WO2011034008A1 - Microstructure et son procédé de production - Google Patents

Microstructure et son procédé de production Download PDF

Info

Publication number
WO2011034008A1
WO2011034008A1 PCT/JP2010/065633 JP2010065633W WO2011034008A1 WO 2011034008 A1 WO2011034008 A1 WO 2011034008A1 JP 2010065633 W JP2010065633 W JP 2010065633W WO 2011034008 A1 WO2011034008 A1 WO 2011034008A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
micropore
micropores
aluminum
treatment
Prior art date
Application number
PCT/JP2010/065633
Other languages
English (en)
Japanese (ja)
Inventor
義治 田川
優介 畠中
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Publication of WO2011034008A1 publication Critical patent/WO2011034008A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/12—Anodising more than once, e.g. in different baths
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/10—Moulds; Masks; Masterforms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers

Definitions

  • the present invention relates to a microstructure, and more particularly to a microstructure having a long-period micropore array and a method for manufacturing the same.
  • Examples of such a fine structure manufacturing method include a method of directly manufacturing a nano structure by a semiconductor processing technique including a fine pattern forming technique such as photolithography, electron beam exposure, and X-ray exposure.
  • anodized alumina film obtained by anodizing aluminum in an electrolytic solution
  • a plurality of fine pores having a diameter of about several nm to several hundred nm are regularly formed in the anodized film.
  • hexagonal prism cells with a regular hexagonal bottom centered around the micropores are formed, and adjacent micropores are formed.
  • the connecting line forms an equilateral triangle.
  • Patent Document 1 describes that pores are sealed with metal to generate local plasmon resonance and applied to a Raman optical analyzer.
  • a self-ordering method using the self-ordering property of the anodized film is known. This is a method for improving the regularity by utilizing the property that the micropores of the anodized film are regularly arranged and removing the factors that disturb the regular arrangement.
  • Patent Document 2 discloses that anodization is performed with an anodic oxidation voltage obtained by gradually reducing the interval (period) of the recesses of the micropores at 2.5 nm / V, that is, the pore period can be adjusted by a voltage value. Is described. However, there is no description of an anodic oxide film having a pore period exceeding 500 nm.
  • JP 2007-231336 A Japanese Patent No. 3714507
  • the film growth rate of the anodized film is set to a speed necessary for the honeycomb arrangement. It was difficult to maintain the structure of the ordered micropores, and it was difficult to grow the film in the axial direction of the micropores.
  • the present inventor performs anodizing treatment using an electrolytic solution containing a specific carboxylic acid, so that the honeycomb arrangement of the micropores arranged in the honeycomb is not destroyed.
  • the inventors have found that a fine structure having a large distance between centers of micropores and a film thickness of 50 ⁇ m or more can be produced, and the present invention has been completed.
  • the present invention provides the following (1) to (4).
  • a microstructure comprising an anodized film of aluminum or an aluminum alloy, wherein the degree of ordering of the plurality of micropores defined by the following general formula (1) is 70% or more on the bottom surface, A fine structure having a center-to-center distance of 600 nm or more and an axial length of the micropore of 50 ⁇ m or more:
  • General formula (1) Ordering degree (%) B / A ⁇ 100
  • A represents the total number of micropores in the measurement range.
  • the shape of the cross section perpendicular to the major axis of the pore is not a perfect circle, it means the center of gravity of the cross section in the perpendicular direction.
  • the distance (cycle) between the centers means an average value of a plurality of micropores unless otherwise specified.
  • the length, density, and the like of the micropores in the axial direction are average values of a plurality of micropores unless otherwise specified.
  • the bottom surface is the surface of the fine structure perpendicular to the axis of the annular micropore, and has a plurality of holes in the micropore, and when the fine structure is manufactured from aluminum or an aluminum alloy plate, It is a plane close to the aluminum alloy plate and refers to the surface obtained by removing the aluminum or aluminum alloy plate.
  • the microstructure When the micropore is filled with a conductive material, the microstructure has conductivity in the micropore penetrating direction (axial direction of the annular micropore) and has insulation on a surface perpendicular to the micropore penetrating direction. It can be used as an anisotropic conductive film. In addition, it is expected to be used as a precision filter using the uniformity of micropore diameter, the finely packed structure of micropores, and the straight pipe structure.
  • the present invention provides a microstructure in which the degree of ordering defined by the general formula (1) is 70% or more, the distance between the centers of the micropores is 600 nm or more, and the thickness of the micropores is 50 ⁇ m or more.
  • the body can be provided.
  • the manufacturing method of this invention can manufacture the microstructure of this invention.
  • FIGS. 1A and 1B are simplified views showing an example of a preferred embodiment of the anisotropic conductive member of the present invention.
  • FIG. 1A is a front view
  • FIG. FIG. 6 is a cross-sectional view taken along section line IB-IB in FIG. 2A and 2B are explanatory diagrams of a method for calculating the degree of ordering of pores.
  • 3A to 3D are schematic end views for explaining an example of anodizing treatment in the production method of the present invention.
  • the present invention is described in detail below.
  • the microstructure of the present invention comprises an anodized film of aluminum or an aluminum alloy having micropores.
  • the microstructure of the present invention will be described with reference to FIG.
  • the microstructure has a plurality of micropores. In the present specification, unless otherwise specified, the definition of micropores is indicated by an average value of 25 or more micropores.
  • FIGS. 1A and 1B are simplified views showing an example of a preferred embodiment of the microstructure of the present invention.
  • FIG. 1A is a front view
  • FIG. 1B is a cross-sectional line IB- in FIG. It is sectional drawing seen from IB.
  • the microstructure 1 of the present invention is composed of an oxide film 2 and micropores 3.
  • the micropore 3 is an annular hole, and is preferably provided so as to be substantially parallel to the thickness direction of the oxide film 2 (parallel in FIG. 1).
  • the distance between the centers of the micropores 3 of the microstructure 1 of the present invention is 600 nm or more.
  • the thickness of the oxide film (the portion represented by reference numeral 6 in FIG. 1B), which is the axial length of the annular micropore, is 50 ⁇ m or more.
  • the thickness is preferably 50 to 200 ⁇ m, more preferably 50 to 150 ⁇ m, and even more preferably 50 to 100 ⁇ m.
  • the mechanical strength is high and handling is easy.
  • the micropore density is preferably 3.55 / ⁇ m 2 or less, 0.10 / ⁇ m 2 or more, more preferably 3.55 / ⁇ m 2 or less, 0.50 / ⁇ m 2 or more, and further 3.
  • the number is preferably 53 / ⁇ m 2 or less and 0.81 / ⁇ m 2 or more. Within this range, a microstructure having a sufficiently large distance between the centers of the micropores can be obtained.
  • the oxide film 2 constituting the microstructure of the present invention is an oxide film of aluminum or an aluminum alloy plate, and is formed by an anodic oxidation treatment.
  • the diameter of the micropore (portion represented by reference numeral 8 in FIG. 1B) is preferably 10 to 590 nm, and more preferably 150 to 360 nm. This is because the micropore diameter at the time of the formation of the anodizing treatment is excellent in uniformity, which is preferable.
  • the microstructure 1 has a bottom surface of a plurality of micropores defined by the following general formula (1) having a degree of ordering of 70% or more.
  • the bottom surface is the surface of the fine structure perpendicular to the axis of the annular micropore.
  • the aluminum or aluminum alloy plate has a plurality of micropores.
  • the plane 4 on the side represented by the symbol Z2 is meant.
  • the other of the bottom surface 4 of the microstructure 1 is a surface 5, which is a plane on the side represented by reference sign Z ⁇ b> 1 in FIG.
  • the measurement of the degree of ordering of the micropores on the bottom surface is carried out in a method for producing a microstructure according to the present invention, which will be described later, by performing film dissolution after anodizing treatment, and using a predetermined image from an image obtained by observing the bottom surface with a scanning electron microscope.
  • the number of micropores is visually confirmed and calculated from the following general formula (1). Further, the shape which becomes the starting point of the final anodizing treatment may be observed in the same manner.
  • Ordering degree (%) B / A ⁇ 100 (1)
  • A represents the total number of micropores in the measurement range.
  • B when a circle with the shortest radius inscribed in the edge of the other micropore is drawn from the center of the cross section perpendicular to the major axis of one micropore, the micropores other than the micropore are inside the circle. This represents the number in the measurement range of the one micropore that will contain six pore centers.
  • FIG. 2 is an explanatory diagram of a method for calculating the degree of ordering of micropores.
  • the above formula (1) will be described more specifically with reference to FIG.
  • the micropore 101 shown in FIG. 2A is centered on the center of gravity of the micropore 101 and has the shortest radius 103 inscribed in the edge of another micropore (in the figure, inscribed in the micropore 102). ) Includes six micropore centers other than the micropore 101 inside the circle 103. Therefore, the micropore 101 is included in B.
  • the micropore 104 shown in FIG. 2B is centered on the center of gravity of the micropore 104 and has the shortest radius 106 inscribed in the edge of another micropore (in the figure, inscribed in the micropore 105).
  • the micropore 107 shown in FIG. 2B is centered on the center of gravity of the micropore 107 and has the shortest radius 109 inscribed in the edge of another micropore (inscribed in the micropore 108). Is drawn, the circle 109 includes seven centroids of micropores other than the micropore 107. Therefore, the micropore 107 is not included in B.
  • the above-mentioned fine structure is expected to be used as an anisotropic conductive film by filling a micropore with metal by electrolytic plating or electroless plating. Further, by immersing the fine structure in an alkaline solution, the micropore bottom surface is penetrated, and the use as a precision filter is expected.
  • the microstructure of the present invention is anodized by applying a voltage of 195 V or more in an acidic aqueous solution containing an aliphatic carboxylic acid having 3 or more carbon atoms or an aromatic carboxylic acid to an aluminum or aluminum alloy plate. It can be manufactured by processing.
  • FIG. 3 is a schematic cross-sectional view of an aluminum member and a microstructure for explaining the manufacturing method of the microstructure of the present invention.
  • the aluminum or aluminum alloy substrate is not particularly limited.
  • a pure aluminum plate an alloy plate containing aluminum as a main component and containing a small amount of foreign elements; a substrate obtained by depositing high-purity aluminum on low-purity aluminum (for example, recycled material)
  • the surface on which the anodized film is provided by anodization treatment has an aluminum purity of preferably 99.5% by mass or more, more preferably 99.9% by mass or more, and 99.99% by mass. % Is more preferable.
  • the aluminum purity is in the above range, the regularity of the micropore array is sufficient.
  • the surface of the aluminum substrate is preferably preliminarily degreased and mirror-finished.
  • the mirror finishing process is performed to eliminate unevenness on the surface of the aluminum substrate and improve the uniformity and reproducibility of the particle forming process by an electrodeposition method or the like.
  • corrugation of the surface of an aluminum member the rolling rebar generated at the time of rolling in the case where an aluminum member is manufactured through rolling is mentioned, for example.
  • the mirror finish processing is not particularly limited, and a conventionally known method can be used. Examples thereof include mechanical polishing, chemical polishing, and electrolytic polishing. Examples of the mechanical polishing include a method of polishing with various commercially available polishing cloths, and a method of combining various commercially available abrasives (for example, diamond, alumina) and a buff.
  • a method using an abrasive and a method of changing the used abrasive from coarse particles to fine particles over time are preferably exemplified.
  • the final polishing agent is preferably # 1500.
  • the glossiness can be 50% or more (in the case of rolled aluminum, both the rolling direction and the width direction are 50% or more).
  • Examples of chemical polishing include various methods described in “Aluminum Handbook”, 6th edition, edited by Japan Aluminum Association, 2001, p.164-165. Further, the phosphoric acid-nitric acid method, Alupol I method, Alupol V method, Alcoa R5 method, H 3 PO 4 —CH 3 COOH—Cu method, and H 3 PO 4 —HNO 3 —CH 3 COOH method are preferably mentioned. Of these, the phosphoric acid-nitric acid method, the H 3 PO 4 —CH 3 COOH—Cu method, and the H 3 PO 4 —HNO 3 —CH 3 COOH method are preferable.
  • the glossiness can be set to 70% or more (in the case of rolling, 70% or more in both the rolling direction and the width direction).
  • the electrolytic polishing examples include various methods described in “Aluminum Handbook”, 6th edition, edited by Japan Aluminum Association, 2001, p.164-165. Further, a method described in US Pat. No. 2,708,655 is preferably exemplified. "Practical surface technology", vol. 33, No. 3, 1986, p32-38 is also preferred.
  • the gloss can be 70% or more (in the case of rolled aluminum, both the rolling direction and the width direction are 70% or more).
  • a method of using an abrasive is preferably performed by changing the abrasive to be used from coarse particles to fine particles over time, and then performing electrolytic polishing.
  • a surface having an average surface roughness Ra, 0.1 ⁇ m or less, and a glossiness of 50% or more can be obtained.
  • the average surface roughness is preferably 0.03 ⁇ m or less, and more preferably 0.02 ⁇ m or less.
  • the glossiness is preferably 70% or more, and more preferably 80% or more.
  • the glossiness is a regular reflectance obtained in accordance with JIS Z8741-1997 “Method 3 60 ° Specular Gloss” in the direction perpendicular to the rolling direction.
  • variable angle gloss meter for example, VG-1D, manufactured by Nippon Denshoku Industries Co., Ltd.
  • the incident reflection angle is 60 degrees and the regular reflectance is 70%.
  • the incident / reflection angle is 20 degrees.
  • Degreasing treatment uses acids, alkalis, organic solvents, etc. to dissolve and remove the organic components such as dust, fat, and resin that adhere to the aluminum surface, and removes defects in each treatment described below caused by the organic components. It is performed for the purpose of preventing the occurrence. Further, it is also used for the purpose of removing the oxide film formed on the film during the mirror finishing process.
  • a conventionally known degreasing agent can be used for the degreasing treatment. Specifically, for example, various commercially available degreasing agents can be used by a predetermined method.
  • a method of bringing an organic solvent such as alcohol (for example, methanol), ketone, benzine, or volatile oil into contact with the aluminum surface at room temperature (organic solvent method); contacting an organic solvent such as acetone with the aluminum surface at room temperature and using ultrasonic waves Method (ultrasonic cleaning method); Method of bringing a solution containing a surfactant such as soap and neutral detergent into contact with the aluminum surface at a temperature from room temperature to 80 ° C., and then washing with water (surfactant method); concentration
  • a 10 to 200 g / L sulfuric acid aqueous solution is brought into contact with an aluminum surface at a temperature from room temperature to 70 ° C.
  • a sodium hydroxide aqueous solution having a concentration of 5 to 20 g / L is applied to the aluminum surface at a normal temperature.
  • the aluminum surface is electrolyzed by applying a direct current of a current density of 1 ⁇ 10A / dm 2 in the cathode, then the concentration 100 ⁇ 500 g / L How neutralized by contacting the aqueous solution of nitric acid; while various known anodizing electrolytic solution is brought into contact with the aluminum surface at ordinary temperature, by passing a direct current of a current density of 1 ⁇ 10A / dm 2 of the aluminum surface in the cathode
  • Neutralization method A method in which an emulsion prepared by mixing a surfactant, water, etc. with light oil, kerosene, etc. is brought into contact with the aluminum surface at a temperature from room temperature to 50 ° C. for 30 to 180 seconds and then washed with water (emulsification and degreasing) Method): A method in which a mixed solution of sodium carbonate, phosphates, surfactant, etc. is brought into contact with the aluminum surface at a temperature from room temperature to 50 ° C. for 30 to 180 seconds and then washed with water. Phosphate method) can be exemplified.
  • ⁇ Micropore starting point formation method> As a method for forming the starting point of the micropore, a conventionally known method can be used. Specifically, it is preferable to use the self-ordering method described later.
  • the self-ordering method is a method of improving the regularity by utilizing the property that the micropores of the anodized film are regularly arranged and removing the factors that disturb the regular arrangement. Specifically, high-purity aluminum is used, and an anodized film is formed at a voltage corresponding to the type of the electrolyte. In this method, since the micropore diameter depends on the voltage, a desired micropore diameter can be obtained to some extent by controlling the voltage.
  • the average flow rate during the anodizing treatment is preferably 0.5 to 20.0 m / min, more preferably 1.0 to 15.0 m / min, and 2.0 to 10.0 m / min. More preferably, it is min.
  • the method of flowing the electrolytic solution under the above conditions is not particularly limited, but for example, a method using a general stirring device such as a stirrer is used. It is preferable to use a stirrer capable of controlling the stirring speed by digital display because the average flow rate can be controlled. Examples of such a stirring device include a magnetic stirrer HS-50D manufactured by AS ONE.
  • the anodizing treatment is performed by applying a voltage of 195 V or more in an acidic aqueous solution containing an aliphatic carboxylic acid having 3 or more carbon atoms or an aromatic carboxylic acid.
  • the voltage used for the anodizing treatment can be 195 to 600V, preferably 195V to 500V, and more preferably 195V to 400V.
  • the average micropore density corresponding to the processing voltage is 0.57 to 3.53 / ⁇ m 2 .
  • the generated current density during the anodizing treatment can be used at 1000 A / m 2 or less, preferably 500 A / m 2 or less, more preferably 400 to 100 A / m 2 , and even more preferably 250 A / m 2 . As long as it is within the above voltage / current density range, either constant voltage processing or constant current processing can be performed.
  • the electrolytic solution used for the anodizing treatment is an acidic aqueous solution containing an aliphatic carboxylic acid having 3 or more carbon atoms or an aromatic carboxylic acid.
  • an aliphatic carboxylic acid propionic acid, butyric acid, valeric acid, Caproic acid, enanthic acid, caprylic acid, pelargonic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, docosahexaenoic acid, eicosapentanoic acid, malonic acid, Succinic acid, adipic acid, tartaric acid, malic acid, and citric acid can be used, malonic acid, succinic acid, adipic acid, and tartaric acid are preferable, and malonic acid, succinic acid, and tartaric acid are more preferable.
  • aromatic carboxylic acids benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimesic acid, melophanoic acid, planitic acid, pyromellitic acid, mellitic acid, diphenic acid, toluic acid, Xylyl acid, hemelic acid, mesitylene acid, prenicylic acid, jurylic acid, cumic acid are preferable, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid can be used, and benzoic acid, phthalic acid, isophthalic acid, terephthalic acid are preferable.
  • phthalic acid More preferred are phthalic acid, isophthalic acid, and terephthalic acid.
  • Said carboxylic acid may be used independently and may be used in mixture of 2 or more types. Acids other than the above carboxylic acids may be used as long as the effects of the present invention are not impaired, but the total acid concentration in the aqueous solution is 50% by mass or less.
  • acids other than the above carboxylic acids sulfuric acid, phosphoric acid, boric acid and the like may be used together with the above carboxylic acids.
  • the concentration of the carboxylic acid can be 0.01 mol / L to 10 mol / L, preferably 0.05 to 5 mol / L, and more preferably 0.1 to 5.0 mol / L.
  • the electrolyte temperature used for the anodizing treatment can be 0-100 ° C., preferably 0-50 ° C., more preferably 0-20 ° C.
  • the micropore density is preferably 3.55 / ⁇ m 2 or less, 0.10 / ⁇ m 2 or more, more preferably 3.55 / ⁇ m 2 or less, 0.50 / ⁇ m 2 or more, and further 3.
  • the number is preferably 53 / ⁇ m 2 or less and 0.81 / ⁇ m 2 or more.
  • the ordering process is a process in which a process consisting of a film dissolving process for dissolving the anodized film and an anodizing process after the film dissolving process is performed once or more.
  • the film dissolution treatment is a treatment for dissolving the anodized film of the aluminum member described above. Thereby, a part of the irregular arrangement on the surface of the anodized film is partially dissolved, so that the regularity of the arrangement of the micropores becomes high. In addition, by dissolving the film, the current density rises during the first anodic oxidation after the film is dissolved, and as a result, the regularity of the arrangement of micropores increases.
  • the film dissolution treatment is performed by bringing the aluminum member into contact with an acidic aqueous solution or an alkaline aqueous solution.
  • the method of making it contact is not specifically limited, For example, the immersion method and the spray method are mentioned. Of these, the dipping method is preferred.
  • an aqueous acid solution When an aqueous acid solution is used for the film dissolution treatment, it is preferable to use an aqueous solution of an inorganic acid such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, or a mixture thereof. Especially, the aqueous solution which does not contain chromic acid is preferable at the point which is excellent in safety
  • the concentration of the acid aqueous solution is preferably 1 to 10% by mass.
  • the temperature of the aqueous acid solution is preferably 25 to 40 ° C.
  • an alkaline aqueous solution of at least one alkali selected from the group consisting of sodium hydroxide, potassium hydroxide and lithium hydroxide.
  • the concentration of the alkaline aqueous solution is preferably 0.1 to 5% by mass.
  • the temperature of the alkaline aqueous solution is preferably 20 to 35 ° C. Specifically, for example, 50 g / L, 40 ° C. phosphoric acid aqueous solution, 0.5 g / L, 30 ° C. sodium hydroxide aqueous solution or 0.5 g / L, 30 ° C. potassium hydroxide aqueous solution is preferably used. .
  • the immersion time in the acid aqueous solution or alkali aqueous solution is preferably 8 to 60 minutes, more preferably 10 to 50 minutes, and further preferably 15 to 30 minutes.
  • the anodizing treatment is performed after the above-described film dissolution treatment. Thereby, the oxidation reaction of the aluminum substrate proceeds, and the anodic oxide film dissolved by the film dissolution treatment becomes thick.
  • the anodizing treatment may be performed by a conventionally known method, but is preferably performed under the same conditions as the method of the present invention used in the self-ordering method described above.
  • the electrolysis time is preferably 1 to 100 hours, more preferably 30 to 80 hours, and further preferably 40 to 50 hours.
  • the above-described film dissolution treatment and the subsequent anodic oxidation treatment may be performed once or more.
  • the regularization treatment when the above steps are repeated twice or more, the conditions of each film dissolution treatment and anodization treatment may be the same or different.
  • FIG. 3A shows an aluminum substrate 12a and an anodized film 14a having micropores 16a present on the surface of the aluminum substrate 12a.
  • FIG. 3B the surface of the anodized film 14a shown in FIG. 3A and the inside of the micropores 16a are dissolved by the first film dissolution treatment, and the micropores 16a are formed on the aluminum substrate 12a.
  • An anodized film 14b having a pore 16b is formed, and the anodized film 14b remains on the bottom surface of the micropore 16b.
  • FIG. 3C the oxidation reaction of the aluminum substrate 12a shown in FIG.
  • FIG. 3B proceeds by the next anodic oxidation treatment, and the micropores 16c deeper than the micropores 16b are formed on the aluminum substrate 12b.
  • An anodic oxide film 14c that is thicker than the anodic oxide film 14b is obtained.
  • FIG. 3D the surface of the anodic oxide film 14c shown in FIG. 3C and the inside of the micropore 16c are dissolved by the second film dissolution treatment, and the micropore 16d is formed on the aluminum substrate 12b.
  • the microstructure 20 having the anodic oxide film 14d is obtained.
  • the barrier layer is indicated by 18d.
  • the anodic oxide film 14d remains in FIG. 3D, the anodic oxide film may be completely dissolved in the second film dissolution treatment. When all of the anodized film is dissolved, the depressions present on the surface of the aluminum substrate become micropores of the fine structure.
  • the fine structure of the present invention is obtained by the manufacturing method described above. Moreover, the aluminum or aluminum alloy substrate of the microstructure of the present invention described below may be removed, or micropore penetration processing may be performed.
  • a treatment solution is used in which the anodized film (alumina) is difficult to dissolve and aluminum is easily dissolved. That is, the aluminum dissolution rate is 1 ⁇ m / min or more, preferably 3 ⁇ m / min or more, more preferably 5 ⁇ m / min or more, and the anodic oxide film dissolution rate is 0.1 nm / min or less, preferably 0.05 nm / min or less, more preferably Uses a treatment liquid having a condition of 0.01 nm / min or less.
  • Such a treatment liquid is based on an acid or alkali aqueous solution, for example, manganese, zinc, chromium, iron, cadmium, cobalt, nickel, tin, lead, antimony, bismuth, copper, mercury, silver, palladium, platinum,
  • a gold compound for example, chloroplatinic acid
  • a fluoride thereof, a chloride thereof, or the like is preferably used.
  • an acid aqueous solution base is preferable, and it is preferable to blend a chloride.
  • a treatment liquid (hydrochloric acid / mercury chloride) in which mercury chloride is blended with an aqueous hydrochloric acid solution and a treatment liquid (hydrochloric acid / copper chloride) in which copper chloride is blended with an aqueous hydrochloric acid solution are preferable from the viewpoint of treatment latitude.
  • the composition of such a treatment liquid is not particularly limited, and for example, a bromine / methanol mixture, a bromine / ethanol mixture, aqua regia and the like can be used.
  • the acid or alkali concentration of such a treatment liquid is preferably 0.01 to 10 mol / L, and more preferably 0.05 to 5 mol / L.
  • the treatment temperature using such a treatment liquid is preferably ⁇ 10 ° C. to 80 ° C., and preferably 0 ° C. to 60 ° C.
  • the aluminum substrate is dissolved by bringing the aluminum substrate after the anodizing treatment step into contact with the treatment liquid described above.
  • the method of making it contact is not specifically limited, For example, the immersion method and the spray method are mentioned. Of these, the dipping method is preferred.
  • the contact time at this time is preferably 10 seconds to 5 hours, more preferably 1 minute to 3 hours.
  • the following treatment (2-a) or (2-b) is preferably performed.
  • the bottom of the anodized film is removed by pre-soaking in a pH buffer solution and filling the hole with the pH buffer solution from the opening side of the micropore, and then on the opposite side of the opening, that is, on the bottom of the anodized film. It is preferably carried out by a method of contacting with an acid aqueous solution or an alkali aqueous solution.
  • an aqueous solution of an inorganic acid such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid or a mixture thereof.
  • the concentration of the acid aqueous solution is preferably 1 to 10% by mass.
  • the temperature of the aqueous acid solution is preferably 25 to 40 ° C.
  • an alkaline aqueous solution it is preferable to use an aqueous solution of at least one alkali selected from the group consisting of sodium hydroxide, potassium hydroxide and lithium hydroxide.
  • the concentration of the alkaline aqueous solution is preferably 0.1 to 5% by mass.
  • the temperature of the alkaline aqueous solution is preferably 20 to 35 ° C.
  • a 50 g / L, 40 ° C. phosphoric acid aqueous solution, a 0.5 g / L, 30 ° C. sodium hydroxide aqueous solution, or a 0.5 g / L, 30 ° C. potassium hydroxide aqueous solution is suitably used. It is done.
  • the immersion time in the acid aqueous solution or alkali aqueous solution is preferably 8 to 120 minutes, more preferably 10 to 90 minutes, and further preferably 15 to 60 minutes. Moreover, when immersing in a pH buffer solution beforehand, the buffer solution corresponding to the acid / alkali mentioned above is used appropriately.
  • a CMP slurry such as PNINERLITE-7000 manufactured by Fujimi Incorporated, GPXHSC800 manufactured by Hitachi Chemical Co., Ltd., CL-1000 manufactured by Asahi Glass (Seimi Chemical) Co., Ltd. can be used.
  • Example 1 Electrolytic polishing treatment A high-purity aluminum substrate (Sumitomo Light Metal Co., Ltd., purity 99.99 mass%, thickness 0.4 mm) was cut in an area of 10 cm square, and using an electrolytic polishing liquid having the following composition, a voltage of 10 V, liquid The electropolishing treatment was performed at a temperature of 65 ° C.
  • the cathode was a carbon electrode, and the power source was GPO-250-30R (manufactured by Takasago Seisakusho).
  • Degreasing treatment The sample after the polishing treatment obtained above was degreased by immersing it for 10 to 60 seconds under the condition of a liquid temperature of 60 ° C. using a degreasing treatment liquid having the following composition.
  • the obtained surface has an average surface roughness Ra, It was 0.1 ⁇ m or less and the glossiness was 50% or more.
  • ⁇ Degreasing solution composition > 1.75 mol / L sodium hydroxide 0.16 mol / L sodium nitrate 3.
  • the sample obtained above was subjected to a constant voltage anodizing treatment with an electrolyte of 0.30 mol / L succinic acid aqueous solution for 45 hours under conditions of a voltage of 252 V and a liquid temperature of 0 ° C. 4).
  • Film dissolution treatment The sample obtained above was immersed for 12 hours under the condition of a liquid temperature of 60 ° C. using an oxide film removal treatment liquid having the following composition to perform an oxide film removal treatment.
  • Anodizing treatment The sample obtained above was subjected to anodizing treatment in the same manner except that the treatment time was 43 hours. 6).
  • micropore cycle and thickness measurement The micropore cycle is a cross section of the sample obtained by anodizing, observed with FE-SEM (S-900, manufactured by Hitachi, Ltd.), and a photograph (150,000 times). In other words, it is a value obtained by measuring the period of 25 or more micropores and averaging them. The micropore thickness was also measured and averaged in the same manner.
  • Example 2 The electrolytic conditions for the ordered anodizing treatment are as follows: a constant voltage anodizing treatment is carried out for 47 hours with a 0.3 mol / L aqueous solution of citric acid and a voltage of 375 V and a solution temperature of 0 ° C .; Example 2 was obtained in the same manner as in Example 1 except that the treatment time in the anodizing treatment was 45 hours, and the scanning microscope observation field of view in the calculation of the degree of ordering was 4000 times. (Example 3) 3.
  • the electrolytic conditions for the ordered anodizing treatment are as follows: a constant voltage anodizing treatment is carried out for 49 hours using a 0.03 mol / L phthalic acid aqueous solution at a voltage of 320 V and a liquid temperature of 0 ° C .; Example 3 was obtained in the same manner as in Example 1 except that the treatment time in the anodizing treatment was 47 hours and the scanning microscope observation field of view in the calculation of the degree of ordering was 5000 times.
  • the electrolytic condition of the ordered anodizing treatment is a constant voltage anodizing treatment for 17 hours with a 0.1 mol / L tartaric acid aqueous solution under the conditions of a voltage of 263 V and a liquid temperature of 5 ° C.
  • Example 4 was obtained in the same manner as in Example 1 except that the treatment time in the anodizing treatment was 20 hours.
  • Comparative Example 1 was obtained in the same manner as in Example 1 except that the scanning microscope observation field for calculating the degree of ordering was set to 10000 times.
  • Comparative Example 2 3. above.
  • Example 2 As the electrolytic conditions for the ordered anodizing treatment, a constant voltage anodizing treatment was performed for 8 hours with an electrolyte solution of 0.5 mol / L oxalic acid at a voltage of 40 V and a liquid temperature of 15 ° C. The treatment time in the anodizing treatment is 9 hours, and the above 6. Comparative Example 2 was obtained in the same manner as in Example 1 except that the scanning microscope observation field for calculating the degree of ordering was 10,000 times.
  • Comparative Example 3 As the electrolytic conditions for the ordered anodizing treatment, a constant voltage anodizing treatment was performed for 0.3 hours with a 0.5 mol / L oxalic acid electrolytic solution at a voltage of 195 V and a liquid temperature of 0 ° C. Comparative Example 3 was obtained in the same manner as in Example 1 except that the treatment time in the anodizing treatment was 0.3 hour. The formed anodized film “burned”. ("Burning" refers to a phenomenon in which local film growth occurs and uniform film formation does not occur). Therefore, the calculation of the micropore period, the micropore thickness, and the degree of bottom ordering cannot be performed. (Comparative Example 4) 3. above. The processing time of the ordered anodizing treatment is 10 hours, and the above 5. Comparative Example 4 was obtained in the same manner as in Example 1 except that the treatment time in the anodizing treatment was 11 hours.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

La présente invention concerne une microstructure comportant un film d'aluminium ou d'un alliage d'aluminium anodisé, dans lequel le degré de régularisation d'une pluralité de micropores sur la surface inférieure est égal ou supérieur à 70%, la distance entre les centres des micropores est égale ou supérieure à 60 nm, et la longueur de chaque micropore dans la direction axiale est égale ou supérieure à 50 μm. L'invention concerne également un procédé pour la production de la microstructure.
PCT/JP2010/065633 2009-09-16 2010-09-10 Microstructure et son procédé de production WO2011034008A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009-214428 2009-09-16
JP2009214428 2009-09-16

Publications (1)

Publication Number Publication Date
WO2011034008A1 true WO2011034008A1 (fr) 2011-03-24

Family

ID=43758613

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/065633 WO2011034008A1 (fr) 2009-09-16 2010-09-10 Microstructure et son procédé de production

Country Status (2)

Country Link
JP (1) JP2011084810A (fr)
WO (1) WO2011034008A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105543931A (zh) * 2016-01-13 2016-05-04 西安交通大学 一种基于铝合金表面尺寸可调纳米孔阵列及其快速制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101923897B1 (ko) * 2018-05-30 2018-11-29 백승현 피처리물의 양극산화 방법

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009114470A (ja) * 2007-11-01 2009-05-28 Fujifilm Corp 微細構造体の製造方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009114470A (ja) * 2007-11-01 2009-05-28 Fujifilm Corp 微細構造体の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105543931A (zh) * 2016-01-13 2016-05-04 西安交通大学 一种基于铝合金表面尺寸可调纳米孔阵列及其快速制备方法

Also Published As

Publication number Publication date
JP2011084810A (ja) 2011-04-28

Similar Documents

Publication Publication Date Title
JP4870544B2 (ja) 微細構造体の製造方法および微細構造体
JP4813925B2 (ja) 微細構造体の製造方法および微細構造体
JP5463052B2 (ja) 金属部材
JP4603402B2 (ja) 微細構造体およびその製造方法
JP2008270157A (ja) 異方導電性部材およびその製造方法
JP4800860B2 (ja) 微細構造体の製造方法および微細構造体
JP4768478B2 (ja) 微細構造体の製造方法および微細構造体
JP2006322067A (ja) 構造体の製造方法
JP2007238988A (ja) 微細構造体の製造方法および微細構造体
JP4800799B2 (ja) 微細構造体の製造方法および微細構造体
JP2007204802A (ja) 構造体の製造方法
JP5274097B2 (ja) 微細構造体およびその製造方法
WO2011034008A1 (fr) Microstructure et son procédé de production
JP4884202B2 (ja) 微細構造体の製造方法および微細構造体
JP4990737B2 (ja) 微細構造体の製造方法
JP2008238048A (ja) 精密フィルターユニット
JP2010168617A (ja) 微細構造体の製造方法
JP2008057018A (ja) 微細構造体の製造方法および微細構造体
JP2008063643A (ja) 微細構造体の製造方法および微細構造体
JP2009132959A (ja) アルミニウム除去処理方法及びアルミニウム除去処理液
Valota Anodic Titanium Oxide: From Metal Surface Preparation to Self-Ordered Growth of Nanotubes

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10817121

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10817121

Country of ref document: EP

Kind code of ref document: A1