CN101243212A - Method for chemical conversion treatment of valve action metal material - Google Patents
Method for chemical conversion treatment of valve action metal material Download PDFInfo
- Publication number
- CN101243212A CN101243212A CNA2006800301657A CN200680030165A CN101243212A CN 101243212 A CN101243212 A CN 101243212A CN A2006800301657 A CNA2006800301657 A CN A2006800301657A CN 200680030165 A CN200680030165 A CN 200680030165A CN 101243212 A CN101243212 A CN 101243212A
- Authority
- CN
- China
- Prior art keywords
- chemical transformation
- metal material
- valve action
- action metal
- chemical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Semiconductor Integrated Circuits (AREA)
- Chemical Treatment Of Metals (AREA)
- Formation Of Insulating Films (AREA)
Abstract
Disclosed is a method for forming a dielectric coating film on the surface of a microporous valve active metal material by a chemical conversion treatment. A method for manufacture of solid electrolytic capacitor, comprising a step of performing a thermal treatment and, prior to and subsequent to the step, a step of chemically converting in an electrolytic solution containing an adipate salt, wherein each of the steps is performed once or more times; and a solid electrolytic capacitor manufactured by the method. It becomes possible to provide an oxide coating film for use as a dielectric body in a solid electrolytic capacitor, which has an improved stability, a reduced deterioration in leakage current property, and improved yield and reliability.
Description
Relation with related application
The application is the regulation according to United States Code the 35th volume the 111st (b), according to this roll up the 119th (e) (1) advocate the U.S. Provisional Application the 60/710880th that proposes on August 25th, 2005 the applying date interests, roll up application of the 111st (a) regulation based on this.
Technical field
The manufacture method and the solid electrolytic capacitor that the present invention relates to the method for chemical conversion treatment of valve action metal material and adopt the solid electrolytic capacitor of this method.More particularly, relate to and the valve action metal material with minute aperture is being carried out the chemical transformation processing, form in the method for dielectric medium epithelium on the surface, form the method for the few dielectric medium epithelium of defective, and the method that adopts this method manufacturing to contain the solid electrolytic capacitor of the few dielectric medium epithelium of defectiveness reaches the solid electrolytic capacitor of the reliability excellence of making in this wise.
Background technology
Solid electrolytic capacitor, it generally is the surperficial asperitiesization of the anode bodies that will form by the valve metals of aluminium, tantalum, niobium, titanium and alloy thereof etc. by etching, forming micron-sized minute aperture comes enlarged surface long-pending, form the dielectric medium oxide scale film by the chemical transformation operation in the above, and then make barrier film between between itself and the anode portion and make the solid electrolyte infiltration, after formation contains the cathode conductive layer of carbon paste, metallic conductive paste in the above, be welded on the lead frame that becomes outer electrode, thereby and the externally mounted part that forms Resins, epoxy etc. constitute.
Particularly use the solid electrolytic capacitor of electric conductive polymer as solid electrolyte, compare with the solid electrolytic capacitor that with Manganse Dioxide etc. is solid electrolyte, can reduce equivalent series resistance and leakage current, applicable conduct can be tackled the electrical condenser of electronics high performance, miniaturization, has therefore proposed a lot of manufacture method.
When using electric conductive polymer to make high performance solid electrolytic capacitor, particularly when there is defective part in the oxide scale film that forms on the valve metals paper tinsel, can take place directly to contact the short circuit that is caused with valve metal by formed electroconductive polymer, in addition, because the difference of the thermal stresses of the material of composed component etc. during soft heat in the installation procedure, oxide scale film suffers damage to produce defective, become reason of short circuit or the like, the stability of oxide scale film is the important factor of left and right sides capacitor element performance.
Method as the chemical transformation of the stability that improves oxide scale film, for example open to disclose in the flat 11-150041 communique (patent documentation 1) valve metals is carried out the chemical transformation processing the spy, form oxide scale film, then form the manufacture method of the solid electrolytic capacitor of solid electrolyte layer, wherein, by the operation of carrying out after handle forming oxide scale film heat-treating under than 150 ℃ of high temperature by the 1st chemical transformation, with the operation of after this operation, carrying out the processing of the 2nd chemical transformation, even the thermal treatment of when forming solid electrolyte, burning till etc., also can suppress the generation of crackle, even and because the thermal treatment when being installed in printed wiring board etc. and going up, oxide scale film also is difficult to crack, thereby it is bad bad with proof voltage to reduce leakage current.
The spy opens in the 2000-68159 communique (patent documentation 2 (US6243256)) and discloses: formed after the chemical transformation paper tinsel as dielectric obstruct epithelium by the aluminium foil surface that is breaking at asperitiesization, its notch form as porous matter oxide scale film, thickness is the porous epithelium of 5～100 times scope of above-mentioned obstruct leather film thickness, the useful area of electrode foil be can not reduce, and only proof voltage and stable on heating epithelium formed at notch.
The spy opens in the 2003-158044 communique (patent documentation 3 (WO02/103727)) and has proposed: use the oxide compound that contains silicon and valve metals and oxygen will have surface-coated at least a portion of valve metals of dielectric medium epithelium, thereby the lining area of solid electrolyte (electric conductive polymer) on the dielectric medium epithelium increases, raisings such as adhesivity, the static capacity of electrical condenser increases, and reduces the deviation of static capacity of each electrical condenser and leakage current value or the like.
Yet, in the Te Kaiping 11-150041 communique (patent documentation 1), the 1st chemical transformation is handled and the processing of the 2nd chemical transformation all mainly is to set the chemical transformation that adopts mineral acid to carry out to handle, as embodiment, only put down in writing the technology that comprises " chemical transformation that chemical transformation processing → thermal treatment → employing phosphoric acid carries out that adopts phosphoric acid to carry out is handled ".And, improve effect and insufficient by what thermal treatment obtained.In addition, do not relate to the stabilization of the oxide scale film that the qualification be made up of the importing and the chemical transformation liquid of different chemical transformation methods brings yet.
The spy opens the described technology of 2000-68159 communique (patent documentation 2), it is one of the chemical transformation method that is used to improve the steeple shape of aluminum chemistry conversion foil cut-out portion, not that upgrading with whole of aluminium anode foil is a target, and in preferred embodiment, only enumerated this combination of oxalic acid-thermal treatment-hexanodioic acid, do not relate to the repetition of the chemical transformation processing of identical chemical species, or further chemical transformation imports the stabilization of the oxide scale film that is brought.
Open 2003-158044 communique (patent documentation 3) for the spy, also require further to improve.
Patent documentation 1: the spy opens flat 11-150041 communique
Patent documentation 2: the spy opens the 2000-68159 communique
Patent documentation 3: the spy opens the 2003-158044 communique
Summary of the invention
Therefore, the objective of the invention is to solve above-mentioned prior art problems, the method for chemical conversion treatment that forms stable improved oxide scale film is provided, the manufacture method of stay in gradeization that makes solid electrolytic capacitor and the solid electrolytic capacitor that can boost productivity is provided thus.
The result that present inventors discuss with great concentration in view of above-mentioned problem, discovery is by heat-treating, and before the above-mentioned thermal treatment and carry out carrying out in the electrolytic solution that is containing adipate more than 1 time the processing of chemical transformation afterwards respectively, can improve the stability of oxide scale film, and then this method is used for the solid electrolytic capacitor anode foils, be used to solidify the manufacturing of electrolytic condenser, can improve the various characteristics of electrical condenser, thereby finished the present invention.That is manufacture method and the solid electrolytic capacitor that the invention provides the method for chemical conversion treatment of following valve action metal material and adopt the solid electrolytic capacitor of this method.
1. the method for chemical conversion treatment of a valve action metal material, be the valve action metal material with minute aperture to be carried out chemical transformation handle, form the method for dielectric medium epithelium on the surface, it is characterized in that, comprise heat treatment step, and before the above-mentioned heat treatment step and contain the operation of carrying out chemical transformation in the electrolytic solution that is containing adipate more than 1 time afterwards respectively.
2. as the method for chemical conversion treatment of above-mentioned 1 described valve action metal material, wherein, in the electrolytic solution that is containing oxalic acid that contains before the above-mentioned heat treatment step more than 1 time, carry out the operation of chemical transformation.
3. as above-mentioned 1 or the method for chemical conversion treatment of 2 described valve action metal materials, wherein, in the electrolytic solution that is containing silicate that contains before the above-mentioned heat treatment step more than 1 time, carry out the operation of chemical transformation.
4. as the method for chemical conversion treatment of above-mentioned 1 described valve action metal material, wherein, in severing the chemical transformation of chemical transformation paper tinsel in, after cutting surface is carried out chemical transformation, carry out above (i)～(iv) operation of 1 circulation,
(i) in containing the electrolytic solution of adipate, carry out the operation of chemical transformation;
(ii) in containing the electrolytic solution that is selected from least a composition among oxalic acid, nitric acid, sulfuric acid, hexanodioic acid, phosphoric acid, silicic acid and their salt, carry out at least 1 time operation of chemical transformation;
(iii) heat treatment step; And
(iv) in containing the electrolytic solution of adipate, carry out the operation of chemical transformation.
5. as the method for chemical conversion treatment of above-mentioned 4 described valve action metal materials, wherein, in containing the electrolytic solution that is selected from least a composition among oxalic acid, sulfuric acid, hexanodioic acid, phosphoric acid and their salt, carry out the chemical transformation of chemical transformation paper tinsel cutting surface.
6. as the method for chemical conversion treatment of each described valve action metal material of above-mentioned 1～5, wherein, adipate is an ammonium adipate.
7. as the method for chemical conversion treatment of each described valve action metal material of above-mentioned 1～6, wherein, silicate is water glass.
8. as the method for chemical conversion treatment of each described valve action metal material of above-mentioned 1～7, wherein, valve action metal material contains at least a metal among aluminium, tantalum, niobium, titanium, the zirconium.
9. as the method for chemical conversion treatment of each described valve action metal material of above-mentioned 1～8, wherein, the thickness of the dielectric medium epithelium on surface is the scope of 1nm～1000nm.
10. as the method for chemical conversion treatment of each described valve action metal material of above-mentioned 1～9, wherein, the thermal treatment temp in the heat treatment step is 250 ℃～400 ℃.
11. the method for chemical conversion treatment of each the described valve action metal material as above-mentioned 1～10, wherein, each chemical transformation temperature is 10 ℃～85 ℃.
12. as the method for chemical conversion treatment of each described valve action metal material of above-mentioned 1～11, wherein, when the voltage of chemical transformation forms for the chemical transformation paper tinsel in containing the electrolytic solution of adipate 0.75～1.2 times of voltage.
13. the manufacture method of a solid electrolytic capacitor, be to form minute aperture on the surface of the anode substrate of making by valve action metal material, form the dielectric medium oxide scale film by the chemical transformation operation in the above, form the manufacture method of the solid electrolytic capacitor of solid electrolyte layer again, it is characterized in that the chemical transformation that adopts each described method of above-mentioned 1～12 to carry out anode substrate is handled.
14. a solid electrolytic capacitor, each the described method that contains employing above-mentioned 1～12 has been carried out the valve action metal material that chemical transformation is handled.
The invention effect
According to method for chemical conversion treatment of the present invention, the stability of oxide scale film improves.Therefore, method for chemical conversion treatment of the present invention is applicable in the manufacture method of solid electrolytic capacitor, the stability of bringing into play the oxide scale film of function as the dielectric medium of solid electrolytic capacitor increases, and can prevent the deterioration of leakage current characteristic, and yield rate and reliability improve simultaneously.
Embodiment
Method for chemical conversion treatment of the present invention is the valve action metal material with minute aperture to be carried out chemical transformation handle, form the method for dielectric medium epithelium on the surface, it is characterized in that, comprise heat treatment step, and before the above-mentioned heat treatment step and contain the operation of carrying out chemical transformation in the electrolytic solution that is containing adipate more than 1 time afterwards respectively.In addition, also can carry out the operation of chemical transformation and/or contain the operation of carrying out chemical transformation in the electrolytic solution of silicate containing the electrolytic solution that is containing oxalic acid more than 1 time before the above-mentioned heat treatment step.
Below, each key element and the operation that constitutes the inventive method described.
Method for chemical conversion treatment of the present invention be suitable for to as if having a valve action metal material of minute aperture.Valve metals is selected from aluminium, tantalum, niobium, titanium, zirconium or contains more than one alloy among them, and material is selected from the metal sheet, paper tinsel, rod, line of these materials or is sintered compact of principal constituent etc. with these materials more specifically.These metals adopt known method to carry out etch processes etc. in advance, form minute aperture on the surface.
Method of the present invention generally can be used for the chemical transformation of above-mentioned valve metals to be handled, and is useful as making the isochronous method for chemical conversion treatment of solid electrolytic capacitor by the chemical transformation paper tinsel particularly.Promptly, metallic substance with valve action, after it carries out asperitiesization (porous materialization), carrying out chemical transformation according to known method handles, the material that formation dielectric medium oxide scale film forms is by commercially available, and be used to (following short of specified otherwise in solid electrolytic capacitor etc., so-called " chemical transformation paper tinsel " is meant so commercially available chemical transformation substrate or implemented the chemical transformation substrate of chemical transformation according to commercially available condition among the application), but these materials must severing become suitable shape when reality is used, and the cutting surface that do not contain the chemical transformation layer this moment exposes.In addition, near damage of the dielectric medium epithelium the portion of severing sometimes or destruction.
For example, in the manufacturing process of solid electrolytic capacitor, use the material that the above-mentioned materials severing is become to meet the size of article shape.Change according to the application target different thickness, but usually used thickness is the paper tinsel of about 40～150 μ m.In addition, size is also different and different according to purposes with shape, but as the plate-shaped element unit, preferred wide is that about 1～50mm, length are the orthogonal tinsel of about 1～50mm, more preferably wide is about 2～20mm, long about 2～20mm of being, further preferred wide is that about 2～5mm, length are about 2～6mm.
Therefore,, also contain the part of after severing, exposing valve metals, need carry out chemical transformation even use the occasion of commercially available chemical transformation paper tinsel.Method of the present invention is suitable for such chemical transformation and handles.
For method of the present invention being applicable to the chemical transformation paper tinsel after the severing, preferably carry out: at first revise through severing, exposed the steeple shape of the part of valve metals, form the processing (below, be called " Incision Chemical conversion ") of chemical transformation epithelium again.
Use the electrolytic solution of acid and/or its salt during the Incision Chemical conversion, for example the electrolytic solution of at least a acid in phosphoric acid, sulfuric acid, oxalic acid, the hexanodioic acid etc.Wherein, preferred oxalic acid.The Incision Chemical conversion is preferably at concentration of electrolyte 0.1 quality %～30 quality %, 0 ℃～90 ℃ of temperature, current density 0.1mA/cm
2～1000mA/cm
2, 100 minutes time is with under the interior condition, is that anode carries out the continuous current chemical transformation with the core of chemical transformation substrate, carries out the constant voltage chemical transformation after reaching assigned voltage.Further preferred selected concentration of electrolyte 1 quality %～20 quality %, 20 ℃～80 ℃ of temperature, current density 1mA/cm
2～400mA/cm
2, 60 minutes time is with interior condition.
Moreover, in Incision Chemical conversion, the regulation zone of paper tinsel is immersed in the chemical transformation liquid, electric current and voltage density is in accordance with regulations carried out chemical transformation, but preferably at the position of regulation coating masking material implement chemical transformation in order to make the dipping liquid level horizontal stableization of chemical transformation liquid this moment.Can use the material of being narrated in the back as separating the dipolar masking material of negative and positive as masking material.
Among the present invention, behind the Incision Chemical EOC, the adipate chemical transformation more than before thermal treatment described later, carrying out at least once.As this chemical transformation condition, preferably at its concentration of electrolyte 0.1 quality %～30 quality %, 0 ℃～90 ℃ of temperature, current density 0.1mA/cm
2～1000mA/cm
2, 100 minutes time is with under the interior condition, is that anode carries out the continuous current chemical transformation with the core of chemical transformation substrate, carries out the constant voltage chemical transformation after reaching assigned voltage.Further preferred selected concentration of electrolyte 1 quality %～20 quality %, 20 ℃～80 ℃ of temperature, current density 1mA/cm
2～400mA/cm
2, 60 minutes time is with interior condition.Moreover, as adipate, preferred ammonium adipate, hexanodioic acid sodium, Potassium Adipate etc.
Also can after the adipate chemical transformation before implementing thermal treatment, further use other electrolytic solution to carry out chemical transformation.Can preferably use the aqueous solution of oxalic acid and/or oxalate, nitric acid and/or nitrate, sulfuric acid and/or vitriol, hexanodioic acid and/or adipate, phosphoric acid and/or phosphoric acid salt, silicate base metal-salt etc. particularly.The silicate base metal-salt can be the silicate base metal-salt with following characteristic: with alkali hydroxide metal-salt or carbonic acid an alkali metal salt and silicate (by SiO
2With the salt that metal oxide forms, general formula xM
2OySiO
2) fusion, can obtain material to water dissolvable, dissolving valve metals and the oxide scale film that forms on the surface of valve metals, the silicate base metal-salt can use potassium silicate, water glass, Calucium Silicate powder, lithium silicate etc.As the condition of this chemical transformation, preferably at its concentration of electrolyte 0.1 quality %～30 quality %, 0 ℃～90 ℃ of temperature, current density 0.1mA/cm
2～1000mA/cm
2, 100 minutes time was that anode carries out the continuous current chemical transformation with the core with the chemical transformation substrate under the interior condition, carried out the constant voltage chemical transformation after reaching assigned voltage.Further preferred selected concentration of electrolyte 1 quality %～20 quality %, 20 ℃～50 ℃ of temperature, current density 1mA/cm
2～400mA/cm
2, 60 minutes time is with interior condition.
Then, heat-treat.
Heat treatment step preferably carries out under 250 ℃～400 ℃ temperature.More preferably more than 270 ℃ below 390 ℃, more preferably more than 340 ℃ below 380 ℃.Cross when temperature and can not obtain effect of the present invention when low.Moreover, when temperature is too high, often instead cause the damage of oxide scale film.Heat treatment time can be in the scope of the stability that can expect oxide scale film, or not set the time arbitrarily for the scope of the damage more than necessary can not for the dielectric medium epithelium.
Chemical transformation voltage can be to expect the reparation of oxide scale film and the scope of stabilization, when being preferably the chemical transformation paper tinsel and forming 0.75～1.2 times of voltage, and more preferably 0.80～1.15 times.More preferably 0.85～1.10 times.When being below 0.80 times the time, the reparation of the chemical transformation epithelium that is damaged when severing etc. is insufficient, when for more than 1.1 times the time, can make the further growth of established chemical transformation epithelium in addition, cause electric capacity reduction etc., the characteristic as electrical condenser is impacted.Moreover, no matter how the proof voltage of the present invention's goods all is effectively, be effective particularly for the high withstand voltage goods more than the 10V that is difficult to form stable oxide scale film when the method that adopts in the past.
In the adipate chemical transformation of carrying out after the thermal treatment more than at least 1 time.As this chemical transformation condition, preferably at its concentration of electrolyte 0.1 quality %～30 quality %, 0 ℃～90 ℃ of temperature, current density 0.1mA/cm
2～1000mA/cm
2, 100 minutes time is with under the interior condition, is that anode carries out the continuous current chemical transformation with the core of chemical transformation substrate, carries out the constant voltage chemical transformation after reaching assigned voltage.Further preferred selected concentration of electrolyte 1 quality %～20 quality %, 20 ℃～80 ℃ of temperature, current density 1mA/cm
2～400mA/cm
2, 60 minutes time is with interior condition.Moreover, as the preferred ammonium adipate of adipate.
Handle the thickness of the oxide skin rete that forms by chemical transformation of the present invention, so long as oxide scale film is stabilized, and can make the thickness of the oxide scale film that capacitor specific characteristics improves, then there is not particular restriction, but the scope of 1nm～1000nm preferably, the further scope of 20nm～500nm preferably.
Moreover, the condition that above-mentioned chemical transformation is handled is as commercial run and suitable condition, but in the limit that does not make in surperficial established dielectric medium oxide scale film destruction of valve action metal material or deterioration, and under the limit that the adipate of essential operation is handled in above-mentioned heat treated front and back are contained as the present invention, can at random select kind, concentration of electrolyte, chemical transformation temperature, current density, the chemical transformation time of electrolytic solution, the various conditions such as thickness of oxide skin rete.
As previously discussed, according to preferred implementation of the present invention, be provided at severing the chemical transformation of chemical transformation paper tinsel in, comprise the multistage method for chemical conversion treatment of following operation, described operation is:
(o) chemical transformation of chemical transformation paper tinsel cutting surface (Incision Chemical conversion) operation;
(i) in containing the electrolytic solution of adipate, carry out the operation of chemical transformation;
(ii) in containing the electrolytic solution that is selected from least a composition among oxalic acid, nitric acid, sulfuric acid, hexanodioic acid, phosphoric acid, silicic acid and their salt, carry out at least 1 time operation of chemical transformation;
(iii) heat treatment step; And
(iv) in containing the electrolytic solution of adipate, carry out the operation of chemical transformation.Here, circulation (i)～(iv) can be carried out repeatedly, and the method for chemical conversion treatment that their circulation is carried out 2 valve action metal materials more than the circulation is also included within the scope of the present invention.
Method for chemical conversion treatment of the present invention is useful as the manufacture method of solid electrolytic capacitor.Below enumerate concrete manufacture method.But this is an illustration, and the present invention is not limited to following record.
As mentioned above, in handling, chemical transformation, preferably is coated with masking material in order to make the anodic part that becomes solid electrolytic capacitor reliable with the insulation of solid electrolyte (anode part).
As masking material, can use general heat-resistant resin, but heat-resistant resin or its precursor of preferably solvable or swelling (swelling), contain the composition (spy opens flat 11-80596 communique) of inanimate matter micro mist and cellulose-based resin etc., but material is not limited solvent.Can enumerate Polyphenylene Sulfone (PPS), polyethersulfone (PES), cyanate ester resin, fluoro-resin (tetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), polyimide and their derivative etc. as concrete example.Preferred polyimide, polyethersulfone, fluoro-resin and their precursor especially preferably have sufficient adhesive power, fillibility, can tolerate the polyimide up to the insulativity excellence of about 450 ℃ pyroprocessing valve metals.As polyimide, can preferably use: by below 200 ℃, the thermal treatment under preferred 100～200 ℃ low temperature can fully be solidified, the few polyimide of external impact of the breakage that the lip-deep dielectric layer of anode foils causes because of thermal conductance and destruction etc.As the preferred molecular-weight average of polyimide, be about 1000～1000000, more preferably about 2000～200000.
These materials can dissolve in organic solvent or disperse, and can easily modulate the solution or the dispersion liquid of the solid component concentration arbitrarily that is suitable for being coated with operation (thereby, viscosity).As preferred concentration is about 10～60 quality %, is about 15～40 quality % as preferred concentration.The line of masking material is spread and sunk in and is oozed when for the lower concentration side, causes that when for the high density side wire drawing etc., line width become unstable.
Concrete example as polyimide solution, can preferably use in few solvent such as the water absorbability that will be dissolved in 2-methoxy ethyl ether, triglyme etc. (for example selling as ユ ピ コ one ト (trade mark) FS-100L) by the emerging product of space portion (strain) by the thermal treatment low molecular weight polycaprolactone imide that be cured after the coating, or will be dissolved in solution (for example, by new Japanese physics and chemistry (strain)) company conduct " リ カ コ one ト (the trade mark) " sale that forms among NMP (N-N-methyl-2-2-pyrrolidone N-), the DMAc (N,N-DIMETHYLACETAMIDE)) by the polyimide resin of above-mentioned formula (5) expression.The masking material layer that adopts masking material solution to form can carry out the processing of drying, heating, rayed etc. as required after the masking material solution coat.
In addition, chemical transformation is handled the back and is formed solid electrolyte layer at negative pole part.
Among the present invention, as solid electrolyte, can enumerate contain by the compound with thiophene skeleton, have polycyclic thioether skeleton compound, have pyrrole skeleton compound, have the furans skeleton compound, have the aniline skeleton the structure of expression such as compound as the electric conductive polymer of repeating unit, but the electric conductive polymer that forms solid electrolyte is not limited to this.
As compound with thiophene skeleton, can enumerate 3 methyl thiophene, 3-ethylthiophene, 3-propyl group thiophene, 3-butyl thiophene, 3-amylic thiophene, 3-hexyl thiophene, 3-heptyl thiophene, 3-octyl group thiophene, 3-nonyl thiophene, 3-decylthiophene, 3-fluorine thiophene, 3-chlorothiophene, 3 bromo thiophene, 3-cyano thiophene, 3,4-thioxene, 3,4-diethyl thiophene, 3,4-butylidene thiophene, 3,4-methylendioxythiopheunits, 3, the derivative of 4-Ethylenedioxy Thiophene etc.These compounds can be general commercially available compounds or adopt known method (Synthetic Metals will for example,, 15 volumes, 169 pages in 1986) to prepare, but be not limited to these in the present invention.
In addition, for example,, can use particularly to have 1, the compound of 3-dihydro polycyclic thioether (another name, 1,3-dihydrobenzo [c] thiophene) skeleton, have 1, the compound of 3-dihydro-naphtho [2,3-c] thiophene skeleton as compound with polycyclic thioether skeleton.And then can enumerate and have 1, the compound of 3-dihydroanthracene [2,3-c] thiophene skeleton, have 1,3-dihydro-naphtho naphthalene (naphthaceno) [2,3-c] compound of thiophene skeleton, can adopt known method, for example the spy opens the described method of flat 8-3156 communique (US5530139) and prepares.
In addition, for example, have 1,3-dihydro-naphtho [1,2-c] compound of thiophene skeleton can use 1,3-dihydro phenanthro-[2,3-c] thiophene derivant has 1,3-dihydro three benzos [2,3-c] compound of thiophene skeleton also can use 1,3-dihydrobenzo [a] anthra anthracene (anthraceno) [7,8-c] thiophene derivant etc.
Also at random contain nitrogen or N-oxide compound sometimes on condensed ring, for example can enumerate 1, the 3-dihydro-thiophene is [3,4-b] quinoxaline also, or 1, the 3-dihydro-thiophene is [3,4-b] quinoxaline-4-oxide compound, 1 also, 3-dihydro-thiophene also [3,4-b] quinoxaline-4,9-dioxide etc., but be not limited to these.
In addition, as compound with pyrrole skeleton, can enumerate 3-methylpyrrole, 3-N-ethyl pyrrole N-, 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-dimethyl pyrrole, 3,4-diethyl pyrroles, 3,4-butylidene pyrroles, 3,4-methylene-dioxy pyrroles, 3,4-ethylenedioxy pyrroles's etc. derivative.These compounds can be commercially available products or adopt known method to prepare, but be not limited to these among the present invention.
In addition, as compound with furans skeleton, can enumerate 3-methyl furan, 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-dimethyl furan, 3,4-diethyl furans, 3,4-butylidene furans, 3,4-methylene-dioxy furans, 3, the derivative of 4-ethylenedioxy furans etc.These compounds can be commercially available products or adopt known method to prepare, but be not limited to these among the present invention.
In addition, as compound with aniline skeleton, can enumerate 2-aminotoluene, 2-ethylaniline, 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, 2-chloroaniline, 2-bromaniline, 2-cyano-aniline, 2,5-xylidine, 2,5-Diethyl Aniline, 3,4-butylidene aniline, 3,4-methylene dioxo group aniline, 3, the derivative of 4-ethylenedioxy aniline etc.These compounds can be commercially available products or adopt known method to prepare, but the invention is not restricted to these.
In addition, can also will be selected from above-claimed cpd group's compound and usefulness, form the three component system multipolymer and use.This moment, the ratio of components etc. of polymerizable monomer depended on polymerizing condition etc., and preferred ratio of components, polymerizing condition can be confirmed by simple test.
Among the present invention, the oxygenant that uses in the manufacturing of the electric conductive polymer that is used as solid electrolyte can be the oxygenant of oxidizing reaction that can carry out 4 electronics oxidizing reactions of dehydrogenation fully.Say that at length operation is easy to compound in preferred industrial cheapness, the manufacturing.For example can enumerate FeCl particularly
3, FeClO
4, Fe (organic anion) salt etc. Fe (III) based compound, or the manganese class, 2 of Aluminum chloride anhydrous/cuprous chloride, alkali metal persulphate class, ammonium persulphate salt, peroxide, potassium permanganate etc., 3-two chloro-5,6-dicyano-1,4-benzoquinones (DDQ), tetrachloro-1,4-benzoquinones, four cyano-1, the combination of sulfonic acid such as halogens such as quinones such as 4-benzoquinones, iodine, bromine, peracid, sulfuric acid, oleum, sulphur trioxide, chlorsulfonic acid, fluosulfonic acid, thionamic acid, ozone etc. and these multiple oxygenants.
Wherein, as the basic compound of the organic anion that forms above-mentioned Fe (organic anion) salt, can enumerate organic sulfonic acid or organic carboxyl acid, organic phosphoric acid, organic boronic.As the concrete example of organic sulfonic acid, can use Phenylsulfonic acid, tosic acid, methylsulfonic acid, ethyl sulfonic acid, alpha-sulfo naphthalene, β-sulfo group naphthalene, naphthalene disulfonic acid, alkyl naphthalene sulfonic acid (is butyl, triisopropyl, di-t-butyl etc. as alkyl) etc.
In addition, as the concrete example of organic carboxyl acid, can enumerate acetate, propionic acid, phenylformic acid, oxalic acid etc.In addition, also can use the polymer electrolyte negatively charged ion of polyacrylic acid, polymethyl acrylic acid, polystyrolsulfon acid, polyvinylsulfonic acid, polyvinyl sulfuric acid, poly--Alpha-Methyl sulfonic acid, poly-ethylidene sulfonic acid, polyphosphoric acid etc. among the present invention, but the example of these organic sulfonic acids or organic carboxyl acid is simple illustration, is not limited to this.In addition, above-mentioned anionic balance cation is H
+, Na
+, K
+Deng alkalimetal ion or by the ammonium ion of replacements such as hydrogen atom, tetramethyl-, tetraethyl-, the tetrabutyl, tetraphenyl, but be not subjected to particular determination among the present invention.The preferred especially oxygenant that contains tervalent Fe based compound or cuprous chloride system, persulfuric acid alkaline metal salt, ammonium persulphate salt, mangaic acid class, quinones that uses in the oxygenant recited above.
Among the present invention, in the manufacturing of the electric conductive polymer that is used as solid electrolyte, Gong Cun the balance anion with doping ability as required, electrolyte compound or other the negatively charged ion that can enumerate have the oxygenant negatively charged ion that produced by above-mentioned oxygenant in counterion (oxygenant go back substance) are ionogen.For example can enumerate PF particularly
6 -, SbF
6 -, AsF
6 -And so on the halogenation negatively charged ion of 5B family element, BF
4 -And so on the halogenation negatively charged ion of 3B family element, I
-(I
3 -), Br
-, Cl
-And so on halide anion, ClO
4 -And so on the hydracid negatively charged ion, A1C1
4 -And FeCl
4 -, SnCl
5 -Deng and so on Lewis acid anion, or NO
3 -, SO
4 2-And so on inorganic anion, perhaps tosic acid and naphthene sulfonic acid, carbon number are 1～5 alkyl substituted sulfonic acid, CH
3SO
3 -, CF
3SO
3 -And so on the organic sulfonic acid negatively charged ion, or CF
3COO
-, C
6H
5COO
-And so on carboxylate anion's etc. protonic acid negatively charged ion.Equally, also can enumerate the polymer electrolyte negatively charged ion of polyacrylic acid, polymethyl acrylic acid, polystyrolsulfon acid, polyvinylsulfonic acid, polyvinyl sulfuric acid, poly-Alpha-Methyl sulfonic acid, poly-ethylidene sulfonic acid, polyphosphoric acid etc. etc., but not necessarily be defined.
Yet, preferably enumerate macromolecular or low organic sulfonic acid compound or the polyphosphoric acid that divides subsystem, preferably using arylsulphonate is hotchpotch.For example, can use the salt of Phenylsulfonic acid, toluenesulphonic acids, naphthene sulfonic acid, anthracene sulfonic acid, anthraquinone sulfonic acid and their derivative etc.
Be formed on the monomeric concentration of the electric conductive polymer that uses in the used solid electrolyte of the present invention, different and different according to the substituent kind of this compound with the kind of solvent etc., but generally be preferably 10
-3The scope of～10 mol, more preferably 10
-2The scope of～5 mol.In addition, temperature of reaction determines there is not particular determination respectively according to reaction method, but generally selects-70 ℃ to 250 ℃ temperature range.Preferably-30 ℃～150 ℃, further preferably react-10 ℃～30 ℃ temperature range.
Among the present invention, employed reaction solvent can be can be with monomer or oxygenant, there is the counterion of doping ability to dissolve together or dissolved solvent individually respectively, for example can use tetrahydrofuran (THF) and two alkane, ethers such as diethyl ether, or dimethyl formamide and acetonitrile, benzonitrile, N-Methyl pyrrolidone, non-proton property such as dimethyl sulfoxide (DMSO) polar solvent, ester such as ethyl acetate and butylacetate class, the chlorine series solvent of non-aromatics such as chloroform and methylene dichloride, Nitromethane 99Min. and nitroethane, nitro-compounds such as oil of mirbane, or methyl alcohol and ethanol, alcohols such as propyl alcohol, or formic acid and acetate, organic acids such as propionic acid or this organic acid acid anhydrides (for example diacetyl oxide etc.), water, the mixed solvent of alcohols or ketone or these solvents.In addition, above-mentioned oxygenant and/or the counterion of doping ability is arranged and monomer also can be in dissolved solvent system, i.e. operation in two liquid system or the three liquid system individually respectively.
The specific conductivity of the solid electrolyte of Zhi Zaoing is more than the 1S/cm like this, is more than the 5S/cm under preferred condition, further preferably more than the 10S/cm.
In addition, thus the conductive layer that carbon paste layer and containing metal powder be set on the surface of solid electrolyte layer forms the negative pole part of electrical condenser.The conductive layer of containing metal powder is and the solid electrolyte layer adhesive bond, when working as negative electrode, become the bonding coat of the cathode lead terminal that is used to engage final electrical condenser goods, the thickness of metallic conductive layer is unqualified, but generally be about 1～100 μ m, be preferably about 5～50 μ m.
Solid electrolytic capacitor, be by with lead frame that anode portion engages on the bonding wire terminal, at the negative pole part bonding wire of the conductive layer that comprises solid electrolyte layer, carbon paste layer and containing metal powder, and then use insulative resin such as Resins, epoxy that integral sealing is obtained.
Electrical condenser anode foils of the present invention, the capacitor element as lamination-type uses usually.Laminated solid electrolytic condenser for example can form by cascade capacitor element on lead frame.
Embodiment
Below, enumerate embodiment and explain the present invention, but the present invention is not limited by these embodiment.
Embodiment 1
It is wide that the chemical transformation aluminium foil (63.4V chemical transformation product) of thickness 110 μ m is cut into 3.3mm, cuts into the length of each 13mm again, is fixed on the metal system guider (guide) by the short leg of welding with this paillon foil.In order to carry out Incision Chemical conversion, in that to depict polyimide resin solution (the emerging product corporate system of space portion) as 0.8mm by wire apart from the position of a loose end 7mm wide, about 180 ℃ of dryings 30 minutes.Part that will be from loose aluminium foil front end to the polyimide resin that is coated with is as the 1st chemical transformation (Incision Chemical conversion), in 5 quality % oxalic acid aqueous solutions, current density 10mA/cm
2, after the chemical transformation of carrying out 10 minutes under 25 ℃ of the chemical transformation voltage 63.1V, temperature handles, wash, drying.Then, as the 2nd chemical transformation operation, in the 9 quality % ammonium adipate aqueous solution, current density 5mA/cm
2, after the chemical transformation of carrying out 10 minutes under 65 ℃ of the chemical transformation voltage 65V, temperature handles, similarly wash, drying.Then, as the 3rd chemical transformation, in the sodium silicate aqueous solution of 1 quality %, current density 5mA/cm
2, after the chemical transformation of carrying out 10 minutes under 65 ℃ of the chemical transformation voltage 65V, temperature handles, similarly wash, drying.Then, carry out 30 minutes 350 ℃ thermal treatment.And then, as the 4th chemical transformation, in the 9 quality % ammonium adipate aqueous solution, current density 5mA/cm
2, the chemical transformation of carrying out 10 minutes under 65 ℃ of the chemical transformation voltage 65V, temperature handles, similarly wash, drying.
Then, be the center with the part of the front end 5mm of distance aluminium foil, it is wide that the polyimide resin that separates anode portion and negative pole part is coated with into 0.8mm by wire, 180 ℃ of dryings 1 hour.Solid electrolyte as cathode layer forms solid electrolyte as described below.
That is, (3.5mm * 4.6mm) is immersed in and contains 3, in the aqueous isopropanol of 4-Ethylenedioxy Thiophene (solution 1), is lifted out and places with negative pole part.Then be immersed in the aqueous solution (solution 2) that contains ammonium persulphate, be dried, carry out oxypolymerization.Be immersed in the solution 2 after repeating to be immersed in the solution 1, carry out the operation of oxypolymerization.After then using 50 ℃ warm water washing, under 100 ℃, make its drying, formed solid electrolyte layer.And then use carbon paste, silver paste to form electrode at negative pole part, finish capacitor element.
On lead frame, use Ag cream to engage on one side and contain the part of the masking material of coating to some extent, overlapping 3 on one side, by welding anode lead terminal is connected with the part with solid electrolyte not, use Resins, epoxy with integral sealing, at 135 ℃ of voltages that apply 28V, wear out, made 30 chip-type solid electrolytic capacitors of total.
For these 30 electrical condensers, as equivalent series resistance (hereinafter referred to as ESR) and the leakage current under the electric capacity under the initial stage characteristic measurement 120Hz and loss factor (tan δ), the 100kHz.Moreover leakage current is to apply voltage rating 16V, measures after one minute.Measurement result is as follows.
Electric capacity (mean value): 10.0 μ F
Tan δ (mean value): 0.81%
ESR (mean value): 31m Ω
Leakage current (mean value): 0.26 μ A
Fraction defective when in addition, leakage current that 0.8 μ A (0.005CV) is above is as defective products is 10%.
In addition, show the result that moisture-proof (moisture resistance) test that reaching continues with it carries out is tested in soft heat.Soft heat test (being also referred to as the soldering thermal test) adopts following method to estimate.That is, preparing 20 capacitor elements, this element was passed through for 10 seconds under 255 ℃ temperature, repeat 3 these operations, measure and apply the leakage current of voltage rating after 1 minute, is that the above element of 16 μ A (0.1CV) is as defective products then with this value.In addition, humidity test be 60 ℃, the hot and humid of 90%RH placed 500 hours down, was that the above element of 48 μ A (0.3CV) is as defective products with applying the leakage current value of voltage rating after 1 minute.
Leakage current after the soft heat test: 6.2 μ A
Leakage current after the humidity test: 5.1 μ A
Fraction defective all is 0.
These results are shown in table 1～3 with other illustration.
Embodiment 2
As the 1st chemical transformation, in 5 quality % oxalic acid aqueous solutions, current density 5mA/cm
2, the chemical transformation of carrying out 10 minutes under 25 ℃ of the chemical transformation voltage 63.4V, temperature handles, make electrical condenser in addition similarly to Example 1 and estimate.
Embodiment 3
As the 3rd chemical transformation, in the 9 quality % ammonium adipate aqueous solution, current density 5mA/cm
2, the chemical transformation of carrying out 10 minutes under 65 ℃ of the chemical transformation voltage 65V, temperature handles, in addition, make electrical condenser similarly to Example 1 and estimate.
Embodiment 4
The thermal treatment that to carry out after the 3rd chemical transformation is defined as 300 ℃, in addition, makes electrical condenser similarly to Example 1 and estimates.
Comparative example 1
Do not carry out as chemical transformation the 2nd chemical transformation, in the 9 quality % ammonium adipate aqueous solution, in addition, make electrical condenser similarly to Example 1 and estimate.
Comparative example 2
Do not carry out as chemical transformation the 4th chemical transformation, in the 9 quality % ammonium adipate aqueous solution, in addition, make electrical condenser similarly to Example 1 and estimate.
Table 1 chemical transformation condition
*: do not implement
Table 2 electrical condenser initial stage characteristic
Table 3 electrical condenser reliability test result
Industrial applicibility
The invention provides the method for chemical conversion treatment that forms stable improved oxide scale film. Cause This, it is useful forming in the operation at various oxide scale films, particularly by being used for the solid electrolytic electricity The manufacture method of container makes as the dielectric of solid electrolytic capacitor and brings into play the oxide scale film of function Stability increase, prevent the deterioration of leakage current characteristic, help to improve yield rate and reliability, be Very suitable.
Among the present invention the expression number range " more than " and " following " include given figure.
Claims (14)
1. the method for chemical conversion treatment of a valve action metal material, be the valve action metal material with minute aperture to be carried out chemical transformation handle, form the method for dielectric medium epithelium on the surface, it is characterized in that, comprise heat treatment step, and before the above-mentioned heat treatment step and contain the operation of carrying out chemical transformation in the electrolytic solution that is containing adipate more than 1 time afterwards respectively.
2. the method for chemical conversion treatment of valve action metal material as claimed in claim 1 wherein, carries out the operation of chemical transformation in the electrolytic solution that is containing oxalic acid that contains before the above-mentioned heat treatment step more than 1 time.
3. the method for chemical conversion treatment of valve action metal material as claimed in claim 1 or 2 wherein, carries out the operation of chemical transformation in the electrolytic solution that is containing silicate that contains before the above-mentioned heat treatment step more than 1 time.
4. the method for chemical conversion treatment of valve action metal material as claimed in claim 1, wherein, in severing the chemical transformation of chemical transformation paper tinsel in, after cutting surface is carried out chemical transformation, carry out above (i)～(iv) operation of 1 circulation,
(i) in containing the electrolytic solution of adipate, carry out the operation of chemical transformation;
(ii) in containing the electrolytic solution that is selected from least a composition among oxalic acid, nitric acid, sulfuric acid, hexanodioic acid, phosphoric acid, silicic acid and their salt, carry out at least 1 time operation of chemical transformation;
(iii) heat treatment step; And
(iv) in containing the electrolytic solution of adipate, carry out the operation of chemical transformation.
5. the method for chemical conversion treatment of valve action metal material as claimed in claim 4 wherein, carries out the chemical transformation of chemical transformation paper tinsel cutting surface in containing the electrolytic solution that is selected from least a composition among oxalic acid, sulfuric acid, hexanodioic acid, phosphoric acid and their salt.
6. as the method for chemical conversion treatment of each described valve action metal material of claim 1～5, wherein, adipate is an ammonium adipate.
7. as the method for chemical conversion treatment of each described valve action metal material of claim 1～6, wherein, silicate is water glass.
8. as the method for chemical conversion treatment of each described valve action metal material of claim 1～7, wherein, valve action metal material comprises at least a metal among aluminium, tantalum, niobium, titanium, the zirconium.
9. as the method for chemical conversion treatment of each described valve action metal material of claim 1～8, wherein, the thickness of the dielectric medium epithelium on surface is the scope of 1nm～1000nm.
10. as the method for chemical conversion treatment of each described valve action metal material of claim 1～9, wherein, the thermal treatment temp in the heat treatment step is 250 ℃～400 ℃.
11. as the method for chemical conversion treatment of each described valve action metal material of claim 1～10, wherein, each chemical transformation temperature is 10 ℃～85 ℃.
12. as the method for chemical conversion treatment of each described valve action metal material of claim 1～11, wherein, when the voltage that carries out chemical transformation in containing the electrolytic solution of adipate forms for the chemical transformation paper tinsel 0.75～1.2 times of voltage.
13. the manufacture method of a solid electrolytic capacitor, be to form minute aperture on the surface of the anode substrate of making by valve action metal material, form the dielectric medium oxide scale film by the chemical transformation operation in the above, form the manufacture method of the solid electrolytic capacitor of solid electrolyte layer again, it is characterized in that, adopt each described method of claim 1～12 to carry out the chemical transformation processing of anode substrate.
14. a solid electrolytic capacitor contains each the described method that adopts claim 1～12 and has carried out the valve action metal material that chemical transformation is handled.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005237590 | 2005-08-18 | ||
| JP237590/2005 | 2005-08-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101243212A true CN101243212A (en) | 2008-08-13 |
Family
ID=39933901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800301657A Pending CN101243212A (en) | 2005-08-18 | 2006-08-17 | Method for chemical conversion treatment of valve action metal material |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPWO2007020969A1 (en) |
| CN (1) | CN101243212A (en) |
| TW (1) | TW200732515A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102358947A (en) * | 2011-09-28 | 2012-02-22 | 宁波市鸿博机械制造有限公司 | Surface treatment technique of flow control valve |
| CN103325570A (en) * | 2013-07-03 | 2013-09-25 | 中国振华（集团）新云电子元器件有限责任公司 | Preparation method of high temperature resistant capacitor |
| CN109680316A (en) * | 2019-02-28 | 2019-04-26 | 安徽工业大学 | A kind of method of zirconium-based metallic glass surface preparation structure color film layer |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2964345B2 (en) * | 1990-02-28 | 1999-10-18 | 松下電器産業株式会社 | Method for manufacturing solid electrolytic capacitor |
| JPH09246111A (en) * | 1996-03-14 | 1997-09-19 | Matsushita Electric Ind Co Ltd | Formation of electrode foil for aluminum electrolytic capacitor |
| JP3411237B2 (en) * | 1998-06-09 | 2003-05-26 | 昭和電工株式会社 | Electrode foil for solid electrolytic capacitor, method for producing the same, and solid electrolytic capacitor |
| JP2000348984A (en) * | 1999-06-08 | 2000-12-15 | Nichicon Corp | Manufacture of electrode foil for aluminum electrolytic capacitor |
| JP4001329B2 (en) * | 2001-06-15 | 2007-10-31 | 昭和電工株式会社 | Chemical conversion substrate for solid electrolytic capacitor, method for producing the same, and solid electrolytic capacitor |
| JP4071469B2 (en) * | 2001-10-10 | 2008-04-02 | 昭和電工株式会社 | Anode foil for capacitor, method for producing the anode foil, and solid electrolytic capacitor using the anode foil |
-
2006
- 2006-08-17 CN CNA2006800301657A patent/CN101243212A/en active Pending
- 2006-08-17 TW TW095130253A patent/TW200732515A/en unknown
- 2006-08-17 JP JP2007531021A patent/JPWO2007020969A1/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102358947A (en) * | 2011-09-28 | 2012-02-22 | 宁波市鸿博机械制造有限公司 | Surface treatment technique of flow control valve |
| CN103325570A (en) * | 2013-07-03 | 2013-09-25 | 中国振华（集团）新云电子元器件有限责任公司 | Preparation method of high temperature resistant capacitor |
| CN103325570B (en) * | 2013-07-03 | 2016-05-11 | 中国振华（集团）新云电子元器件有限责任公司 | The preparation method of high temperature resistant capacitor |
| CN109680316A (en) * | 2019-02-28 | 2019-04-26 | 安徽工业大学 | A kind of method of zirconium-based metallic glass surface preparation structure color film layer |
| CN109680316B (en) * | 2019-02-28 | 2020-10-09 | 安徽工业大学 | Method for preparing structural color film layer on surface of zirconium-based metal glass |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200732515A (en) | 2007-09-01 |
| JPWO2007020969A1 (en) | 2009-02-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3187380B2 (en) | Solid electrolytic capacitor and method of manufacturing the same | |
| JP3065286B2 (en) | Solid electrolytic capacitor and method of manufacturing the same | |
| CN101361147A (en) | Solid electrolytic capacitor, method for manufacturing same, and base for solid electrolytic capacitor | |
| EP0617442B1 (en) | Solid electrolytic capacitor and method of manufacturing the same | |
| JP4036466B2 (en) | Capacitor and manufacturing method thereof | |
| CN101015029A (en) | Solid electrolytic capacitor element, solid electrolytic capacitor and production method thereof | |
| JP3228323B2 (en) | Solid electrolytic capacitor and method of manufacturing the same | |
| CN101243212A (en) | Method for chemical conversion treatment of valve action metal material | |
| CN101536127B (en) | Base material for solid electrolytic capacitor, capacitor using the base material, and method for manufacturing the capacitor | |
| JP2007095934A (en) | Conversion treatment method of valve action metal material | |
| WO2011052237A1 (en) | Solid electrolytic capacitor and method for producing same | |
| JP4259794B2 (en) | Manufacturing method of solid electrolytic capacitor | |
| WO2007020969A1 (en) | Method for chemical conversion treatment of valve action metal material | |
| JP2007180260A (en) | Manufacturing method of solid electrolytic capacitor | |
| CN101203926B (en) | Solid electrolytic capacitor and method for manufacturing same | |
| JP5327844B2 (en) | Electrolytic polymerization liquid for forming conductive polymer, conductive polymer, solid electrolytic capacitor using the same, and method for producing the same | |
| JP4925144B2 (en) | Manufacturing method of solid electrolytic capacitor | |
| JP2001006983A (en) | Solid electrolytic capacitor and its manufacture | |
| JP2008045190A (en) | Method for forming oxide film on valve action metal material | |
| JP4811708B2 (en) | Method for forming conductive polymer layer | |
| JPH06325984A (en) | Solid electrolytic capacitor and manufacture thereof | |
| JPH10303080A (en) | Method for manufacturing solid electrolytic capacitor | |
| JPH0541337A (en) | Manufacture of solid electrolytic capacitor | |
| JP2010143996A (en) | Electroconductive polymer, solid electrolytic capacitor using the same, and method for manufacturing the same | |
| JPWO2007074869A1 (en) | Solid electrolytic capacitor and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: MURATA MANUFACTURING CO., LTD Free format text: FORMER OWNER: SHOWA DENKO K. K. Effective date: 20100423 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: TOKYO, JAPAN TO: KYOTO PREFECTURE, JAPAN |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20100423 Address after: Kyoto Japan Applicant after: Murata Manufacturing Co., Ltd. Address before: Tokyo, Japan, Japan Applicant before: Showa Denko K. K. |
|
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080813 |