CN101932628A - Dispersion of electroconductive composition, electroconductive composition, and use thereof - Google Patents
Dispersion of electroconductive composition, electroconductive composition, and use thereof Download PDFInfo
- Publication number
- CN101932628A CN101932628A CN200980103893XA CN200980103893A CN101932628A CN 101932628 A CN101932628 A CN 101932628A CN 200980103893X A CN200980103893X A CN 200980103893XA CN 200980103893 A CN200980103893 A CN 200980103893A CN 101932628 A CN101932628 A CN 101932628A
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- Prior art keywords
- conductive composition
- dispersion liquid
- writing
- acid
- electroconductive polymer
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Classifications
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
Disclosed is an electroconductive composition having high electroconductivity and excellent heat resistance. Also disclosed are an antistatic film that uses the electroconductive composition and has high electroconductivity and excellent heat resistance, and a solid electrolytic capacitor that uses the electroconductive composition and has small ESR and high reliability under high temperature conditions. A dispersion of the electroconductive composition comprises: an electroconductive polymer produced by electrolytic oxidation polymerization of thiophene or a derivative of thiophene in water or an aqueous liquid formed of a mixed liquid composed of water and a water-miscible solvent in the presence of a phenolsulfonic acid novolak resin comprising repeating units represented by general formula (I), wherein R represents hydrogen or a methyl group, a sulfonated polyester, or a polystyrenesulfonic acid; and a high-boiling solvent or an organic acid having a cyclic structure. The antistatic film uses the electroconductive composition as an electric conductor. The solid electrolytic capacitor uses the electroconductive composition as a solid electrolyte.
Description
Technical field
The present invention relates to conductive composition that the dispersion liquid of the dispersion liquid of conductive composition, dry aforementioned conductive composition obtains, use aforementioned conductive composition as the electrostatic prevention film and the antistatic plate of electrical conductor and use the solid electrolytic capacitor of aforementioned conductive composition as solid electrolyte.
Background technology
Electroconductive polymer is because its high conductivity can be used as for example solid electrolyte use of solid electrolytic capacitors such as tantalum solid electrolytic capacitor, Niobiuim solid electrolytic capacitor, solid aluminium electrolytic capacitor.
And, as the electroconductive polymer in this purposes, use be for example by the electroconductive polymer that obtains is synthesized in polymerizable monomer oxypolymerizations such as thiophene or derivatives thereof.
As the oxypolymerization of carrying out polymerizable monomers such as above-mentioned thiophene or derivatives thereof, the particularly doping agent during chemical oxidising polymerisation, the main organic sulfonic acid that uses, wherein, thinking suitable is aromatic sulphonic acid, use transition metal as oxygenant, what wherein see fit is ferric iron, and usually the trivalent iron salt of aromatic sulphonic acid uses as the oxygenant doping agent of holding concurrently in the chemical oxidising polymerisation of polymerizable monomers such as thiophene or derivatives thereof.
And, also reported in the trivalent iron salt of this aromatic sulphonic acid, think that toluenesulphonic acids iron (III) salt or methoxy benzenesulfonic acid iron (III) salt etc. are useful especially, use electroconductive polymer synthetic of these trivalent iron salts, can mix to synthesize the simple and suitable suitability for industrialized production (patent documentation 1, patent documentation 2) of this method by polymerizable monomers such as these oxygenants are held concurrently doping agent and thiophene or derivatives thereofs.
Yet, use toluenesulphonic acids iron (III) salt not have fully to satisfy initial stage resistance value and stable on heating character as the oxygenant electroconductive polymer that doping agent obtains of holding concurrently, in addition, use methoxy benzenesulfonic acid iron (III) salt to compare as the oxygenant electroconductive polymer that doping agent obtains of holding concurrently as hold concurrently electroconductive polymer that doping agent obtains and use toluenesulphonic acids iron (III) salt of oxygenant, the initial stage resistance value is lower, thermotolerance is more excellent, but however, the character that still can't attain full and complete satisfaction and require.
This is because toluenesulphonic acids iron (III) salt or methoxy benzenesulfonic acid iron (III) salt are solids, thus generally to use down by the state that is dissolved in the alcohol, but these solution can produce precipitation when preserving.
Just, because if use the alcoholic solution that has produced sedimentary toluenesulphonic acids iron (III) salt or methoxy benzenesulfonic acid iron (III) salt, then homogeneity is low, the ESR (equivalent series resistance) of the solid electrolytic capacitor of the electroconductive polymer of use gained increases, and perhaps the reliability under hot conditions reduces.
In addition, the electroconductive polymer that uses gained is during as the solid electrolyte of solid electrolytic capacitor, owing to usually solvent is not had solvability by chemical oxidative polymerization synthetic electroconductive polymer, so must on the element of the dielectric layer that anode that the porous insert that has by valve metals such as tantalum, niobium, aluminium constitutes and oxidation overlay film by aforementioned valve metal constitute, directly form the electroconductive polymer layer.
Yet, direct like this when on element, forming the electroconductive polymer layer, must the very harsh operation of condition, so have the shortage reproducibility, the problem that supervision of construction is very difficult.
According to this situation, active research soluble conductive polymer (patent documentation 3).According to this patent documentation 3, reported mixing such as polystyrolsulfon acid, ammonium persulphate, molysite, ethylene oxo thiophene have been reacted, obtain the dispersion liquid of electroconductive polymer.Yet the electroconductive polymer that obtains like this can't think that electroconductibility is enough high, when the solid electrolyte as solid electrolytic capacitor uses, must further improve electroconductibility.
In addition, also reported the electroconductive polymer (patent documentation 4～5) that p-poly-phenyl amino-group doping sulfocarbolic acid novolac resin forms.Yet the specific conductivity of this electroconductive polymer is enough not high yet, when the solid electrolyte as solid electrolytic capacitor uses, also needs further to improve electroconductibility.
In addition, also studied by electrolytic oxidation polymerization method formation soluble conductive polymer (patent documentation 6～7).Yet, when carrying out,, carry out solubility and handle, so have the problem that is difficult in industrial use owing to must take out the insoluble electroconductive polymer that forms on the electrode according to these methods.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2003-160647 communique
Patent documentation 2: TOHKEMY 2004-265927 communique
Patent documentation 3: No. 2636968 communique of Japan's special permission
Patent documentation 4: No. 3906071 communique of Japan's special permission
Patent documentation 5: TOHKEMY 2007-277569 communique
Patent documentation 6: Japanese kokai publication hei 1-161013 communique
Patent documentation 7: Japanese kokai publication sho 62-181328 communique
Summary of the invention
The present invention is according to the problems referred to above, and purpose is: the conductive composition that electroconductibility height and excellent heat resistance are provided; But also use above-mentioned conductive composition as electrical conductor, the electrostatic prevention film of electroconductibility height and excellent heat resistance is provided; In addition, also use above-mentioned conductive composition, ESR is provided the little and high solid electrolytic capacitor of reliability under hot conditions as solid electrolyte.
The inventor is in order to address the above problem, carried out conscientious research, thereby find: at sulfocarbolic acid novolac resin with the repeating unit shown in the following general formula (I), under the existence of sulfonated polyester or polystyrolsulfon acid, with the thiophene or derivatives thereof in water or in the aqueous solution that the mixed solution by water and water-miscible solvent forms, during electrolytic oxidation polymerization, hardly can driving fit on electrode, to be evenly dispersed in the state in the water or in the aqueous solution, obtain the dispersion liquid of electroconductive polymer, by comprising high boiling solvent in this electroconductive polymer dispersion liquid or having the conductive composition that the dispersion liquid of the conductive composition that the organic acid of ring texture forms obtains, electroconductibility height, and excellent heat resistance; Finish the present invention based on this understanding.
(R in the formula is hydrogen or methyl)
Just, the present invention relates to a kind of dispersion liquid of conductive composition, it is characterized in that: the organic acid that comprises electroconductive polymer and high boiling solvent or have ring texture, wherein electroconductive polymer is by in the presence of sulfocarbolic acid novolac resin, sulfonated polyester or polystyrolsulfon acid with the repeating unit shown in the above-mentioned general formula (I), with the thiophene or derivatives thereof in water or in the aqueous solution that the mixed solution by water and water-miscible solvent forms, electrolytic oxidation polymerization obtains.
In addition, the present invention relates to conductive composition that the dispersion liquid drying with aforementioned conductive composition obtains, use electrostatic prevention film and the antistatic plate of aforementioned conductive composition, and use the solid electrolytic capacitor of aforementioned conductive composition as solid electrolyte as electrical conductor.
The transparency of conductive composition of the present invention is high, electroconductibility height, and excellent heat resistance.In addition, the transparency of conductive composition of the present invention is high, and this electroconductive polymer is owing to be by the electrolytic oxidation polymerization synthetic, so the content of this sulfate radical of finding in chemical oxidising polymerisation synthetic electroconductive polymer that forms based on oxygenant is few, electroconductibility is reduced or the transparency reduces to wait and also lacks.
Therefore, based on this character of conductive composition of the present invention,, can obtain that the transparency is high, electroconductibility is high and the electrostatic prevention film of excellent heat resistance, anti-electrostatic resin, antistatic plate etc. by using this conductive composition as electrical conductor.In addition, the conductive composition of the present invention by using this electroconductibility height and excellent heat resistance is as solid electrolyte, can obtain the high solid electrolytic capacitor of reliability under the little and hot conditions of ESR.
Embodiment
In the present invention, when the compositing conducting polymer, use has sulfocarbolic acid novolac resin, sulfonated polyester or the polystyrolsulfon acid of the repeating unit shown in the general formula (I), they are when the compositing conducting polymer, play function as excellent dispersion agent, with as the thiophene or derivatives thereof of polymerizable monomer and the catalyzer that adds as required etc., disperse equably in water or in the aqueous solution, and in the synthetic polymkeric substance, add, thereby form electroconductive polymer with high conductivity as doping agent.And above-mentioned doping agent plays the function of excellent dispersion agent, thinks to synthesize that the transparency is high, electroconductibility is high and the major reason of the electroconductive polymer of excellent heat resistance.
As the sulfocarbolic acid novolac resin preferred number average molecular weight shown in the above-mentioned general formula (I) is 5,000～500,000.This is because following reason.
That is, the number-average molecular weight of above-mentioned sulfocarbolic acid novolac resin is less than 5,000 o'clock, and the electroconductibility of the electroconductive polymer of gained may step-down, and also possible deviation of the transparency.In addition, the number-average molecular weight of above-mentioned sulfocarbolic acid novolac resin was greater than 500,000 o'clock, and the viscosity of the dispersion liquid of conductive composition uprises, and when making solid electrolytic capacitor etc., may be difficult to use.In addition, as this sulfocarbolic acid novolac resin, its number-average molecular weight is in above-mentioned scope, and is preferred more than 10,000, also preferred below 400,000 in addition, more preferably below 80,000.
In addition, above-mentioned sulfonated polyester is that polycondensation forms in the presence of catalyzer such as weisspiessglanz or zinc oxide with the mixture of dicarboxyl Phenylsulfonic acid diester such as dicarboxyl Phenylsulfonic acid such as sulfonation m-phthalic acid, sulfonation terephthalic acid or sulfonation isophthalic acid ester, sulfonation terephthalate and aklylene glycol; Perhaps with the mixture of above-mentioned dicarboxyl Phenylsulfonic acid or dicarboxyl Phenylsulfonic acid diester and aklylene glycol and terephthalic acid or dimethyl terephthalate (DMT), polycondensation forms in the presence of catalyzer such as weisspiessglanz or zinc oxide, number-average molecular weight as this sulfonated polyester is preferably 5,000～300,000.
Just, the number-average molecular weight of above-mentioned sulfonated polyester is less than 5,000 o'clock, and the electroconductibility of the electroconductive polymer of gained may step-down, and the transparency is possible deviation also.In addition, the number-average molecular weight of above-mentioned sulfonated polyester was greater than 300,000 o'clock, and the viscosity of the dispersion liquid of conductive composition uprises, and when making solid electrolytic capacitor etc., may be difficult to use.In addition, as this sulfonated polyester, its number-average molecular weight is in above-mentioned scope, and is preferred more than 10,000, more preferably more than 20,000, also preferred below 100,000 in addition, more preferably below 80,000.
In addition, be 10,000～1,000,000 as preferred its number-average molecular weight of polystyrolsulfon acid.
Just, the number-average molecular weight of above-mentioned polystyrolsulfon acid is less than 10,000 o'clock, and the electroconductibility of the electroconductive polymer of gained may step-down, and also possible deviation of the transparency.In addition, the number-average molecular weight of above-mentioned polystyrolsulfon acid is greater than 1,000, and 000 o'clock, the viscosity of the dispersion liquid of conductive composition uprised, and when making solid electrolytic capacitor etc., may be difficult to use.In addition, as above-mentioned polystyrolsulfon acid, its number-average molecular weight is in above-mentioned scope, and is preferred more than 20,000, further preferred more than 40,000, also preferred below 800,000 in addition, more preferably below 300,000.
The organic acid that contains high boiling solvent or have ring texture in dispersion liquid of the present invention, containing this high boiling solvent is because can improve the film-forming properties of the conductive composition of gained, improves electroconductibility thus.By containing this high boiling solvent, though the reason of the electroconductibility of raising electroconductive polymer is at present uncertain clear and definite, but the dispersed liquid coating that can think for example electroconductibility to be made up is to base material, when dry, the layer density of thickness direction in the time of can improving high boiling solvent and slough, thus, the face between electroconductive polymer narrows down at interval, and the electroconductibility of electroconductive polymer increases.
As above-mentioned high boiling solvent, preferred boiling point is the solvent more than 150 ℃, object lesson as this high boiling solvent, can list for example dimethyl sulfoxide (DMSO) (189 ℃ of boiling points), gamma-butyrolactone (204 ℃ of boiling points), tetramethylene sulfone (285 ℃ of boiling points), N-Methyl pyrrolidone (202 ℃ of boiling points), dimethyl sulfone (233 ℃ of boiling points), ethylene glycol (198 ℃ of boiling points), glycol ether (244 ℃ of boiling points) etc., preferred especially dimethyl sulfoxide (DMSO).And, with respect to the electroconductive polymer in the dispersion liquid, as the content of this high boiling solvent, in quality criteria, be preferably 5～3,000% (just, with respect to 100 mass parts electroconductive polymers, high boiling solvent is 5～3,000 mass parts), be preferably 20～700% especially.When the content of high boiling solvent was lower than above-mentioned scope, the film-forming properties of conductive composition was low, thereby worried to reduce the effect of the electroconductibility that improves conductive composition; When the content of high boiling solvent surpassed above-mentioned scope, the drying of dispersion liquid needed spended time, and may reduce electroconductibility on the contrary.
In addition, in dispersion liquid of the present invention, can comprise the organic acid with ring texture and replace above-mentioned high boiling solvent, containing this organic acid is because can improve the film-forming properties of the conductive composition of gained, improves electroconductibility thus.By containing this organic acid with ring texture, the reason of the electroconductibility of raising electroconductive polymer is at present uncertain clear and definite, but can think because for example with the dispersed liquid coating of conductive composition to base material when dry, organic acid with ring texture enters the interlayer of electroconductive polymer, causes carrying easily the emptying aperture (hole) of electroconductive polymer interlayer.
As organic acid with above-mentioned ring texture, can list for example phthalic acid, O-phthalic aldehydic acid (acid of Off タ Le ア デ ヒ De), carboxylic phenol, carboxyl cresols, carboxyl naphthalene, dicarboxyl naphthalene, thiophene-sulfonic acid, toluenesulphonic acids, sulfocarbolic acid, cresol sulfonic acid, naphthene sulfonic acid, naphthalene disulfonic acid, naphthalene trisulfonic acid, anthraquinone sulfonic acid, anthraquinone disulfonic acid etc., the organic acid of the fragrant same clans such as preferred especially sulfocarbolic acid, naphthene sulfonic acid, anthraquinone sulfonic acid.And, with respect to the electroconductive polymer in the dispersion liquid, has the organic acid content of ring texture as this, in quality criteria, be preferably 5～500% (just, with respect to 100 mass parts electroconductive polymers, the organic acid with ring texture is 5～500 mass parts), more preferably 20～150%.When the organic acid content with ring texture was lower than above-mentioned scope, the film-forming properties of conductive composition was low, thereby worries to reduce the effect of the electroconductibility that improves conductive composition; When the organic acid content with ring texture surpasses above-mentioned scope, play the effect of impurity, thereby reduce the film-forming properties of conductive composition, and may reduce electroconductibility on the contrary.
In addition, the operation the when content of the electroconductive polymer in the dispersion liquid forms film like owing to the dispersion liquid that can influence dry conductive composition etc. are so be preferably usually about 1～10 quality %.Just, when the content of electroconductive polymer was lower than above-mentioned scope, drying needed the time; In addition, when the content of electroconductive polymer surpassed above-mentioned scope, viscosity uprised, the operation in the time of may reducing coating etc.
Drying contains the dry thing that the dispersion liquid of electroconductive polymer and high boiling solvent obtains can think that electroconductive polymer is a main component, also contain a little high boiling solvent, so in this manual, the dry thing that the dispersion liquid drying of conductive composition is obtained is expressed as conductive composition.But, because high boiling solvent also is a solvent, if it is so dry under higher temperature, basically still might evaporate, but in the present invention, it for example can be the dry thing that contains high boiling solvent therein hardly that drying contains the dry thing that the conductive composition of electroconductive polymer and high boiling solvent obtains, and also it is expressed as conductive composition.In addition, when containing organic acid replacement high boiling solvent with ring texture, organic acid with above-mentioned ring texture can not evaporate under common drying, normally contains electroconductive polymer and the organic acid conductive composition with ring texture so will contain electroconductive polymer with the dry thing that the organic acid dispersion liquid drying with ring texture obtains.In addition, in the dispersion liquid of electroconductive polymer of the present invention, also high boiling solvent can be used together with the organic acid with ring texture and contain.
In the present invention, as being used for by the high molecular polymerizable monomer of electrolytic oxidation polymerization compositing conducting, use the thiophene or derivatives thereof, as the thiophene derivant in this thiophene or derivatives thereof, for example can list 3,4-ethylidene dioxy thiophene, 3-alkylthrophene, 3-alkoxy thiophene, 3-alkyl-4-alkoxy thiophene, 3,4-alkylthrophene, 3,4-alkoxy thiophene etc., the carbonatoms of its alkyl or alkoxyl group is preferably 1～16, specially suitable is 1～4, preferred especially carbonatoms be 23,4-ethylidene dioxy thiophene.
Since as the sulfocarbolic acid novolac resin with the repeating unit shown in the general formula (I) of doping agent, sulfonated polyester, polystyrolsulfon acid (below, they might be described with " doping agent " this expression) any one water or the aqueous solution that formed by water and water Combination solvent are had solvability, so the electrolytic oxidation polymerization during the compositing conducting polymer carries out in water or in the aqueous solution.
Water Combination solvent as constituting above-mentioned aqueous solution can list for example methyl alcohol, ethanol, propyl alcohol, acetone, acetonitrile etc.; As the blending ratio of these water Combination solvents and water, be preferably below the 50 quality % of aqueous solution in all.
There is no particular limitation for doping agent during above-mentioned electrolytic oxidation polymerization and the consumption of polymerizable monomer, if but for example so that with sulfocarbolic acid novolac resin with the repeating unit shown in the general formula (I) as doping agent, use is as 3 of thiophene derivant, 4-ethylidene dioxy thiophene describes for example as the situation of polymerizable monomer, their usage ratio then, by quality ratio, be preferably the sulfocarbolic acid novolac resin: 3,4-ethylidene dioxy thiophene=1: 0.05～1: 5, be preferably the sulfocarbolic acid novolac resin especially: 3,4-ethylidene dioxy thiophene=1: 0.1～1: 1.And, use other material as doping agent, use other material also roughly the same as the situation of polymerizable monomer.
Electrolytic oxidation polymerization can carry out under constant current, also can carry out under constant voltage, when for example carrying out electrolytic oxidation polymerization under constant current, as current value, is preferably 0.05mA/cm
2～10mA/cm
2, 0.2mA/cm more preferably
2～4mA/cm
2When under constant voltage, carrying out electrolytic oxidation polymerization, be preferably 0.5V～10V as voltage, more preferably 1.5V～5V.Temperature during as electrolytic oxidation polymerization is preferably 5 ℃～95 ℃, is preferably 10 ℃～30 ℃ especially.In addition, as polymerization time, be preferably 1 hour～72 hours, be preferably 8 hours especially～24 hours.In addition, when electrolytic oxidation polymerization, can add ferrous sulfate (II) or ferric sulfate (III) as catalyzer.If carry out electrolytic oxidation polymerization in the water of the iron ion that contains these catalyzer or in the aqueous solution, then can promote the polymerization of thiophene or derivatives thereof.
The above-mentioned electroconductive polymer that obtains can just obtain with dispersive state in water or in the aqueous solution after polymerization, contains the sulphate of iron that uses as catalyzer or its resolvent etc.Therefore, after the dispersion liquid that contains the electroconductive polymer of this impurity preferably disperses impurity by decollators such as ultrasonic homogenizer or planetary ball mills, remove metal ingredient by Zeo-karb.Particle diameter as electroconductive polymer at this moment is preferably below the 100 μ m, is preferably especially below the 10 μ m.Afterwards, by ethanol precipitation, ultrafiltration process, anionite-exchange resin etc., remove the sulfuric acid that generates by catalyst decomposes etc., the organic acid that adds high boiling solvent or have ring texture.
Because the excellent electric conductivity of conductive composition of the present invention, excellent heat resistance and the transparency are excellent, use so be suitable as the electrical conductor of antistatic materials such as electrostatic prevention film, anti-electrostatic cloth, anti-electrostatic resin.In addition, conductive composition of the present invention is because electroconductibility height and excellent heat resistance, so be suitable as with the solid aluminium electrolytic capacitor is that the solid electrolyte of solid electrolytic capacitors such as tantalum solid electrolytic capacitor, Niobiuim solid electrolytic capacitor of representative uses, and the high solid electrolytic capacitor of reliability under the low and hot conditions of ESR can be provided.
In addition, conductive composition of the present invention utilizes its electroconductibility height and the such character of excellent heat resistance, except electrical conductor, also be suitable as the positive active material of battery, the uses such as substrate resin of rotproofness coating as the solid electrolyte of above-mentioned solid electrolytic capacitor and antistatic material.
As mentioned above, when using conductive composition of the present invention as the solid electrolyte of the electrical conductor of antistatic material or solid electrolytic capacitor, also can be with its direct use; But the conductive composition that is to use that is fit to is dispersed in dispersion liquid in the water or in the aqueous solution, and afterwards, the conductive composition that drying is obtained uses as electrical conductor or solid electrolyte.
When using conductive composition of the present invention to make electrostatic prevention film as electrical conductor, can on substrate sheets, apply the dispersion liquid of aforementioned conductive composition, perhaps substrate sheets is impregnated in the dispersion liquid of conductive composition, after the taking-up, drying forms electrostatic prevention film, peel off this film from substrate sheets, the electrostatic prevention film that can certainly be not the one or both sides of substrate sheets not be formed is peeled off from this substrate sheets, but with this substrate sheets as propping material, use as antistatic plate.In addition, when using conductive composition of the present invention to make anti-electrostatic cloth as electrical conductor, the dispersion liquid of the aforementioned conductive composition of coating perhaps is immersed in cloth in the dispersion liquid of aforementioned conductive composition on cloth, after the taking-up, and drying.Then, as mentioned above, when making antistatic plate or anti-electrostatic cloth,, then can improve the adaptation of conductive composition, so preferred to substrate sheets or cloth if in the dispersion liquid of above-mentioned conductive composition, add adhesive resin.So, adding tackiness agent in the dispersion liquid of conductive composition, is preferred under the situation that the solid electrolyte that uses conductive composition as solid electrolytic capacitor uses too.
As above-mentioned adhesive resin, can list for example urethane, polyester, acrylic resin, polymeric amide, polyimide, Resins, epoxy, polyacrylonitrile resin, polymethacrylonitrile resin, polystyrene resin, novolac resin, silane coupling agent etc., special preferred polyester, urethane, acrylic resin etc.In addition, if picture sulfonation polypropylene (ス Le ホ Application
Port リ ア リ Le), sulfonated polyethylene, sulfonated polystyrene like this, the addition sulfo group then can improve the electroconductibility of conductive composition, so more preferably.
Then, this adhesive resin or other resin are added in the dispersion of aforementioned conductive composition, drying can obtain the anti-electrostatic resin.In addition, as follows when using the solid electrolytic capacitor of conductive composition conduct, can make solid electrolytic capacitor.
At first, with conductive composition of the present invention as tantalum solid electrolytic capacitor, Niobiuim solid electrolytic capacitor, during the solid electrolyte of aluminium stacked solid electrolytic capacitor etc., to have by tantalum, niobium, the capacitor element of anode that the porous insert of valve metals such as aluminium forms and the dielectric layer that forms by the oxide coating film of these valve metals, be impregnated in the dispersion liquid of conductive composition of the present invention, after the taking-up, dry, repeat this operation, behind the solid electrolyte layer that formation is formed by conductive composition, by giving carbon paste, silver is stuck with paste, after the drying, outer enclosure can be made tantalum solid electrolytic capacitor, Niobiuim solid electrolytic capacitor, solid electrolytic capacitors such as aluminium stacked solid electrolytic capacitor.
In addition, for example use non-molysite class organic sulfonate as doping agent, dipping aforementioned capacitor element in the solution that contains polymerizable monomer, oxygenant, after the taking-up, polymerization at room temperature, flood in the water, take out, after the washing, drying, behind the compositing conducting polymer, their mass-impregnations in the dispersion liquid of conductive composition of the present invention, are taken out drying, repeat this operation, also can form the solid electrolyte layer that forms by conductive composition of the present invention, but also can the form opposite with it.
Then, after the element that is covered by the conductive composition carbon paste that forms like this, silver-colored paste covering, outer enclosure also can be made tantalum solid electrolytic capacitor, Niobiuim solid electrolytic capacitor, aluminium stacked solid electrolytic capacitor etc.
In addition, when using conductive composition of the present invention as the solid electrolyte of aluminium coiled solid electrolysis capacitor, after the surface of aluminium foil carried out etch processes, carrying out chemical coating handles, form dielectric layer, on the anode that forms this dielectric layer, pigtail splice is installed, in addition, on the negative electrode that constitutes by aluminium foil, pigtail splice is installed, these anode and negative electrodes that have pigtail splice are reeled by partition, make capacitor element, this capacitor element is impregnated in the dispersion liquid of conductive composition of the present invention, after the taking-up, drying is after drying, in order to remove the conductive composition in the pore that does not enter etching aluminum foil formation, and be impregnated in the pure water, after the taking-up, drying, repeat these the operation after, by outer enclosure material outer enclosure, can make the aluminium coiled solid electrolysis capacitor.
Embodiment
Below, enumerate embodiment the present invention is described more specifically, but the present invention has more than and is limited to the illustrative content of these embodiment.In addition, in following embodiment etc., if not special its benchmark of record of % when indicated concentration or consumption is the % of quality criteria.
Embodiment 1
The sulfocarbolic acid novolac resin (the little westernization manufacturing lotEW00130 (trade(brand)name) of industrial, the number-average molecular weight 60 that 600g are had the repeating unit shown in the general formula (I), 000, R is a hydrogen) 4% aqueous solution put into the stainless steel container made of internal capacity 1L, add the 0.3g ferrous sulfate. heptahydrate, slowly drip 3 of 4mL therein, 4-ethylidene dioxy thiophene.Stirring rake by stainless steel stirs, and anode is installed on container, at the installation root of stirring rake negative electrode is installed, at 1mA/cm
2Constant current under electrolytic oxidation polymerization 18 hours.Behind the above-mentioned electrolytic oxidation polymerization, be diluted with water to 6 times after, carry out 30 minutes dispersion treatment with ultrasonic homogenizer (Hitachi Machinery Co. Ltd make, US-T300 (trade(brand)name)).Afterwards, add the Zeo-karb ア Application バ one ラ イ ト 120B (trade(brand)name) that 100g オ Le ガ ノ company makes, stirred 1 hour with agitator.Then, the filter paper No.131 that makes by Japan filter paper company filters, and repeats the processing and the filtration of 3 these Zeo-karbs, removes the cation constituents such as iron ion in the liquid fully.In addition, during above-mentioned electrolytic oxidation polymerization, become the sulfocarbolic acid novolac resin and the polymerizable monomer 3 of doping agent, the ratio of 4-ethylidene dioxy thiophene is the sulfocarbolic acid novolac resin by quality ratio: 3, and 4-ethylidene dioxy thiophene=1: 0.2.
The strainer of liquid passage aperture 1 μ m after the above-mentioned processing, this solution that passes through is handled by ultra-filtration equipment (Vivaflow200 (trade(brand)name), molecular-weight gradation 50,000 that ザ Le ト リ ウ ス company makes), removes the free low molecular composition in the liquid.Liquid dilute with water after this is handled is 3% with concentration adjustment, to this liquid of 3% of 40g, adds the 4g dimethyl sulfoxide (DMSO) (with respect to electroconductive polymer, dimethyl sulfoxide (DMSO) is about 330%) as high boiling solvent, obtains the dispersion liquid of conductive composition.When the イ オ Application Network ロ マ ト DX120 (trade(brand)name) that the vitriolic content in this dispersion liquid is made by ダ イ オ ネ Network ス company measured, vitriolic content was 25ppm.
Embodiment 2
Except at 600g sulfonated polyester (the プ ラ ス コ one ト Z-561 (trade(brand)name) that mutual induction chemical industrial company makes, number-average molecular weight 27,000) in 3% aqueous solution, add beyond the 0.05g ferrous sulfate heptahydrate, add the same operation of dimethyl sulfoxide (DMSO) etc. and embodiment 1, obtain the dispersion liquid of conductive composition.When vitriolic content in this dispersion liquid and embodiment 1 similarly measured, vitriolic content was 22ppm.
Embodiment 3
Beyond 4% aqueous solution that uses 600g polystyrolsulfon acid (テ イ カ company makes, number-average molecular weight 100,000), add the same operation of dimethyl sulfoxide (DMSO) etc. and embodiment 1, obtain the dispersion liquid of conductive composition.When vitriolic content in this dispersion liquid and embodiment 1 similarly measured, vitriolic content was 26ppm.
Embodiment 4
Except using 600g to have the sulfocarbolic acid novolac resin (lotEG0727 (trade(brand)name) of little westernization industrial manufacturing of the repeating unit shown in the general formula (I), number-average molecular weight 20,000, R in the formula is a hydrogen) 4% aqueous solution beyond, add the same operation of dimethyl sulfoxide (DMSO) etc. and embodiment 1, obtain the dispersion liquid of conductive composition.When vitriolic content in this dispersion liquid and embodiment 1 similarly measured, vitriolic content was 27ppm.
Embodiment 5
Except adding 0.4g naphthene sulfonic acid (with respect to electroconductive polymer, naphthene sulfonic acid is 33%) as organic acid with ring texture, replacing beyond the high boiling solvent dimethyl sulfoxide (DMSO), carry out the operation same with embodiment 3, obtain the dispersion liquid of conductive composition.When vitriolic content in this dispersion liquid and embodiment 1 similarly measured, vitriolic content was 26ppm.
Embodiment 6
Except adding the 0.5g anthraquinone sulfonic acid (with respect to electroconductive polymer, anthraquinone sulfonic acid is 42%) as organic acid with ring texture, replacing beyond the high boiling solvent dimethyl sulfoxide (DMSO), carry out the operation same with embodiment 3, obtain the dispersion liquid of conductive composition.When vitriolic content in this dispersion liquid and embodiment 1 similarly measured, vitriolic content was 26ppm.
Embodiment 7
Except adding the 0.5g sulfocarbolic acid (with respect to electroconductive polymer, sulfocarbolic acid is 42%) as organic acid with ring texture, replacing beyond the high boiling solvent dimethyl sulfoxide (DMSO), carry out the operation same with embodiment 3, obtain the dispersion liquid of conductive composition.When vitriolic content in this dispersion liquid and embodiment 1 similarly measured, vitriolic content was 26ppm.
Comparative example 1
4% aqueous solution of the same sulfocarbolic acid novolac resin (number-average molecular weight 60,000) that 200g and embodiment 1 used is put into the container of internal capacity 1L, add the 2g ammonium persulphate after, use the agitator stirring and dissolving.Then, slowly drip 3 of 3mL while stirring therein, 4-ethylidene dioxy thiophene is spent 24 hours, carries out 3, the chemical oxidising polymerisation of 4-ethylidene dioxy thiophene.
Behind the above-mentioned chemical oxidising polymerisation, after dilute with water was 4 times, (Japanese smart machine manufacturing, US-T300 (trade(brand)name)) carried out 30 minutes dispersion treatment by ultrasonic homogenizer.Afterwards, add the Zeo-karb ア Application バ one ラ イ ト 120B (trade(brand)name) that 100g オ Le ガ ノ company makes, stirred 1 hour with agitator.Then, the filter paper No.131 that makes by Japan filter paper company filters, and repeats the processing and the filtration of 3 these Zeo-karbs, removes the cation constituent in the liquid fully.
With the strainer of the 1 μ m of the liquid passage aperture after the above-mentioned processing, should handle with ultra-filtration equipment (Vivaflow200 (trade(brand)name), molecular-weight gradation 50,000 that ザ Le ト リ ウ ス company makes) by liquid, remove free low molecular composition in the liquid.Liquid dilute with water after this is handled, regulating concentration is 3%, and this 3% liquid of 40g is added the 4g dimethyl sulfoxide (DMSO), obtains the dispersion liquid of conductive composition.When similarly measuring vitriolic content in this dispersion liquid with embodiment 1, vitriolic content is 123ppm.
Comparative example 2
Except not adding the 4g dimethyl sulfoxide (DMSO), carry out the operation same with embodiment 1, obtain the dispersion liquid of conductive composition.In addition, this dispersion liquid is not owing to add the high boiling solvent dimethyl sulfoxide (DMSO), so should be expressed as the dispersion liquid of electroconductive polymer exactly, but for the purpose of convenient, consistent with the dispersion liquid of the conductive composition of embodiment 1～7 and comparative example 1, the dispersion liquid of this comparative example 2 also is expressed as the dispersion liquid of conductive composition.And and embodiment 1 is when similarly measuring vitriolic content in this dispersion liquid, and vitriolic content is 22ppm.
[as the evaluation of conductive composition]
Respectively per 50 μ L ground drip the dispersion liquid of the conductive composition of the foregoing description 1～7 and comparative example 1～2 on the sheet glass of 2.8cm * 4.8cm, after making it evenly with the scraping strip coating machine of No.8, drying is 10 minutes under 60 ℃, then, drying is 10 minutes under 150 ℃, on sheet glass, form the sheet of conductive composition, the electric conductivity of the sheet of this conductive composition is under room temperature (about 25 ℃), according to JIS K7194, measure by the conductivity tester (Mitsubishi Chemical Ind makes MCP-T600 (trade(brand)name)) of 4 probe modes.Its result is as shown in table 1.In addition, measuring each sample all is to carry out 5 points, and the numerical value of table 1 expression is to try to achieve this mean value of 5, with the value of the expression that rounds up below the radix point.
[table 1]
| Electric conductivity (S/cm) | |
| Embodiment 1 | 230 |
| Embodiment 2 | 220 |
| Embodiment 3 | 450 |
| Embodiment 4 | 280 |
| Embodiment 5 | 410 |
| Embodiment 6 | 400 |
| Embodiment 7 | 430 |
| Comparative example 1 | 12 |
| Comparative example 2 | 0.6 |
As shown in table 1, embodiment 1～7 compares with comparative example 1～2, electric conductivity height, excellent electric conductivity.Just, by the high molecular embodiment 1～7 of electrolytic oxidation polymerization method compositing conducting with compare by the high molecular comparative example 1 of chemical oxidative polymerization compositing conducting, electric conductivity is higher, electroconductibility is more excellent; In addition, compare with the organic acid comparative example 2 with ring texture with not adding high boiling solvent, electric conductivity is higher, and electroconductibility is more excellent.
Then, to each sheet of the conductive composition of the foregoing description 1～7 and comparative example 1～2, measure electric conductivity after, each sheet left standstill 100 hours in 150 ℃ thermostatic bath after, take out the electric conductivity of each sheet and aforementionedly similarly measure.The result is as shown in table 2.Wherein, being used in the conservation rate that leaves standstill the electric conductivity after 100 hours under 150 ℃ about electric conductivity represents.
In addition, the conservation rate of electric conductivity be with initial stage electric conductivity (table 1 record electric conductivity) divided by under 150 ℃ through the electric conductivity after 100 hours, with the value of per-cent (%) expression.If it is it is represented with formula, as follows.Conservation rate is high more, and the expression electric conductivity is difficult to reduce to heat more, and thermotolerance is excellent more.
[several 1]
[table 2]
| The conservation rate of electric conductivity (%) | |
| Embodiment 1 | 81 |
| Embodiment 2 | 80 |
| Embodiment 3 | 83 |
| Embodiment 4 | 81 |
| Embodiment 5 | 84 |
| Embodiment 6 | 85 |
| Embodiment 7 | 81 |
| Comparative example 1 | 69 |
| Comparative example 2 | 70 |
As shown in table 2, embodiment 1～7 compares with comparative example 1～2, and the conservation rate of the electric conductivity after high temperature is preserved down is higher, and thermotolerance is more excellent.
[as the evaluation of electrostatic prevention film]
Embodiment 8～12 and comparative example 3～4
To previous embodiment 1～4, the dispersion liquid of the conductive composition of embodiment 7 and comparative example 1～2, add sulfonated polyester resin (the プ ラ ス コ one ト Z-561 (trade(brand)name) that mutual induction chemical industrial company makes), so that the relative electroconductive polymer of resinous principle is respectively about 150%, after the stirring, on the polythene strip of 2.8cm * 4.8cm, Dropwise 50 μ L has added the dispersion liquid of this sulfonated polyester, after making it evenly with the scraping strip coating machine of No.8, drying is 10 minutes under 60 ℃, then, drying is 10 minutes under 150 ℃, and making with each conductive composition is the electrostatic prevention film of electrical conductor.
The surface resistivity of the embodiment 8～12 of gained and the electrostatic prevention film of comparative example 3～4, under room temperature (about 25 ℃), according to JIS K7194, conductivity tester (MCP-T600 (trade(brand)name) that Mitsubishi Chemical Ind makes) by 4 probe-types is measured, by UV-VIS-NIR RECORDING SPECTROPHOTOMETER (UV3100 (trade(brand)name) that Tianjin, island company makes), measure the visible light transmissivity of wavelength 400nm～700nm simultaneously.Kind expression in table 3 together with the conductive composition of this result and use.In addition, mensuration is to each sample, respectively carries out 5 points, and the numerical value shown in the table 3 is to try to achieve this mean value of 5, is the value with the expression that rounds up below the radix point.
[table 3]
| Electrostatic prevention film | The conductive composition that uses | Surface resistivity (Ω) | Visible light transmissivity (%) |
| Embodiment 8 | Embodiment 1 | 2,100 | 90 |
| Embodiment 9 | Embodiment 2 | 2,400 | 90 |
| Embodiment 10 | Embodiment 3 | 740 | 91 |
| Embodiment 11 | Embodiment 4 | 1,800 | 90 |
| Embodiment 12 | Embodiment 7 | 750 | 91 |
| Comparative example 3 | Comparative example 1 | 51,200 | 90 |
| Comparative example 4 | Comparative example 2 | 629,100 | 90 |
As shown in table 3, the electrostatic prevention film of embodiment 8～12 is compared with the electrostatic prevention film of comparative example 3～4, and surface resistivity is littler, can infer the electroconductibility height from this result, the electrostatic-proof function excellence.In addition, the electrostatic prevention film that also shows embodiment 8～12 has electrostatic prevention film with comparative example 3～4 with contour visible light transmissivity, and the transparency is excellent.
[as the evaluation of tantalum solid electrolytic capacitor]
Embodiment 13
Under tantalum sintered object is immersed in state in the phosphate aqueous solution of concentration 0.1%, apply 20V voltage and carry out chemical coating and handle, form the oxidation overlay film on the surface of tantalum sintered object, constitute dielectric layer.Then, concentration be 35% 3, in the ethanolic soln of 4-ethylidene dioxy thiophene, flood above-mentioned tantalum sintered object, take out after 1 minute, placed 5 minutes.Afterwards, with pre-prepd concentration is that 50% the sulfocarbolic acid butylamine aqueous solution (pH5) and concentration are 30% ammonium persulfate aqueous solution, mix at 1: 1 with mass ratio, in holding concurrently dopant solution, the oxygenant that the mixture that is formed by mixing forms floods, take out after 30 seconds, after at room temperature placing 30 minutes, heated 10 minutes down, carry out polymerization at 50 ℃.Afterwards, above-mentioned tantalum sintered object floods in water, places after 30 minutes, takes out, and drying is 30 minutes under 70 ℃.After repeating 6 these operations, be impregnated in the dispersion liquid of conductive composition of embodiment 1, after 30 seconds, take out, 70 ℃ dry 30 minutes down.Repeat 3 times should operation after, placed 60 minutes down at 150 ℃, form the solid electrolyte layer that constitutes by conductive composition.Afterwards, stick with paste the above-mentioned solid electrolyte layer of covering, make tantalum solid electrolytic capacitor with carbon paste, silver.
Embodiment 14
Except the dispersion liquid of the conductive composition that uses embodiment 2 replaces the dispersion liquid of conductive composition of embodiment 1, carry out the operation same with embodiment 13, make tantalum solid electrolytic capacitor.
Embodiment 15
Except the dispersion liquid of the conductive composition that uses embodiment 3 replaces the dispersion liquid of conductive composition of embodiment 1, carry out the operation same with embodiment 13, make tantalum solid electrolytic capacitor.
Embodiment 16
Except the dispersion liquid of the conductive composition that uses embodiment 4 replaces the dispersion liquid of conductive composition of embodiment 1, carry out the operation same with embodiment 13, make tantalum solid electrolytic capacitor.
Comparative example 5
Except the dispersion liquid of the conductive composition that uses comparative example 1 replaces the dispersion liquid of conductive composition of embodiment 1, carry out the operation same with embodiment 13, make tantalum solid electrolytic capacitor.
Comparative example 6
Except the dispersion liquid of the conductive composition that uses comparative example 2 replaces the dispersion liquid of conductive composition of embodiment 1, carry out the operation same with embodiment 13, make tantalum solid electrolytic capacitor.
To the embodiment 13～16 of as above manufacturing and the tantalum solid electrolytic capacitor of comparative example 5～6, measure ESR and electrostatic capacity.Its result is as shown in table 4.In addition, the measuring method of ESR and electrostatic capacity is as follows.The LCR instrument (4284A) that the mensuration of ESR uses HEWLETT PACKARD company to make under 25 ℃, 100kHz, is measured ESR; The LCR instrument (4284A) that the mensuration of electrostatic capacity uses HEWLETT PACKARD company to make is measured electrostatic capacity under 25 ℃, 120Hz.These mensuration are carried out 10 respectively to each sample, and the ESR value of table 4 expression and static capacity value are to try to achieve these mean value of 10, with the value of the expression that rounds up below the radix point.
[table 4]
| ESR(mΩ) | Electrostatic capacity (μ F) | |
| Embodiment 13 | 27 | 150 |
| Embodiment 14 | 28 | 150 |
| Embodiment 15 | 24 | 152 |
| Embodiment 16 | 25 | 151 |
| Comparative example 5 | 220 | 134 |
| Comparative example 6 | 2199 | 121 |
As shown in table 4, can show that the tantalum solid electrolytic capacitor of embodiment 13～16 compares with the tantalum solid electrolytic capacitor of comparative example 5～6, ESR is littler, and electrostatic capacity is bigger, and is more excellent as the function of electrical condenser.
Then, to the tantalum solid electrolytic capacitor of the foregoing description 13～16 and comparative example 5～6 respectively to each 10,125 ℃ of storages after 200 hours and aforementioned ESR and the electrostatic capacity similarly measured down.The result is as shown in table 5.
[table 5]
| ESR(mΩ) | Electrostatic capacity (μ F) | |
| Embodiment 13 | 29 | 146 |
| Embodiment 14 | 30 | 147 |
| Embodiment 15 | 26 | 149 |
| Embodiment 16 | 27 | 147 |
| Comparative example 5 | 279 | 125 |
| Comparative example 6 | 4261 | 108 |
As shown in table 5, the tantalum solid electrolytic capacitor of embodiment 13～16 is compared with the tantalum solid electrolytic capacitor of comparative example 5～6, even after the storage at high temperature, ESR is also littler, electrostatic capacity is bigger, and the reliability under the hot conditions is higher.
[evaluation of aluminium coiled solid electrolysis capacitor]
Embodiment 17
After the surface of aluminium foil carried out etch processes, carry out chemical coating and handle, pigtail splice is installed at the anode that forms dielectric layer, in addition, at the negative electrode that is formed by aluminium foil lead terminal is installed, reeling by partition has the anode and the negative electrode of these lead terminals, makes capacitor element.
Then, the dispersion liquid of the conductive composition that embodiment 3 is obtained, with the butylamine pH5.5 that neutralizes, the above-mentioned capacitor element of dipping took out after 120 seconds in this liquid, 150 ℃ dry 30 minutes down.Repeat 4 times should operation after, 150 ℃ dry 120 minutes down, form the solid electrolyte layer that forms by conductive composition.Afterwards, put into the outer enclosure of aluminium with forming capacitor element behind the above-mentioned solid electrolyte layer, after the sealing, the limit applies the voltage rating of 25V under 130 ℃, and the aluminium coiled solid electrolysis capacitor is made in rim etching.
Embodiment 18
Except using the dispersion liquid of the conductive composition that embodiment 5 is obtained, neutralize beyond the liquid of pH5.5 with glyoxal ethyline, carry out the operation same with embodiment 17, make the aluminium coiled solid electrolysis capacitor.
Embodiment 19
Except using the dispersion liquid of the conductive composition that embodiment 6 is obtained, neutralize beyond the liquid of pH5.5 with glyoxal ethyline, carry out the operation same with embodiment 17, make the aluminium coiled solid electrolysis capacitor.
Embodiment 20
Except using the dispersion liquid of the conductive composition that embodiment 7 is obtained, neutralize beyond the liquid of pH5.5 with 4-methylimidazole, carry out the operation same with embodiment 17, make the aluminium coiled solid electrolysis capacitor.
Comparative example 7
Except using the dispersion liquid of the conductive composition that comparative example 1 is obtained, neutralize beyond the liquid of pH5.5 with butylamine, carry out the operation same with embodiment 17, make the aluminium coiled solid electrolysis capacitor.
To the embodiment 17～20 of as above manufacturing and the aluminium coiled solid electrolysis capacitor of comparative example 7, measure its ESR and electrostatic capacity.Its result is as shown in table 6.In addition, the measuring method of ESR and electrostatic capacity is as follows.The LCR instrument (4284A) that the mensuration of ESR uses HEWLETT PACKARD company to make under 25 ℃, 100kHz, is measured ESR; The LCR instrument (4284A) that the mensuration of electrostatic capacity uses HEWLETT PACKARD company to make is measured electrostatic capacity under 25 ℃, 120Hz.These mensuration are carried out 10 respectively to each sample, and the ESR value of table 6 expression and static capacity value are to try to achieve these mean value of 10, with the value of the expression that rounds up below the radix point.
[table 6]
| ESR(mΩ) | Electrostatic capacity (μ F) | |
| Embodiment 17 | 24 | 107 |
| Embodiment 18 | 23 | 107 |
| Embodiment 19 | 23 | 108 |
| Embodiment 20 | 24 | 107 |
| Comparative example 7 | 940 | 59 |
As shown in table 6, show that the aluminium coiled solid electrolysis capacitor of embodiment 17～20 compares with the aluminium coiled solid electrolysis capacitor of comparative example 7, ESR is littler, and electrostatic capacity is bigger, and is more excellent as the function of electrical condenser.
Then, the aluminium coiled solid electrolysis capacitor of the foregoing description 17～20 and comparative example 7 is measured 10 respectively, 125 ℃ of down storages after 500 hours and aforementioned ESR and the electrostatic capacity similarly measured.Its result is as shown in table 7.
[table 7]
| ESR(mΩ) | Electrostatic capacity (μ F) | |
| Embodiment 17 | 26 | 99 |
| Embodiment 18 | 25 | 105 |
| Embodiment 19 | 25 | 104 |
| Embodiment 20 | 26 | 104 |
| Comparative example 7 | 5500 | 41 |
As shown in table 7, the aluminium coiled solid electrolysis capacitor of embodiment 17～20 is compared with the aluminium coiled solid electrolysis capacitor of comparative example 7, even after the storage at high temperature, ESR is littler, electrostatic capacity is bigger, and the reliability under the hot conditions is higher.
Industrial applicibility
According to the present invention, can provide the conductive composition that the transparency is high, electric conductivity is high and heat resistance is excellent. And, the conductive composition transparency of the invention described above is high, and its electroconductive polymer is synthetic by electrolytic oxidation polymerization, so it is few that the sulfate radical based on oxidant that occurs in the synthetic electroconductive polymer of chemical oxidising polymerisation contains, also few based on the reduction of the electric conductivity of residual sulfate radical and the reduction of the transparency etc.
Therefore, based on the character of this conductive composition of the present invention, by using it as electric conductor, can provide the transparency is high, electric conductivity is high and heat resistance is excellent electrostatic prevention film, antistatic resin, antistatic plate etc. In addition, the conductive composition of the present invention by using this electric conductivity height and heat resistance excellence is as solid electrolyte, and the high solid electrolytic capacitor of reliability under the little and hot conditions of ESR can be provided.
Claims (13)
1. the dispersion liquid of a conductive composition, it is characterized in that: the organic acid that comprises electroconductive polymer and high boiling solvent or have ring texture, wherein electroconductive polymer is by in the presence of sulfocarbolic acid novolac resin, sulfonated polyester or polystyrolsulfon acid with the repeating unit shown in the following general formula (I), with the thiophene or derivatives thereof in water or in the aqueous solution that the mixed solution by water and water-miscible solvent forms, electrolytic oxidation polymerization obtains
R in the formula is hydrogen or methyl.
2. the dispersion liquid of the conductive composition of putting down in writing according to claim 1, it is characterized in that: thiophene derivant is 3,4-ethylidene dioxy thiophene.
3. according to the dispersion liquid of claim 1 or 2 conductive compositions of being put down in writing, it is characterized in that: electrolytic oxidation polymerization carries out in containing the water of iron ion or in the aqueous solution.
4. according to the dispersion liquid of each conductive composition of being put down in writing of claim 1～3, it is characterized in that: the boiling point of high boiling solvent is more than 150 ℃.
5. according to the dispersion liquid of each conductive composition of being put down in writing of claim 1～4, it is characterized in that: high boiling solvent is a dimethyl sulfoxide (DMSO).
6. according to the dispersion liquid of each conductive composition of being put down in writing of claim 1～3, it is characterized in that: the organic acid with ring texture is a fragrant same clan organic acid.
7. the dispersion liquid of the conductive composition of putting down in writing according to claim 6, it is characterized in that: fragrant same clan organic acid is at least a kind that selects from the group that is made of sulfocarbolic acid, naphthene sulfonic acid and anthraquinone sulfonic acid.
8. according to the dispersion liquid of each conductive composition of being put down in writing of claim 1～7, it is characterized in that: further contain tackiness agent.
9. conductive composition is characterized in that: be that dispersion liquid drying with each conductive composition of being put down in writing of claim 1～8 obtains.
10. electrostatic prevention film is characterized in that: use conductive composition that claim 9 puts down in writing as electrical conductor.
11. an antistatic plate is characterized in that: at least one mask of plate substrate electrostatic prevention film that requirement 10 put down in writing of having the right.
12. a solid electrolytic capacitor is characterized in that: the conductive composition that use claim 9 is put down in writing is as solid electrolyte.
13. solid electrolytic capacitor, this solid electrolytic capacitor has by tantalum, niobium, the anode that the porous insert of valve metals such as aluminium forms, the dielectric layer and the solid electrolyte that form by the oxidation overlay film of aforementioned valve metal, it is characterized in that: the conductive composition that aforementioned solid electrolyte is put down in writing by electroconductive polymer and the claim 9 that forms on aforementioned electroconductive polymer forms, wherein aforementioned electroconductive polymer is on aforementioned dielectric layer, use the non-molysite class oxygenant doping agent of holding concurrently, the electroconductive polymer that thiophene or derivatives thereof chemical oxidising polymerisation is formed.
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| CN101932628B (en) | 2013-02-27 |
| TWI357083B (en) | 2012-01-21 |
| WO2009131011A1 (en) | 2009-10-29 |
| KR20100065404A (en) | 2010-06-16 |
| KR100979380B1 (en) | 2010-08-31 |
| JP4454041B2 (en) | 2010-04-21 |
| TW200951993A (en) | 2009-12-16 |
| JPWO2009131011A1 (en) | 2011-08-18 |
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