KR100935502B1 - Process for producing aluminum material for electrode of electrolytic capacitor - Google Patents

Abstract

In manufacturing an aluminum material for electrolytic capacitor electrodes by carrying out hot rolling, cold rolling, and final annealing sequentially to an aluminum slab, the process after the said hot rolling includes the step of heating an aluminum material by contact with a heating body. . The contact heating step with the heating body of the aluminum material may be any time after the hot rolling. It can be performed at least once in the process from the start to the end of the cold rolling, can be performed before the final annealing after cold rolling, and can be carried out after the final annealing.

Hot rolling, cold rolling, final annealing, aluminum materials for electrolytic capacitor electrodes, contact heating process, organic solvents, surfactants, alkali cleaning, acid cleaning

Description

Manufacturing method of aluminum material for electrolytic capacitor electrode {PROCESS FOR PRODUCING ALUMINUM MATERIAL FOR ELECTRODE OF ELECTROLYTIC CAPACITOR}

This application is Japanese Patent Application No. 2001-235940, filed on August 3, 2001, Japanese Patent Application No. 2002-123666, filed on April 25, 2002, and Japanese Patent Application on July 5, 2002. Japanese Patent Application No. 2002-209455, filed July 18, 2002, Japanese Patent Application No. 2002-209459, filed July 18, 2002, and August 17, 2001; It is accompanied by a priority claim in US Provisional Application No. 60 / 312,753, the disclosure of which is hereby incorporated into part.

This application claims the benefit of the date of filing under U.S. Patent Act No. 119 (e) (1) to U.S. Provisional Application No. 60 / 312,753, filed pursuant to U.S. Patent Act No. 111 (b), dated August 17, 2001. And filed under the provisions of Article 111 (a) of the US Patent Act.

This invention relates to the manufacturing method of the aluminum material for electrolytic capacitors, the aluminum material for electrolytic capacitor electrodes, the manufacturing method of the electrode material for electrolytic capacitors, and an aluminum electrolytic capacitor.

In addition, in this specification, the term "aluminum" is used by the meaning containing the alloy, and aluminum material contains foil, a plate, and the molded object using these.

Since aluminum materials generally used as electrode materials for aluminum electrolytic capacitors are required to have large surface areas and large capacitances per unit area, electrochemical or chemical etching treatments are performed to increase the effective area of aluminum materials. have.

Further, for the purpose of increasing the effective area, research has been made in various aspects such as the composition of the material, the manufacturing process, and the etching method for increasing the number of etching holes.

For example, in the production of aluminum materials for electrolytic capacitors, which produce tunnel type pit by direct current etching, usually in an inert atmosphere or vacuum at a temperature of around 500 ° C. in order to develop a crystal orientation of the (100) plane. Final annealing is performed. In addition, final annealing is a process performed after finish cold rolling, or after finish cold rolling and washing | cleaning.

When crystalline oxide particles are formed on the surface of an aluminum material during final annealing, some documents disclose that etch-pits occur around crystals during electrolytic etching (for example, Fukuoka Kiyoshi, Osawa Nobuo, Motoori Tetsuya, Light Metals Society 95th Fall Conference Lecture Outline p.265 (1998), Nobuo Osawa, Fukuoka Yoshi: Surface Technology, 50 [7], 643 (1999)] The production on the surface of the aluminum material is considered to contribute to the improvement of the capacitance.

However, as mentioned above, in the inert gas atmosphere or vacuum atmosphere which is a general atmosphere of final annealing, since oxygen in an atmosphere is very small, it is difficult to crystallize even if it carries out final annealing. On the contrary, when annealing at high temperature in an oxidizing atmosphere, an oxide film becomes thick and the uniformity of an etch pit falls.

As a method of depositing a lot of crystals on the surface of an aluminum material, Japanese Patent Publication No. 58-34926 discloses a method of spraying steam or wet air onto the surface of an aluminum material before final annealing, heating to a temperature of about 200 ° C. in the air, It is disclosed to form a hydration coating film by a so-called boehmite treatment method or the like in which an aluminum material is immersed in heated water or an amine aqueous solution.

The hydrated film is easily precipitated on the surface of the aluminum material by the final annealing afterwards, but has a lot of Al-0H groups on the surface, so that it is adhered to the case of batch annealing in the state of the coil or the overlapping plate. There was a problem that was easy to do. Moreover, in the method of heating to the temperature of about 200 degreeC in air | atmosphere, in order to obtain the reproducibly desired oxide film, accurate atmosphere control, such as control of the amount of water vapor | steam, was required, and there existed a fault which it takes time for the aluminum foil surface to reach a desired temperature.

-Al₂O₃을 석출시키는 기술이 개시되어 있는데, 최종 어닐링 시간이 단시간이기 때문에

-Al₂O₃의 석출이 불충분할 우려가 있었다. In addition, Japanese Patent Laid-Open No. 63-116417 discloses a continuous final annealing in an oxidizing atmosphere containing oxygen or moisture.

A technique for depositing -Al ₂ O ₃ is disclosed, since the final annealing time is short.

There was a fear that precipitation of -Al ₂ O ₃ was insufficient.

In addition, in order to improve etching characteristics and obtain high capacitance, Japanese Patent Application Laid-Open No. 7-201673 discloses a step of removing the surface layer of aluminum foil, and a temperature of 40 to 350 ° C and a dew point of 0 to 0 after removal. Disclosed is a method for producing an aluminum material for an electrolytic capacitor electrode, which comprises performing a step of heating and oxidizing under a condition of 80 ° C. and a time of 30 to 1800 seconds, and annealing in a non-oxidizing atmosphere after the heat oxidation.

In addition, Japanese Patent Application Laid-Open No. 5-279815 discloses that, in the cleaning treatment before final annealing, the thickness of the barrier oxide film on the surface of the aluminum foil is adjusted to 2.5 angstroms or less, and after the cleaning treatment, before the finish annealing treatment The aluminum foil is heat-treated in an oxidizing atmosphere at 150 to 400 ° C., and the thickness of the barrier oxide film on the surface of the aluminum foil is grown to 10 angstroms or less. It is described that the time of the heat treatment is preferably about 5 minutes to 3 hours.

However, in the methods of Japanese Patent Laid-Open Nos. 7-201673 and 5-279815, the surface layer oxide film of a stabilized aluminum material can be obtained because heating is performed after washing, but the heating method is an atmosphere. Since it is heating, the oxide film produced | generated by heating also has a problem which is easy to be influenced by an atmosphere, and takes time for heat processing.

Further, Japanese Patent Laid-Open No. 5-200406 discloses continuous low temperature heating prior to surface layer removal cleaning and final annealing before finishing rolling, thereby increasing the capacitance and reducing the variation in the capacitance in the width direction of the aluminum coil. Is disclosed.

However, in Japanese Patent Laid-Open No. 5-200406, since the heating of the atmosphere is performed before the final annealing, the aluminum surface oxide film becomes stable, but in order to obtain a desired oxide film with high reproducibility, accurate atmosphere control such as the amount of water vapor is required, and at the same time, the heating of the atmosphere is performed. Because of this, there was a problem that the aluminum material takes time to reach the desired temperature.

In addition, Japanese Laid-Open Patent Publication No. 11-36053 discloses that the aluminum material after the final annealing is heated in the air, in a vacuum or in an inert atmosphere to generate a large number of defects which are starting points of pits on the surface, and dissolve other surfaces. A method of preventing and improving capacitance is disclosed. In addition, Japanese Patent Laid-Open No. 5-255821 discloses that after cleaning the aluminum foil after final annealing (finishing annealing) with an aqueous alkali solution, heating the atmosphere at 150 to 400 ° C. improves the capacitance and reduces the variation. It is described.

However, since the conventional heat treatment after the final annealing is performed in the air, in the vacuum, or in an inert gas, it is also easy to be influenced by the amount of oxygen and water vapor, and in order to make the oxide film suitable for etching with good reproducibility, accurate atmosphere control such as the amount of water vapor There is a problem that the aluminum foil surface takes time to reach the desired temperature.

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing an aluminum material for an electrolytic capacitor electrode and an aluminum material for an electrolytic capacitor electrode, which can be processed in a short time without requiring accurate atmosphere control, and the etching characteristics are uniform and the area enlargement ratio by etching is large. Is in.

Another object of the present invention is to provide a method for producing an electrode material for an electrolytic capacitor using the aluminum material and an aluminum electrolytic capacitor.

In the present invention, when hot rolling, cold rolling, and final annealing are sequentially performed on an aluminum slab to produce an aluminum material for an electrolytic capacitor electrode, a step of heating the aluminum material by contact with a heating body in the step after the hot rolling is performed. It is a manufacturing method of the aluminum material for electrolytic capacitor electrodes characterized by including.

The contact heating process of the aluminum material with the heating body may be performed at any time after the hot rolling. Specifically, the contact heating step with the heating body of the aluminum material may be carried out at least once in a step in the middle from the start to the end of the cold rolling.

Or the contact heating process with the heating body of the said aluminum material may be performed before the final annealing after the cold rolling, or may be performed after the final annealing.                 

The use of contact heating as the heating method is that the surface of the aluminum material can be brought to a desired temperature uniformly in a short time according to the surface of the heating body, so that the control is relatively easy and the heating can be rapidly performed in a short time. This is because the impact can be reduced.

Other objects, features and advantages of the present invention will become more apparent from the following description.

(1st embodiment)

This embodiment is a case where the contact heating process with the heating body of an aluminum material is performed at least once in the process in the middle from the start to the end of the said cold rolling.

That is, the inventors of the present invention heat the aluminum material by contact with the heating body at least once in the process from the start to the end of the cold rolling (including the finish cold rolling) to make the aluminum surface layer oxide film dense and homogeneous. By doing this, it was found that after the final annealing, an aluminum material for electrolytic capacitor electrodes having a high etching capacity while having uniform etching characteristics was obtained.

The use of contact heating as the heating method is that the surface of the aluminum material can be brought to a desired temperature uniformly in a short time according to the surface of the heating body, so that the control is relatively easy and the heating can be rapidly performed in a short time. This is because the impact can be reduced.

In the process in the middle of cold rolling, the aluminum material heated by the contact with the heating body at least once is annealed after cold rolling, after washing as necessary.

When crystalline oxide particles are formed on the surface of aluminum during final annealing, some documents describe etch pits around crystals during electrolytic etching [for example, Osawa Nobuo, Fukuoka Kiyoshi: Surface Technology, 50 [7], 643 (1999)], It is considered that the production of the crystalline oxide particles on the aluminum surface contributes to the improvement of the capacitance.

In an aluminum material having a surface oxide film densified and homogenized by contact heating, defects are uniformly present on the entire surface by subsequent cold rolling. The cold rolled aluminum material thus obtained is washed as it is or with a cleaning solution which does not dissolve aluminum, followed by final annealing, whereby an electrolytic capacitor electrode in which substances capable of becoming nuclei of etch pits, such as fine crystalline oxides, are uniformly dispersed on the surface. An aluminum material for the purpose can be obtained.

-Al₂O₃를 포함하는 Al₂O₃, 베마이트를 포함하는 AlOOH, 알루미늄 이외의 함유 금속(예를 들면, Mg, Pb, Cu 등)의 복합 산화물 등이 있지만, 금속 산화물 또는 금속 수산화물 등에 특별히 한정되는 것은 아니다. The material that can be the nucleus of the etch pit includes not only a crystalline oxide but also one having a high density or thickness in amorphous, and one containing crystalline oxide or metallic aluminum in the amorphous state. In addition, as a kind of crystalline oxide

-Al AlOOH containing ₂ O ₃ Al ₂ O _3, boehmite, containing, containing a metal other than aluminum (for example, Mg, Pb, Cu, and so on) such as a composite oxide, but the metal oxide or metal hydroxide or the like of It is not specifically limited.

If the oxide film on the surface of the aluminum material is different from other places, it is considered that it may be a nucleus of the etch pit at the time of etching, and the state before the transition to the crystal or the crystal at the time of annealing by rapid heating before final annealing is considered. It is presumed that materials containing amorphous and metallic aluminum in amorphous and amorphous forms are produced, and these become etch pit nuclei.

In the case of washing with a cleaning liquid that dissolves aluminum before final annealing, the oxides generated on the surface of the aluminum material by the contact heating are removed, but the surface layer is uniformly dissolved by the cleaning liquid as compared with the case where the contact heating is not performed. In the aluminum material obtained after annealing, the substance serving as the etch pit nucleus is uniformly present on the surface.

In the present embodiment, in the middle of the cold rolling step, when the intermediate annealing is carried out for the purpose of eliminating the distortion of the crystal structure of the aluminum material caused by the rolling in the previous step, the aluminum material is contact-heated before the intermediate annealing. By making the surface oxide film of the aluminum material dense and homogeneous, the growth of the oxide film during intermediate annealing can be prevented, and the aluminum surface layer oxide film in the width direction and the longitudinal direction of the aluminum material coil can be made homogeneous.

The manufacturing method of the aluminum material for electrolytic capacitors is demonstrated below.

The purity of the aluminum material is not particularly limited as long as it is in a range used for an electrolytic capacitor, but a purity of 99.9% or more is preferable, particularly 99.95% or more. In addition, in this invention, the purity of an aluminum material shall be made into the value which subtracted the total concentration (%) of Fe, Si, Cu, Mn, Cr, Zn, Ti, and Ga from 100%.                 

The production of the aluminum material is not limited, but is carried out in the order of melting component adjustment, slab casting, cracking treatment, hot rolling, cold rolling including cold rolling (low pressure rolling), and final annealing of the aluminum material. In the process of the cold rolling before completion | finish after the start of cold rolling, an aluminum material is heated at least 1 time by contact with a heating body. For example, contact heating is performed between the primary cold rolling and the finish cold rolling during the first cold rolling before the finish cold rolling. In addition, the manufacturing process conditions of an aluminum material are changed suitably with relationship with the etching conditions, etc. of an aluminum material.

In the middle of the cold rolling step, the intermediate annealing may be performed for the purpose of eliminating the distortion of the crystal structure of the aluminum material produced by the rolling of the previous step. In addition, you may perform washing | cleaning for the purpose of removing the impurity and oil on the surface of an aluminum material before the process before intermediate annealing, or the final annealing after cold rolling.

Contact heating of the aluminum material is performed to obtain an aluminum material for an electrolytic capacitor electrode having a high capacitance and a uniform etching characteristic after final annealing by making the surface oxide film of the aluminum material dense and homogeneous.

However, when the rolling work ratio after contact heating becomes too large, the effect of making the etching characteristics by contact heating uniform becomes small. Therefore, after the last contact heating, the thickness of the aluminum material before rolling restart is A (µm), and the entire cold rolling is finished. When the thickness of the aluminum material after that is B (micrometer), it is preferable that the rolling work rate after contact heating represented by {(AB) / A} x100 (%) is 60% or less, and 30% or less is especially preferable.                 

The means for the contact heating may be one capable of contact heating such as a heat roll, a heating belt, and a heating plate, and may be heated one by one, or only one of the front and back. As a material of the heating surface of the heating body, stainless, plating, ceramics, Teflon resin (registered trademark), silicone resin and the like can be freely selected, but a substance in which the surface oxide film of the aluminum material does not adhere to the surface of the heating body is preferable.

As for the surface temperature of the heating body made to contact an aluminum material, 50-450 degreeC is preferable. If the surface temperature of the heating body is less than 50 ° C., the heating becomes insufficient, and there is a fear that the generation of substances that can become nuclei of etch pits, such as crystalline oxide fine particles during final annealing, may be insufficient. On the other hand, when it is higher than 450 degreeC, an oxide film will become too thick and wrinkles may arise at the time of cooling, and there exists a possibility that an operation problem may arise. More preferable heating body surface temperature is 60-400 degreeC, More preferably, it is 100-350 degreeC. Especially preferable heater surface temperature is 160-290 degreeC.

It is preferable that the contact time of the surface of an aluminum material and the surface of a heating body shall be 0.001 to 60 second. If the contact time is less than 0.001 second, the surface of the aluminum material cannot be sufficiently heated, and there is a fear that a substance capable of being etched may not be produced uniformly. On the other hand, even if it heats longer than 60 second, there exists a possibility that the homogeneous effect of an oxide film may reach saturation. Particularly preferred contact time is 0.01 to 30 seconds. More preferred contact time is 0.1 to 10 seconds.

The surface temperature and the contact time of the heating body can be appropriately selected in consideration of the properties of the aluminum oxide surface oxide film before the contact. The contact heating atmosphere is not particularly limited and can be carried out in air without requiring any special atmosphere control.

As an example of the heating apparatus which used the heat roll as a heating body, the apparatus which has arrange | positioned at least 2 heat rolls in order to contact-heat-heat the front and back surface of an aluminum material at a desired temperature is mentioned. If wrinkles occur when the aluminum material is wound up after the aluminum material is heated by contact with a heat roll or the like, after heating with a heat roll or the like, the aluminum material is cooled by passing through a cooling body such as one or a plurality of cooling rolls. It is good also as a structure to take. Especially by using a cooling roll as a cooling body, cooling can be performed simply and continuously. Moreover, before heating an aluminum material to desired contact heating temperature with a heat roll etc., you may raise the temperature of an aluminum material preliminarily to temperature lower than the target contact heating temperature using another heat roll.

Although the liquid used for the process performed before the intermediate annealing or before the final annealing after cold rolling is not particularly limited, an organic solvent, an aqueous alkali solution, an acid aqueous solution, an amine aqueous solution, ammonia water, or a surfactant added to water is used. .

Examples of the organic solvent include, but are not particularly limited to, aromatic hydrocarbons such as alcohols, diols, toluene and xylene, alkanes, hydrocarbons, cyclohexane, ketones, ethers, esters, petroleum products, and the like. Moreover, you may mix and use a some organic solvent, and in the case of the organic solvent which can be mixed with water, you may mix and use with water as needed.

As a washing | cleaning liquid used for the process performed before the intermediate annealing, or after final rolling after cold rolling, aqueous alkali solution or an acid aqueous solution may be sufficient. Although it does not specifically limit as alkali contained in alkaline aqueous solution, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium silicate, etc. can be illustrated, The aqueous solution containing at least 1 type or more of alkali can be used as a washing | cleaning liquid. In addition, the acid contained in the acid aqueous solution is not particularly limited, and examples include hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, and the like, and an aqueous solution containing at least one or more of these acids can be used as the cleaning liquid.

Although the contact method of the cleaning liquid and aluminum material in the said washing | cleaning is not specifically limited, Dipping, the contact of aluminum material to the cleaning liquid surface, spray, etc. are mentioned.

After finishing cold rolling, after washing, if necessary, it promotes the production of a material that can become the nucleus of the etch pit, and adjusts the orientation of the crystal structure of the aluminum material to the (100) orientation to improve the etching characteristics. The final annealing is performed.

In the final annealing, the total thickness of the oxide film after the final annealing is increased so that the thickness of the oxide film formed in the aluminum material in the contact heating step in the middle of the cold rolling step, which is the previous step, is excessively increased in the final annealing step so as not to deteriorate the etching characteristics. Hunter Hall Law [MS Hunter and P. Fowle, J. Electrochem. Soc., 101 [9], 483 (1954)] is preferably subjected to final annealing to be 2.5 to 5 nm in thickness. Moreover, as for the (100) area ratio of the aluminum material after final annealing, 90% or more is preferable.

Although the processing atmosphere in this final annealing is not specifically limited, It is preferable to heat in the atmosphere with few moisture and oxygen so that the thickness of an oxide film may not be increased too much. Specifically, heating in an inert gas such as argon or nitrogen or in a vacuum of 0.1 Pa or less is preferable.

The method of final annealing is not particularly limited, and may be batch annealed in a state of being wound with a coil, may be wound with a coil after winding the coil continuously and then annealed, or at least one of batch annealing and continuous annealing may be performed a plurality of times. good.

Although the temperature and time at the time of final annealing are not specifically limited, For example, when performing batch annealing in the state of a coil, it is preferable to anneal for 10 to 50 hours at the aluminum substance temperature of 450-600 degreeC. When the aluminum substance temperature is less than 450 ° C. and the time is less than 10 minutes, the material capable of forming the nuclei of the etch pit in the oxide film is insufficient, and the dispersion state becomes excessively coarse, so that the etching is used as an etching nucleus. This is because there is a possibility that the area-expansion effect of N may not be expected, and the development of the crystal orientation of the (100) plane may also become insufficient. On the contrary, when the annealing exceeds 600 ° C., the aluminum material tends to be in close contact when annealing with a coil, and even if the annealing is over 50 hours, the etching area enlargement effect is saturated, and the thermal energy cost is increased. Especially preferable temperature is 460-580 degreeC in aluminum substance temperature, and time is 20 minutes-40 hours.

In addition, a temperature increase rate and a pattern are not specifically limited, You may heat up at a constant speed, You may heat up and cool step repeatedly, repeating temperature rising and temperature maintenance, and a total of 10 minutes in the temperature range of aluminum substance temperature 450-600 degreeC in an annealing process. You may anneal for 50 hours. The thickness of the aluminum material for electrolytic capacitor electrodes obtained after the final annealing is not particularly specified.

The aluminum material after the final annealing is subjected to an etching process for improving the area enlargement ratio. Although the etching process conditions are not specifically limited, Preferably, the direct current etching method is employ | adopted. By the direct current etching method, in the final annealed portion, which becomes the nucleus of the etch pit that is promoted to be produced, deep and thick etching are performed to generate a large number of tunnel-type pits, and a fixed capacitance is realized.

After the etching treatment, preferably, chemical conversion treatment is performed to form the cathode material, and in particular, it is preferable to use the electrolytic capacitor electrode material for medium pressure and high pressure. Of course, it does not interfere with using as a negative electrode material.

An aluminum electrolytic capacitor is constructed by using the above positive electrode material and / or negative electrode material as an electrode material. In this electrolytic capacitor, since the area expansion ratio of the electrode material is increased, it has a large capacitance.

In this embodiment, since an aluminum material is heated by contact with a heating body in the middle of a cold rolling process, and finally annealed, the aluminum material for electrolytic capacitors with uniform etching characteristics can be manufactured. In particular, since contact heating is used as the heating method, the surface of the aluminum foil can be reached at a desired temperature uniformly in a short time, and thus the temperature control is relatively easy, and the heating can be rapidly performed in a short time. Can be less. Therefore, by etching this electrolytic capacitor aluminum material, the etch pits are uniformly generated and effectively etched, and as a result, the area enlargement ratio can be improved, and further, the electrolytic capacitor electrode material having increased capacitance can be obtained. As a result, an aluminum electrolytic capacitor having a large capacitance can be obtained.

(2nd embodiment)

This embodiment is a case where the contact heating process with the heating body of an aluminum material is performed before the final annealing after the said cold rolling.

That is, in the step after cold rolling, by heating the aluminum material by contact with the heating body, a substance capable of becoming an etch pit nucleus is deposited on the surface of the aluminum material by subsequent annealing. The use of contact heating as the heating method is that the surface of the aluminum material can be brought to a desired temperature uniformly in a short time according to the surface of the heating body, so that the control is relatively easy and the heating can be rapidly performed in a short time. This is because the impact can be reduced.

In the production of aluminum materials for electrolytic capacitors, in general, in order to develop a crystal orientation of the (100) plane, final annealing is performed in an inert atmosphere or vacuum at a temperature range of 450 to 600 ° C, but etched pit such as crystalline oxide. There is not enough material to make the nucleus of. Thus, rapid heating by contact heating before final annealing promotes the production of a substance that can become nuclei of etch pits, such as crystalline oxide fine particles, during final annealing.

-Al₂O₃를 포함하는 Al₂O₃, 베마이트를 포함하는 AlOOH, 알루미늄 이외의 함유 금속(예를 들면, Mg, Pb, Cu 등)의 복합 산화물 등이 있지만, 금속 산화물 또는 금속 수산화물 등으로 특별히 한정되는 것은 아니다. The material that can be the nucleus of the etch pit includes not only a crystalline oxide, but also one having a high density or thickness even in amorphous, and one containing crystalline oxide or metallic aluminum in the amorphous state. In addition, as a kind of crystalline oxide,

_{-Al 2 O 3 Al 2 O 3} , AlOOH containing boehmite containing, containing a metal other than aluminum (for example, Mg, Pb, Cu, and so on) such as a composite oxide, but the metal oxide and a metal hydroxide such as It is not specifically limited to.

If the oxide film on the surface of the aluminum material is different from other places, it is considered that it may be the nucleus of the etch pit during etching, and is rapidly heated before the final annealing, so that the state before the transition to the crystal or the crystal during the annealing is considered. It is presumed that materials containing amorphous and metallic aluminum in amorphous and amorphous forms, and these become etch pit nuclei.

The use of contact heating with a heating body as a method of rapid heating, as described above, can reach the desired temperature of the aluminum material surface in a very short time and is excellent in productivity, and can be heated in a short time. It is because it is difficult and the temperature of the surface of the heating body which contacts the surface of an aluminum material is uniform, because it has the advantage that a uniform oxide film can be formed in the width direction and the length direction of an aluminum coil.

The manufacturing method of the aluminum material for electrolytic capacitors is demonstrated below.

The purity of the aluminum material is not particularly limited as long as it is in a range used for an electrolytic capacitor, but a purity of 99.9% or more is preferable, particularly 99.95% or more. In addition, the purity of an aluminum material shall be the value which subtracted the total concentration (%) of Fe, Si, Cu, Mn, Cr, Zn, Ti, and Ga from 100%.                 

The production of the aluminum material is not limited, but is carried out in the order of melting component adjustment, slab casting, cracking treatment, hot rolling, cold rolling, finish cold rolling (low pressure rolling), and contact heating of the aluminum material. It is preferable that the (100) area ratio of an aluminum material is 90% or more, and the manufacturing process conditions of an aluminum material are changed suitably from the relationship with the etching conditions of an aluminum material. In addition, you may perform annealing (called intermediate | middle annealing) in the middle of a rolling process in order to eliminate the distortion of the crystal structure of the aluminum material produced by rolling of the previous process. In addition, in the process before intermediate annealing, you may wash | clean in order to remove the impurity and oil component of an aluminum surface.

Although the washing | cleaning liquid used at the process before intermediate annealing is not specifically limited, Alkali aqueous solution, an acidic aqueous solution, an organic solvent, etc. are used.

Since the oil material exists in the surface of the aluminum material which finished the rolling process, it is preferable to wash at least any time before contact heating mentioned later or after contact heating before final annealing as needed. By performing such washing | cleaning, the effect of contact heating is further exhibited and a big electrostatic capacitance can be obtained.

It is preferable to remove by washing | cleaning, when contact heating is performed and washing | cleaning is carried out after completion | finish of rolling, and big abrasion powder etc. adhere to the aluminum material surface.

Since the washing | cleaning liquid used for the washing | cleaning before the said contact heating or after the contact heating is aimed at degreasing, what added surfactant to the organic solvent and water is used.

As the organic solvent, a substance which does not dissolve aluminum can be used, and examples thereof include aromatic hydrocarbons such as alcohols, diols and toluene xylenes, alkanes, hydrocarbons, cyclohexane, ketones, ethers, esters, petroleum products, and the like. It is not specifically limited.

Examples of the alcohol include methanol (CH ₃ OH), ethanol (C ₂ H ₅ 0H), 1-propanol (CH ₃ CH ₂ CH ₂ OH), 2-propanol (CH ₃ CH ₂ (0H) CH ₃ ), 1 -Butanol (CH ₃ CH ₂ CH ₂ CH ₂ OH), 2-butanol (CH ₃ CH ₂ CH ₂ (0H) CH ₃ ), 1-pentanol (CH ₃ CH ₂ CH ₂ CH ₂ CH ₂ OH), 2 -Pentanol (CH ₃ CH ₂ CH ₂ CH ₂ (0H) CH ₃ ) and the like, and are preferably represented by C _n H _{2n + 1} 0H (natural number of n = 1 to 10). In addition, aliphatic hydrocarbons such as cyclohexanol can also be used.

Examples of the diol include 1,2-ethanediol (H0CH ₂ CH ₂ OH), 1,2-propanediol (CH ₃ CH (OH) CH ₂ OH), 1,3-propanediol (HOCH ₂ CH ₂ CH ₂ OH) etc. can be illustrated.

Examples of the alkane hydrocarbons include pentane (C ₅ H ₁₂ ), hexane (C ₆ H ₁ 4), heptane (C ₇ H ₁₆ ), octane (C ₈ H ₁₈ ), nonane (C ₉ H ₂₀ ), and decane ( C ₁₀ H ₂₂ ), and the like, and are preferably represented by C _n H _{2n + 2} (a natural number of n = 5 to 15). In addition, application of a dry-dry hydrocarbon, such as cyclohexane, is also possible.

Examples of the ketones include acetone (CH ₃ COCH ₃ ), 2-butanone (CH ₃ COC ₂ H ₅ ), 3-pentanone (CH ₃ CH ₂ COCH ₂ CH ₃ ), and 3-methyl-2-butanone ( CH ₃ COCH (CH ₃ ) ₂ ) and the like, and R ¹ COR ² (R ¹ and R ^{2 are} aliphatic hydrocarbon groups, and the sum of the carbon number of R ¹ and R ² is 8 or less). desirable. It is also possible to use a cyclic ketone such as cyclohexanone (C ₆ H ₁₀ O).

Examples of the ether, R ¹ -OR ² (R ¹ and R ^2: an aliphatic hydrocarbon group, R ¹ and less than the total number of carbon atoms of R ² 8) represented by the material, 2-methoxy ethanol (CH ₃ 0CH ₂ CH ₂ OH), 2- ethoxyethanol _{(CH 3 CH 2 OCH 2 CH} 2 OH), 2- butoxyethanol _{(CH 3 CH 2 CH 2 CH} 2 OCH 2 CH 2 OH) 2 - ( 2-ethoxy) Glycol ethers such as ethoxyethanol (CH ₃ CH ₂ OCH ₂ CH ₂ 0CH ₂ CH ₂ 0H) are also included.

Examples of the ester, CH ₃ COOR: there can be mentioned acetic acid ester represented by (R 1 to 5 carbon atoms in the aliphatic hydrocarbon group).

Examples of the petroleum products include industrial gasoline (JIS K 2201), automobile gasoline (JIS K 2202), aviation gasoline (JIS K 2206), kerosene (JIS K 2203), diesel oil (JIS K 2204), aviation gasoline (JIS K 2206). ), Petroleum ether (JIS K 8593), petroleum benzine (JIS K 8594), ligroin (JIS K8937), kerosene and the like.

As said organic solvent, you may mix and use a some organic solvent, and in the case of the organic solvent which can be mixed with water, you may mix and use with water as needed.

On the other hand, as surfactant contained in the washing | cleaning liquid which added surfactant to water used for the said washing | cleaning, anionic surfactant, cationic surfactant, and nonionic surfactant can be used.

As the anionic surfactant, sulfuric acid ester salts and sulfonates can be used.                 

As the sulfuric acid ester salt, R-OSO ₃ Na (unsaturated hydrocarbon group having one or two double bonds or a saturated hydrocarbon group having 8 to 18 carbon atoms) may be used, and specifically, sodium dodecyl sulfate (C ₁₂ H). _{25 0} SO ₃ Na), hexadecyl sulfate (C ₁₆ H ₃₃ OSO ₃ Na), stearyl sodium sulfate (C ₁₈ H ₃₇ OSO ₃ Na), sodium oleic sulfate (C ₁₈ H ₃₅ OSO ₃ Na), and the like. can do.

The sulfonate may be selected from the group consisting of R-S0 ₃ Na (unsaturated hydrocarbon group having 8 to 18 carbon atoms or an unsaturated hydrocarbon group having one double bond) or sodium dodecyl benzene sulfonate (C ₁₂ H ₂₅ -C ₆ H _4- SO ₃ Na), such as the R-S0 ₃ Na (R: alkyl group may be used is the unsaturated hydrocarbon group represented by alkyl benzyl group) having one of a combination of a saturated hydrocarbon group or two of the carbon atoms from 8 to 14.

As the cationic ^{_{surfactant, RN + (CH 3) 3}} · Cl - can be used a quaternary ammonium salt represented by (R = saturated hydrocarbon group having 8 to 16).

As the nonionic surfactant, R-0 - (- CH 2 CH 2 O) n H (R = number of carbon atoms from 8 to 16 groups of the unsaturated hydrocarbon having one binding of a saturated hydrocarbon group or a 2, n = 6 to 14), or Polyethylene glycol represented by RO-(-CH ₂ CH ₂ O) _n H (alkyl phenyl group in which an R = alkyl group is a saturated hydrocarbon group having 8 to 12 carbon atoms or a double bond, n = 6 to 14) Type nonionic surfactants can be exemplified. In addition, more than n of the said range may contain 50% or less of molar ratio in nonionic surfactant.

Moreover, at least 1 type or more of the said surfactant can be added to water, and it can use as a washing | cleaning liquid. Surfactant with less carbon number of surfactant than the said range may be added in 50% or less molar ratio. In addition, mixing is preferably avoided when anionic surfactants and cationic surfactants are mixed in water to cause precipitation.

Although the addition density | concentration of surfactant is not specifically defined, In order to exhibit a washing | cleaning effect, it is preferable that it is more than a critical micelle concentration.

In the said washing | cleaning process, although it does not specifically limit as a contact method of the organic solvent or surfactant aqueous solution used as a washing | cleaning liquid, and an aluminum material, Dipping, a contact of the aluminum material to the surface of a washing | cleaning liquid, spray, etc. are mentioned.

In addition, in order to further remove oil or abrasion on the surface of the aluminum material, the aluminum material may be further rubbed with a brush or sponge during contact between the cleaning liquid and the aluminum material.

Although the contact time of a cleaning liquid and an aluminum material in a washing process is not specifically limited, It is preferable that they are 0.5 second or more and 10 minutes or less. If the contact time between the cleaning liquid and the aluminum material is less than 0.5 seconds, the cleaning is insufficient, and the cleaning effect reaches saturation even if the cleaning liquid is brought into contact for longer than 10 minutes. It is preferable that the liquid temperature of the washing | cleaning liquid is 5-80 degreeC in the case of the washing | cleaning liquid which added surfactant to 5 to 60 degreeC and water in the case of an organic solvent. When the liquid temperature of three semens is less than a lower limit, washing | cleaning power is inadequate, and even if it wash | cleans at the temperature higher than an upper limit, washing | cleaning power reaches saturation.

After washing the aluminum material, it may be dried as necessary. As a drying method, air heating, inert atmosphere heating, and vacuum heating can be used, for example. It is preferable that the atmospheric temperature in the case of drying in air is 200 degrees C or less, and a drying time is 10 minutes or less. This is because if the drying temperature is higher than 200 ° C. or the heating time is longer than 10 minutes, the oxide film may grow excessively and the etching characteristics may be deteriorated.

The aluminum material after the end of rolling or the aluminum material which has been washed again after the end of rolling is contact-heated in order to generate many nuclei of etch pits by subsequent annealing. The heating means may be any one capable of contact heating such as a heat roll, a heating belt, a heating plate, etc., but a heat roll is preferable since the heating means can be simply and continuously performed. In addition, you may heat by one surface and you may heat only one side of front and back. As a material of the heating surface of the heating body, stainless, plating, ceramics, Teflon resin (registered trademark), silicone resin and the like can be freely selected, but a material in which the surface oxide film of the aluminum material does not adhere to the surface of the heating body is preferable.

As for the surface temperature of the heating body made to contact an aluminum material, 50-450 degreeC is preferable. If the surface temperature of the heating body is less than 50 ° C., the heating becomes insufficient, and there is a fear that the generation of substances that can become nuclei of etch pits, such as crystalline oxide fine particles during annealing performed after contact heating, may be insufficient. On the other hand, when it becomes higher than 450 degreeC, an oxide film becomes thick too much, wrinkles generate | occur | produce at the time of cooling, and there exists a possibility that an operation problem may arise. More preferable heating body surface temperature is 80-400 degreeC, More preferably, it is 100-350 degreeC. Especially preferable heater surface temperature is 160-290 degreeC.

It is preferable that the contact time of the surface of an aluminum material and the surface of a heating body shall be 0.001 to 60 second. If the contact time is less than 0.001 second, the surface of the aluminum material cannot be sufficiently heated, and there is a fear that the production of a substance that can also become an etch pit nucleus becomes insufficient. On the other hand, if it is longer than 60 seconds, there is a fear that the oxide film becomes too thick and etch pits are less likely to occur. More preferable contact time is 0.001 to 30 second, More preferably, it is 0.01 to 10 second. Particularly preferred contact time is 0.1 to 7 seconds.

The surface temperature and the contact time of the heating body may be appropriately selected in consideration of the characteristics of the oxide film on the surface of the aluminum material before the contact. The contact heating atmosphere is not particularly limited and can be carried out in air without requiring any special atmosphere control.

As an example of the heating apparatus which used the heat roll as a heating body, the apparatus which has arrange | positioned at least 2 heat rolls in order to contact-heat-heat the front and back surface of an aluminum material at a desired temperature is mentioned. If wrinkles occur when the aluminum material is wound up after the aluminum material is heated by contact with a heat roll or the like, after cooling by the heat roll or the like, a cooling body such as one or a plurality of cooling rolls is passed through to cool the aluminum material. It is good also as a structure to wind up. Especially by using a cooling roll as a cooling body, cooling can be performed simply and continuously. Moreover, you may preliminarily raise the temperature of aluminum material to temperature lower than a desired contact heating temperature using another heat roll, before heating an aluminum material to desired contact heating temperature with a heat roll etc.                 

After contact heating, the above-mentioned cleaning is performed as necessary, and then, while promoting the production of a material capable of becoming the nucleus of the etch pits, the orientation of the crystal structure of the aluminum material is adjusted to the (100) orientation to improve the etching characteristics. Final annealing takes place for the purpose.

In addition, of course, you may perform another process other than the process mentioned above, for example, the slit process for dividing an aluminum material coil, etc. after final rolling after final rolling.

In the final annealing, the total thickness of the oxide film after the final annealing is hunter so as not to increase the thickness of the oxide film formed in the aluminum material in the contact heating step, which is the previous step, in the final annealing step so as to eliminate the possibility of becoming an etching nucleus. Hall method [MS Hunter and P. Fowle, J. Electrochem. Soc., 101 [9], 483 (1954)] is preferably subjected to the final annealing to be 2.5 to 5.0 nm in thickness. Moreover, as for the (100) area ratio of the aluminum material after final annealing, 90% or more is preferable.

Although the processing atmosphere in this final annealing is not specifically limited, It is preferable to heat in atmosphere with few moisture and oxygen so that the thickness of an oxide film may not be increased too much. Specifically, heating in an inert gas such as argon or nitrogen or in a vacuum of 0.1 Pa or less is preferable.

The method of final annealing is not particularly limited, and may be batch annealed in a state of being wound with a coil, or may be wound with a coil after rewinding the coil and continuous annealing, or at least one of batch annealing and continuous annealing a plurality of times. You may carry out.

Although the temperature and time at the time of final annealing are not specifically limited, For example, when performing batch annealing in the state of a coil, it is preferable to anneal for 10 minutes-50 hours at 450-600 degreeC of aluminum substance temperature. When the aluminum substance temperature is less than 450 ° C. and the time is less than 10 minutes, the generation of a substance capable of becoming the nucleus of the etch pit in the oxide film is insufficient, and the dispersion state is too coarse, and the etching is performed when the crystal is used as an etching nucleus. This is because there is a possibility that the area-expansion effect of N may not be expected, and the development of the crystal orientation of the (100) plane may also become insufficient. On the contrary, when the annealing exceeds 600 ° C., the annealing with a coil tends to cause the aluminum material to be in close contact, and even if the annealing is over 50 hours, the area enlargement effect due to etching is saturated, resulting in an increase in thermal energy cost. do. More preferable temperature is 460-600 degreeC, especially 500-580 degreeC by aluminum substance temperature, and time is 20 minutes-40 hours.

In addition, the temperature increase rate and pattern of final annealing are not specifically limited, It can raise temperature at a constant speed, It can heat up and cool step repeatedly, repeatedly raising temperature and temperature maintenance, The temperature of aluminum substance temperature 450-600 degreeC in an annealing process. It is good to anneal in total for 10 minutes-50 hours. In addition, the thickness of the aluminum material for electrolytic capacitor electrodes obtained after final annealing is not specifically defined.

The aluminum material after the final annealing is subjected to an etching process for improving the area enlargement ratio. Although the etching process conditions are not specifically limited, Preferably, the direct current etching method is employ | adopted. By the direct current etching method, in the portion that becomes the nucleus of the etch pit that is promoted in the final annealing, a deep and thick etching is performed to generate a large number of tunnel-type pits, and a fixed capacitance is realized.

After the etching treatment, preferably, chemical conversion treatment is performed to form an anode foil, and in particular, it is preferable to use the electrolytic capacitor electrode material for medium pressure and high pressure. Of course, it does not interfere with using as a negative electrode material.

An aluminum electrolytic capacitor is constructed by using the above positive electrode material and / or negative electrode material as an electrode material. In this electrolytic capacitor, since the area expansion ratio of the electrode material is increased, it has a large capacitance.

In this embodiment, an aluminum material for electrolytic capacitors having excellent etching characteristics in which a large number of substances that can become an etch pit nucleus is deposited on the foil surface by annealing after heating the aluminum material by contact with a heating body after cold rolling. can do. In particular, since contact heating is used as the heating method, the surface of the aluminum material can be uniformly brought to a desired temperature in a short time, so temperature control is relatively easy, and the heat can be rapidly heated in a short time, thereby reducing the influence of the atmosphere. have. Therefore, by etching this electrolytic capacitor aluminum material, the etching is effectively performed at the position of the substance that can be the nucleus of the etch pit, and as a result, the area enlargement ratio can be improved, and further, the capacitance is increased. An electrolytic capacitor electrode material can be obtained, and as a result, an aluminum electrolytic capacitor having a large capacitance can be obtained.

In addition, the effect of increasing the capacitance can be further obtained by cleaning the aluminum material at least either before or after contact with the heating element.                 

(Third embodiment)

This embodiment is a case where the aluminum material is washed with a liquid capable of dissolving aluminum after the cold rolling, and then a contact heating step with a heating body of the aluminum material is performed before final annealing.

The contact heating for heating the aluminum material by contact with the heating body is excellent in that the surface of the aluminum material can be brought to a desired temperature in a short time by the heating body contact surface, and furthermore, the heating can be heated in a short time. It has the advantage of low temperature control.

When the aluminum material obtained by the above-mentioned manufacturing method is etched, the effective area is increased, and the oxide film of the surface of the aluminum material can be stabilized by contact heating before annealing, whereby the crystal which becomes an etch pit nucleus on the surface during annealing. This is because the oxidized oxide particles are produced uniformly.

-Al₂O₃를 포함하는 Al₂O₃, 베마이트를 포함하는 AlOOH, 알루미늄 이외의 함유 금속(예를 들면, Mg, Pb, Cu 등)의 산화물 및 수산화물, 알루미늄과 알루미늄 이외의 함유 금속(예를 들면, Mg, Pb, Cu 등)의 복합 금속 산화물 또는 수산화물이 있지만, 특별히 한정되는 것은 아니고, 또한, 단결정, 다결정 중 어느 것이라도 좋다. 또한, 단일 또는 복수의 결정이 무정형 물질에 덮여서 하나의 입자를 형성하는 것이라도 좋고, 응집한 산화물 결정 사이에 무정형 산화물이 존재하고 있어도 좋다. As a kind of the said crystalline oxide particle,

-Al ₂ O ₃ other than the AlOOH, Al containing Al ₂ O _3, boehmite containing the metal-containing oxides, hydroxides, containing a metal other than aluminum and aluminum (for example, Mg, Pb, Cu, etc.) ( For example, although there exist a composite metal oxide or hydroxide of Mg, Pb, Cu, etc., it is not specifically limited, Any of single crystal and polycrystal may be sufficient. In addition, one or a plurality of crystals may be covered with an amorphous material to form one particle, or an amorphous oxide may be present between the aggregated oxide crystals.

The manufacturing method of the aluminum material for electrolytic capacitor electrodes by this invention is demonstrated below.

The purity of the aluminum material used in the present production method is not particularly limited as long as it is within the range used for the electrolytic capacitor electrode, but a purity of 99.9% or more is preferable, particularly 99.95% or more. In addition, in this invention, the purity of an aluminum material shall be made into the value which subtracted the total concentration (%) of Fe, Si, Cu, Mn, Cr, Zn, Ti, and Ga from 100%.

Moreover, the aluminum material wash | cleaned with the liquid which can melt | dissolve aluminum is generally of melt | dissolution, a component adjustment, slab casting, a cracking process, hot rolling, cold rolling, intermediate annealing, finishing cold rolling (low pressure rolling) of an aluminum material. It is manufactured through each process. These steps may follow the general method and are not particularly limited, but may be appropriately changed in the manufacturing process conditions of the aluminum material in relation to the etching conditions of the aluminum material.

In addition, you may perform annealing (intermediate annealing) in the middle of a rolling process in order to eliminate the distortion of the crystal structure of the aluminum material produced by the rolling of the previous process. In addition, in the process before intermediate annealing, you may wash | clean using acid aqueous solution, aqueous alkali solution, or the organic solvent in order to remove the surface impurity and oil.

In order to produce a homogeneous and stable oxide film on the surface layer of the aluminum material and to produce dispersible crystalline oxide particles which become etch pit nuclei at the time of final annealing on the surface of the aluminum material, the aluminum material after the final rolling can be dissolved in aluminum. After washing with a liquid, contact heating is performed.                 

As a liquid which can dissolve aluminum, the aqueous solution containing at least 1 sort (s) chosen from the group which consists of acid, alkali, ammonia, amines, etc. is mentioned, It is what wash | cleans at least any one of alkali washing or acid washing after final rolling. desirable.

Although it does not specifically limit as alkali of the alkali washing liquid used for the said alkali washing, Sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium silicate, trisodium phosphate, a sodium dihydrogen phosphate, sodium hypochlorite etc. can be illustrated, and at least 1 type is mentioned. The aqueous solution containing the above alkali can be used as a washing liquid.

It is preferable that the alkali concentration in an alkali washing liquid is 0.005 to 50% (mass% or less, the same), the liquid temperature is 5 to 80 ° C, and the washing time is 1 second to 10 minutes. When alkali concentration is less than 0.005% and liquid temperature is less than 5 degreeC, there exists a possibility that the effect of surface uniformity by washing may not be acquired. When the alkali concentration exceeds 50%, the removal of alkali remaining on the surface of the aluminum material after alkali cleaning is more likely to occur, and when the liquid temperature exceeds 80 ° C., the aluminum material may dissolve quickly, which may make controlling of cleaning difficult. If the alkali cleaning time is less than 1 second, the cleaning may be insufficient, and even if the cleaning is longer than 10 minutes, the cleaning effect may be saturated and the aluminum material may be dissolved more than necessary. Especially preferably, they are 0.05-1100% of alkali concentration in alkaline washing liquid, 10-70 degreeC of liquid temperature, and 2 second-5 minutes of washing | cleaning time.

It is preferable to wash with water for the purpose of removing the residue of the washing | cleaning liquid component adhering to the surface of an aluminum material after alkali washing.                 

On the other hand, the acid of the acid cleaning liquid used for acid cleaning is not particularly limited, Lewis acid may be used, for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, boric acid, hydrofluoric acid, and acetic acid, oxalic acid, citric acid Organic acids, such as these, can be illustrated, The aqueous solution containing at least 1 type or more of these acids can be used as a washing | cleaning liquid. Moreover, you may add surfactant to an acid aqueous solution in order to improve the degreasing force. It is preferable that the concentration of the acid is 0.05 to 50%, the liquid temperature is 5 to 80 ° C, and the washing time is 0.5 seconds to 10 minutes. If the acid concentration, the liquid temperature and the washing time at the time of acid washing are less than the lower limit, the washing may be insufficient. If the acid concentration, the liquid temperature and the washing time exceed the upper limit, the washing effect reaches saturation. There is a risk of cost increase. Especially preferably, it is 0.05-30% of acid concentration, 10-70 degreeC of liquid temperature, and 1 second-5 minutes of washing | cleaning time.

It is preferable to wash with water for the purpose of preventing excessive residual of the acid liquid component adhering to the surface of the aluminum material after the acid washing.

Examples of the alkali cleaning and acid cleaning methods include an immersion method and a spray method, but the cleaning method is not particularly limited.

At least one of alkali washing and acid washing may be performed, but both may be performed at least once. In the case of performing both, the order is not particularly limited, but it is preferable to perform acid washing first after alkali washing first. After the contamination layer on the surface is removed efficiently by alkali washing, the surface of the aluminum material is neutralized by performing acid washing, whereby a more homogeneous and stable oxide film can be formed.                 

In addition, the acid concentration in the case of acid washing after alkali washing may be lower than 0.05 to 50%, and the washing time may be shorter than 0.5 seconds to 10 minutes.

Before alkali washing or acid washing, the aluminum material may be washed with an organic solvent for the purpose of degreasing. Examples of the organic solvent include alcohols, aromatic hydrocarbons such as toluene and xylene, pentane-hexane aliphatic hydrocarbons, acetone, ketones, esters, and the like, but are not particularly limited and may be used by mixing a plurality of organic solvents.

Next, the aluminum material which wash | cleaned with the liquid which can melt | dissolve aluminum is heated by contact with a heating body.

The heating body may be anything as long as contact heating is possible, such as a heat roll, a heating plate, a heating belt, or a plurality of contact heating means may be combined. In addition, the front and back of an aluminum material may be heated simultaneously, one surface may be heated, and only one of the front and back may be heated. As a material of the heating surface of the heating body, stainless steel, plating, ceramics, Teflon (registered trademark), silicone resin and the like can be freely selected, but a material in which the surface oxide film of the aluminum material does not adhere to the surface of the heating body is preferable.

As for the surface temperature of the heating body made to contact an aluminum material, 50-450 degreeC is preferable. If the surface temperature of the heating body is less than 50 ° C, the crystallization rate of the surface oxide film after annealing and the control of the crystalline oxide fine particles are not sufficient. If the surface temperature is higher than 450 ° C, the oxide film becomes excessively thick and wrinkles or the like occurs during heating and cooling. This is because there may be a problem in fishing. Especially preferable surface temperature is 80-400 degreeC, and 80-300 degreeC is the best.

It is preferable that the contact time of the surface of an aluminum material and the surface of a heating body shall be 0.001 to 60 second. If the contact time is less than 0.001 second, the surface of the aluminum material cannot be sufficiently heated, and if the surface of the aluminum material is heated longer than 60 seconds, the oxide film becomes too thick, and there is a possibility that etch pits are less likely to occur in any case. More preferable contact time is 0.001-30 second, Furthermore, 0.01-20 second, 0.05-15 second is the best.

What is necessary is just to select the surface temperature of a heating body and the contact time with an aluminum material suitably in consideration of the characteristic of the oxide film of the aluminum material surface before contact heating. The contact heating atmosphere is not particularly limited and is sufficient even in the atmosphere without requiring any special atmosphere control.

After the contact heating, the final annealing is achieved with the main purpose of improving the etching characteristics by adjusting the orientation of the crystal structure of the aluminum material to the (100) orientation.

In the final annealing, the thickness of the oxide film formed on the surface of the aluminum material in the contact heating step, which is its previous step, is excessively increased in the final annealing step, so as not to eliminate the possibility of the crystalline oxide becoming an etching nucleus. The total thickness is obtained from the Hunter Hall method [MS Hunter and P. Fowl, J. Electrochem. Soc. 101 [9], 483 (1954)], it is preferable to perform final annealing so as to be 2.5 to 5 nm. Moreover, as for the (100) area ratio of the aluminum material after final annealing, 90% or more is preferable.

Although the processing atmosphere in this final annealing is not specifically limited, It is preferable to heat in atmosphere with few moisture and oxygen so that the thickness of an oxide film may not be increased too much. Specifically, heating in an inert gas such as argon or nitrogen or in a vacuum of 0.1 Pa or less is preferable.

The method of final annealing is not particularly limited, and may be batch annealed in a state of being wound with a coil, or may be wound up with a coil after winding the coil continuously and then annealed, or at least one of batch annealing and continuous annealing is performed a plurality of times. Also good.

Although the holding temperature and time at the time of final annealing are not specifically limited, For example, when performing batch annealing in the state of a coil, it is preferable to anneal for 10 minutes-50 hours at 450-600 degreeC of aluminum substance temperature. If the aluminum substance temperature is less than 400 ° C. and the time is less than 10 minutes, the formation of crystalline oxide particles that can form nuclei of etch pits in the oxide film is not sufficient, and the dispersed state becomes excessively coarse, so that the crystals are etched. It is because there exists a possibility that the area enlargement effect at the time of etching may not be expected, and development of the crystal orientation of the (100) plane is also inadequate. On the contrary, when the annealing exceeds 600 ° C., the aluminum material tends to be in close contact when batch annealed with a coil. Furthermore, even if the annealing is over 50 hours, the etching surface area enlargement effect is saturated, and the thermal energy cost is increased. . Especially preferable temperature is 460-560 degreeC in aluminum substance temperature, and time is 30 minutes-40 hours.

In addition, the temperature increase rate and pattern in an annealing process are not specifically limited, You may heat up at a constant speed, and you may heat up and cool step repeatedly, heating up and maintaining temperature. What is necessary is just to anneal in total for 10 minutes-50 hours in the temperature range of aluminum substance temperature 450-600 degreeC.

The thickness of the aluminum material for electrolytic capacitor electrodes obtained after the final annealing is not particularly specified.

The aluminum material after final annealing is subjected to an etching treatment in order to enlarge the surface area. Although the etching process conditions are not specifically limited, It is good to employ | adopt the direct current etching method. By the direct current etching, the crystalline oxide particles present on the surface of the aluminum material become etch pit nuclei, and a large number of tunnel-type pits are generated.

After the etching treatment, chemical treatment may be performed to form a cathode material, and in particular, it may be used as a medium pressure and high pressure electrolytic capacitor electrode material. Of course, it does not impede the use for negative electrode material or low pressure use.

In this embodiment, an electrolytic capacitor which is excellent in etching characteristics and obtains a fixed capacitance is obtained by stabilizing the surface oxide film of the aluminum material by contact heating of the aluminum material after washing with a liquid capable of dissolving aluminum. The aluminum material for electrodes can be manufactured. In particular, as the heating method, since contact heating is used, the surface of the aluminum material can be uniformly brought to a desired temperature in a short time, so that temperature control is relatively easy, and the heating can be rapidly performed in a short time. You can do less.

(4th embodiment)

This embodiment is related with the case where the contact heating process with the heating body of an aluminum material is performed after the said final annealing.

That is, by heating the aluminum material by contact with the heating body after the final annealing, the surface oxide film of the aluminum material is made uniform, whereby an aluminum material for electrolytic capacitor electrodes excellent in etching characteristics can be obtained. Contact heating is used as a heating method because the surface of the aluminum material can be brought to a desired temperature uniformly in a short time, depending on the surface of the heating body, the control is relatively easy, the productivity is excellent, and the heating can be performed quickly in a short time. It is because it is hard to be influenced by, and has the advantage of forming a uniform oxide film in the width direction and the length direction of the aluminum material.

The manufacturing method of the aluminum material for electrolytic capacitors is demonstrated below.

The purity of the aluminum material is not particularly limited as long as it is in a range used for an electrolytic capacitor, but a purity of 99.9% or more is preferable, particularly 99.95% or more. In addition, the purity of an aluminum material shall be the value which subtracted the total concentration (%) of Fe, Si, Cu, Mn, Cr, Zn, Ti, and Ga from 100%.

The production of the aluminum material is not particularly limited and is performed in the order of melting component adjustment, slab casting, cracking treatment, hot rolling, cold rolling, finish cold rolling (low pressure rolling), final annealing, and contact heating of the aluminum material. In relation to etching conditions, the manufacturing process conditions of an aluminum material are changed suitably. Moreover, in the middle of a rolling process, annealing (intermediate annealing) can be performed in order to eliminate the distortion of the crystal structure of the aluminum material produced by the rolling of the previous process.

In addition, after hot rolling, during cold rolling or before final annealing after finishing cold rolling, you may wash | clean for the purpose of removing the impurity and oil of an aluminum surface. Although the washing | cleaning liquid used for the said washing | cleaning is not specifically limited, For example, alkaline aqueous solution, acid aqueous solution, an organic solvent, etc. are used.

The aluminum material after the hot rolling may be treated in the state of a coil until contact heating after the final annealing, or the aluminum material may be cut and treated as a cut sample in the middle step. When processing in the state of a coil, you may slit between arbitrary processes, for example, before final annealing, after final annealing, and after contact heating.

After finishing cold rolling, final annealing is performed with the main purpose of improving the etching characteristics by adjusting the orientation of the aluminum material crystal structure to (100) orientation after washing or the like if necessary.

In this final annealing, the total thickness of the oxide film after the final annealing is hunter hole method [MS Hunter and P. Fowle, J. Electrochem. Soc., So as not to increase the thickness of the oxide film excessively in the final annealing step and deteriorate the etching characteristics. 1O1 [9], which is subjected to the final annealing such that 2.5 to 5㎚ in thickness by 483 (1954) reference is preferred. Moreover, as for the (100) area ratio of the aluminum material after final annealing, 90% or more is preferable.

Although the processing atmosphere in this final annealing is not specifically limited, It is preferable to heat in atmosphere with few moisture and oxygen so that the thickness of an oxide film may not be increased too much. Specifically, heating in an inert gas such as argon or nitrogen or in a vacuum of 0.1 Pa or less is preferable.                 

The method of final annealing is not particularly limited, and may be batch annealed in a state of being wound with a coil, or may be wound up with a coil after winding the coil continuously and then annealed, or at least one of batch annealing and continuous annealing is performed a plurality of times. Also good.

Although the temperature and time at the time of final annealing are not specifically limited, For example, when performing batch annealing in the state of a coil, it is preferable to anneal for 10 to 50 hours at the aluminum substance temperature of 450-600 degreeC. If the aluminum substance temperature is less than 450 ° C. and the time is less than 10 minutes, the state of the aluminum surface layer may not be suitable for etching, and the development of the crystal orientation of the (100) plane may be insufficient. On the contrary, if the annealing exceeds 600 ° C., the aluminum material tends to be in close contact when batch annealed with a coil. Furthermore, even if the annealing exceeds 50 hours, the etching area enlargement effect is saturated, resulting in an increase in thermal energy cost. . Especially preferable temperature is 460-580 degreeC in aluminum substance temperature, and time is 20 minutes-40 hours.

In addition, a temperature increase rate and a pattern are not specifically limited, You may heat up at a constant speed, You may heat up and cool step repeatedly, repeating temperature rising and temperature maintenance, and a total of 10 minutes in the temperature range of aluminum substance temperature 450-600 degreeC in an annealing process. It is good to anneal for 50 hours.

The aluminum material after final annealing is contact-heated in order to make the surface oxide film homogeneous after cleaning the surface as needed. The heating means may be one capable of contact heating such as a heat roll, a heating belt, and a heating plate, and may be heated one by one, or only one of the front and back. As a material of the heating surface of the heating body, stainless, plating, ceramics, Teflon resin (registered trademark), silicone resin and the like can be freely selected, but a substance in which the surface oxide film of the aluminum material does not adhere to the surface of the heating body is preferable.

As for the surface temperature of the heating body made to contact an aluminum material, 50-450 degreeC is preferable. When the surface temperature of a heating body is less than 50 degreeC, heating will become inadequate and there exists a possibility that etch pit may not be produced uniformly by etching. On the other hand, when it becomes higher than 450 degreeC, an oxide film becomes thick too much, wrinkles generate | occur | produce at the time of cooling, and there exists a possibility that an operation problem may arise. More preferable heating body surface temperature is 80-400 degreeC, More preferably, it is 100-350 degreeC. Especially preferable heater surface temperature is 160-290 degreeC.

It is preferable that the contact time of the surface of an aluminum material and the surface of a heating body shall be 0.001 to 60 second. If the contact time is less than 0.001 second, the surface oxide film of the aluminum material cannot be made homogeneous, and there is a fear that the generation of etch pits becomes uneven. On the other hand, if it is longer than 60 seconds, there is a fear that the oxide film becomes too thick and etch pits are less likely to occur. Preferable contact time is 0.01 to 30 second, especially 0.05 to 10 second.

The surface temperature and the contact time of the heating body may be appropriately selected in consideration of the properties of the surface oxide film of the aluminum material before the contact. The contact heating atmosphere is not particularly limited and can be carried out in air without requiring any special atmosphere control.

As an example of the heating apparatus which used the heat roll as a heating body, the apparatus which arrange | positioned at least 2 heat rolls is mentioned in order to contact-heat-heat the front and back surface of an aluminum material at a desired temperature. When wrinkles arise at the time of winding up the aluminum material after contact-heating an aluminum material with a heat roll, etc., after heating by a heat roll etc., it passes through cooling bodies, such as one or several cooling rolls, and cools the aluminum material, It is good also as a structure to take. Especially by using a cooling roll as a cooling body, cooling can be performed simply and continuously. In addition, before heating an aluminum material to desired contact heating temperature with a heat roll etc., you may raise the temperature of an aluminum material preliminarily to temperature lower than a desired contact heating temperature using another heat roll.

The thickness of the aluminum material for electrolytic capacitor electrodes obtained by the contact heating after the final annealing is not particularly specified.

The aluminum material which finished contact heating after final annealing is subjected to etching treatment for improving the area enlargement ratio. Although the etching process conditions are not specifically limited, Preferably, the direct current etching method is employ | adopted. By the direct current etching method, the aluminum material having the homogeneous surface layer oxide film is etched deep and thick, so that a large number of tunnel-type pits are generated and a fixed capacitance is realized.

After the etching treatment, preferably, a chemical conversion treatment is performed to form a cathode material, and in particular, an electrolytic capacitor electrode material for medium pressure and high pressure may be used. Of course, it does not interfere with using as a negative electrode material.

An aluminum electrolytic capacitor is constructed by using the above positive electrode material and / or negative electrode material as an electrode material. In this electrolytic capacitor, since the area expansion ratio of the electrode material is increasing, it has a large capacitance.

In this embodiment, by heating an aluminum material by contact with a heating body after final annealing, the surface oxide film of an aluminum material can be made homogeneous, and the aluminum material for electrolytic capacitors excellent in the etching characteristic can be manufactured. In particular, since contact heating is used as the heating method, the surface of the aluminum foil can be uniformly brought to a desired temperature in a short time, and thus the temperature control is relatively easy, and the heating can be performed quickly in a short time, thereby reducing the influence of the atmosphere. Can be. Therefore, by etching the aluminum material for electrolytic capacitors, the etch pit is uniformly generated, and as a result, the area enlargement ratio can be improved, and further, the electrolytic capacitor electrode material with increased capacitance can be obtained. An aluminum electrolytic capacitor can be obtained.

[First Embodiment]

This example corresponds to the first embodiment.

(Example 1)

The plate obtained by hot rolling an aluminum slab was cold rolled, and the aluminum coil of 250 micrometers in thickness and purity 99.99% was obtained. After cold-rolling this aluminum material coil to 140 micrometers in thickness, aluminum material was made to contact a heat roll whose surface temperature is 200 degreeC for 2 second, and then it contacted the cooling roll whose surface temperature is 30 degreeC. Next, the coiled aluminum material was held at a substantial temperature of 250 ° C. under a nitrogen atmosphere for 24 hours and subjected to intermediate annealing, followed by cold rolling of the finish.

The aluminum material after finish cold rolling was wash | cleaned with n-hexane, The aluminum material after washing was heated up at 50 degree-C / h from room temperature to 540 degreeC under argon atmosphere, and it hold | maintained at 540 degreeC for 24 hours, Then, after cooling, it removed from the furnace and obtained the aluminum material for electrolytic capacitor electrodes of width 500mm and length 1000m.

(Examples 2 to 16)

In the same manner as in Example 1, the plate obtained by hot rolling the aluminum slab was cold rolled to obtain an aluminum coil having a thickness of 250 µm and a purity of 99.99%. Next, the process shown in Table 1 was performed in order, and the aluminum material for electrolytic capacitor electrodes of width 500m and length 1000m was obtained.

(Comparative Example 1)

Except not performing contact heating in the middle of cold rolling, it carried out similarly to Example 1, and obtained the aluminum material for electrolytic capacitor electrodes.

Examples and electrolytic processing the aluminum material obtained in Comparative Example, in HCl 1.0㏖ / ℓ and H ₂ SO ₄ 3.5㏖ / liquid temperature containing ℓ was immersed in an aqueous solution of 75 ℃, current density of 0.2A / cm ² Carried out. The aluminum material after electrolytic treatment was further immersed at 90 degreeC for 360 second in the hydrochloric acid-sulfuric acid mixed aqueous solution of the said composition, the pit diameter was thickened, and the etching foil was obtained. The obtained etching foil was made into the electrostatic capacity measurement sample which formed the chemical conversion process according to EIAJ standard at the chemical conversion voltage of 270V.

In addition, the electrostatic capacitance of the aluminum material obtained by each Example and the comparative example is 100 mm inside from the width direction center and left and right edge part in two places of 100 m of length directions and 900 m in the winding outer end part of the aluminum material coil of the final annealing completion, respectively. We measured at three places mainly on position, six places in total.

The electrostatic capacitance measured about each sample is shown in Table 1 by the relative value at the time of making comparative example 1 into 100.                 

Table 1

However, in Table 1, the contents of each process and * 1, * 2, and * 3 are as follows.

Process ① contact heating: The aluminum material of thickness 250micrometer is contact-heated in air atmosphere.

Step ② Cold rolling: An aluminum material having a thickness of 250 µm is cold rolled to a thickness of 140 µm.

Process ③ Contact heating: An aluminum material having a thickness of 140 µm is contact heated in an air atmosphere.

Step ④ Intermediate Annealing: Annealing at 250 ° C. for 24 hours in a nitrogen atmosphere.

Process (5) Contact heating: An aluminum material having a thickness of 140 µm is contact heated in an air atmosphere.

Process (6) Finish cold rolling: The aluminum material having a thickness of 140 µm is cold rolled to a thickness of 110 µm.

Process ⑦ washing: It is immersed in n-hexane.

Process (8) Final Annealing: The annealing temperature in the table is the actual substance holding temperature of aluminum material. The rate of temperature increase from room temperature to the holding temperature is 50 ° C./h.

* 1: There is cooling by a cooling roll (roll surface temperature: 30 degreeC) after contact heating.

* 2: The relative value of the average capacitance of each sample is shown as the capacitance average value of six places in the aluminum coil of the comparative example 1 as 100.

※ 3: capacitance variation

1: All six capacitances are less than the average value ± 1.5%.                 

2: Six locations All capacitances are below ± 2% on average, and there are also places where the capacitance is above 1.5% above or below 1.5% below average.

3: There exists a location where the capacitance is 2% or more higher than the average value or 2% or lower.

From the Example and the comparative example of the said Table 1, it turns out that the variation of an electrostatic capacitance becomes small and electrostatic capacity improves by performing contact heating in the middle of cold rolling.

Second Embodiment

This example corresponds to the second embodiment.

[Examples 101 to 112 and Comparative Examples 101 to 103]

(Example 101)

An aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was prepared. The obtained aluminum material was immersed in an alkane hydrocarbon for 2 seconds, dried at 90 ° C. for 1 minute in air, and the aluminum material was sandwiched between two stainless steel heating plates having a surface temperature of 200 ° C., followed by contact heating in air for 2 seconds. . In the state which superimposed the aluminum material after contact heating, after heating up the substance temperature of aluminum material from room temperature to 540 degreeC in 50 degreeC / h in argon atmosphere, it hold | maintained at 540 degreeC for 24 hours, and after cooling, it took out from a furnace and electrolyzed A high purity aluminum material for capacitors was obtained.

(Example 102)

In the same manner as in Example 101, an aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane hydrocarbon for 2 seconds, dried at 90 ° C. for 1 minute in air, and the aluminum material was sandwiched between two stainless steel heating plates having a surface temperature of 250 ° C., followed by contact heating in air for 2 seconds. . In the state which superimposed the aluminum material after contact heating, after heating up the substance temperature of aluminum material from room temperature to 540 degreeC in 50 degreeC / h in argon atmosphere, it hold | maintained at 540 degreeC for 24 hours, and after cooling, it took out from a furnace and electrolyzed A high purity aluminum material for capacitors was obtained.

(Example 103)

In the same manner as in Example 101, an aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane hydrocarbon for 2 seconds, dried at 90 ° C. for 1 minute in air, and the aluminum material was sandwiched between two stainless steel heating plates having a surface temperature of 200 ° C., followed by contact heating in air for 2 seconds. . In the state which superimposed the aluminum material after contact heating, after heating up the substance temperature of aluminum material from room temperature to 560 degreeC at 50 degree-C / h in argon atmosphere, it hold | maintained at 560 degreeC for 24 hours, and after cooling, it took out from a furnace and electrolyzed A high purity aluminum material for capacitors was obtained.

(Example 104)

In the same manner as in Example 101, an aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane hydrocarbon for 2 seconds, dried at 90 ° C. for 1 minute in air, and the aluminum material was sandwiched between two stainless steel heating plates having a surface temperature of 200 ° C., followed by contact heating in air for 1 second. . In the state which superposed the aluminum material after contact heating, after heating up the substance temperature of aluminum material from room temperature to 540 degreeC in 50 degreeC / h in argon atmosphere, it hold | maintained at 540 degreeC for 24 hours, and after cooling, it took out from a furnace and electrolyzed A high purity aluminum material for capacitors was obtained.

(Example 105)

In the same manner as in Example 101, an aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane hydrocarbon for 2 seconds, and it dried in air at 90 degreeC for 1 minute. Next, two heat rolls (hard chromium plated on the surface) set at a surface temperature of 200 ° C. were prepared, and the aluminum material surface was brought into contact with the first heat roll for 1 second, followed by the second heat. Contact heating was performed by making the aluminum back surface contact with a roll for 1 second. In the state which superimposed the aluminum material after contact heating, after heating up the substance temperature of aluminum material from room temperature to 540 degreeC in 50 degreeC / h in argon atmosphere, it hold | maintained at 540 degreeC for 24 hours, and after cooling, it took out from a furnace and electrolyzed A high purity aluminum material for capacitors was obtained.

(Example 106)

In the same manner as in Example 101, an aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane hydrocarbon for 2 seconds, and it dried in air at 90 degreeC for 1 minute. Next, an aluminum material was sandwiched between two stainless steel heating plates having a surface temperature of 90 ° C., and contact heating was performed in air for 1 second. In the state which superimposed the aluminum material after contact heating, after heating up the substance temperature of aluminum material from room temperature to 540 degreeC in 50 degreeC / h in argon atmosphere, it hold | maintained at 540 degreeC for 24 hours, and after cooling, it took out from a furnace and electrolyzed A high purity aluminum material for capacitors was obtained.

(Example 107)                 

In the same manner as in Example 101, an aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane hydrocarbon for 2 seconds, and it dried in air at 90 degreeC for 1 minute. Next, two heat rolls (hard chromium plated on the surface) set at a surface temperature of 380 ° C. were prepared, and the aluminum material surface was brought into contact with the first heat roll for 0.1 second. Contact heating was performed by carrying out the contact heating of the aluminum material back surface to a roll for 0.1 second. In the state which superimposed the aluminum material after contact heating, after heating up the substance temperature of aluminum material from room temperature to 540 degreeC in 50 degreeC / h in argon atmosphere, it hold | maintained at 540 degreeC for 24 hours, and after cooling, it took out from a furnace and electrolyzed A high purity aluminum material for capacitors was obtained.

(Example 108)

In the same manner as in Example 101, an aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane hydrocarbon for 2 seconds, and it dried in air at 90 degreeC for 1 minute. Next, two heat rolls (hard chromium plated on the surface) set at a surface temperature of 250 ° C. were prepared, and the surface of the aluminum material was brought into contact with the first heat roll for 0.005 seconds, followed by the second heat. Contact heating was performed by bringing the aluminum back surface into contact with the roll for 0.005 seconds. In the state which superimposed the aluminum material after contact heating, after heating up the substance temperature of aluminum material from room temperature to 540 degreeC in 50 degreeC / h in argon atmosphere, it hold | maintained at 540 degreeC for 24 hours, and after cooling, it took out from a furnace and electrolyzed A high purity aluminum material for capacitors was obtained.

(Example 109)                 

In the same manner as in Example 101, an aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane hydrocarbon for 2 seconds, dried at 90 ° C. for 1 minute in air, and the aluminum material was sandwiched between two stainless steel heating plates having a surface temperature of 150 ° C., followed by contact heating in air for 30 seconds. . In the state which superimposed the aluminum material after contact heating, after heating up the substance temperature of aluminum material from room temperature to 540 degreeC in 50 degreeC / h in argon atmosphere, it hold | maintained at 540 degreeC for 24 hours, and after cooling, it took out from a furnace and electrolyzed A high purity aluminum material for capacitors was obtained.

(Example 110)

In the same manner as in Example 101, an aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane hydrocarbon for 2 seconds, dried at 90 ° C. for 1 minute in air, and the aluminum material was sandwiched between two stainless steel heating plates having a surface temperature of 200 ° C., followed by contact heating in air for 2 seconds. . In the state which superimposed the aluminum material after contact heating, after heating up the substance temperature of aluminum material from room temperature to 480 degreeC at 50 degree-C / h in argon atmosphere, it hold | maintained at 480 degreeC for 24 hours, and after cooling, it took out from a furnace and electrolyzed A high purity aluminum material for capacitors was obtained.

(Example 111)

In the same manner as in Example 101, an aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane hydrocarbon for 2 seconds, dried at 90 ° C. for 1 minute in air, and the aluminum material was sandwiched between two stainless steel heating plates having a surface temperature of 200 ° C., followed by contact heating in air for 2 seconds. . After heating the aluminum material after contact heating, the actual temperature of the aluminum material was raised to 50 ° C./h from room temperature to 580 ° C. under argon atmosphere, and then maintained at 580 ° C. for 24 hours, and then cooled and taken out of the furnace, A high purity aluminum material for an electrolytic capacitor was obtained.

(Example 112)

After contact heating, the high-purity aluminum material for electrolytic capacitors was obtained in the same manner as in Example 101, except that the aluminum material was sandwiched and cooled between the stainless plates having a surface temperature of 10 ° C for 10 seconds.

(Comparative Example 101)

In the same manner as in Example 101, an aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was produced. After the obtained aluminum material was immersed in an alkane hydrocarbon for 2 seconds and dried in air for 1 minute at 90 degreeC, after heating up the substance temperature of aluminum material from room temperature to 540 degreeC under argon atmosphere in 50 degreeC / h in an argon atmosphere, It kept at 540 degreeC for 24 hours, and after cooling, it took out from a furnace and obtained the high purity aluminum material for electrolytic capacitors.

(Comparative Example 102)

In the same manner as in Example 101, an aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was produced. After the obtained aluminum material was immersed in an alkane hydrocarbon for 2 seconds and dried in air at 90 degreeC for 1 minute, after heating up the substance temperature of aluminum material to 50 degree-C / h from room temperature to 480 degreeC in argon atmosphere in the state which overlapped, It kept at 480 degreeC for 24 hours, and after cooling, it took out from a furnace and obtained the high purity aluminum material for electrolytic capacitors.

(Comparative Example 103)                 

In the same manner as in Example 101, an aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was produced. The obtained aluminum material was immersed in an alkane hydrocarbon for 2 seconds, dried at 90 ° C. for 1 minute in air, and after heating the actual temperature of the aluminum material to 50 ° C./h from room temperature to 580 ° C. under argon atmosphere in an overlapping state, It kept at 580 degreeC for 24 hours, and after cooling, it took out from a furnace and obtained the high purity aluminum material for electrolytic capacitors.

After the aluminum material obtained in the said Example and the comparative example was immersed in the acid, it electrolytically etched with hydrochloric acid-sulfuric acid aqueous solution, and then pit diameter was thickened by immersing again in the acid solution, and etching foil was obtained. The obtained etching foil was chemically processed at the chemical conversion voltage of 270V according to EIAJ standard, and used as the sample for capacitance measurement.

Table 2 shows the contact heating conditions of the examples and the comparative examples, the actual temperature of the aluminum material at the time of annealing, and the capacitance evaluation. The electrostatic capacity evaluation shows the value at the time of making comparative example 101 100.                 

[Table 2]

As can be seen from the above Table 2, in the Examples, contact heating is performed using a heating plate or a heat roll before annealing, thereby showing an improvement in capacitance compared with Comparative Examples 101 to 103 which do not perform contact heating.

[Examples 113 to 230 and Comparative Example 104]

What added surfactant to the organic solvent shown in Table 3 and Table 4, and water shown in Table 5 was prepared as a washing | cleaning liquid.                 

Table 3

Table 4

Table 5

(Example 113)

The aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was immersed in the A1 liquid of Table 3 for 2 seconds, and then dried at 90 ° C. for 60 seconds in air. Next, an aluminum material is sandwiched between two stainless steel heating plates having a surface temperature of 200 ° C., and contact heating is performed for 2 seconds.

Subsequently, after heating the aluminum material after contact heating, the temperature of the aluminum material was raised to 50 ° C./h from room temperature to 540 ° C. under argon atmosphere, and then maintained at 540 ° C. for 24 hours, followed by cooling, and then taken out of the furnace, An aluminum material for electrolytic capacitor electrodes was obtained.

(Examples 114 to 188)

After cleaning and drying the aluminum material of purity 99.99% rolled to the thickness of 110 micrometers like Example 113 by the process conditions of Tables 6-9, the aluminum material was carried out between two stainless steel heating plates whose surface temperature is 200 degreeC. It was sandwiched and subjected to contact heating for 2 seconds. In Examples 253 to 282, the brush was in contact with the surface of the aluminum material and slid while the aluminum material was immersed in the cleaning liquid.

After raising the temperature of the aluminum material at room temperature to 540 ° C. at 50 ° C./h in an argon atmosphere in a state in which aluminum materials after contact heating were superimposed, held at 540 ° C. for 24 hours, and then cooled, taken out of the furnace, and electrolytic capacitor An aluminum material for electrodes was obtained.

(Examples 189-196)                 

An aluminum material having a purity of 99.99% rolled to a thickness of 110 μm as in Example 113 was sandwiched between two 200 ° C. stainless steel heating plates, and contact heating was performed for 2 seconds.

Next, it wash | cleaned and dried on the conditions of the process 3 of Table 8. In addition, the brush was brought into contact with the surface of the aluminum material and slid while the aluminum material was immersed in the cleaning liquid.

After raising the temperature of the aluminum material from room temperature to 540 ° C at 50 ° C / h in a state in which the aluminum material after washing and drying was superposed, it was kept at 540 ° C for 24 hours, and then cooled, taken out of the furnace, and electrolytically An aluminum material for capacitor electrodes was obtained.

(Examples 197 to 202)

After cleaning and drying the aluminum material of purity 99.99% rolled to the thickness of 110 micrometers like Example 113 on condition of the process 1 of Table 8, an aluminum material is sandwiched between two stainless steel heating plates with a surface temperature of 200 degreeC. Then, contact heating was performed for 2 seconds. Next, the aluminum material after contact heating was washed and dried under the conditions of Step 3 in Table 8.

After raising the temperature of the aluminum material from room temperature to 540 ° C. at 50 ° C./h in an argon atmosphere in a state in which the aluminum material washed and dried under the conditions of Step 3 was superimposed, it was kept at 540 ° C. for 24 hours, and then cooled Was taken out to obtain an aluminum material for an electrolytic capacitor electrode.

(Examples 203 to 207)

After cleaning and drying an aluminum material having a purity of 99.99% rolled to a thickness of 110 μm as in Example 113 under the process conditions shown in Table 8, the aluminum material was sandwiched between two sheets of stainless steel heating plates having a surface temperature of 200 ° C. Contact heating was performed for a second.

After raising the temperature of the aluminum material at room temperature to 540 ° C. at 50 ° C./h in an argon atmosphere in a state in which aluminum materials after contact heating were superimposed, held at 540 ° C. for 24 hours, and then cooled, taken out of the furnace, and electrolytic capacitor An aluminum material for electrodes was obtained.

(Examples 208 to 211)

An aluminum material having a purity of 99.99% rolled to a thickness of 110 μm as in Example 113 was sandwiched between two 200 ° C. stainless steel heating plates, and contact heating was performed for 2 seconds. Next, washing and drying were carried out under the conditions of Step 3 of Table 9 and Table 10. In addition, the brush was brought into contact with the surface of the aluminum material and slid while the aluminum material was immersed in the cleaning liquid.

After raising the temperature of the aluminum material from room temperature to 540 ° C at 50 ° C / h in a state in which the aluminum material after washing and drying was superposed, it was kept at 540 ° C for 24 hours, and then cooled, taken out of the furnace, and electrolytically An aluminum material for capacitor electrodes was obtained.

(Examples 212-228)

About the aluminum material of purity 99.99% rolled to the thickness of 110 micrometers like Example 113, washing | cleaning and drying on the conditions of the process 1 of Table 10, and contact heating on the conditions of the process 2 of Table 9 were performed.

After heating the aluminum material after contact heating in the state which overlapped, the actual temperature of aluminum material was heated to 50 degreeC / h from room temperature to 540 degreeC in argon atmosphere, and it hold | maintained at 540 degreeC for 24 hours, and after cooling, it took out from a furnace and electrolyzed An aluminum material for capacitor electrodes was obtained.

(Example 229)

An aluminum material having a purity of 99.99% rolled to a thickness of 110 μm as in Example 113 was sandwiched between two 200 ° C. stainless steel heating plates, and contact heating was performed for 2 seconds. After raising the temperature of the aluminum material at room temperature to 540 ° C. at 50 ° C./h in an argon atmosphere in a state in which aluminum materials after contact heating were superimposed, held at 540 ° C. for 24 hours, and then cooled, taken out of the furnace, and electrolytic capacitor An aluminum material for electrodes was obtained.

(Example 230)

The aluminum material for electrolytic capacitor electrodes was obtained like Example 224 except having including the process of contacting an aluminum material with the cooling roll of surface temperature 25 degreeC after the contact heating in a hot roll.

(Comparative Example 104)

An aluminum material having a purity of 99.99%, rolled to a thickness of 110 μm as in Example 113, was heated at 50 ° C./h from room temperature to 540 ° C. under an argon atmosphere, and then maintained at 540 ° C. for 24 hours, followed by cooling. Then, it took out from the furnace and obtained the aluminum material for electrolytic capacitor electrodes.

The aluminum material obtained in Examples 113-230 and Comparative Example 104 was immersed in an aqueous solution having a liquid temperature of 75 ° C. containing HCl 1.0 mol.dm ⁻³ and H ₂ SO ₄ 3.5 mol.dm ⁻³ , and then the current density was 0.2. Electrolytic treatment was performed at A / cm ² . The foil after the electrolytic treatment was further immersed in a hydrochloric acid-sulfuric acid mixed aqueous solution of the above composition at 90 ° C. for 360 seconds to thicken the pit diameter to obtain an etching foil. The obtained etching foil was made into the electrostatic capacity measurement sample which formed the chemical conversion process according to EIAJ standard at the chemical conversion voltage of 270V. The electrostatic capacitance measured about each sample is shown in Table 6-Table 10 by the relative value at the time of making comparative example 104 into 100.

Table 6

Table 7

Table 8

Table 9

Table 10

By comparing Example 229 of Table 10 with Comparative Example 104 above, electrostatic capacitance is improved by performing contact heating before final annealing. In addition, the comparison of Examples 113 to 211 and Example 229 shows that the electrostatic capacity is further improved by washing at least either before or after contact heating.

In addition, in Examples 203 to 211, the electrostatic capacity is improved when the drying temperature after washing is 200 ° C or lower, and the capacitance is higher at 90 ° C or lower.

Third Embodiment

This example corresponds to the third embodiment.

Table 11 shows the organic solvent washing | cleaning liquid used for the organic solvent washing | cleaning used before alkali-cleaning or acid-cleaning the aluminum material after final rolling, Table 12 shows an alkali washing liquid, Table 13 shows an acid washing liquid.

Table 11

Organic Solvent Cleaning Liquid

sign Organic solvents Liquid temperature (℃) A101 Acetone 25 A102 Hexane 25 A103 Propanol 25

Table 12

Types of alkaline cleaning solution (aqueous solution)

sign Type of alkali Concentration / mass% Temperature (℃) B101 Sodium hydroxide 0.1 35 B102 Potassium hydroxide 0.1 35 B103 Calcium hydroxide 0.1 35 B104 Sodium metasilicate 0.2 35 B105 Sodium orthosilicate 0.2 35 B106 Sodium orthosilicate 0.2 50 B107 Trisodium Phosphate 0.2 50

Table 13

Type of acid cleaning solution (aqueous solution)

sign Kind of the mountain Concentration / mass% Liquid temperature (℃) C101 Hydrochloric acid 3 30 C102 Sulfuric acid 3 30 C103 nitric acid 3 30 C104 Phosphoric Acid 3 30 C105 nitric acid 3 50

(Example 301)

For aluminum foil (aluminum material) having a purity of 99.99% rolled to a thickness of 110 μm, washing with A102 liquid of Table 11, drying, washing for 40 seconds with B106 liquid of Table 12, washing with water, drying, C101 of Table 13 Each process of washing | cleaning, water washing, and drying for 60 second with liquid was performed sequentially.

Next, the aluminum foil was sandwiched between two stainless steel heating plates having a surface temperature of 250 ° C., and contact heating was performed for 2 seconds.

Subsequently, after raising the temperature of the aluminum foil from 50 degreeC / h from room temperature to 500 degreeC in argon atmosphere in the state which superimposed the aluminum foil after contact heating, it hold | maintains at 500 degreeC for 24 hours, and after cooling, it takes out from a furnace And aluminum foil for electrolytic capacitor electrodes were obtained.                 

(Examples 302 to 349)

The aluminum foil of purity 99.99% rolled to the thickness of 110 micrometers like Example 301 was wash | cleaned and dried in the conditions of Table 14 or Table 15 and process order, and then contact heating was performed on the conditions of Table 4 or Table 5.

In addition, after washing | cleaning the organic solvent, water washing was performed after acid washing and after alkali washing. In addition, in Example 341, Example 343, and Example 344, the heat roll which chromium-plated on the surface was used as a heating body.

In the state which superimposed the aluminum foil after contact heating, after heating up the substance temperature of aluminum foil from 50 degreeC / h from room temperature to the annealing substance temperature shown in Table 14 or Table 15 in argon atmosphere, it hold | maintains for 24 hours at the said annealing substance temperature. Then, after cooling, it took out from the furnace and obtained the aluminum foil for electrolytic capacitor electrodes.

(Comparative Examples 301 to 304)

For aluminum foil having a purity of 99.99% rolled to a thickness of 110 占 퐉 as in Example 301, washing and drying with A101 liquid of Table 11 and 40 seconds with B105 liquid of Table 2 were carried out under the conditions of Table 15. Carried out.

Next, the temperature of the aluminum foil was increased from room temperature to the annealing substance temperature shown in Table 5 at 50 ° C./h under argon atmosphere without performing contact heating treatment, and then the annealing substance temperature. It was kept for 24 hours, then cooled and then taken out of the furnace to obtain an aluminum foil for an electrolytic capacitor electrode.                 

The foil obtained in the Examples and Comparative Examples with HCl 1.0㏖ · dm ^-3 and H ₂ SO ₄ 3.5㏖ · was immersed in an aqueous solution of a liquid temperature of 75 ℃ containing dm ^-3, a current density of 0.2A / cm ² Electrolytic treatment was performed. The foil after the electrolytic treatment was further immersed in a hydrochloric acid-sulfuric acid mixed aqueous solution of the above composition at 90 ° C. for 360 seconds to thicken the pit diameter to obtain an etching foil.

The obtained etching foil was chemically processed at the formation voltage of 270V according to the EIAJ standard to obtain a sample for capacitance measurement. The electrostatic capacitance measured about each sample is shown in Table 14 and Table 15 by the relative value at the time of making comparative example 301 100.                 

Table 14

Table 15

As understood from the above table, in the examples of the present invention, it is understood that the electrostatic capacity is higher than that of the comparative example in which the contact heating is not performed by performing contact heating after alkali cleaning and / or acid cleaning.

[Example 4]

This example corresponds to the fourth embodiment.

(Example 401)

An aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was immersed in a 0.1 mass% sodium hydroxide aqueous solution at 35 ° C. for 10 seconds, and then washed with water. The temperature of the aluminum material was raised to 50 ° C./h from room temperature to 540 ° C. under an argon atmosphere in a state in which the aluminum material after drying was superimposed, held at 540 ° C. for 4 hours, and then cooled and taken out of the furnace. Next, the aluminum material was sandwiched between two stainless steel heating plates having a surface temperature of 200 ° C., and contact heating was performed for 2 seconds to obtain an aluminum material for an electrolytic capacitor electrode.

(Example 402)

An aluminum material for electrolytic capacitor electrodes was obtained in the same manner as in Example 401 except that the heating plate surface temperature was 80 ° C and the contact time to the heating body was 28 seconds.

(Example 403)

An aluminum material for electrolytic capacitor electrodes was obtained in the same manner as in Example 401 except that the heating plate surface temperature was 100 ° C and the contact time to the heating body was 20 seconds.

(Example 404)

An aluminum material for electrolytic capacitor electrodes was obtained in the same manner as in Example 401 except that the heating plate surface temperature was 160 ° C and the contact time to the heating body was 10 seconds.

(Example 405)

An aluminum material for electrolytic capacitor electrodes was obtained in the same manner as in Example 401 except that the heating plate surface temperature was 290 ° C. and the contact time to the heating body was 2 seconds.

(Example 406)

An aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was immersed in a 0.1 mass% sodium hydroxide aqueous solution at 35 ° C. for 10 seconds, and then washed with water. The temperature of the aluminum foil was raised to 50 ° C./h from room temperature to 500 ° C. under an argon atmosphere in a state in which the aluminum material after drying was superimposed, held at 500 ° C. for 4 hours, and then cooled and taken out of the furnace. Next, the aluminum material was sandwiched between two stainless steel heating plates having a surface temperature of 200 ° C., and contact heating was performed for 3 seconds to obtain an aluminum material for an electrolytic capacitor electrode.

(Example 407)

An aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was immersed in a 0.1 mass% sodium hydroxide aqueous solution at 35 ° C. for 10 seconds, and then washed with water. The temperature of the aluminum material was raised from room temperature to 470 ° C. at 50 ° C./h in an argon atmosphere in a state where the aluminum material after drying was superimposed, held at 470 ° C. for 4 hours, and then cooled and taken out of the furnace. Next, the aluminum material was sandwiched between two stainless steel heating plates having a surface temperature of 200 ° C., and contact heating was performed for 15 seconds to obtain an aluminum material for an electrolytic capacitor electrode.

(Example 408)

An aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was immersed in a 0.1 mass% sodium hydroxide aqueous solution at 35 ° C. for 10 seconds, and then washed with water. The temperature of the aluminum material was raised to 50 ° C./h from room temperature to 560 ° C. in an argon atmosphere in a state where the aluminum material after drying was overlapped, and then held at 560 ° C. for 4 hours, and then cooled and taken out of the furnace. Next, the aluminum material was sandwiched between two stainless steel heating plates having a surface temperature of 200 ° C., and contact heating was performed for 2 seconds to obtain an aluminum material for an electrolytic capacitor electrode.

(Example 409)

An aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was immersed in a 0.1 mass% sodium hydroxide aqueous solution at 35 ° C. for 10 seconds, and then washed with water. The temperature of the aluminum material was raised to 50 ° C./h from room temperature to 540 ° C. under an argon atmosphere in a state in which the aluminum material after drying was superimposed, held at 540 ° C. for 4 hours, and then cooled and taken out of the furnace. Next, the aluminum material was heated by contacting the heat roll having a surface temperature of 350 ° C. for 0.01 seconds to obtain an aluminum material for an electrolytic capacitor electrode.

(Example 410)

An aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was immersed in a 0.1 mass% sodium hydroxide aqueous solution at 35 ° C. for 10 seconds, and then washed with water. The temperature of the aluminum material was raised from room temperature to 500 ° C. at 50 ° C./h in an argon atmosphere in a state in which the aluminum material after drying was superimposed, held at 500 ° C. for 4 hours, and then cooled and taken out of the furnace. Next, the aluminum material was heated by contacting the heat roll having a surface temperature of 380 ° C. for 0.01 seconds to obtain an aluminum material for an electrolytic capacitor electrode.

(Example 411)                 

An aluminum material for electrolytic capacitor electrodes was obtained in the same manner as in Example 410 except that the surface temperature of the heat roll was 200 ° C. and the contact time between the aluminum material and the heat roll surface was 0.05 second.

(Example 412)

An aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was immersed in a 0.1 mass% sodium hydroxide aqueous solution at 35 ° C. for 10 seconds, and then washed with water. After heating up the aluminum material after drying, the temperature of the aluminum material was raised to 50 ° C./h from room temperature to 520 ° C. under an argon atmosphere, and then maintained at 520 ° C. for 4 hours, and then cooled and taken out of the furnace. Next, the aluminum material was heated by contacting the heat roll having a surface temperature of 200 ° C. for 0.1 second to obtain an aluminum material for an electrolytic capacitor electrode.

(Example 413)

An aluminum material having a purity of 99.99% rolled to a thickness of 110 μm was immersed in a 0.1 mass% sodium hydroxide aqueous solution at 35 ° C. for 10 seconds, and then washed with water. The temperature of the aluminum material was raised from room temperature to 500 ° C. at 50 ° C./h in an argon atmosphere in a state in which the aluminum material after drying was superimposed, held at 500 ° C. for 4 hours, and then cooled and taken out of the furnace. Next, after heating an aluminum material by making it contact a heat roll whose surface temperature is 200 degreeC for 2 second, it contacted the cooling roll whose surface temperature is 30 degreeC, and obtained the aluminum material for electrolytic capacitor electrodes.

(Comparative Example 401)

An aluminum material for electrolytic capacitor electrodes was obtained in the same manner as in Example 401 except that contact heating was not performed.                 

The foils obtained in Examples 401 to 413 and Comparative Example 401 were immersed in an aqueous solution having a liquid temperature of 75 ° C. containing 1.0 mol / l HCl and 3.5 mol / l H ₂ SO ₄ , followed by a current density of 0.2 A / cm ^2. The electrolytic treatment was performed. The foil after the electrolytic treatment was further immersed in a hydrochloric acid-sulfuric acid mixed aqueous solution of the above composition at 90 ° C. for 360 seconds to thicken the pit diameter to obtain an etching foil. The obtained etching foil was used as the sample for capacitance measurement which chemical-ized according to the ElAJ standard at the chemical conversion voltage of 270V. The electrostatic capacitance measured about each sample is shown in Table 16 by the relative value at the time of making comparative example 401 100.

Table 16

By comparison of the said Example with a comparative example, it turns out that an electrostatic capacity improves by performing contact heating after final annealing.

INDUSTRIAL APPLICABILITY The present invention can be used as a method for producing an aluminum material for an electrolytic capacitor electrode, an aluminum material for an electrolytic capacitor electrode, a method for producing an electrode material for an electrolytic capacitor, and an aluminum electrolytic capacitor.

Claims (38)

delete delete When the aluminum slab is subjected to hot rolling, cold rolling, and final annealing sequentially to produce an aluminum material for an electrolytic capacitor electrode, in the step after the hot rolling, a step of heating the aluminum material by contact with a heating body, , The contact heating process with the heating body of the said aluminum material is performed at least once in the process in the middle from the start to the end of the cold rolling, When the thickness of the aluminum material after the last contact heating in the said contact heating performed in the middle of the said cold rolling and before rolling resumption is A (micrometer), and the thickness of the aluminum material after complete cold rolling is B (micrometer), {( The manufacturing method of the aluminum material for electrolytic capacitor electrodes whose rolling work rate after contact heating represented by AB) / A} x100 (%) is 60% or less. The manufacturing method of the aluminum material for electrolytic capacitor electrodes of Claim 3 whose rolling work rate after contact heating is 30% or less. delete delete delete delete delete When the aluminum slab is subjected to hot rolling, cold rolling, and final annealing sequentially to produce an aluminum material for an electrolytic capacitor electrode, a step of heating the aluminum material by contact with a heating body in the step after the hot rolling; A step of washing the aluminum material at least either before or after contact with the heating element, The step of heating the contact with the heating body of the aluminum material before the final annealing after the cold rolling The washing | cleaning liquid used for the said washing process is an organic solvent, The organic solvent is alcohol represented by C _n H _{2n + 1} OH (n = 1 to 10 natural water), cyclohexanol (C ₆ H ₁₁ OH), 1,2-ethanediol (HOCH ₂ CH ₂ OH), 1,2-propanediol (CH ₃ CH (OH) CH ₂ OH), 1,3-propanediol (HOCH ₂ CH ₂ CH ₂ 0H), C _n H _{2n + 2} (n = 5 to 15 natural numbers) Ketone, cyclohexanone (C ₆ H) which is represented by alkane hydrocarbon, cyclohexane, R ¹ COR ² (R ¹ and R ^{2 are} aliphatic hydrocarbon groups and the sum of carbon number of R ¹ and R ² is 8 or less). ₁₀ O), an ether represented by R ¹ -OR ² (R ¹ and R ² : aliphatic hydrocarbon groups, and the sum of the carbon number of R ¹ and R ² is 8 or less), 2-methoxy ethanol (CH ₃ OCH ₂ CH ₂ OH), 2-ethoxyethanol (CH ₃ CH ₂ OCH ₂ CH ₂ OH), 2-butoxy ethanol (CH ₃ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ OH) 2- (2-ethoxy) ethoxyethanol _{(CH 3 CH 2 0CH 2 CH} 2 OCH 2 CH 2 OH), CH 3 COOR: acetic acid ester represented by (R is an aliphatic hydrocarbon group having 1 to 5), and toluene One or two of an electrolytic capacitor electrode material manufacturing method for the aluminum or more mixtures selected from xylene. delete When the aluminum slab is subjected to hot rolling, cold rolling, and final annealing sequentially to produce an aluminum material for an electrolytic capacitor electrode, a step of heating the aluminum material by contact with a heating body in the step after the hot rolling; A step of washing the aluminum material at least either before or after contact with the heating element, The step of heating the contact with the heating body of the aluminum material before the final annealing after the cold rolling The washing | cleaning liquid used for the said washing process adds surfactant to water, The anionic surfactant (sulfuric acid ester salt) represented by R-OSO ₃ Na (R = saturated hydrocarbon group having 8 to 18 carbon atoms or unsaturated hydrocarbon group having one double bond), R-SO ₃ Na (R = unsaturated hydrocarbon group having 8 to 18 carbon atoms or one double bond) or R-SO ₃ Na (R: alkyl group having saturated hydrocarbon group or one double bond having 8 to 14 carbon atoms anionic surface active agents represented by the unsaturated hydrocarbon group alkyl benzyl group) (sulfonic acid _{^{salts), RN + (CH 3)}} 3 · Cl - (R: class cationic surfactant (4 represented by a saturated hydrocarbon group) having 8 to 16 Ammonium salt), RO-(-CH ₂ CH ₂ O) _n H (R: saturated hydrocarbon group having 8 to 16 carbon atoms or unsaturated hydrocarbon group having one double bond, n = 6 to 14) or RO-(-CH ₂ CH ₂ O) _n H (R = alkyl group is a saturated hydrocarbon group having 8 to 12 carbon atoms or a double bond A mixture of one or more anionic surfactants, a mixture of a plurality of cationic surfactants, and a plurality of nonionics selected from a polyethyleneglycol nonionic surfactant represented by one alkyl group having an unsaturated hydrocarbon group, n = 6 to 14) A method of producing an aluminum material for an electrolytic capacitor electrode, which is a mixture of a surfactant, a mixture of at least one anionic surfactant and at least one nonionic surfactant, and a mixture of at least one cationic surfactant and at least one nonionic surfactant. When the aluminum slab is subjected to hot rolling, cold rolling, and final annealing sequentially to produce an aluminum material for an electrolytic capacitor electrode, in the step after the hot rolling, a step of heating the aluminum material by contact with a heating body, , The step of heating the contact with the heating body of the aluminum material before the final annealing after the cold rolling, The aluminum material is washed before contact with the heating body, and then the aluminum material is heated by contact with the heating body without drying or drying, The manufacturing method of the aluminum material for electrolytic capacitor electrodes whose drying temperature after washing | cleaning is 200 degrees C or less. When the aluminum slab is subjected to hot rolling, cold rolling, and final annealing sequentially to produce an aluminum material for an electrolytic capacitor electrode, in the step after the hot rolling, a step of heating the aluminum material by contact with a heating body, , The step of heating the contact with the heating body of the aluminum material before the final annealing after the cold rolling, The aluminum material is washed before contact with the heating body, and then the aluminum material is heated by contact with the heating body without drying or drying, The manufacturing method of the aluminum material for electrolytic capacitor electrodes whose drying temperature after washing | cleaning is 90 degrees C or less. delete delete When the aluminum slab is subjected to hot rolling, cold rolling, and final annealing sequentially to produce an aluminum material for an electrolytic capacitor electrode, in the step after the hot rolling, a step of heating the aluminum material by contact with a heating body, , After the cold rolling, the aluminum material is washed with a liquid capable of dissolving aluminum, followed by a contact heating step with a heating body of the aluminum material before final annealing, The manufacturing method of the aluminum material for electrolytic capacitor electrodes whose washing with the liquid which can melt | dissolve the said aluminum is acid washing. When the aluminum slab is subjected to hot rolling, cold rolling, and final annealing sequentially to produce an aluminum material for an electrolytic capacitor electrode, in the step after the hot rolling, a step of heating the aluminum material by contact with a heating body, , After the cold rolling, the aluminum material is washed with a liquid capable of dissolving aluminum, followed by a contact heating step with a heating body of the aluminum material before final annealing, The manufacturing method of the aluminum material for electrolytic capacitor electrodes whose washing with the liquid which can melt | dissolve the said aluminum is sequentially performing alkali washing and acid washing. When the aluminum slab is subjected to hot rolling, cold rolling, and final annealing sequentially to produce an aluminum material for an electrolytic capacitor electrode, in the step after the hot rolling, a step of heating the aluminum material by contact with a heating body, , After the cold rolling, the aluminum material is washed with a liquid capable of dissolving aluminum, followed by a contact heating step with a heating body of the aluminum material before final annealing, The manufacturing method of the aluminum material for electrolytic capacitor electrodes which wash | cleans an organic solvent before alkali-washing or acid-cleaning an aluminum material. The electrolytic capacitor electrode according to claim 18, wherein the alkaline cleaning liquid used for alkali cleaning is an aqueous solution containing one or two or more alkalis selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium orthosilicate, sodium metasilicate and trisodium phosphate. Method for producing aluminum for The method for producing an aluminum material for an electrolytic capacitor electrode according to claim 17 or 18, wherein the acid cleaning liquid used for acid cleaning is an aqueous solution containing one or two or more acids selected from hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. When the aluminum slab is subjected to hot rolling, cold rolling, and final annealing sequentially to produce an aluminum material for an electrolytic capacitor electrode, in the step after the hot rolling, a step of heating the aluminum material by contact with a heating body, , The manufacturing method of the aluminum material for electrolytic capacitor electrodes which performs a contact heating process with the heating body of the said aluminum material after final annealing. When the aluminum slab is subjected to hot rolling, cold rolling, and final annealing sequentially to produce an aluminum material for an electrolytic capacitor electrode, in the step after the hot rolling, a step of heating the aluminum material by contact with a heating body, , The manufacturing method of the aluminum material for electrolytic capacitor electrodes whose surface temperature of a heating body is 50-450 degreeC, and the contact time of an aluminum material and a heating body is 0.001 to 60 second. The manufacturing method of the aluminum material for electrolytic capacitor electrodes of Claim 23 whose surface temperature of a heating body is 60-400 degreeC. The manufacturing method of the aluminum material for electrolytic capacitor electrodes of Claim 23 whose surface temperature of a heating body is 80-400 degreeC. The manufacturing method of the aluminum material for electrolytic capacitor electrodes of Claim 23 whose contact time of an aluminum material and a heating body is 0.001 to 60 second. The manufacturing method of the aluminum material for electrolytic capacitor electrodes of Claim 23 whose contact time of an aluminum material and a heating body is 0.001-30 seconds. delete delete delete delete When the aluminum slab is subjected to hot rolling, cold rolling, and final annealing sequentially to produce an aluminum material for an electrolytic capacitor electrode, in the step after the hot rolling, a step of heating the aluminum material by contact with a heating body, , After contact with the heating body, the aluminum material is cooled, The manufacturing method of the aluminum material for electrolytic capacitor electrodes which performs cooling of an aluminum material by contact with a cooling roll. delete delete delete delete delete delete