion exchange resin is removed the residual ion in the solution, obtains the aqueous solution of the polystyrolsulfon acid of mazarine 1.0wt%-poly-(3,4-ethylene dioxy base) thiophene and poly acrylic acid-poly Hydroxyethyl acrylate-sodium polystyrene sulfonate.
After the mixing of the ethanol of the aforesaid aqueous solution of 1g and 6g, obtain the mixed ethanol aqueous solution.After being applied to this aqueous ethanolic solution on the polyester film, in 120 ℃ of baking ovens after dry 30 minutes, the electroconductibility thin coating film that obtains.Estimate the resistivity of electroconductibility thin coating film, its result is as shown in table 1.
(comparative example 1)
The ethanol of the Baytron-P that buys on market (1.2%, the H.C.Starck system) 1g and 6g obtains the mixed ethanol aqueous solution after mixing.After being applied to this aqueous ethanolic solution on the polyester film, in 120 ℃ of baking ovens after dry 30 minutes, the electroconductibility thin coating film that obtains.Estimate the resistivity of electroconductibility thin coating film, its result is as shown in table 1.
Table 1
| Resistivity (Ω/) | 80 ℃ of resistivity after 500 hours (Ω/) | Close property | |
| Embodiment 1 | 2×10 5 | 5×10 5 | 100/100 |
| Embodiment 2 | 3×10 5 | 2×10 6 | 100/100 |
| Embodiment 3 | 1×10 5 | 4×10 5 | 100/100 |
| Embodiment 4 | 2×10 4 | 4×10 4 | 100/100 |
| Embodiment 5 | 6×10 4 | 9×10 4 | 100/100 |
| Embodiment 6 | 3×10 5 | 6×10 5 | 100/100 |
| Embodiment 7 | 5×10 4 | 6×10 4 | 100/100 |
| Embodiment 8 | 6×10 6 | 9×10 6 | 100/100 |
| Comparative example 1 | 8×10 6 | 4×10 7 | 80/100 |
Embodiment 9,10, and 11,12
(preparation of winding capacitance work in-process sub-prime)
With the anode foils that changes into processing of guide pin on the fourth, the negative foil roll coiled specification 16V-330 μ F winding capacitance work in-process sub-prime of guide pin on solid electrolytic paper and the fourth.
(preparation of solid electrolyte solution)
Respectively with ammoniacal liquor with the aqueous solution 1, the aqueous solution 2, the aqueous solution 3, after the aqueous solution 4 is handled, the Diethylene Glycol that adds 6g in the aqueous solution of 100g is mixed stir respectively, obtain solid electrolyte solution 1, solid electrolyte solution 2, solid electrolyte solution 3, solid electrolyte solution 4.
(making of solid electrolytic capacitor)
With the vacuum decompression method respectively the solid electrolyte solution 1 that obtains, solid electrolyte solution 2, solid electrolyte solution 3, after solid electrolyte solution 4 is impregnated in the winding capacitance work in-process sub-prime, in 120 ℃ of baking ovens, carry out drying, obtain containing the sub-prime 1 (embodiment 9) of solid electrolyte, the sub-prime 2 of solid electrolyte (embodiment 10), the sub-prime 3 of solid electrolyte (embodiment 11), the sub-prime 4 of solid electrolyte (embodiment 12).Then, behind the ammonium adipate aqueous solution of dipping 10wt%, drying is after 30 minutes in 120 ℃ of baking ovens, after the sub-prime that will contain solid electrolyte with shell and Jiao Gai seals, obtain solid electrolytic capacitor 1 (embodiment 9), solid electrolytic capacitor 2 (embodiment 10), solid electrolytic capacitor 3 (embodiment 11), solid electrolytic capacitor 4 (embodiment 12).(capacity, ESR), its result is as shown in table 2 for the performance of evaluation solid electrolytic capacitor.
(comparative example 2)
After the Baytron-P (1.2%, the H.C.Starck system) that will buy on market with ammoniacal liquor handles, the Diethylene Glycol that adds 4.8g in the aqueous solution of 100g mixed stir, obtain solid electrolyte solution 5.
Obtain solid electrolytic capacitor 6 in embodiment 9 same hairdos.Method evaluation similarly to Example 9, its result is as shown in table 2.
Table 2
Claims (10)
1. a conductive composite body is characterized in that by the compd B beyond electric conductive polymer A and this electric conductive polymer in conjunction with forming.
2. conductive composite body according to claim 1, it is characterized in that described electric conductive polymer A is by polypyrrole class and derivative thereof, polythiophene class and derivative thereof, polyaniline and derivative thereof, metaldehyde class and derivative thereof, poly-vinylene thiophene-based and derivative thereof, at least a in polyethylene click and derivative thereof and these the multipolymer.
3. conductive composite body according to claim 1 and 2, it is characterized in that described compd B is by replacing or unsubstituted polyethylene kind and derivative thereof, replace or unsubstituted glymes and derivative thereof, replace or unsubstituted polyacrylamide and derivative thereof, replace or unsubstituted polyacrylic and derivative thereof, replace or unsubstituted poly-phthalimide class and derivative thereof, replace or unsubstituted poly-phthalein amine and derivative thereof, replace or unsubstituted polyvinyl alcohol and derivative thereof, replace or unsubstituted polyethylene glycols and derivative thereof, replace or unsubstituted poly-vinegar class and derivative thereof, replace or unsubstituted poly-fluorochemical class and derivative thereof, siliceous class and derivative thereof, and at least a in these the copolymerization.
4. conductive composite body according to claim 1 is characterized in that containing alkyl in the described compd B, carboxyl, amino,-oxyl, carbonyl, sulfonic group, amide group, fat-oxyl, ester group, ether, epoxy group(ing), aryl, aromatic series contains halogen, and is silica-based, fluorine-based, at least a in the nitrogenous base of aromatic series.
5. conductive composite body according to claim 1 is characterized in that by electric conductive polymer, solvent, and in the solution that oxygenant or catalyzer are formed, the reaction by the compd B beyond the electric conductive polymer forms.
6. conductive composite body according to claim 1, it is characterized in that the plural number electric conductive polymer and the plural number this electric conductive polymer beyond compd B in conjunction with and form.
7. conductive composite body according to claim 1 is characterized in that containing polyanion.
8. a conductive polymer composition comprises conductive composite body according to claim 1 at least.
9. conductive polymer composition according to claim 8 is characterized in that also containing doping agent, and electroconductibility is adjusted wedding agent, resinous principle, at least a in the conductive particle.
10. use electronic component according to described conductive composite body of claim 1-9 or conductive polymer composition.
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