CN1193057C - Conductive polymer, solid electrolytic capacitor and process for producing these - Google Patents

Conductive polymer, solid electrolytic capacitor and process for producing these Download PDF

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CN1193057C
CN1193057C CNB998010766A CN99801076A CN1193057C CN 1193057 C CN1193057 C CN 1193057C CN B998010766 A CNB998010766 A CN B998010766A CN 99801076 A CN99801076 A CN 99801076A CN 1193057 C CN1193057 C CN 1193057C
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polymerization
polymer
high conductivity
solution
ring
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CN1273677A (en
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大籏英树
白根浩朗
门田隆二
坂井厚
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Resonac Holdings Corp
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Showa Denko KK
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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

Abstract

A solid electrolytic capacitor which has an electrode obtained by forming a solid electrolyte layer made of a polymer having repeating units of at least one kind selected among thiophene, isothianaphthene, pyrrole, furan, and aniline skeletons and having a fibril structure on a porous dielectric film made of a valve metal; a process for producing the capacitor; a highly conductive polymer obtained by polymerizing a monomer with an oxidizing agent through chemical oxidative polymerization at the interface therebetween; and a process for producing the polymer.

Description

Electric conductive polymer, Solid electrolytic capacitor And Manufacturing approach
The application system with regard to the 60/129th, No. 044 temporary patent application of the U.S. (applying date: on April 13rd, 1999) and the 60/129th, No. 045 temporary patent application of the U.S. (applying date: content on April 13rd, 1999) proposes claim.
Technical field
The present invention relates to a kind of electric conductive polymer, carry the Solid electrolytic capacitor And Manufacturing approach of holding this polymkeric substance.In more detail, the present invention relates to a kind of small-sized, heavy body, low-impedance Solid electrolytic capacitor And Manufacturing approach, described solid electrolytic capacitor moisture-proof part throttle characteristics is good, and has excellent thermotolerance; The present invention also relates to a kind ofly to be used for described electrical condenser, have the high conductivity polymer of novel fibrillar structure and the manufacture method of this high conductivity polymer.
Background technology
Solid electrolytic capacitor is a kind of like this element, this electrolytic condenser normally by through etch processes, have on the anode substrate that the tinsel of big specific surface area forms and form dielectric oxidation film layer, this oxidation film layer outside form solid semiconductor layer as opposite electrode (below, abbreviate solid electrolyte as), and, be more preferably, at the conductor layer of its outside formation as conduction pasting etc., connect lead-in wire again.Actual element, its integral body fully by Resins, epoxy etc. seal, be widely used in the electric product as capacitor part.
In recent years, be to adapt to the needs of the numberization of electrical equipment, the high speed of special-purpose small-size computer etc., for employed electrical condenser wherein, also proposed miniaturization, large vol, in characteristic requirements such as the high-frequency region medium or low resistance are anti-.
As miniaturization, jumbo electrical condenser, the solid electrolytic capacitor of aluminium electrolutic capacitor and tantalum electrolytic capacitor etc. is arranged.Yet, because the aqueous ionogen that has used ionic conductivity in the aluminium electrolutic capacitor is as electrolytic solution, so the problem that aluminium electrolutic capacitor exists is: the resistance value height in its high-frequency region, and its temperature profile deterioration.On the other hand, use manganese oxide in the tantalum electrolytic capacitor, because the problem that the higher tantalum electrolytic capacitor of the ratio resistance of manganese oxide exists is: the resistance value height in its high-frequency region as ionogen.
Therefore, for satisfying above-mentioned these requirements, someone proposes to have the electroconductive polymer of electronic conductivity as solid electrolyte, more the someone proposes to use that to contain pi-conjugated be high molecular electroconductibility organism class polyaniline (spy opens clear 61-239617 communique), poly-arsenic is coughed up (spy opens clear 61-240625 communique), polythiofuran derivative (spy opens flat 2-15611 communique, No. 4901645, United States Patent (USP)), the polyisothianaphthene (spy opens clear 62-239617 communique) that does not contain doping agent, be in the polyisothianaphthene (spy opens clear 62-118511 communique) of dopant states, specific conductivity is 10 -3-10 3The intrinsic conductivity polymer of S/cm scope (spy opens flat 1-169914 communique, U.S. Patent number 4803596).
Promptly, because of usually by aniline, arsenic cough up, the polymer that contains conjugated double bond of polymkeric substance representative such as thiophene has special conductivity, so, this is carried out multiple research, exploitation, wherein, the special electricity of the electron conjugated system that electroconductive polymer had, magnetic, optical characteristics are noticeable especially.What these electroconductive polymers were main is to make with electrolytic polymerization method and chemical oxidative polymerization.
Yet, in manufacture method in the past, if by poor at the adhesive property of made low-molecular weight polymer that obtains of the redox reaction that electrode surface carried out and electrode surface, low-molecular weight polymer dissolves or is piled up in the electrolyte solution.Again, when having large-area article for acquisition, the electrode that needs its size and this item sizes to adapt, this also makes manufacturing cost increase.
On the other hand, when utilizing chemical oxidative polymerization, can be by polymerization be mixed with monomer and proper amount of oxidant, and easily make electroconductive polymer.For this reason, this method comes into one's own and research and development as industrial easy polymerization process.
But a big problem of chemical oxidative polymerization is: because of its polymerization velocity is directly proportional with the activity of oxygenant, therefore, require to use active big oxygenant.Yet, when using active big oxygenant to carry out polymerization, undesirable side reaction takes place easily, can only obtain that compound with regular structure is low, the polymkeric substance of poorly conductive.Its reason can be thought: the electric conductive polymer with conjugated double bond of generation stays in the reactive system for a long time, in reactive system under the influence of thing such as remaining oxygenant, polymer backbone with conjugated double bond suffers destruction partly, and its result causes conductivity low.
Have again, be generally insoluble not fusant, particularly, have very operational problem such as difficulty of its post-treatment by electrolytic polymerization or the prepared electroconductive polymer of chemical oxidative polymerization.For addressing these problems, people have done multiple research.
For example, open the manufacture method that discloses a kind of solid electrolytic capacitor on the flat 7-130579 communique (No. 5567209 United States Patent (USP)) the spy, the oxide film that valve action is formed in the metallic surface is as electricity price matter layer, on dielectric layer, form the electroconductive polymer layer, with its manufacture method as the solid electrolytic capacitor of solid electrolyte, in the method, monomeric compound solution is coated aforementioned oxide film surface, dry, form after the monomeric compound of solid state, described solid state monomeric compound is contacted with oxidizing agent solution, form the electroconductive polymer layer, thus, obtain capacity utilization ratio height, the solid electrolytic capacitor that high frequency characteristics is good.
Te Kaiping 6-340754 communique discloses a kind of inside or surface oxidation polymeric method that makes the polycycle aromatic amines compound at body material, described method system makes it contact and oxypolymerization with the solution that contains oxygenant after the polycycle aromatic amines compound is adhered to or impregnated on the insulating body material.
Again, Te Kaiping 10-50558 communique has disclosed a kind of manufacture method of solid electrolytic capacitor: as the application of electroconductive polymer to solid electrolytic capacitor, such manufacture for solid electrolytic capacitor is arranged: will impregnated in as the electric conductive polymer of catholyte to be equipped with and form in the capacitor element that closes film forming anode component.In this manufacture method, described capacitor element is immersed in by oxypolymerization, oxygenant is dissolved in to be become in the monomeric solution of electric conductive polymer, by this, forms the electric conductive polymer layer in described capacitor element, makes small-sized, jumbo electrical condenser.
Have again, Te Kaiping 10-50559 communique has disclosed a kind of method that improves the high-temperature load characteristic of solid electrolytic capacitor: as the application of electroconductive polymer to solid electrolytic capacitor, after impregnated in capacitor element in the oxidizing agent solution, make the volatilization of solvent composition, oxide compound is separated out in this electrolytic condenser element.Then, this capacitor element is immersed in to contain by oxypolymerization to be become in the monomeric solution of electric conductive polymer, and aforementioned oxygenant and described monomer effect thus, improve the high-temperature load characteristic.
Again, Te Kaiping 9-289141 communique (EP A803885 number) has proposed a kind of electrode porous pledge that makes and impregnated in the solution that contains oxygenant, make the method for solid electrolytic capacitor, this method system impregnated in temperature with electrode porous pledge and remains in the monomer salts solution more than the solvent temperature, after the cooling, separate out monomer salt on its surface.
As the solid electrolyte that is formed on the dielectric film, noticeablely be to expect to substantially improve basically the appearance of the conductive metal oxide of specific conductivity and electroconductive polymer etc.But the problem that exists is: if specific conductivity too greater than suitable scope, then leakage current values increases, its result causes short circuit; In addition, if specific conductivity is low excessively, then frequency response characteristic worsens, and capacity is low.So the problem that must develop is: the OK range of specific conductivity control, and the thermal stability problems of solution solid electrolyte.
In the electrical condenser that in the past uses electroconductive polymer such as polypyrrole, the problem of existence is that according to the difference of moisture-proof load, the characteristic of electrical condenser can change a lot.Again, with its relatively, stable on heating requirement is increased, for example, also to pay attention to the thermotolerance (adverse current) of the scolding tin when capacitor element is configured as capacitor part, require the high capacitor element of thermotolerance.That is, conventional art has problems on solid electrolyte that generates on the oxide film and manufacture method thereof.
Specifically, above-mentioned spy opens the technology that flat 7-130579 communique is disclosed, be to become the solid state monomer after the monomeric compound solution drying, increase along with the polymer constituent polymerization degree, because being solid mutually, monomer suppressed monomeric diffusion, the danger that existence may make polymerization velocity descend fully.
The technology that Te Kaiping 6-340754 communique is disclosed relates to form the manufacture method of transparent conducting film on isolator, do not speak of high molecular form of the high conductivity that is had fibrillar structure by positive interfacial polymerization and performance.
The technology that Te Kaiping 10-50558 communique is disclosed is a kind of method that forms electroconductive polymer thin film on synthetic film.But because aforesaid method is oxygenant directly to be dissolved in the monomer that becomes electric conductive polymer by oxypolymerization, so, in the monomer solution of preparation, before using and among using, all carry out oxidative polymerization, make described monomer polymerization materialization, be difficult to often keep the monomer solution of homogeneous, so, this method a kind of stable production method that can give full play to the stably manufactured performance of can not saying so.
A kind of like this method of technology system that Te Kaiping 10-50559 communique is disclosed, aforesaid method is that oxygenant is imported in the micropore as solution, then, evaporating solvent is separated out oxygenant crystalline oxypolymerization method.But, this method is from process, the operation that oxygenant is separated out in the synthetic tinsel micropore of handling is indispensable, because the contact area between oxidant with solid and monomer is very little, so, the polyreaction of this method is carried out very slowly, is not a high efficiency method, and it is to industrialized production and be not suitable for.
Have, open in the technology that flat 9-289141 communique (EP A803885) disclosed the spy, the polymerization monomer is a solid, and therefore, it is the same that its existing problems and above-mentioned spy open the problem that exists in the flat 10-50559 communique.
Invention discloses
Problem of the present invention is: a kind of high conductivity polymer is provided, and described high conductivity polymer is suitable to the solid electrolyte in the solid electrolytic capacitor, and has conjugated double bond (πDian Zi conjugated system).
Other problem of the present invention is: a kind of manufacture method of polymkeric substance of novelty is provided, and the polymkeric substance of described novelty has same chemical constitution by oxidative polymerization method, simultaneously, has the more conjugated double bond of high conductivity (πDian Zi conjugated system).
A problem more of the present invention is: a kind of Solid electrolytic capacitor And Manufacturing approach is provided: above-mentioned high conductivity polymer is used as solid electrolyte, this electrolytic condenser not only has excellent initial characteristic, and also excellence of long-term reliabilities such as high temperature, high humidity weather resistance down.
Present inventors are in view of above-mentioned problem, carried out research painstakingly, found that: will dissolve the monomeric solution of polymerization separately, maybe will dissolve polymerization with monomer and have doping can electrolytical solution, make above-mentioned solution and oxidizing agent solution carry out slowly stable contacting at the interface with polymerization threshold energy, make it polymerization, by this, can obtain having the high conductivity polymer of flakey fibrillar structure.In addition, by on dielectric film, carrying out described polymerization methods, resulting, as to have fibrillar structure membranaceous composition is used as solid electrolyte, can obtain having the electrical condenser of the long-term reliability (weather resistance under high temperature, the high humidity etc.) of excellent initial characteristic (equivalent serial resistance of loss factor, leakage current, thermotolerance, high-frequency region and low resistance etc.) and excellence, thereby, finished the present invention.
That is, the present invention is a kind of solid electrolytic capacitor as described below, its manufacture method, electric conductive polymer and manufacture method thereof.
[1] a kind of solid electrolytic capacitor, described electrolytic condenser tie up to porous matter, have on the inter metal dielectric film of valve action and form the solid electrolyte layer of being made up of the polymkeric substance with fibrillar structure.
[2] as above-mentioned 1 described solid electrolytic capacitor, wherein, described polymkeric substance is repeating unit, has an electric conductive polymer of fibrillar structure for containing with the represented thiophene skeleton structure of following general formula (1).
Figure C9980107600121
(in the formula, R 1And R 2Represent independently hydrogen atom respectively, carbonatoms is saturated or undersaturated alkyl, alkoxyl group or the carbalkoxy of the straight or branched of 1-10; Or expression is selected from halogen atom, nitro, cyano group, primary, the second month in a season or tertiary amine groups, CF 3Base, the univalent perssad in phenyl and the substituted-phenyl.Again, R 1And R 2Hydrocarbon chain can interosculate in position arbitrarily, also can be by the bonded group, form the divalence chain of the ring texture that is formed with 3-7 unit's ring filling or unsaturated hydrocarbons with the carbon atom of accepting to replace.Described ring-type marriage chain can locate to contain the key of carbonyl, ether, ester, acid amides, sulphur (thioether), sulfinyl, alkylsulfonyl, imino-at an arbitrary position.Again, δ represents the scope of 0-1.Z represents negatively charged ion, and j represents the valence mumber of Z, is 1 or 2.)
[3] as above-mentioned 1 described solid electrolytic capacitor, wherein, described polymkeric substance is repeating unit, has an electric conductive polymer of fibrillar structure for containing with the represented condensation polycyclic formula skeleton structure of following general formula (2).
Figure C9980107600131
(in the formula, R 3, R 4, R 5, R 6, R 7And R 8Represent independently hydrogen atom respectively, carbonatoms is saturated or undersaturated alkyl, alkoxyl group or the carbalkoxy of the straight or branched of 1-10; Or expression is selected from halogen atom, nitro, cyano group, primary, the second month in a season or tertiary amine groups, CF 3Base, the univalent perssad in phenyl and the substituted-phenyl.Again, R 3, R 4, R 5, R 6, R 7And R 8Hydrocarbon chain can interosculate in position arbitrarily, also can be by the bonded group, form the divalence chain of the ring texture that is formed with more than 1 3～7 yuan of ring fillings or unsaturated hydrocarbons at least with the carbon atom of accepting to replace.Described ring-type marriage chain can locate to contain the key of carbonyl, ether, ester, acid amides, sulphur, sulfinyl, alkylsulfonyl, imino-at an arbitrary position.K represents by thiphene ring and has substituent R 3-R 6The condensed ring number that phenyl ring surrounded; O represents the integer of 0-1.(nitrogen or the N-oxygen base that also can contain any number on the condensed ring in the formula, but this number is also represented substituent R 3-R 8The number of corresponding minimizing.δ is in the scope of 0-1; Z represents negatively charged ion; J represents the valence mumber of Z, is 1 or 2.)
[4] as above-mentioned 1 described solid electrolytic capacitor, wherein, described polymkeric substance is repeating unit, has an electric conductive polymer of fibrillar structure for containing with the represented pyrrole skeleton structure of following general formula (3).
(in the formula, R 9And R 10Represent independently saturated or undersaturated alkyl, alkoxyl group or the carbalkoxy of the straight or branched of hydrogen atom, carbonatoms 1-10 respectively; Or expression is selected from halogen atom, nitro, cyano group, primary, the second month in a season or tertiary amine groups, CF 3Base, the univalent perssad in phenyl and the substituted-phenyl.Again, R 9And R 10Hydrocarbon chain can interosculate in position arbitrarily, also can be by the bonded group, form the divalence chain of the ring texture that is formed with at least 1 above 3-7 unit's ring filling or undersaturated hydrocarbon with the carbon atom of accepting to replace.Described ring-type marriage chain locates to contain the key of carbonyl, ether, ester, acid amides, sulphur, sulfinyl, alkylsulfonyl, imino-at an arbitrary position.Again, δ is in the scope of 0-1; Z represents negatively charged ion; J represents the valence mumber of Z, is 1 or 2.)
[5] as above-mentioned 1 described solid electrolytic capacitor, wherein, described polymkeric substance is repeating unit, has an electric conductive polymer of fibrillar structure for containing with the represented furans skeleton structure of following general formula (4).
Figure C9980107600141
(in the formula, substituent R 11And R 12Represent independently hydrogen atom respectively, carbonatoms is saturated or undersaturated alkyl, alkoxyl group or the carbalkoxy of the straight or branched of 1-10; Or expression is selected from halogen atom, nitro, cyano group, primary, the second month in a season or tertiary amine groups, CF 3Base, the univalent perssad in phenyl and the substituted-phenyl.Again, R 11And R 12Hydrocarbon chain can interosculate in position arbitrarily, also can be by the bonded group, form the divalence chain of the ring texture that is formed with at least 1 above 3-7 unit's ring filling or undersaturated hydrocarbon with the carbon atom of accepting to replace.Described ring-type marriage chain can locate to contain the key of carbonyl, ether, ester, acid amides, sulphur, sulfinyl, alkylsulfonyl, imino-at an arbitrary position.δ is in the scope of 0-1; Z represents negatively charged ion; J represents the valence mumber of Z, is 1 or 2.)
[6] as above-mentioned 1 described solid electrolytic capacitor, wherein, described polymkeric substance is repeating unit, has an electric conductive polymer of fibrillar structure for containing with the represented aniline skeleton structure of following general formula (5).
(in the formula, R 13, R 14, R 15And R 16Represent independently hydrogen atom respectively, carbonatoms is saturated or undersaturated alkyl, alkoxyl group or the carbalkoxy of the straight or branched of 1-10; Or expression is selected from halogen atom, nitro, cyano group, primary, the second month in a season or tertiary amine groups, CF 3Base, the univalent perssad in phenyl and the substituted-phenyl.Again, R 13, R 14, R 15And R 16Hydrocarbon chain can interosculate in position arbitrarily, also can be by the bonded group, form the divalence chain of the ring texture that is formed with at least 1 above 3-7 unit's ring filling or undersaturated hydrocarbon with the carbon atom of accepting to replace.Described marriage chain can locate to contain the key of carbonyl, ether, ester, acid amides, sulphur, sulfinyl, alkylsulfonyl, imino-at an arbitrary position.δ is in the scope of 0-1; Z represents negatively charged ion; J represents the valence mumber of Z, is 1 or 2.)
[7] as each described solid electrolytic capacitor of above-mentioned 2-6, the electroconductibility of the solid electrolyte layer of described polymkeric substance is 0.1-200S/cm.
[8] a kind of manufacture method that on dielectric film, is formed with the solid electrolytic capacitor of solid electrolyte layer, described solid electrolyte series of strata are made up of the polymkeric substance with fibrillar structure, described method ties up to porous matter, have the solid electrolyte layer that is provided with on the dielectric film of metal of valve action to be made up of polymkeric substance, it is characterized in that, in described method, comprise operation as described below:
On above-mentioned dielectric film, polymerization is contacted with the single solution that is maintained at saturated or hypersaturated state, as to have polymerization threshold energy oxygenant with monomer, or polymerization is contacted with the electrolytical mixing solutions with doping energy with described oxygenant with monomer, on the aforementioned electric deielectric-coating, form the membranaceous composition of polymkeric substance with fibrillar structure.
[9] a kind of manufacture method that on dielectric film, is formed with the solid electrolytic capacitor of solid electrolyte layer, described solid electrolyte series of strata are made up of the polymkeric substance with fibrillar structure, described method ties up to porous matter, have the solid electrolyte layer that is provided with on the dielectric film of metal of valve action to be made up of polymkeric substance, it is characterized in that described method comprises operation as described below:
On above-mentioned dielectric film, make polymerization with monomer solution or make be dissolved with polymerization with monomer with have doping can electrolytical mixing solutions contact with the single solution that is maintained at saturated or hypersaturated state, have an oxygenant of polymerization threshold energy; Make described polymerization with monomer solution or make be dissolved with polymerization with monomer with have doping can electrolytical mixing solutions and described oxygenant with described have doping can electrolytical mixing solutions contact, formation has the membranaceous composition of the polymkeric substance of fibrillar structure on the aforementioned electric deielectric-coating.
[10] as above-mentioned 8 or the manufacture method of 9 described solid electrolytic capacitors, it is characterized in that, make with the represented polymerization of following general formula (6) with monomer with contain oxidizing agent solution and contact with polymerization threshold energy, on the aforementioned electric deielectric-coating, form the membranaceous composition of polymkeric substance with fibrillar structure.
(in the formula, substituent R 1And R 2Represent independently hydrogen atom respectively, carbonatoms is saturated or undersaturated alkyl, alkoxyl group or the carbalkoxy of the straight or branched of 1-10; Or expression is selected from halogen atom, nitro, cyano group, primary, the second month in a season or tertiary amine groups, CF 3Base, the univalent perssad in phenyl and the substituted-phenyl.Again, R 1And R 2Hydrocarbon chain can interosculate in position arbitrarily, also can be by the bonded group, form the divalence chain of the ring texture that is formed with 3-7 unit's ring filling or unsaturated hydrocarbons with the carbon atom of accepting to replace.Described ring-type marriage chain can locate to contain the key of carbonyl, ether, ester, acid amides, sulphur, sulfinyl, alkylsulfonyl, imino-at an arbitrary position.)
[11] as the manufacture method of 8 or 9 described solid electrolytic capacitors, it is characterized in that, make with the represented polymerization of following general formula (7) with monomer with contain oxidizing agent solution and contact with polymerization threshold energy, on the aforementioned electric deielectric-coating, form the membranaceous composition of polymkeric substance with fibrillar structure.
Figure C9980107600162
(in the formula, substituent R 3, R 4, R 5, R 6, R 7And R 8Represent independently hydrogen atom respectively, carbonatoms is saturated or undersaturated alkyl, alkoxyl group or the carbalkoxy of the straight or branched of 1-10; Or expression is selected from halogen atom, nitro, cyano group, primary, the second month in a season or tertiary amine groups, and CF 3Base, the univalent perssad in phenyl and the substituted-phenyl.Again, R 3, R 4, R 5, R 6, R 7And R 8Hydrocarbon chain can interosculate in position arbitrarily, also can be by the bonded group, form the divalence chain of the ring texture that is formed with at least 1 above 3-7 unit's ring filling or unsaturated hydrocarbons with the carbon atom of accepting to replace.Described ring-type marriage chain can locate to contain the key of carbonyl, ether, ester, acid amides, sulphur, sulfinyl, alkylsulfonyl, imino-at an arbitrary position.K represents by thiphene ring and has substituent R 3-R 6The number of the condensed ring that phenyl ring surrounded; O represents the integer of 0-1; (nitrogen or the N-oxygen base that also can contain any number on the condensed ring in the formula, but just this number is also represented substituent R 3-R 8The number of corresponding minimizing.
[12] as above-mentioned 8 or the manufacture method of 9 described solid electrolytic capacitors, it is characterized in that, make with the represented polymerization of following general formula (8) with monomer with contain oxidizing agent solution and contact with polymerization threshold energy, on the aforementioned electric deielectric-coating, form the membranaceous composition of polymkeric substance with fibrillar structure.
(in the formula, R 9And R 10Represent independently hydrogen atom respectively, carbonatoms is saturated or undersaturated alkyl, alkoxyl group or the carbalkoxy of the straight or branched of 1-10; Or expression is selected from halogen atom, nitro, cyano group, primary, the second month in a season or tertiary amine groups, CF 3Base, the univalent perssad in phenyl and the substituted-phenyl.Again, R 9And R 10Hydrocarbon chain can interosculate in position arbitrarily, also can be by the bonded group, form the divalence chain of the ring texture that is formed with at least 1 above 3-7 unit's ring filling or unsaturated hydrocarbons with the carbon atom of accepting to replace.Described ring-type marriage chain can locate to contain the key of carbonyl, ether, ester, acid amides, sulphur, sulfinyl, alkylsulfonyl, imino-at an arbitrary position.)
[13] as above-mentioned 8 or 9 described solid electrolytic capacitors, wherein, described polymkeric substance forms the membranaceous composition of the polymkeric substance with fibrillar structure for to contact with the solution that contains the oxygenant with polymerization threshold energy with monomer with the represented polymerization of following general formula (9) on above-mentioned dielectric film.
(in the formula, substituent R 11And R 12Represent independently hydrogen atom respectively, carbonatoms is saturated or undersaturated alkyl, alkoxyl group or the carbalkoxy of the straight or branched of 1-10; Or expression is selected from halogen atom, nitro, cyano group, primary, the second month in a season or tertiary amine groups, CF 3Base, the univalent perssad in phenyl and the substituted-phenyl.Again, R 11And R 12Hydrocarbon chain can interosculate in position arbitrarily, also can be by the bonded group, form the divalence chain of the ring texture that is formed with at least 1 above 3-7 unit's ring filling or undersaturated hydrocarbon with the carbon atom of accepting to replace.Described ring-type marriage chain can locate to contain the key of carbonyl, ether, ester, acid amides, sulphur, sulfinyl, alkylsulfonyl, imino-at an arbitrary position.)
[14] as above-mentioned 8 or the manufacture method of 9 described solid electrolytic capacitors, wherein, described polymkeric substance forms the membranaceous composition of the polymkeric substance with fibrillar structure for to contact with the solution that contains the oxygenant with polymerization threshold energy with monomer with the represented polymerization of following general formula (10) on above-mentioned dielectric film.
Figure C9980107600181
(in the formula, substituent R 13, R 14, R 15And R 16Represent independently hydrogen atom respectively, carbonatoms is saturated or undersaturated alkyl, alkoxyl group or the carbalkoxy of the straight or branched of 1-10; Or expression is selected from halogen atom, nitro, cyano group, primary, the second month in a season or tertiary amine groups, CF 3Base, the univalent perssad in phenyl and the substituted-phenyl.Again, R 13, R 14, R 15And R 16Hydrocarbon chain can interosculate in position arbitrarily, also can be by the bonded group, form the divalence chain of the ring texture that is formed with more than 13 and even 1 yuan of ring fillings or unsaturated hydrocarbons at least with the carbon atom that accept to replace, this divalence chain forms more than 1 at least.Described marriage chain can locate to contain the key of carbonyl, ether, ester, acid amides, sulphur, sulfinyl, alkylsulfonyl, imino-at an arbitrary position.)
As the manufacture method of above-mentioned 9 described solid electrolytic capacitors, it is characterized in that [15] described polymerization is the 0.01-5 mol with monomeric concentration.
[16] as above-mentioned 8 or the manufacture method of 9 described solid electrolytic capacitors, it is characterized in that, described have doping can electrolyte concentration in the scope of 0.001-2.5 mol.
As above-mentioned 8 or the manufacture method of 9 described solid electrolytic capacitors, it is characterized in that [17] described oxygenant with polymerization threshold energy is at least a compound that is selected from the molysite class of persulfuric acid salt, dichromic acid salt, 3 valencys.
[18] as above-mentioned 8 or the manufacture method of 9 described solid electrolytic capacitors, it is characterized in that described oxidant concentration with polymerization threshold energy is polymerization 0.01～5 times with monomer concentration.
[19] as the manufacture method of above-mentioned each described solid electrolytic capacitor of 8 to 14, it is characterized in that, repeat to form the operation of the solid electrolyte of forming by polymkeric substance repeatedly for 2-30 time, to form membranaceous composition.
[20] a kind of high conductivity polymer, described polymer system is repeating unit, has a high conductivity polymer of fibrillar structure with the represented thiophene skeleton structure of following general formula (1).
(in the formula, substituent R 1And R 2Represent independently hydrogen atom respectively, carbonatoms is saturated or undersaturated alkyl, alkoxyl group or the carbalkoxy of the straight or branched of 1-10; Or expression is selected from halogen atom, nitro, cyano group, primary, the second month in a season or tertiary amine groups, CF 3Base, the univalent perssad in phenyl and the substituted-phenyl.Again, R 1And R 2Hydrocarbon chain can interosculate in position arbitrarily, also can be by the bonded group, form the divalence chain of the ring texture that is formed with 3-7 unit's ring filling or unsaturated hydrocarbons with the carbon atom of accepting to replace.Described ring-type marriage chain can locate to contain the key of carbonyl, ether, ester, acid amides, sulphur, sulfinyl, alkylsulfonyl, imino-at an arbitrary position.Again, δ is in the scope of 0-1; Z represents negatively charged ion; J represents the valence mumber of Z, is 1 or 2.)
[21] a kind of high conductivity polymer, described polymer system is repeating unit, has an electric conductive polymer of fibrillar structure with the represented condensation polycyclic structure of following general formula (2).
(in the formula, substituent R 3, R 4, R 5, R 6, R 7And R 8Represent independently hydrogen atom respectively, carbonatoms is saturated or undersaturated alkyl, alkoxyl group or the carbalkoxy of the straight or branched of 1-10; Or expression is selected from halogen atom, nitro, cyano group, primary, the second month in a season or tertiary amine groups, and CF 3Base, the univalent perssad in phenyl and the substituted-phenyl.Again, R 3, R 4, R 5, R 6, R 7And R 8Hydrocarbon chain can interosculate in position arbitrarily, also can be by the bonded group, form the divalence chain of the ring texture that is formed with at least 1 above 3-7 unit's ring filling or unsaturated hydrocarbons with the carbon atom of accepting to replace.Described ring-type marriage chain can locate to contain the key of carbonyl, ether, ester, acid amides, sulphur, sulfinyl, alkylsulfonyl, imino-at an arbitrary position.K represents by thiphene ring and has substituent R 3-R 6The number of the condensed ring that phenyl ring surrounded, o represents the integer of 0-1.(nitrogen or the N-oxygen base that also can contain any number on the condensed ring in the formula, but just this number is also represented substituent R 3-R 8The number of corresponding minimizing.δ is in the scope of 0-1; Z represents negatively charged ion; J represents the valence mumber of Z, is 1 or 2.)
[22] a kind of high conductivity polymer, described polymer system is repeating unit, has an electric conductive polymer of fibrillar structure with the represented pyrrole skeleton structure of following general formula (3).
Figure C9980107600201
(in the formula, R 9And R 10Represent independently hydrogen atom respectively, carbonatoms is saturated or undersaturated alkyl, alkoxyl group or the carbalkoxy of the straight or branched of 1-10; Or expression is selected from halogen atom, nitro, cyano group, primary, the second month in a season or tertiary amine groups, and CF 3Base, the univalent perssad in phenyl and the substituted-phenyl.Again, R 9And R 10Hydrocarbon chain can interosculate in position arbitrarily, also can be by the bonded group, form the divalence chain of the ring texture that is formed with at least 1 above 3-7 unit's ring filling or unsaturated hydrocarbons with the carbon atom of accepting to replace.Described ring-type marriage chain can locate to contain the key of carbonyl, ether, ester, acid amides, sulphur, sulfinyl, alkylsulfonyl, imino-at an arbitrary position.Again, δ is in the scope of 0-1; Z represents negatively charged ion; J represents the valence mumber of Z, is 1 or 2.)
[23] a kind of high conductivity polymer, described polymer system is repeating unit, has an electric conductive polymer of fibrillar structure with the represented furans skeleton structure of following general formula (4).
(in the formula, substituent R 11And R 12Represent independently hydrogen atom respectively, carbonatoms is saturated or undersaturated alkyl, alkoxyl group or the carbalkoxy of the straight or branched of 1-10; Or expression is selected from halogen atom, nitro, cyano group, primary, the second month in a season or tertiary amine groups, CF 3Base, the univalent perssad in phenyl and the substituted-phenyl.Again, R 11And R 12Hydrocarbon chain can interosculate in position arbitrarily, also can be by the bonded group, form the divalence chain of the ring texture that is formed with at least 1 above 3-7 unit's ring filling or unsaturated hydrocarbons with the carbon atom of accepting to replace.Described ring-type marriage chain can locate to contain carbonyl, ether, ester, acid amides, sulphur, sulfinyl, alkylsulfonyl, imido base key at an arbitrary position.δ is in the scope of 0-1; Z represents negatively charged ion; J represents the valence mumber of Z, is 1 or 2.)
[24] a kind of high conductivity polymer, described polymer system is repeating unit, has an electric conductive polymer of fibrillar structure with the represented aniline skeleton structure of following general formula (5).
Figure C9980107600211
(in the formula, substituent R 13, R 14, R 15And R 16Represent independently hydrogen atom respectively, carbonatoms is saturated or undersaturated alkyl, alkoxyl group or the carbalkoxy of the straight or branched of 1-10; Or expression is selected from halogen atom, nitro, cyano group, primary, the second month in a season or tertiary amine groups, and CF 3Base, the univalent perssad in phenyl and the substituted-phenyl.Again, R 13, R 14, R 15And R 16Hydrocarbon chain can interosculate in position arbitrarily, also can be by the bonded group, form the divalence chain of the ring texture that is formed with more than 13 and even 1 yuan of ring fillings or unsaturated hydrocarbons at least with the carbon atom that accept to replace, this divalence chain forms more than 1 at least.Described marriage chain can locate to contain the key of carbonyl, ether, ester, acid amides, sulphur, sulfinyl, alkylsulfonyl, imino-at an arbitrary position.δ is in the scope of 0-1; Z represents negatively charged ion; J represents the valence mumber of Z, is 1 or 2.)
[25] a kind of manufacture method with high conductivity polymer of fibrillar structure is characterized in that, makes with following general formula (6):
(in the formula, R 1And R 2Expression is 10 described same meanings as described above.)
With following general formula (7):
(in the formula, R 3, R 4, R 5, R 6, R 7And R 8The meaning of expression is as aforementioned 11 described contents.)
With following general formula (8):
(in the formula, R 9And R 10The meaning of expression is as aforementioned 12 described contents.)
With following general formula (9):
(in the formula, substituent R 11And R 12The meaning of expression is as aforementioned 13 described contents.)
Reach with following general formula (10):
Figure C9980107600224
(in the formula, R 13, R 14, R 15And R 16The meaning of expression is as aforementioned 14 described contents.) in represented at least a polymerization contact with the solution that contains oxygenant with monomer with polymerization threshold energy so that both form the interface, and carry out polymerization at described interface.
[26] a kind of as preceding 25 described manufacture method with high conductivity polymer of fibrillar structure, it is characterized in that, make aforementioned 25 describedly to be dissolved in prepared solution in the solvent with monomer with general formula (6), (7), (8), (9) and (10) represented at least a polymerization, contact with the solution that contains oxygenant with polymerization threshold energy, so that both form the interface, and carry out polymerization at described interface.
[27] a kind of as preceding 25 or 26 described manufacture method with high conductivity polymer of fibrillar structure is characterized in that, the described solution that contains the oxygenant with polymerization threshold energy contains the ionogen with doping energy.
[28] as each described manufacture method of preceding 25～27, it is characterized in that the described solution that contains the oxygenant with polymerization threshold energy is saturated solution or supersaturated solution with high conductivity polymer of fibrillar structure.
[29] as preceding 25 or 26 described manufacture method with high conductivity polymer of fibrillar structure, it is characterized in that, make the saturated solution of oxygenant with polymerization threshold energy, under the temperature of the making temperature that is lower than this saturated solution, described oxidizing agent solution is contacted with monomer with polymerization, so that the two forms the interface, then, carry out polymerization.
[30] as preceding 25 or 26 described manufacture method, it is characterized in that, use at least a conduct that is selected from persulphate, dichromate and the 3 valency molysite to have the oxygenant of polymerization threshold energy with high conductivity polymer of fibrillar structure.
[31] as preceding 26 described manufacture method, it is characterized in that with high conductivity polymer of fibrillar structure, use soluble polymeric with monomeric hydrophilic organic solvent as solvent.
[32] a kind of stacking polymer composition, manufacture method with high conductivity polymer of fibrillar structure, it is characterized in that, in manufacture method as the high conductivity polymer that has fibrillar structure as described in 25, polymerization is contacted with the solution that contains oxygenant with monomer, the high conductivity polymer that has fibrillar structure with generation, this polymkeric substance is cleaned or do not cleaned, on the surface of high conductivity polymer with fibrillar structure, repeatedly repeat 25 described manufacture method as described above again, form the lamination of said composition with high conductivity polymer of fibrillar structure.
[33] a kind of stacking polymer composition, have the manufacture method of the high conductivity polymer of fibrillar structure, it is characterized in that, as 26 described manufacture method in, polymerization is contacted with the solution that contains oxygenant with monomer, the high conductivity polymer that has fibrillar structure with generation, this polymkeric substance is cleaned or do not cleaned, on the surface of high conductivity polymer with fibrillar structure, repeatedly repeat 26 described manufacture method as described above again, form the lamination of this polymer composition with high conductivity polymer of fibrillar structure.
The simple declaration of accompanying drawing
Figure 1 shows that, in the embodiments of the invention 1, form the electron scanning micrograph (* 50,000) of the anode aluminium foil section of electric conductive polymer layer.
Figure 2 shows that the electron scanning micrograph (* 50,000) of implementing the synthetic aluminium foil of handling.
Figure 3 shows that, resulting 3 in embodiments of the invention 14, the electron scanning micrograph (* 50,000) of 4-vinyl dioxy thiophene high conductivity polymer.
Figure 4 shows that the electron scanning micrograph that the fibrillar structure of high conductivity polymer partly amplifies among Fig. 3 (* 50,000).
Figure 5 shows that, resulting 3 by comparative example 3, the electron scanning micrograph (* 50,000) of 4-vinyl dioxy thiophene polymkeric substance.
Figure 6 shows that, resulting 3 by embodiment 15, the electron scanning micrograph (* 2,000) of 4-vinyl dioxy thiophene high conductivity polymer.
Figure 7 shows that the electron scanning micrograph (* 20,000) of the amplification of the fibrillar structure of high conductivity polymer part among Fig. 6.
Figure 8 shows that, resulting 1 by embodiment 16, the electron scanning micrograph (* 50,000) of 3-dihydroxyl isothianaphthene high conductivity polymer fibrillar structure.
Figure 9 shows that, resulting 1 by comparative example 4, the electron scanning micrograph of the polymkeric substance of 3-dihydroxyl isothianaphthene (* 50,000).
Detailed description of the invention
By the present invention contain the chemical constitution represented take above-mentioned general formula (1)-(5) as repetitive, have the high conductivity polymer of fibrillar structure, do not exist up to now. This point, if have the oxidant of polymerization threshold energy with the represented polymerization in general formula (6)-(10) with monomer and use more once, the polymer of under stirring condition, making, show Fig. 2 and Fig. 7 of fibrillar structure and do not show Fig. 5 and Fig. 9 of fibrillar structure, its difference can be obvious. Particularly, from following embodiment 12,13,15,16 and comparative example 2,3,4,5 can understand to have fibrillar structure and do not have between the electric conductive polymer of fibrillar structure, conductivity difference is very big.
Why polymer with fibrillar structure of the present invention has high conductivity, and its concrete principle is not still understood. But, its reason can be thought: in the present invention, make the solution that contains the oxidant with polymerization threshold energy, be preferably highly concentrated solution, be more preferably saturated solution or supersaturated solution (below, be called for short this two be " saturated solution etc. ") and polymerization with monomer or contain polymerization and come in contact quietly with the solution of monomer, form the interface (in the present invention, so-called " interface " means oxidizing agent solution layer and polymerization with monomer layer or contains polymerization with the mutual dissolving that part takes place at contact-making surface between the solution layer of monomer, even there is the gradient layer of concentration, but still exist separately the respectively state of level), because at above-mentioned interface polymerization reaction take place, the electric conductive polymer that generates is not subjected to the impact of superfluous oxidant, so the regularity of structure does not wreck.
As other reason, can to think have: used oxidant as the solution of high concentration or saturated solution etc., at this moment, oxidant exists with the state of very tiny nucleus, in the measured response field of this nucleating surface, carry out the polymerization polymerization of monomer, so, generate the higher high conductivity polymer of legislate. On those grounds, can generate the serve as reasons 10-1000 high conductivity polymer doubly of polymer of the same composition that same polymerization obtains with monomer of its electric conductivity, this polymer shows as fibrillar structure under electron microscope.
As the thiophene derivant with general formula (6) expression of above-mentioned high conductivity polymer raw material, can enumerate such as 3 methyl thiophene 3-ethylthiophene, 3-propyl group thiophene, the 3-butyl thiophene, 3-amylic thiophene, 3-hexyl thiophene, 3-heptyl thiophene, 3-octyl group thiophene, 3-nonyl thiophene, 3-decylthiophene, 3-fluorine thiophene, the 3-chlorothiophene, 3 bromo thiophene, 3-cyano thiophene, 3,4-methylene dioxy base thiophene, 3,4-ethylene dioxythiophene, 3,4-propylene dioxy base thiophene etc., and without particular limitation.
The represented condensed heterocyclic compounds of general formula (7) as above-mentioned high conductivity polymer raw material, particularly, can enumerate and have such as 1 of k=0,3-dihydroxy isothianaphthene (another name: 1,3-dihydroxy benzo [c] thiophene) compound of skeleton, or has such as 1 of k=1 the compound of 3-dihydroxy naphtho-[2,3-c] thiophene skeleton. Have again, can enumerate have 1,3-dihydroxy-anthracene [2,3-c] thiophene) compound of skeleton and have 1,3-dihydroxy aphthacene (naphthonaphthalene) [2,3-c] thiophene) compound of skeleton.
In the substituent R with the represented condensed heterocyclic compounds of general formula (7)3、R 4、R 5、R 6In, also comprise adjacent two substituting groups mutually with the unsaturated bond combination, form the compound of 6 yuan of rings of condensation ring system (ortho position replacement). For example, have such as 1 of k=0 3-dihydroxy naphtho-[1,2-c] thiophene derivant, or 1 during k=1,3-dihydroxy phenanthrene [2,3-c] thiophene derivant and 1,3-dihydroxy triphenylo (triphen) [2,3-c] thiophene derivant; Have again, when K=2 1,3-dihydroxy benzo [a] anthryl [7,8-c] thiophene derivant etc.
Also can at random contain nitrogen or nitrogen-containing oxide in the contracting ring. During k=, described condensed ring nitrogenous or that contain oxynitrides can be enumerated such as 1,3-dihydroxy thieno [3,4-b] quinoxaline, 1,3-dihydroxy thieno [3,4-b] quinoxaline-4-oxide, 1,3-dihydroxy thieno [3,4-b] quinoxaline-4,9-dioxide etc., and without particular limitation.
As above-mentioned high conductivity polymer raw material with the represented azole derivatives of general formula (8), can enumerate the methylpyrrole such as 3-, the 3-N-ethyl pyrrole N-, the 3-propyl pyrrole, 3-butyl pyrroles, 3-amyl group pyrroles, 3-hexyl pyrroles, 3-heptyl pyrroles, 3-octyl group pyrroles, 3-nonyl pyrroles, 3-decyl pyrroles, 3-fluorine pyrroles, 3-chlorine pyrroles, 3-bromine pyrroles, 3-cyanopyrrole, 3,4-methylene dioxy base pyrroles, 3,4-ethene (ethylene) dioxy base pyrroles, 3,4-propylene dioxy base pyrroles, 3, the 4-dimethyl pyrrole, 3,4-diethyl pyrroles's etc. derivative, and without particular limitation.
As the furan derivatives with general formula (9) expression of above-mentioned high conductivity polymer raw material, can enumerate the methylfuran such as 3-, 3-ethyl furan, 3-propyl group furans, 3-butyl furans, 3-pentyl furan, 3-hexylfuran, 3-heptyl furans, 3-octyl group furans, 3-nonyl furans, 3-decyl furans, 3-fluorine furans, 3-chlorine furans, 3-bromine furans, 3-cyano group furans, 3,4-methylene dioxy base furans, 3,4-ethylene dioxy base furans, 3,4-propylene dioxy base furans etc., and without particular limitation.
As the anil with general formula (10) expression of above-mentioned high conductivity polymer raw material, can enumerate such as 2-aminotoluene the 2-MEA, 2-propyl group aniline, 2-butylaniline, 2-amyl aniline, 2-hexyl aniline, 2-heptyl aniline, 2-octyl group aniline, 2-nonyl aniline, 2-decyl aniline, 2-fluoroaniline, the 2-chloroaniline, the 2-bromaniline, the derivative of 2-cyano-aniline etc., and without particular limitation.
As the preferably example of above-mentioned general formula (1)～(10) described substituted-phenyl, can enumerate and be selected from such as CF3Base, Br, Cl, F, methyl, ethyl, at least a group in cyano group and the nitro is at the ortho position, a position and contraposition substituted-phenyl at random.
As employed metal with valve action in the solid electrolytic capacitor of the present invention, aluminium, tantalum are arranged, rubidium, titanium, zirconium, magnesium, monometallic or their alloys such as silicon. In addition, on form, then so long as the form of the porous molded bodies such as the etchant of roll compacting metal forming, sintered powder can.
Can be used for the oxidant in the manufacturing of electric conductive polymer layer of the present invention, then so long as can fully carry out the oxidant of oxidation reaction of 4 electronics oxidation reactions of dehydrogenation and get final product, be preferably, industrial cheap, operation is easy to compound in the manufacturing. Specifically, for example, FeCl3、Fe(ClO 4) 3, Fe (organic acid aniline) salt etc. Fe (III) based compound; Or the manganese class of high aluminium chloride/copper chloride, alkali metal persulphate class, ammonium persulfate salt, peroxide, potassium permanganate etc.; 2,3-, two chloro-5,6-dicyano-Isosorbide-5-Nitrae-benzoquinones (DDQ), tetrachloro-Isosorbide-5-Nitrae-benzoquinones, the quinones of four cyano-Isosorbide-5-Nitrae-benzoquinones etc.; Such as the halogen of iodine, bromine etc., such as the sulfonic acid of peracid, sulfuric acid, oleum, sulfur trioxide, sulfuric chlorohydrin, fluorosulfuric acid, acid amides sulfuric acid etc., the combination of ozone etc. and multiple oxidant thereof.
Wherein, as the basic compound of the organic anion that forms described organic anion iron (III) salt, can enumerate such as organic sulfonic acid or organic carboxyl acid, organic phosphoric acid, organic boronic etc. As the concrete example of organic sulfonic acid, can enumerate such as benzene sulfonic acid and p-methyl benzenesulfonic acid, pyrovinic acid, ethyl sulfonic acid, α-sulfonic acid naphthalene, β-sulfonic acid naphthalene, naphthalenedisulfonic acid, alkyl naphthalene sulfonic acid (alkyl is butyl, triisopropyl, di-t-butyl etc.) etc.
On the other hand, as the object lesson of organic carboxyl acid, can enumerate such as acetic acid, propionic acid, benzoic acid, oxalic acid etc. Have again, in the present invention, also can use the polyelectrolyte anion of polyacrylic acid, polymethylacrylic acid, polystyrolsulfon acid, polyvinyl sulfonic acid, polyvinyl sulfuric acid, poly--Alpha-Methyl sulfonic acid, poly-ethylidene sulfonic acid, polyphosphoric acid etc., but the example of these organic sulfonic acids or organic carboxyl acid is some giving an example, and is not so limited.
Again, the corresponding cation of above-mentioned anion is H+、Na +、K +Deng alkali metal ion, or the ammonium ion that replaces with hydrogen atom and tetramethyl, tetraethyl, the tetrabutyl, tetraphenyl etc., but in the present invention and be not particularly limited. In aforementioned oxidant, especially desirable what use is the oxidant that contains 3 valency Fe based compound classes or copper chloride system, persulfuric acid alkali salt class, ammonium persulfate salt, mangaic acid class, quinones.
Has the solution concentration of oxidant of polymerization threshold energy so long as can enough carry out the concentration of polymerisation and get final product. But its concentration is more high then more good, is more preferably to use saturated solution or supersaturated solution. As the method for using described saturated solution or supersaturated solution, temperature will be according to the slightly higher temperature of reaction temperature, in addition, also according to oxidant solubility to the dependence of temperature and different, when oxidant solubility is big to the dependence of temperature, reduce temperature difference; In oxidant solubility to the dependence of temperature hour, then increase temperature difference. For example, be higher than polymerization temperature several times～20 during ℃ left and right sides in temperature, oxidant is dissolved under strong stirring in water and the ethanol equal solvent. Take out the oxidizing agent solution of supernatant part, pour in the reaction vessel. Temperature Setting is the temperature when being lower than dissolving in the container, then polymerization is supplied to above the oxidizing agent solution quietly with monomer or its solution, and these two kinds of solution are mixed, and makes above-mentioned two kinds of reactants contact, to form the interface.
Reaction is carried out at both interfaces, generates high conductivity polymer, by methods such as evaporation or decants polymer is separated from reactant liquor, cleans intuitively to be lepidiod high conductivity polymer. Goods after fully cleaning, also can be used as high conductivity polymer, perhaps, clean or do not clean, place generation polymer above, make once again have starting polymerization can oxidizing agent solution and polymerization with monomer or contain polymerization and contact with the solution of monomer, repeat repeatedly, obtain the high conductivity polymer of lamination.
At this moment, as long as the concentration of oxidizing agent solution can be carried out polymerization fully, but be preferably high concentration, use saturated solution or supersaturated solution then better.
The method saturated, hypersaturated state that forms the oxidant with starting polymerization energy at dielectric film is also without particular limitation, both can adopt the highly concentrated solution with this oxidant directly to import method in the minute aperture, also can import in advance low concentration solution, make mentioned solution fully flood in the minute aperture, then, by placing or cross the method such as heated drying, make that it reaches capacity, the satiety state in the metal forming minute aperture.
In the manufacture method of high conductivity polymer of the present invention, because the oxidant anion (Reduction Body of oxidant) that produces from above-mentioned oxidant becomes adulterant, so, can omit the doping operation, but when being preferably in polymerization, also have other electrolyte with doping energy to exist, both use simultaneously.
As on demand simultaneous, have doping can electrolyte, can enumerate that to have the electrolyte compound or other the anion that produce from the equilibrium ion of the oxidant anion (oxidant Reduction Body) of aforementioned oxidant be electrolyte.
Particularly, can enumerate such as PF6 -、SbF 6 -、AsF 6 -Halide anions Deng 5B family element; Such as BF- 4The halide anions of 3B family element; Such as I-(I 3 -)、Br -、Cl -Deng halide anion, such as ClO4 -Deng the hydracid anion; Such as AlCl4 -And FeCl4 -、SnCl 5 -Deng the lewis acid anion. Perhaps, such as NO3 -、SO 4 2-Deng inorganic anion; Or p-methyl benzenesulfonic acid and naphthalene sulfonic acids, carbon number is the naphthalene sulfonic acids that replaces of 1～5 alkyl, anthraquinone sulfonic acid, such as CF3SO 3 -、CH 3SO 3 -, etc. the organic sulfonic acid anion; Perhaps, such as CF3COO -、C 6H 5COO -Deng carboxylate anion etc. Bronsted acid anion. Equally, also can enumerate such as polyacrylic acid, polymethylacrylic acid, polystyrolsulfon acid, polyvinylsulfonic acid, polyvinyl sulfuric acid, gather-Alpha-Methyl sulfonic acid, gather the polyelectrolyte anion of ethylene sulfonic acid, polyphosphoric acid etc. etc., but be not restricted to these. Wherein, be preferably macromolecular or low organic sulfonic acid compound or the polyphosphoric acid that divides subsystem, what preferably use is aromatic azochlorosulfonate acid compound.
In the manufacture method of high conductivity polymer of the present invention, employed concentration with the represented polymerization usefulness monomer in above-mentioned general formula (6)-(10) is complied with the substituting group kind of its compound and the kind of solvent, or other monomeric species of copolymerization and use amount and different, but usually be preferably 10-3The scope of-10 mol/L, again, 10-2The scope of-5 mol/L is better.
Reaction temperature according to the kind of various monomers, solvent, oxidant, and reaction method change, and without particular limitation, get final product so long as when the beginning polymerization, can keep the temperature of the saturation state of oxidant. In addition, after polymerization begins, solvent evaporates, even separate out after the oxidant with solid, when polymerization still existed with liquid phase with monomer, the interface of this polymerization system was held, polymerization is proceeded. Usually, reaction temperature can be selected from-70 ℃-250 ℃ scope. Be preferably 0 ℃-150 ℃ scope, be more preferably 15 ℃～100 ℃ scope.
Employed reaction dissolvent in manufacture method of the present invention so long as can be at the same time or separately individually dissolved monomer, oxidant and have doping can electrolytical solvent get final product. For example, can use the ethers such as oxolane (THF) and dioxanes, diethyl ether; Or non-proton such as dimethyl formamide and acetonitrile, phenylcyanide, N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO) etc. be polar solvent; Such as ester classes such as ethyl acetate and butyl acetates; Chlorine series solvent such as non-aromatics such as chloroform and carrene; Such as nitro compounds such as nitromethane and nitroethane, nitrobenzene; Or such as alcohols such as methyl alcohol and ethanol, propyl alcohol; Such as organic acid or this organic acid acid anhydrides (for example, acetic anhydride etc.) such as formic acid and acetic acid, propionic acid; Water, or the mixture of these solvents. Again, above-mentioned oxidant and/or have doping can electrolyte and the monomer dicyandiamide solution that also can use respectively independent dissolving, that is, adopt respectively two liquid system or three liquid system to process.
From the represented polymerization monomer in general formula (6)-(10), can obtain respectively containing the chemical constitution represented take general formula (1)-(5) as repetitive, have the high conductivity polymer of fibrillar structure.
As above the electrical conductivity of prepared electric conductive polymer is high, shown in embodiment and comparative example, like that, relatively it is in the reaction system that is made up of with monomer the oxidant with starting polymerization energy and polymerization, the electrical conductivity of prepared electric conductive polymer under stirring, then the available electrical conductivity height of the present invention to 10-100 doubly about, its electrical conductivity is in the 0.1-200S/cm scope. Under desirable condition, can obtain its electrical conductivity at 1-100S/cm, be more preferably the electric conductive polymer in the 10-100S/cm scope.
Again, as above the thickness of prepared electric conductive polymer layer with a polymerization process, as the solid electrolyte layer of solid electrolytic capacitor, only can form the thickness about the 0.1-0.3 micron usually. So, be preferably, polymerization is contacted with the oxidant with starting polymerization energy with monomer, generation has the electric conductive polymer of fibrillar structure, make it clean or not clean, on the electro-conductive polymer surfaces with fibrillar structure that obtains by polymerization (on the Porous valve metals), carry out at least same operation three times, from practicality, be more preferably the synthetic of the solid polymer that carries out more than 5 times. But, if the thickness of solid electrolyte layer is then also undesirable more than necessary thickness, so the aggregation number of solid electrolyte layer is generally about 2-25 time. Be more preferably, described aggregation number thus, can be guaranteed required solid electrolyte layer thickness at about 7-25 time.
Again, be preferably, at the solid electrolyte layer of the electric conductive polymer that forms as mentioned above conductor layer be set, so that good with contacting of cathode reed terminal. For example, can form the solid of electric conductivity paste or impose and electroplate or metal evaporation, form conductive resin film etc. Secondly, connect the cathode reed terminal, impose the external packing such as resin mold, resin-case, metallic casing, resin-dipping shaping etc., make the solid electrolytic capacitor of supplying with purposes.
In solid electrolytic capacitor of the present invention, make in the minute aperture of the Porous valve metals paper tinsel after the high conductivity polymer of fibrillation state has been done synthetic processing coated with oxide-film, as the solid electrolyte on the electrode, and via polymerization process repeatedly, thus in negative electrode inside and the metal forming outer surface form fibriilar layer structure, and leave segment space between these adjacent layers. Thus, can effectively relax Yin Wendu and change up and down the thermal stress that produces. In addition, owing to also formed minute aperture on the composition surface of electric conductive polymer, so, the electric conductivity paste layer that connects usefulness can be entered in the minute aperture of outer surface, thus, can guarantee good sealing property. Have again, also have the electric conductive polymer of fibrillation state in the minute aperture, and the space segment that forms because of lamination operation repeatedly, so, can guarantee the supply of oxygen, the repair ability of dielectric oxide film during the raising conducting.
Be formed at the polymer form of the fibrillar structure on the dielectric film of solid electrolytic capacitor, be preferably, its external diameter is more preferably in the scope of the about 100nm of about 3nm-, and its external diameter is in the scope of the about 50nm of about 5nm-.
The best mode that carries out an invention
Below, exemplify embodiment and comparative example, explain the present invention, but scope of the present invention is not limited to these embodiment.
Embodiment 1
In the 10mm centre on one side of the synthetic paper tinsel of the etching aluminium that cuts into 3mm * 10mm size, this face is divided into 4mm and 5mm part like that at its two polyimide solutions that respectively apply wide 1mm, then, drying causes mask (shielding).The part of the 3mm * 4mm size of the synthetic paper tinsel of this etching aluminium in the aqueous solution of the ammonium adipate of 10% (weight), is imposed the impressed voltage of 13V, do synthetic the processing, form dielectric oxide film.
Secondly, the 3mm * part of 4mm size of described aluminium foil be impregnated in the ammonium persulfate aqueous solution (claiming solution 1) of 2 mol after, take out, place under the room temperature dry 3 minutes.Then, the part of the 3mm * 4mm size of described aluminium foil be impregnated in 3 of 1 mol, in the aqueous isopropanol of 4-ethylidene (ethene) dioxy base thiophene (claiming solution 2) after, take out, place 40 ℃ following 10 minutes of atmosphere, carry out oxypolymerization.Then, repeat the above-mentioned solution 1 that impregnated in earlier, impregnated in solution 2 again, and then the operation of carrying out oxypolymerization reaches after 20 times, in 50 ℃ of warm water, clean 10 minutes, thereafter, under 100 ℃ temperature, dry 30 minutes, form the electric conductive polymer layer.
The photo (aluminium foil sectional drawing) of the scanning electronic microscope after resulting electric conductive polymer layer amplifies 50,000 times herein is shown in Fig. 1.Again, the electron scanning micrograph (aluminium foil sectional drawing) after 50,000 times of the amplifications of the aluminium foil of resulting synthetic processing herein is shown in Fig. 2.
Reference, comparison diagram 2, can see, in Fig. 1, aluminum metal part (a) in the microtexture, the oxygen alumina dielectric medium part (b) of oxidation, the electric conductive polymer of the protofibril shape of alumina dielectric medium surface sediment (can see the membranaceous of protofibril ramify pattern among Fig. 1) is gathered tufted part (c), can confirm the about 0.06 μ m of electric conductive polymer thickness.From Fig. 1 as seen, fibriilar external diameter probably is about 5-50nm.Again, the structure of (c) protofibril shape electric conductive polymer (membranaceous) part with described in embodiment 14 and the embodiment 15, make and on the interface, react " 3,4-ethylidene dioxy base thiophene " and " polymerization starter (containing initiator) " resulting high conductivity polymer structure similar.
Secondly the paste of coating carbon and the paste of silver, have been formed on the part of electric conductive polymer layer at above-mentioned aluminium foil, 4 pieces on stacked described aluminium foil, connect the cathode reed terminal, do not forming on the aluminium foil part of electric conductive polymer layer, melting welding connects the anode reed terminal.Again with this element with after the epoxy sealing, at 125 ℃, add voltage rating, carry out 2 hours declining, finish 30 electrical condensers altogether.
With regard to these 30 capacitor elements, record condenser capacity and loss factor (tan δ), the impedance under resonant frequency and leakage current under the 120Hz, as the initial characteristic of electrical condenser.Again, leakage current ties up to and adds voltage rating and record after 1 minute.Shown in the table 1 the said determination value mean value and, with leakage current be the above electrical condenser of 0.16 μ A (0.002CV) during as substandard products fraction defective and the number of short circuit product.
Here, the mean value of leakage current is to remove the numerical value that is calculated after the substandard products.In addition, shown backflow test in the table 2 and the test-results of the humidity test carried out subsequently.But the leakage current value in the humidity test is to be substandard products more than the 3.2 μ A (0.002CV).Here, backflow test (also claiming the scolding tin thermal test) is estimated with following method.That is, preparing 30 capacitor elements, this capacitor element was passed through 30 seconds down at 230 ℃, record and add 1 minute leakage current afterwards of voltage rating, is substandard products with the element of its measured value more than 0.04CV (μ A).Again, humidity test ties up to place under 85 ℃, the hot and humid condition of 85%RH and carried out in 500 hours.
Embodiment 2
In embodiment 1, except replacing ammonium persulphate, replace 3 with the dihydroxyl isothianaphthene again with ferric sulfate, outside the 4-ethylidene dioxy base thiophene, other makes 30 electrical condensers equally as embodiment 1.Similarly to Example 1, the characteristic of these capacitor elements is estimated.It the results are shown in table 1 and table 2.
Embodiment 3
In embodiment 1, except replacing 3 with the pyrroles, outside the 4-ethylidene dioxy base thiophene, other makes 30 electrical condensers equally as embodiment 1.Similarly to Example 1, the characteristic of these capacitor elements is estimated.It the results are shown in table 1 and table 2.
Embodiment 4
In embodiment 1, except replacing 3 with aniline, outside the 4-ethylidene dioxy base thiophene, other makes 30 electrical condensers equally as embodiment 1.Similarly to Example 1, the characteristic of these capacitor elements is estimated.It the results are shown in table 1 and table 2.
Embodiment 5
In embodiment 1, except in the ammonium persulfate aqueous solution of 2 mol, add anthraquinone-2-sodium as outside the compound with starting polymerization energy with the ratio of 0.07 mol, other makes 30 electrical condensers equally as embodiment 1.Similarly to Example 1, the characteristic of these capacitor elements is estimated.It the results are shown in table 1 and table 2.
Embodiment 6
In embodiment 1, except with 3, the concentration of the aqueous isopropanol of 4-ethylidene dioxy base thiophene makes outside 5 mol, and other makes 30 electrical condensers equally as embodiment 1.Similarly to Example 1, the characteristic of these capacitor elements is estimated.It the results are shown in table 1 and table 2.
Embodiment 7
In embodiment 1, except with 3, the concentration of the aqueous isopropanol of 4-ethylidene dioxy base thiophene makes outside 0.01 mol, and other makes 30 electrical condensers equally as embodiment 1.Similarly to Example 1, the characteristic of these capacitor elements is estimated.It the results are shown in table 1 and table 2.
Embodiment 8
In embodiment 5,,, make 30 electrical condensers equally as embodiment 1 except the 6-methoxynaphthalene sodium sulfonate that uses 0.07 mol replaces the anthraquinone-2-sodium of 0.07 mol.Similarly to Example 1, the characteristic of these capacitor elements is estimated.It the results are shown in table 1 and table 2.
Embodiment 9
In embodiment 1, except the concentration with ammonium persulfate aqueous solution made 0.01 mol, other made 30 electrical condensers equally as embodiment 1.Similarly to Example 1, the characteristic of these capacitor elements is estimated.It the results are shown in table 1 and table 2.
Embodiment 10
In embodiment 1, except the concentration with ammonium persulfate aqueous solution made 4 mol, other made 30 electrical condensers equally as embodiment 1.Similarly to Example 1, the characteristic of these capacitor elements is estimated.It the results are shown in table 1 and table 2.
Embodiment 11
In embodiment 1, except repeating the secondary to the operation of carrying out till the oxypolymerization from impregnated in solution 1, other makes 30 electrical condensers equally as embodiment 1.Similarly to Example 1, the characteristic of these capacitor elements is estimated.It the results are shown in table 1 and table 2.
Embodiment 12
In embodiment 1, except replacing 3 with furans, 4-ethylidene dioxy base thiophene replaces outside the ammonium persulphate of 2 mol with the hexahydrate of the tosic acid iron (III) of 1.4 mol, and other makes 30 electrical condensers equally as embodiment 1.Similarly to Example 1, the characteristic of these capacitor elements is estimated.It the results are shown in table 1 and table 2.Prepared herein electric conductive polymer layer carries out electron scanning micrograph under the condition identical with embodiment 1 observes, and can observe the form that obtains being similar to Fig. 1.
Comparative example 1
Open flat 10-50558 patent gazette with reference to the spy, 29.8 hexahydrates that restrain (0.044 mole) tosic acid iron (III) are dissolved in 3 of 2.87 grams (0.002 mole) simultaneously, in the 4-ethylidene dioxy base thiophene, form chemical polymerization liquid.With aluminium foil dipping wherein once after, under 100 ℃, heat-treat again, in aluminium foil, form polymkeric substance.Then, coating electrically conductive paste (carbon and silver powder) on the part of this formation electric conductive polymer layer.Other makes 30 electrical condensers equally as embodiment 1.Similarly to Example 1, the characteristic of these capacitor elements is estimated.It the results are shown in table 1 and table 2.
Table 1
The initial stage characteristic
Capacity (μ F) Loss factor (%) Impedance (m Ω) Leakage current (μ A) Fraction defective Short circuit
Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10 embodiment 11 embodiment 12 comparative examples 1 48.7 47.9 48.6 48.3 48.1 48.8 47.6 48.2 47.9 48.3 47.8 48.2 47.9 0.7 0.9 0.8 0.8 0.9 1.0 1.1 0.9 1.2 0.9 1.3 0.9 2.2 12 14 13 17 13 11 18 16 21 14 24 18 80 0.03 0.05 0.06 0.07 0.09 0.07 0.07 0.08 0.08 0.10 0.13 0.06 0.17 0/30 0/30 0/30 0/30 0/30 0/30 0/30 0/30 0/30 0/30 0/30 0/30 2/30 0 0 0 0 0 0 0 0 0 0 0 0 2
Table 2
The initial stage characteristic
Fraction defective Short circuit Leakage current (μ A) Fraction defective Short circuit
Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 0/30 0/30 0/30 0/30 0/30 0/30 0/30 0 0 0 0 0 0 0 0.49 0.54 0.59 0.57 0.61 0.61 0.55 0/30 0/30 0/30 0/30 0/30 0/30 0/30 0 0 0 0 0 0 0
Embodiment 8 embodiment 9 embodiment 10 embodiment 11 embodiment 12 comparative examples 1 0/30 0/30 0/30 0/30 0/30 3/27 0 0 0 0 0 3 0.56 0.42 0.68 0.69 0.60 1.68 0/30 0/30 0/30 0/30 0/30 5/27 0 0 0 0 0 3
Embodiment 13
Weigh iron(ic) chloride 6.49 grams (0.04 mole) in the test tube of 30ml, pour water 8ml into, preparation obtains ferric chloride in aqueous solution.This solution is injected as polymerization quietly with monomeric thiophene 1.68 grams (0.02 mole).Thiophene becomes the upper solution of the aqueous solution, generates the interface therebetween.Test tube be impregnated in 40 ℃ the warm water bath, make it to begin polymerization.Stop heating after 2 hours, take out test tube, leaching goes out polymkeric substance.Add entry 100ml in the solid composition, stir after 1 hour, filter, too much iron(ic) chloride is removed in dissolving.Then, add acetone 100ml, stir 1 hour after-filtration, the low-grade polymer of removing unreacted thiophene and solubility makes it refining.Vacuum-drying diel at room temperature.Resulting polymkeric substance 10 tons of (t) pressure in addition continuously under vacuum are shaped, and make the pelleting that radius is 1cm.Use Loresta IP MCP-250 (Mitsubishi's petroleum chemistry corporate system), record the surface resistivity of described pelleting, calculate specific conductivity, be 16S/cm.
Comparative example 2
Weigh iron(ic) chloride 6.49 gram (0.04 mole) in inserting the 100ml round-bottomed flask of agitator, pour water 16ml into, iron(ic) chloride is dissolved fully, flask impregnated in 40 ℃ the warm water bath.Thiophene 1.68 grams (0.02 mole) as the polymerization monomer, are heated after 30 ℃, be dissolved among the Virahol 24ml, import in the reactive system, begin to mix.In polymerization process, keep stirring.After 2 hours, stop heating, take out flask, filter the back and take out polymkeric substance.Make with extra care through following operation: add entry 100ml in the solid composition, stir after 1 hour, filter, too much iron(ic) chloride is removed in dissolving.Then, add acetone 100ml, stir 1 hour after-filtration, remove unreacted thiophene and solubility low-grade polymer.
Secondly, with resulting purified polymkeric substance vacuum-drying diel at room temperature.Obtain the micronized thing.Resulting polymers 10 tons of (t) pressure 3 minutes in addition continuously under vacuum is shaped, and makes the pelleting that radius is 1cm.Use Loresta IP MCP-250 (Mitsubishi's petroleum chemistry corporate system), record the surface resistivity of described pelleting, calculate specific conductivity, be 0.0054S/cm.
Embodiment 14
Weigh iron(ic) chloride 6.85 grams (0.03 mole) in the test tube of 30ml, pour water 8ml into, preparation obtains ferric chloride in aqueous solution.Above-mentioned ferric chloride Solution is injected as polymerization quietly with monomeric 3 4-ethylidene dioxy base thiophene 2.87 grams (0.02 mole).Make 3, generate the interface between the 4-ethylidene dioxy base thiophene and the aqueous solution.Test tube be impregnated in 40 ℃ the warm water bath, make it to begin polymerization.Confirm that polymerization is in the aqueous solution that contains oxygenant and 3, carry out on the interface that 4-ethylidene dioxy base thiophene forms.Stop heating after 2 hours, take out test tube, leach polymkeric substance.Make with extra care through following operation: add entry 100ml in the solid composition, stir after 1 hour, filter, too much ammonium persulphate is removed in dissolving.Then, add acetone 100ml, stir 1 hour after-filtration, remove too much unreacted 3,4-ethylidene dioxy base thiophene and solubility oligopolymer.
Prepared purified polymkeric substance is enlarged into 5,100 times SEM photo and is shown in Fig. 3.Fibrillar structure among Fig. 3 partly amplifies 50,000 times SEM photo and is shown in Fig. 4.Among Fig. 4, clearly shown fibrillar structure.Can understand that from Fig. 4 the protofibril external diameter is roughly 10-60nm.
Then, with purified polymkeric substance vacuum-drying diel at room temperature.Resulting polymkeric substance continued in addition 10 tons of (t) pressure 3 minutes under vacuum, be shaped, and made the pelleting that radius is 1cm.Use LorestaIP MCP-250 (Mitsubishi's petroleum chemistry corporate system), record the surface resistivity of described pelleting, calculate specific conductivity, be 20S/cm.
Comparative example 3
Except using 3,4-ethylidene dioxy base thiophene 2.87 grams (0.02 mole) use ammonium persulphate 6.85 grams (0.03 mole) as outside the polymerization oxidation agent as the polymerization monomer, and other is as comparative example 2, and preparation obtains polymkeric substance.
The SEM photo that prepared refining polymkeric substance amplification is 50,000 times is shown in Fig. 5.But do not observe fibrillar structure.
Then, with purified polymkeric substance vacuum-drying diel at room temperature.Resulting polymkeric substance continued in addition 10 tons of (t) pressure 3 minutes under vacuum, be shaped, and made the pelleting that radius is 1cm.Use LorestaIP MCP-250 (Mitsubishi's petroleum chemistry corporate system), record the surface resistivity of described pelleting, calculate specific conductivity, be 0.064S/cm.
Embodiment 15
Weigh ammonium persulphate 6.85 grams (0.03 mole) in the test tube of 30ml, pour water 1ml into, preparation obtains containing the saturated solution of undissolved ammonium persulphate.This ammonium persulfate solution is injected as polymerization quietly with monomeric 3 4-ethylidene dioxy base thiophene 2.87 grams (0.02 mole).Test tube be impregnated in 40 ℃ the warm water bath, make it to begin polymerization through open system.Stop heating after 2 hours, take out test tube, filter, take out polymkeric substance.Make with extra care through following operation: add entry 100ml in the solid composition, stir after 1 hour, filter, too much ammonium persulphate is removed in dissolving.Then, add acetone 100ml, stir 1 hour after-filtration, remove unreacted 3, the solubility oligopolymer of 4-ethylidene dioxy base thiophene.
The SEM photo that prepared refining polymkeric substance amplification is 2,000 times is shown in Fig. 6.The SEM photo that fibrillar structure among Fig. 6 partly amplifies 20,000 times amplification is shown in Fig. 7.Clearly shown fibrillar structure.
Then, with purified polymkeric substance vacuum-drying diel at room temperature.Resulting polymkeric substance continued in addition 10 tons of (t) pressure 3 minutes under vacuum, be shaped, and made the pelleting that radius is 1cm.Use LorestaIP MCP-250 (Mitsubishi's petroleum chemistry corporate system), record the surface resistivity of described pelleting, calculate specific conductivity, be 21S/cm.
Embodiment 16
In the test tube of 30ml, weigh ammonium persulphate 6.85 gram (0.03 mole), pour water 8ml into, prepare solution.Will be as polymerization with monomeric 1,3-dihydroxyl isothianaphthene 1.86 grams (0.014 mole) are heated to 30 ℃, inject above-mentioned solution quietly, make between itself and oxidizing agent solution and generate the interface.Test tube be impregnated in 40 ℃ the warm water bath, make it to begin polymerization.Stop heating after 6 hours, take out test tube, then, at room temperature placed 7, make it to finish polyreaction.Take out test tube, leaching goes out polymkeric substance.Make with extra care through following operation: add entry 100ml in the solid composition, stir after 1 hour, filter, too much ammonium persulphate is removed in dissolving.Then, add acetone 100ml, stir 1 hour after-filtration, remove unreacted 1,3-dihydroxyl isothianaphthene and solubility oligopolymer.
Prepared refining polymkeric substance is enlarged into 50,000 times SEM photo with scanning electronic microscope (SEM) and is shown in Fig. 8.Fibrillar structure among Fig. 8 clearly shows.Can understand that from observing Fig. 8 fibriilar external diameter is roughly 10-50nm.
Then, with purified polymkeric substance vacuum-drying diel at room temperature.Resulting polymkeric substance continued in addition 10 tons of (t) pressure 3 minutes under vacuum, be shaped, and made the pelleting that radius is 1 cm.Use LorestaIP MCP-250 (Mitsubishi's petroleum chemistry corporate system), record the surface resistivity of described pelleting, calculate specific conductivity, be 14S/cm.
Comparative example 4
Except using 1,3-dihydroxyl isothianaphthene 1.86 grams (0.014 mole) are as the polymerization monomer, and polymerization time is outside 2 hours, and other is as comparative example 2, and preparation obtains polymkeric substance.Resulting polymers after the drying is continued in addition 10 tons of (t) pressure 3 minutes under vacuum, be shaped, make the pelleting that radius is 1cm.Use Loresta IP MCP-250 (Mitsubishi's petroleum chemistry corporate system), record the surface resistivity of described pelleting, calculate specific conductivity, be 0.00033S/cm.
Resulting polymkeric substance is amplified to 50,000 SEM photo and is shown in Fig. 9.Wherein not seeing has fibrillar structure.
Embodiment 17
In the test tube of 30ml, weigh ammonium persulphate 6.85 grams (0.03 mole), pour the HCl aqueous solution 8ml of 0.1N into, be mixed with solution.This solution is injected as polymerization quietly with monomeric aniline 1.86 grams (0.02 mole).Test tube be impregnated in 40 ℃ the warm water bath, make it to begin polymerization.Stop heating after 2 hours, take out test tube, leaching goes out polymkeric substance.Make with extra care through following operation: add entry 100ml in the solid composition, stir after 1 hour, filter, moltenly remove too much ammonium persulfate.Then, add acetone 100ml, stir 1 hour after-filtration, unreacted aniline and solubility oligopolymer are removed in dissolving.Under the room temperature, vacuum-drying diel, resulting polymkeric substance continued in addition 10 tons of (t) pressure 3 minutes under vacuum, be shaped, and made the pelleting that radius is 1cm.Use Loresta IP MCP-250 (Mitsubishi's petroleum chemistry corporate system), record the surface resistivity of described pelleting, calculating its specific conductivity is 10S/cm.
Comparative example 5
Except using aniline 1.86 grams (0.02 mole) to use the monomer as polymerization, other is as comparative example 3, and preparation obtains polymkeric substance.The polymkeric substance that obtains after the drying continued in addition 10 tons of (t) pressure 3 minutes under vacuum, be shaped, and made the pelleting that radius is 1cm.Use Loresta IP MCP-250 (Mitsubishi's petroleum chemistry corporate system), record the surface resistivity of described pelleting, calculate specific conductivity, be 0.00245/cm.
Embodiment 18
In the test tube of 30ml, weigh ammonium persulphate 6.85 grams (0.03 mole) and anthraquinone-2-sodium 0.465 gram (0.0014 mole), pour water 8ml into, obtain solution.With 3,4-ethylidene dioxy base thiophene 2.87 grams (0.02 mole) inject with monomer silently as polymerization.Test tube be impregnated in 40 ℃ the warm water bath, make it to begin polymerization.Stop heating after 2 hours, take out test tube, leaching goes out polymkeric substance.Make with extra care through following operation: add entry 100ml in the solid composition, stir after 1 hour, filter, too much ammonium persulphate and anthraquinone-2-sodium are removed in dissolving.Then, add acetone 100ml, stir 1 hour after-filtration, remove unreacted 3,4-ethylidene dioxy base thiophene and solubility oligopolymer etc.Vacuum-drying diel at room temperature.Resulting polymkeric substance continued in addition 10 tons of (t) pressure 3 minutes under vacuum, be shaped, and made the pelleting that radius is 1cm.Use Loresta IP MCP-250 (Mitsubishi's petroleum chemistry corporate system), record the surface resistivity of described pelleting, calculate specific conductivity, be 26S/cm.
Embodiment 19
In the test tube of 30ml, weigh ammonium persulphate 6.85 grams (0.03 mole), pour water 8ml into, obtain solution.This solution is injected as polymerization quietly with monomeric 3 4-ethylidene dioxy base thiophene 2.87 grams (0.02 mole).Test tube be impregnated in 40 ℃ the warm water bath, make it to begin polymerization.Stop heating after 2 hours, take out test tube, leaching goes out polymkeric substance.Then, in the test tube of 30ml, weigh ammonium persulfate 6.85 grams (0.03 mole) once more, pour water 8ml into, obtain solution.This solution is injected polymerization monomer 3 quietly, 4-ethylidene dioxy base thiophene 2.87 grams (0.02 mole).The polymkeric substance that takes out is put into system, test tube be impregnated in 40 ℃ the warm water bath, makes it to begin polymerization.Repeat above-mentioned operation 3 times, obtain the laminated polymeric thing.Make with extra care through following operation: add entry 100ml in the solid composition, stir after 1 hour, filter, it is unreacted 3 that dissolving is removed, 4-ethylidene dioxy base thiophene and solubility oligopolymer.Under the room temperature, vacuum-drying diel, resulting polymkeric substance continued in addition 10 tons of (t) pressure 3 minutes under vacuum, be shaped, and made the pelleting that radius is 1cm.Use Loresta IP MCP-250 (Mitsubishi's petroleum chemistry corporate system), record the surface resistivity of described pelleting, calculating its specific conductivity is 29S/cm.
Embodiment 20
In the test tube of 30ml, weigh tosic acid iron (III) hexahydrate 27.10 gram (0.04 mole), pour water 8ml into, prepare aqueous oxidizing agent solution.This aqueous solution is injected as polymerization quietly with monomeric furans 1.36 grams (0.02 mole).Furans becomes the upper strata of the aqueous solution, generates the interface therebetween.Test tube be impregnated in 40 ℃ the warm water bath, make it to begin polymerization.Stop heating after 2 hours, take out test tube, leaching goes out polymkeric substance.Make with extra care through following operation: add entry 100ml in the solid composition, stir after 1 hour, filter molten too much tosic acid (III) hexahydrate that goes.Then, add acetone 100ml, stir 1 hour after-filtration, remove unreacted furans and solubility oligopolymer etc.Vacuum-drying diel at room temperature.Described polymkeric substance continued in addition 10 tons of (t) pressure 3 minutes under vacuum, be shaped, and made the pelleting that radius is 1cm.Use Loresta IP MCP-250 (Mitsubishi's petroleum chemistry corporate system), record the surface resistivity of described pelleting, calculate specific conductivity, be 13S/cm.
When prepared electric conductive polymer layer is herein observed with electron scanning micrograph, can observe the protofibril form that obtains being similar to Fig. 3 and Fig. 4 under the condition identical with embodiment 14 again.
Embodiment 21
Weigh iron(ic) chloride 6.49 grams (0.04 mole) in the test tube of 30ml, pour water 8ml into, preparation obtains ferric chloride in aqueous solution.Pyrroles's 1.34 grams (0.02 mole) are injected with monomer silently as polymerization, and the pyrroles becomes aqueous solution upper strata, generates the interface therebetween.Test tube be impregnated in 40 ℃ the warm water bath, make it to begin polymerization.Stop heating after 2 hours, take out test tube, leaching goes out polymkeric substance.Make with extra care through following operation: add entry 100ml in the solid composition, stir after 1 hour, filter, moltenly remove too much iron(ic) chloride.Then, add acetone 100ml, stir 1 hour after-filtration, remove unreacted pyrroles and solubility oligopolymer.Vacuum-drying diel at room temperature.Resulting polymkeric substance continued in addition 10 tons of (t) pressure 3 minutes under vacuum, be shaped, and made the pelleting that radius is 1cm.Use Loresta IP MCP-250 (Mitsubishi's petroleum chemistry corporate system), record the surface resistivity of described pelleting, calculate specific conductivity, be 21S/cm.
When prepared electric conductive polymer layer is herein observed with electron scanning micrograph, can observe the protofibril form that obtains being similar to Fig. 3 and Fig. 4 under the condition identical with embodiment 14 again.
Utilizability on the industry
According to the present invention, can be by easy chemical oxidative polymerization, namely, make with the polymerization shown in general formula (6)～(10) with monomer individually, or make described polymerization with monomer with have doping can electrolyte, with contain have starting polymerization can oxidant contact, the chemical oxidative polymerization that carries out polymerization at formed interface, acquisition has the composition of the membranaceous polymer of high conductivity, the membranaceous polymer of described high conductivity has fibrillar structure, have excellent anisotropy and filming property, and contain take the structure shown in general formula (1)-(5) as repetitive. The composition of such high conductivity polymer can be used for the purposes headed by the solid electrolytic capacitor as the high conductivity solid electrolyte; As conductive material, can be used in the various uses on the industries such as preventing charged material, electric wave absorbing materials.
Again, according to the present invention, in the solid electrolytic capacitor take electric conductive polymer as solid electrolyte, anisotropy and the filming property that will have fibrillar structure, excellence, and the solid electrolyte that contains take the structure shown in general formula (1)-(5) as repetitive is formed on the dielectric film, by this, can obtain having excellent thermal stress relaxes ability and glues the solid electrolyte layer of close property with the excellence of cream slurry interlayer.
Have, the present invention is in the minute aperture of anode again, and coated with the membranaceous solid electrolyte of the fibrillation with high conductivity, so that wherein leave space segment, by this, the overlay film in the time of can obtaining current lead-through has the solid electrolyte layer of excellent repair ability.
Thus, the present invention can provide a kind of solid electrolytic capacitor element, described electrolytic capacitor element not only has excellent initial characteristic (loss factor, leakage current, heat resistance, equivalent series resistance in high-frequency region and impedance etc.), and, excellent long-term dependability (durability under hot and humid etc.) also had.

Claims (16)

1. high conductivity polymer is characterized in that described polymer system is repeating unit, has an electric conductive polymer of fibrillar structure with the represented thiophene skeleton structure of following general formula (1):
In the formula, substituent R 1And R 2Represent independently hydrogen atom respectively, carbonatoms is saturated or undersaturated alkyl, alkoxyl group or the carbalkoxy of the straight or branched of 1-10; Or expression is selected from halogen atom, nitro, cyano group, primary, the second month in a season or tertiary amine groups, CF 3Base, the univalent perssad in phenyl and the substituted-phenyl; Again, R 1And R 2Hydrocarbon chain can interosculate in position arbitrarily, also can be by the bonded group, form the divalence chain of the ring texture that is formed with 3-7 unit's ring filling or unsaturated hydrocarbons with the carbon atom of accepting to replace; Described ring-type marriage chain can locate to contain the key of carbonyl, ether, ester, acid amides, sulphur, sulfinyl, alkylsulfonyl, imino-at an arbitrary position; Again, δ is in the scope of 0-1; Z represents negatively charged ion; J represents the valence mumber of Z, is 1 or 2.
2. high conductivity polymer is characterized in that described polymer system is repeating unit, has an electric conductive polymer of fibrillar structure with the represented condensation polycyclic structure of following general formula (2):
In the formula, substituent R 3, R 4, R 5, R 6, R 7And R 8Represent independently hydrogen atom respectively, carbonatoms is saturated or undersaturated alkyl, alkoxyl group or the carbalkoxy of the straight or branched of 1-10; Or expression is selected from halogen atom, nitro, cyano group, primary, the second month in a season or tertiary amine groups, CF 3Base, the univalent perssad in phenyl and the substituted-phenyl.Again, R 3, R 4, R 5, R 6, R 7And R 8Hydrocarbon chain can interosculate in position arbitrarily, also can be by the bonded group, form the divalence chain of the ring texture that is formed with at least 1 above 3-7 unit's ring filling or unsaturated hydrocarbons with the carbon atom of accepting to replace; Described ring-type marriage chain can locate to contain the key of carbonyl, ether, ester, acid amides, sulphur, sulfinyl, alkylsulfonyl, imino-at an arbitrary position; K represents by thiphene ring and has substituent R 3-R 6The number of the condensed ring that phenyl ring surrounded, o represents the integer of 0-1; The nitrogen or the N-oxygen base that also can contain any number on the condensed ring in the formula, but just this number is also represented substituent R 3-R 8The number of corresponding minimizing; δ is in the scope of 0-1; Z represents negatively charged ion; J represents the valence mumber of Z, is 1 or 2.
3. high conductivity polymer is characterized in that described polymer system is repeating unit, has an electric conductive polymer of fibrillar structure with the represented pyrrole skeleton structure of following general formula (3):
Figure C998010760003C1
In the formula, R 9And R 10Represent independently hydrogen atom respectively, carbonatoms is saturated or undersaturated alkyl, alkoxyl group or the carbalkoxy of the straight or branched of 1-10; Or expression is selected from halogen atom, nitro, cyano group, primary, the second month in a season or tertiary amine groups, CF 3Base, the univalent perssad in phenyl and the substituted-phenyl; Again, R 9And R 10Hydrocarbon chain can interosculate in position arbitrarily, also can be by the bonded group, form the divalence chain of the ring texture that is formed with at least 1 above 3-7 unit's ring filling or undersaturated hydrocarbon with the carbon atom of accepting to replace; Described ring-type marriage chain can locate to contain carbonyl, ether, ester, acid amides, sulphur, sulfinyl, alkylsulfonyl, imido key at an arbitrary position; Again, δ is in the scope of 0-1; Z represents negatively charged ion, and j represents the valence mumber of Z, is 1 or 2.
4. high conductivity polymer is characterized in that described polymer system is repeating unit, has an electric conductive polymer of fibrillar structure with the represented furans skeleton structure of following general formula (4):
In the formula, substituent R 11And R 12Represent independently hydrogen atom respectively, carbonatoms is saturated or undersaturated alkyl, alkoxyl group or the carbalkoxy of the straight or branched of 1-10; Or expression is selected from halogen atom, nitro, cyano group, primary, the second month in a season or tertiary amine groups, CF 3Base, the univalent perssad in phenyl and the substituted-phenyl; Again, R 11And R 12Hydrocarbon chain can interosculate in position arbitrarily, also can be by the bonded group, form the divalence chain of the ring texture that is formed with at least 1 above 3-7 unit's ring filling or undersaturated hydrocarbon with the carbon atom of accepting to replace; Described ring-type marriage chain can locate to contain the key of carbonyl, ether, ester, acid amides, sulphur, sulfinyl, alkylsulfonyl, imino-at an arbitrary position; δ is in the scope of 0-1; Z represents negatively charged ion; J represents the valence mumber of Z, is 1 or 2.
5. high conductivity polymer is characterized in that described polymer system is repeating unit, has an electric conductive polymer of fibrillar structure with the represented aniline skeleton structure of following general formula (5):
In the formula, substituent R 13, R 14, R 15And R 16Represent independently hydrogen atom respectively, carbonatoms is saturated or undersaturated alkyl, alkoxyl group or the carbalkoxy of the straight or branched of 1-10; Or expression is selected from halogen atom, nitro, cyano group, primary, the second month in a season or tertiary amine groups, and CF 3Base, the univalent perssad in phenyl and the substituted-phenyl; Again, R 13, R 14, R 15And R 16Hydrocarbon chain can interosculate in position arbitrarily, also can be by the bonded group, form with the carbon atom that accept to replace and to be formed with more than 13 and even form the divalence chain of the ring texture of 1 yuan of ring filling or undersaturated hydrocarbon at least, this divalence chain forms more than 1 at least; Described marriage chain can locate to contain the key of carbonyl, ether, ester, acid amides, sulphur, sulfinyl, alkylsulfonyl, imino-at an arbitrary position; δ is in the scope of 0-1; Z represents negatively charged ion; J represents the valence mumber of Z, is 1 or 2.
6. the manufacture method with high conductivity polymer of fibrillar structure is characterized in that,
Make with following general formula (6):
Figure C998010760005C1
In the formula, R 1And R 2The meaning of expression is as the described content of claim 10;
With following general formula (7):
Figure C998010760005C2
In the formula, R 3, R 4, R 5, R 6, R 7And R 8The meaning of expression is as the described content of claim 11;
With following general formula (8):
In the formula, R 9And R 10The meaning of expression is as the described content of claim 12;
With following general formula (9):
Figure C998010760005C4
In the formula, substituent R 11And R 12The meaning of expression is as the described content of claim 13;
Reach with following general formula (10):
Figure C998010760006C1
In the formula, R 13, R 14, R 15And R 16The meaning of expression is as the described content of claim 14; In represented at least a polymerization contact with the solution that contains oxygenant with monomer with the initial energy of initiation of polymerization so that both form the interface, and carry out polymerization at described interface.
7. manufacture method with high conductivity polymer of fibrillar structure as claimed in claim 6, it is characterized in that, make that claim 6 is described to be dissolved in prepared solution in the solvent with general formula (6), (7), (8), (9) and (10) represented at least a polymerization with monomer, contact with the solution that contains oxygenant with polymerization threshold energy, so that both form the interface, and carry out polymerization at described interface.
8. as claim 6 or 7 described manufacture method, it is characterized in that the described solution that contains the oxygenant with polymerization threshold energy contains the ionogen with doping energy with high conductivity polymer of fibrillar structure.
9. as each described manufacture method of claim 6-8, it is characterized in that the described solution that contains the oxygenant with polymerization threshold energy is saturated solution or supersaturated solution with high conductivity polymer of fibrillar structure.
10. as claim 6 or 7 described manufacture method with high conductivity polymer of fibrillar structure, it is characterized in that, make the saturated solution of oxygenant with polymerization threshold energy, make described oxidizing agent solution under the temperature of the making temperature that is lower than this saturated solution, contact with monomer with polymerization, so that both form the interface, then, carry out polymerization.
11. as claim 6 or 7 described manufacture method, it is characterized in that, use at least a conduct that is selected from persulphate, dichromate and the 3 valency molysite to have the oxygenant of polymerization threshold energy with high conductivity polymer of fibrillar structure.
12. the manufacture method with high conductivity polymer of fibrillar structure as claimed in claim 7 is characterized in that, use soluble polymeric with monomeric hydrophilic organic solvent as solvent.
13. be used for the purposes of solid electrolytic capacitor as each described high conductivity polymer of claim 1-5, it is characterized in that described electrolytic condenser ties up to porous matter, have on the inter metal dielectric film of valve action and form the solid electrolyte layer of being made up of the polymkeric substance with fibrillar structure.
14. high conductivity polymer as claimed in claim 13 is used for the purposes of solid electrolytic capacitor, it is characterized in that, the electroconductibility of the solid electrolyte layer of described polymkeric substance is 0.1-200S/cm.
15. high conductivity polymer as claimed in claim 13 is used for the purposes of solid electrolytic capacitor, it is characterized in that, on above-mentioned dielectric film, polymerization is contacted with the single solution that is maintained at saturated or hypersaturated state, as to have polymerization threshold energy oxygenant with monomer; Or polymerization is contacted with the electrolytical mixing solutions with doping energy with described oxygenant with monomer, on the aforementioned electric deielectric-coating, form the membranaceous composition of polymkeric substance with fibrillar structure.
16. high conductivity polymer as claimed in claim 13 is used for the purposes of solid electrolytic capacitor, it is characterized in that,
On above-mentioned dielectric film, make polymerization with monomer solution or make be dissolved with polymerization with monomer with have doping can electrolytical mixing solutions contact with the single solution that is maintained at saturated or hypersaturated state, have an oxygenant of polymerization threshold energy; Make described polymerization with monomer solution or make be dissolved with polymerization with monomer with have doping can electrolytical mixing solutions and described oxygenant with described have doping can electrolytical mixing solutions contact, formation has the membranaceous composition of the polymkeric substance of fibrillar structure on the aforementioned electric deielectric-coating.The key of imino-.
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