JP2009030079A - Manufacturing method of fine structure and fine structure - Google Patents

Abstract

A porous alumina membrane filter having an excellent filtration flow rate and an excellent flatness, a microstructure that can be suitably used as the porous alumina membrane filter, and a method for producing the same.
An anodizing treatment for forming an oxide film having micropores by anodizing an aluminum substrate;
A separation treatment for removing the aluminum substrate after the anodizing treatment and separating the oxide film from the aluminum substrate;
A penetration treatment for penetrating the micropores of the oxide film separated by the separation treatment;
A heat treatment in which the oxide film penetrating the micropores by the penetration treatment is heated at a temperature of 100 ° C. or higher while applying a load of 0.5 g / cm ² or more;
A method for producing a fine structure, in which a fine structure having micropores on the surface is obtained by applying at least in this order.
[Selection figure] None

Description

  The present invention relates to a method for manufacturing a fine structure and a fine structure.

  Organic membrane filters and inorganic membrane filters are known as membrane filters in practical use in the field of microfiltration.

  Many organic membrane filters do not have independent pores and have a relatively wide pore size distribution, so that the most important functions of the filter are specific substances (for example, CMP slurry particles; resist pigments and dyes; IJ In order to improve the separation accuracy of ink, magnetic material, cells (cell culture insert use, etc.), molecules having a size fraction such as fullerene, solvents such as DMSO, etc., various researches are being conducted.

For example, Non-Patent Document 1 discloses so-called track etching in which an organic film made of a polymer is irradiated with high-energy particles generated from a nuclear reactor, and the tracks through which the particles have passed through the organic film are etched. A scheme has been proposed.
However, this track etching method can obtain independent narrow pores with a narrow pore size distribution perpendicular to the organic film, but in order to avoid the generation of double holes due to the incidence of particles overlapping during track formation, There was a problem that the pore density, so-called porosity, could not be increased.

On the other hand, a porous alumina membrane filter using an anodic oxide film of aluminum is known as an inorganic membrane filter without such problems (for example, see Non-Patent Document 2).
This porous alumina membrane filter is made by anodizing aluminum in an acidic electrolyte so that independent pores with a narrow pore size distribution are arranged with a high porosity, so the filtration flow rate per hour is high, Moreover, it can be manufactured at low cost.

  However, since the porous alumina membrane filter itself is an anodized film of aluminum, it is necessary to suppress the occurrence of warpage and to flatten it in order to improve its durability.

T.A. D. Block, Membrane Filtration, Sci. Tech, Inc. , Madison (1983) Hideki Masuda, “New Technology of Porous Membrane Using Anodization”, Altopia, July 1995

  Accordingly, an object of the present invention is to provide a porous alumina membrane filter excellent in filtration flow rate and excellent in flatness, a microstructure that can be suitably used as the porous alumina membrane filter, and a method for manufacturing the same. To do.

As a result of intensive studies to achieve the above object, the present inventor has made a porous structure using a fine structure obtained by forming a anodic oxide film having micropores and then performing heat treatment under a predetermined load. The present inventors have found that an alumina membrane filter is excellent in filtration flow rate and flatness, and completed the present invention.
That is, the present invention provides the following (1) to (5).

(1) Anodizing to form an oxide film having micropores by anodizing an aluminum substrate;
A separation treatment for removing the aluminum substrate after the anodizing treatment and separating the oxide film from the aluminum substrate;
A penetration treatment for penetrating the micropores of the oxide film separated by the separation treatment;
A heat treatment in which the oxide film penetrating the micropores by the penetration treatment is heated at a temperature of 100 ° C. or higher while applying a load of 0.5 g / cm ² or more;
A method for producing a fine structure, in which a fine structure having micropores on the surface is obtained by applying at least in this order.

  (2) The method according to (1) above, wherein the method of applying the load in the heat treatment is a method of sandwiching and pressing the oxide film with a flat material that does not change in shape at the temperature in the heat treatment. Manufacturing method of structure.

  (3) A fine structure obtained by the method for producing a fine structure according to (1) or (2).

  (4) The microstructure according to (3), wherein the pore diameter dispersion of the micropores is within 3% of the average diameter, and the warpage per 10 mm width is 20 μm or less.

  (5) A porous alumina membrane filter using the microstructure described in (3) or (4) above.

As described below, according to the present invention, a porous alumina membrane filter having excellent filtration flow rate and excellent flatness, a microstructure that can be suitably used as the porous alumina membrane filter, and a method for manufacturing the same. Can be provided.
Further, the porous alumina membrane filter of the present invention is very useful because it has high durability, and thus the filter itself is not easily broken even during filtration under high pressure conditions, and the filtration flow rate can be further improved.

The present invention is described in detail below.
The method for producing a microstructure of the present invention includes an anodizing treatment (hereinafter also referred to as “anodic oxidation treatment (A)”) in which an aluminum substrate is anodized to form an oxide film having micropores, and the above-described anodizing. After the treatment, the aluminum substrate is removed, and a separation process for separating the oxide film from the aluminum substrate (hereinafter also referred to as “separation process (B)”) and a micropore of the oxide film separated by the separation process are passed through. A penetration treatment (hereinafter also referred to as “penetration treatment (C)”) and an oxide film penetrating the micropores by the penetration treatment are performed at 100 ° C. or higher while applying a load of 0.5 g / cm ² or more. At least in this order, to obtain a fine structure having micropores on the surface, by performing a heat treatment (hereinafter also referred to as “heat treatment (D)”) at a temperature of It is a manufacturing method of the structure.
Below, an aluminum substrate and each process are explained in full detail.

[Aluminum substrate]
The aluminum substrate is not particularly limited, and specific examples thereof include a pure aluminum plate; an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements; and depositing high-purity aluminum on low-purity aluminum (for example, recycled material). Examples of the substrate include: a substrate in which high purity aluminum is coated on the surface of a silicon wafer, quartz, glass or the like by a method such as vapor deposition or sputtering; a resin substrate in which aluminum is laminated;

  In the present invention, of the aluminum substrate, the surface to be anodized, which will be described later, preferably has an aluminum purity of 99.5% by mass or more, more preferably 99.9% by mass or more, 99 More preferably, it is at least 99 mass%. When the aluminum purity is in the above range, the regularity of the pore arrangement of the micropores is sufficient.

  Further, in the present invention, the surface of the aluminum substrate to be subjected to anodization described later is preferably subjected to degreasing and mirror finishing in advance, particularly from the viewpoint of improving the regularity of the pore arrangement, Heat treatment is preferably performed.

<Heat treatment>
When heat treatment is performed, it is preferably performed at 200 to 350 ° C. for about 30 seconds to 2 minutes. Specifically, for example, a method of placing an aluminum substrate in a heating oven can be used.
By performing such heat treatment, the regularity of the arrangement of micropores generated by an anodic oxidation process described later is improved.
Moreover, it is preferable to cool the aluminum substrate after heat treatment rapidly. As a method for cooling, for example, a method of directly putting it into water or the like can be mentioned.

<Degreasing treatment>
The degreasing treatment uses acid, alkali, organic solvent, etc. to dissolve and remove the organic components such as dust, fat, and resin adhered to the surface of the aluminum substrate, and in each treatment described later due to the organic components. This is done for the purpose of preventing the occurrence of defects.

Specifically, as the degreasing treatment, for example, a method in which an organic solvent such as various alcohols (for example, methanol), various ketones (for example, methyl ethyl ketone), benzine, volatile oil or the like is brought into contact with the aluminum substrate surface at room temperature (organic Solvent method); a method of bringing a liquid containing a surfactant such as soap or neutral detergent into contact with the aluminum substrate surface at a temperature from room temperature to 80 ° C., and then washing with water (surfactant method); concentration of 10 to 200 g A method in which an aqueous solution of sulfuric acid / L is brought into contact with the aluminum substrate surface at a temperature from room temperature to 70 ° C. for 30 to 80 seconds and then washed with water; while contacting about seconds, the aluminum substrate surface and the electrolyte by passing a direct current of a current density of 1 to 10 a / dm ² in the cathode, the , A method of neutralizing by bringing a nitric acid aqueous solution having a concentration of 100 to 500 g / L into contact; while bringing various known anodizing electrolytes into contact with the aluminum substrate surface at room temperature, the aluminum substrate surface is used as a cathode and a current density of 1 to A method in which a 10 A / dm ² direct current is applied or an alternating current is applied for electrolysis; an alkaline aqueous solution having a concentration of 10 to 200 g / L is brought into contact with the aluminum substrate surface at 40 to 50 ° C. for 15 to 60 seconds; A method of neutralizing by bringing a nitric acid aqueous solution having a concentration of 100 to 500 g / L into contact; an emulsion obtained by mixing light oil, kerosene, etc. with a surfactant, water, etc. is brought into contact with the aluminum substrate surface at a temperature from room temperature to 50 ° C. Then, a method of washing with water (emulsification and degreasing method); a mixed solution of sodium carbonate, phosphates, surfactant and the like on the surface of the aluminum substrate at a temperature from room temperature to 50 ° C. Contacting 0-180 seconds, then, a method of washing with water (phosphate method); and the like.

  Among these, the organic solvent method, the surfactant method, the emulsion degreasing method, and the phosphate method are preferable from the viewpoint that the fat content on the aluminum surface can be removed while the aluminum hardly dissolves.

  Moreover, a conventionally well-known degreasing agent can be used for a degreasing process. Specifically, for example, various commercially available degreasing agents can be used by a predetermined method.

<Mirror finish processing>
The mirror finishing process is performed in order to eliminate unevenness on the surface of the aluminum substrate, for example, rolling streaks generated during the rolling of the aluminum substrate, and improve the uniformity and reproducibility of the sealing process by an electrodeposition method or the like.
In the present invention, the mirror finish 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, a method of combining various commercially available abrasives (for example, diamond, alumina) and a buff. Specifically, when an abrasive is used, a method in which the abrasive used is changed from coarse particles to fine particles over time is preferably exemplified. In this case, the final polishing agent is preferably # 1500. Thereby, 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).

As chemical polishing, for example, “Aluminum Handbook”, 6th edition, edited by Japan Aluminum Association, 2001, p. Examples thereof include various methods described in 164 to 165.
Further, phosphoric acid - nitric acid method, Alupol I method, Alupol V method, Alcoa R5 _{method, H 3 PO 4 -CH 3 COOH} -Cu _{method, H 3 PO 4 -HNO 3 -CH} 3 COOH method are preferable. Among 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.
By chemical polishing, the glossiness can be made 70% or more (in the case of rolled aluminum, both the rolling direction and the width direction are 70% or more).

As electrolytic polishing, for example, “Aluminum Handbook”, 6th edition, edited by Japan Aluminum Association, 2001, p. 164-165; various methods described in US Pat. No. 2,708,655; “Practical Surface Technology”, vol. 33, no. 3, 1986, p. The method described in 32-38;
By electropolishing, 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).

  These methods can be used in appropriate combination. Specifically, for example, a method of performing mechanical polishing in which the abrasive is changed from coarse particles to fine particles with time, and then performing electrolytic polishing is preferable.

By mirror finishing, for example, a surface having an average surface roughness R _{a of} 0.1 μm or less and a glossiness of 50% or more can be obtained. The average surface roughness _Ra is preferably 0.03 μm or less, and more preferably 0.02 μm or less. Further, 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. Specifically, using a variable angle gloss meter (for example, VG-1D, manufactured by Nippon Denshoku Industries Co., Ltd.), when the regular reflectance is 70% or less, the incident reflection angle is 60 degrees and the regular reflectance is 70%. In the case of exceeding, the incident / reflection angle is 20 degrees.

[Anodic oxidation treatment (A)]
The anodizing treatment (A) is a treatment for forming an oxide film having micropores on the surface of the aluminum substrate by anodizing the aluminum substrate.
As the anodizing treatment, 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 low speed over a long period of time (for example, several hours to several tens of hours) at a voltage according to the type of the electrolytic solution.
In this method, since the pore diameter depends on the voltage, a desired pore diameter can be obtained to some extent by controlling the voltage.

  In order to form micropores by the self-ordering method, anodizing treatment (a-1) described later may be performed, but preferably anodizing treatment (a-1) described later, film removal treatment (a- It is preferable to form by the method of implementing 2) and re-anodizing treatment (a-3) in this order.

<Anodizing treatment (a-1)>
The average flow rate during the anodizing treatment (a-1) is preferably 0.5 to 20.0 m / min, more preferably 1.0 to 15.0 m / min, and 2.0 More preferably, it is -10.0 m / min. By performing anodizing treatment at a flow rate in the above range, uniform and high regularity can be obtained.
Moreover, the method of flowing the electrolytic solution under the above-mentioned conditions is not particularly limited, but, for example, a method using a general stirring device such as a stirrer is used. In particular, it is preferable to use a stirrer that can control the stirring speed with a digital display because the average flow rate can be controlled. Examples of such a stirring apparatus include “Magnetic Stirrer HS-50D (manufactured by AS ONE)” and the like.

For the anodizing treatment (a-1), for example, a method in which an aluminum substrate is used as an anode in a solution having an acid concentration of 0.01 to 5 mol / L can be used.
The solution used for the anodizing treatment (a-1) is preferably an acid solution, and sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, amidosulfonic acid, glycolic acid, tartaric acid, Malic acid, citric acid, and the like are more preferable, and sulfuric acid, phosphoric acid, and oxalic acid are particularly preferable. These acids can be used alone or in combination of two or more.

The conditions for the anodizing treatment (a-1) vary depending on the electrolyte used, and thus cannot be determined unconditionally. In general, however, the electrolyte concentration is 0.01 to 5 mol / L, and the solution temperature is -10 to 10. It is preferably 30 ° C., current density 0.01 to 20 A / dm ² , voltage 3 to 300 V, electrolysis time 0.5 to 30 hours, electrolyte concentration 0.05 to 3 mol / L, liquid temperature −5 to 25 It is more preferable that it is C, current density 0.05-15A / dm < ² >, voltage 5-250V, electrolysis time 1-25 hours, electrolyte concentration 0.1-1 mol / L, liquid temperature 0-20 degreeC, current More preferably, the density is 0.1 to 10 A / dm ² , the voltage is 10 to 200 V, and the electrolysis time is 2 to 20 hours.

  The treatment time for the anodizing treatment (a-1) is preferably 0.5 minutes to 16 hours, more preferably 1 minute to 12 hours, and even more preferably 2 minutes to 8 hours.

  The anodizing treatment (a-1) can be performed under a constant voltage, or a method of changing the voltage intermittently or continuously. In this case, it is preferable to decrease the voltage sequentially. This makes it possible to reduce the resistance of the anodized film, and fine micropores are formed in the anodized film, which is preferable in terms of improving uniformity, particularly when sealing treatment is performed by electrodeposition. .

  In the present invention, the thickness of the anodized film formed by such anodizing treatment (a-1) is preferably 0.1 to 2000 μm, more preferably 1 to 1000 μm. More preferably, it is -500 micrometers.

In the present invention, the pore diameter of the micropore formed by such anodizing treatment (a-1) is preferably 0.01 to 0.5 μm.
In addition, the micropores formed by such anodizing treatment (a-1) preferably have a pore diameter dispersion within 3% of the average diameter within a range of 1 μm ² and within 2%. Is more preferable. In addition, the average diameter and dispersion | distribution of a pore diameter can each be calculated | required by a following formula.
Average diameter: μ _x = (1 / n) ΣXi
Dispersion: σ ² = (1 / n) (ΣXi ² ) −μ _x ²
Dispersion / average diameter = σ / μ _x ≦ 0.03
Here, Xi is the pore diameter of one micropore measured in the range of 1 μm ² .

Furthermore, in the present invention, the average pore density of the micropores formed by such anodizing treatment (a-1) is preferably 50 to 1500 / μm ² .
Furthermore, the area ratio occupied by the micropores formed by such anodizing treatment (a-1) is preferably 20 to 50%.
Here, the area ratio occupied by the micropores is defined by the ratio of the total area of the openings of the micropores to the area of the aluminum surface.

<Film removal treatment (a-2)>
The film removal process (a-2) is a process for dissolving and removing the anodized film formed on the surface of the aluminum substrate by the anodizing process (a-1).
After forming the anodized film on the surface of the aluminum substrate by the anodizing treatment (a-1), the separation treatment (B) described later may be performed immediately, but after the anodizing treatment (a-1), It is preferable to perform a separation treatment (B) described later after performing a film removal treatment (a-2) and a re-anodizing treatment (a-3) described later in this order.

  Since the anodic oxide film has higher regularity as it gets closer to the aluminum substrate, the anodic oxide film once removed by this film removal treatment (a-2) and remaining on the surface of the aluminum substrate. The bottom portion can be exposed on the surface to obtain regular depressions. Therefore, in the film removal process (a-2), aluminum is not dissolved, but only the anodized film made of alumina (aluminum oxide) is dissolved.

  Alumina solution includes chromium compound, nitric acid, phosphoric acid, zirconium compound, titanium compound, lithium salt, cerium salt, magnesium salt, sodium fluorosilicate, zinc fluoride, manganese compound, molybdenum compound, magnesium compound, barium compound and An aqueous solution containing at least one selected from the group consisting of simple halogens is preferred.

Specific examples of the chromium compound include chromium (III) oxide and anhydrous chromium (VI) acid.
Examples of the zirconium-based compound include zircon ammonium fluoride, zirconium fluoride, and zirconium chloride.
Examples of the titanium compound include titanium oxide and titanium sulfide.
Examples of the lithium salt include lithium fluoride and lithium chloride.
Examples of the cerium salt include cerium fluoride and cerium chloride.
Examples of the magnesium salt include magnesium sulfide.
Examples of the manganese compound include sodium permanganate and calcium permanganate.
Examples of the molybdenum compound include sodium molybdate.
Examples of magnesium compounds include magnesium fluoride pentahydrate.
Examples of barium compounds include barium oxide, barium acetate, barium carbonate, barium chlorate, barium chloride, barium fluoride, barium iodide, barium lactate, barium oxalate, barium perchlorate, barium selenate, selenite. Examples thereof include barium, barium stearate, barium sulfite, barium titanate, barium hydroxide, barium nitrate, and hydrates thereof. Among the barium compounds, barium oxide, barium acetate, and barium carbonate are preferable, and barium oxide is particularly preferable.
Examples of halogen alone include chlorine, fluorine, and bromine.

Among them, the alumina solution is preferably an aqueous solution containing an acid. Examples of the acid include sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like, and a mixture of two or more acids may be used.
The acid concentration is preferably 0.01 mol / L or more, more preferably 0.05 mol / L or more, and still more preferably 0.1 mol / L or more. There is no particular upper limit, but generally it is preferably 10 mol / L or less, more preferably 5 mol / L or less. An unnecessarily high concentration is not economical, and if it is higher, the aluminum substrate may be dissolved.

  The alumina solution is preferably −10 ° C. or higher, more preferably −5 ° C. or higher, and still more preferably 0 ° C. or higher. In addition, since the starting point of ordering will be destroyed and disturbed if it processes using the boiling alumina solution, it is preferable to use it without boiling.

  The alumina solution dissolves alumina and does not dissolve aluminum. Here, the alumina solution may not dissolve aluminum substantially or may dissolve it slightly.

  The film removal treatment (a-2) is performed by bringing the aluminum substrate on which the anodized film is formed into contact with the above-described alumina 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.

The dipping method is a treatment in which an aluminum substrate on which an anodized film is formed is dipped in the above-described alumina solution. Stirring during the dipping process is preferable because a uniform process is performed.
The dipping treatment time is preferably 10 minutes or longer, more preferably 1 hour or longer, and further preferably 3 hours or longer and 5 hours or longer.

<Re-anodizing treatment (a-3)>
After removing the anodic oxide film by the film removal treatment (a-2) to form regular depressions on the surface of the aluminum substrate, the degree of ordering of the micropores is higher by performing the anodic oxidation treatment again. An anodized film can be formed.
For the re-anodizing treatment (a-3), a conventionally known method can be used, but it is preferably performed under the same conditions as the above-described anodizing treatment (a-1).
Also, a method of repeatedly turning on and off the current intermittently while keeping the DC voltage constant, and a method of repeatedly turning on and off the current while intermittently changing the DC voltage can be suitably used. According to these methods, fine micropores are generated in the anodic oxide film, which is preferable in that uniformity is improved particularly when sealing treatment is performed by electrodeposition.

When the re-anodizing treatment (a-3) is performed at a low temperature, the arrangement of micropores becomes regular and the pore diameter becomes uniform.
On the other hand, by performing the re-anodizing treatment (a-3) at a relatively high temperature, the arrangement of the micropores can be disturbed, and the variation in pore diameter can be made within a predetermined range. Also, the pore diameter variation can be controlled by the processing time.

  In the present invention, the thickness of the anodized film formed by such re-anodizing treatment (a-3) is preferably 0.1 to 1000 μm, more preferably 1 to 500 μm, More preferably, it is 10-500 micrometers.

In the present invention, the pore diameter of the micropore formed by such anodizing treatment (a-3) is preferably 0.01 to 0.5 μm.
Further, the micropores formed by such re-anodizing treatment (a-3) preferably have a pore diameter dispersion within 3% of the average diameter within a range of 1 μm ² , and within 2%. It is more preferable.

Furthermore, in the present invention, the average pore density of the micropores formed by such anodizing treatment (a-3) is preferably 50 to 1500 / μm ² .
Furthermore, the area ratio occupied by the micropores formed by such anodizing treatment (a-3) is preferably 20 to 50%.

  In the present invention, instead of the above-described anodic oxidation treatment (a-1) and film removal treatment (a-2), for example, a physical method, a particle beam method, a block copolymer method, a resist pattern / exposure / etching method, etc. Thus, a depression that is a starting point for generating micropores by the re-anodizing treatment (a-3) described above may be formed.

<Physical method>
For example, a method using an imprint method (a transfer method or a press patterning method in which a substrate or a roll having a protrusion is pressed against an aluminum plate to form a recess) can be used. Specifically, a method of forming a depression by pressing a substrate having a plurality of protrusions on the surface thereof against the aluminum surface can be mentioned. For example, a method described in JP-A-10-121292 can be used.
Another example is a method in which polystyrene spheres are arranged in a dense state on the aluminum surface, SiO ₂ is vapor-deposited thereon, then the polystyrene spheres are removed, and the substrate is etched using the vapor-deposited SiO ₂ as a mask to form depressions. It is done.

<Particle beam method>
The particle beam method is a method in which a hollow is formed by irradiating the aluminum surface with a particle beam. The particle beam method has an advantage that the position of the depression can be freely controlled.
Examples of the particle beam include a charged particle beam, a focused ion beam (FIB), and an electron beam.
As the particle beam method, for example, a method described in JP-A-2001-105400 can be used.

<Block copolymer method>
The block copolymer method is a method in which a block copolymer layer is formed on an aluminum surface, a sea-island structure is formed in the block copolymer layer by thermal annealing, and then an island portion is removed to form a depression.
As a block copolymer method, the method described in Unexamined-Japanese-Patent No. 2003-129288 can be used, for example.

<Resist pattern, exposure, etching method>
In the resist pattern / exposure / etching method, the resist on the surface of the aluminum plate is exposed and developed by photolithography or electron beam lithography to form a resist pattern, which is then etched. In this method, a resist is provided and etched to form a recess penetrating to the aluminum surface.

Moreover, in this invention, you may form the oxide film which has a micropore on the aluminum substrate surface by performing the process of following (1)-(4) in this order as said anodizing process (A).
(1) Step of forming an anodic oxide film having micropores on the surface of the aluminum substrate by anodizing the surface of the aluminum substrate (2) Step of partially dissolving the anodic oxide film using acid or alkali (3) A step of growing the micropores in the depth direction by performing anodization treatment (4) A step of removing the anodized film above the inflection point of the cross-sectional shape of the micropores

<Step (1)>
In the step (1), at least one surface of the aluminum substrate is anodized to form an anodized film having micropores on the surface of the aluminum substrate.
Step (1) can be carried out in the same procedure as in the anodizing treatment (a-1).
FIG. 1 is a schematic end view of an aluminum substrate and an anodized film formed on the aluminum substrate.
FIG. 1A shows a state in which the anodized film 14a having the micropores 16a is formed on the surface of the aluminum substrate 12a by the step (1).

<Step (2)>
In step (2), the anodized film formed in step (1) is partially dissolved using acid or alkali.
Here, partially dissolving the anodic oxide film does not completely dissolve the anodic oxide film formed in the step (1), but on the aluminum substrate 12a as shown in FIG. 1A shows that the surface of the anodized film 14a shown in FIG. 1A and the inside of the micropore 16a are partially dissolved so that the anodized film 14b having the micropores 16b remains.
Further, the dissolution amount of the anodized film is preferably 0.001 to 50% by mass of the whole anodized film, more preferably 0.005 to 30% by mass, and 0.01 to 15% by mass. More preferably. When the dissolution amount is in the above range, the irregular part of the surface of the anodic oxide film can be dissolved to increase the regularity of the micropore array, and the anodic oxide film is formed on the bottom part of the micropore. Thus, the starting point of the anodizing treatment performed in the step (3) can be left.

  Step (2) is performed by bringing the anodized film formed on the aluminum substrate into contact with an aqueous acid solution or an aqueous alkali 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.

When an acid aqueous solution is used in step (2), 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 | security. The concentration of the acid aqueous solution is preferably 0.01 to 1 mol / L. The temperature of the acid aqueous solution is preferably 25 to 60 ° C.
When an alkaline aqueous solution is used in step (2), 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 0.01 to 1 mol / L. The temperature of the alkaline aqueous solution is preferably 20 to 35 ° C.
Specifically, for example, 0.5 mol / L, 40 ° C. phosphoric acid aqueous solution, 0.05 mol / L, 30 ° C. sodium hydroxide aqueous solution or 0.05 mol / L, 30 ° C. potassium hydroxide aqueous solution is suitable. Used.
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 still more preferably 15 to 60 minutes.

<Step (3)>
In step (3), the anodization process is again performed on the aluminum substrate in which the anodized film is partially dissolved in step (2) to grow micropores in the depth direction.
As shown in FIG. 1 (C), the oxidation reaction of the aluminum substrate 12a shown in FIG. 1 (B) proceeds by the anodizing treatment in the step (3), and the aluminum substrate 12b is more than the micropores 16b. An anodic oxide film 14c having micropores 16c grown in the depth direction is formed.

A conventionally known method can be used for the anodizing treatment, but it is preferably performed under the same conditions as the above-described anodizing treatment (a-1).
Also, a method of repeatedly turning on and off the current intermittently while keeping the DC voltage constant, and a method of repeatedly turning on and off the current while intermittently changing the DC voltage can be suitably used. According to these methods, fine micropores are generated in the anodic oxide film, which is preferable in that uniformity is improved particularly when sealing treatment is performed by electrodeposition.
In the above-described method of intermittently changing the voltage, it is preferable to decrease the voltage sequentially. As a result, the resistance of the anodized film can be lowered, and can be made uniform when the electrodeposition treatment is performed later.

  The amount of increase in the thickness of the anodized film is preferably from 0.1 to 100 μm, and more preferably from 0.5 to 50 μm. When the increase amount is in the above range, the regularity of the pore arrangement can be further increased.

<Process (4)>
In step (4), the anodized film above the inflection point 30 in the cross-sectional shape of the micropore 16c shown in FIG. As shown in FIG. 1C, the micropore formed by the self-ordering method has a substantially straight tube shape in cross section except for the upper portion of the micropore 16c. In other words, a portion (a deformed portion) 20 having a cross-sectional shape different from that of the remaining portion of the micropore 16c exists in the upper portion of the micropore 16c. In step (4), the anodized film above the inflection point 30 of the cross-sectional shape of the micropore 16c is removed in order to eliminate the deformed portion 20 existing on the upper portion of the micropore 16c.
Here, the inflection point 30 refers to a portion where the shape changes remarkably with respect to the main shape (here, a substantially straight pipe shape) formed by the cross-sectional shape of the micropore 16c. In the cross-sectional shape of 16c, it refers to a portion where the continuity of the shape is lost with respect to the main shape (substantially straight pipe shape).
By removing the anodized film above the inflection point 30 of the cross-sectional shape of the micropore 16c, the entire micropore 16d has a substantially straight tube shape as shown in FIG.

  In the step (4), the inflection point 30 of the cross-sectional shape of the micropore 16c is specified by photographing an FE-SEM of the anodized film 14c after the execution of the step (3) from the cross-sectional direction. The anodic oxide film above may be removed.

However, the deformed portion is generated in the micropore mainly when the anodized film 14a is newly formed on the aluminum substrate 12a as in the step (1). Therefore, in order to remove the anodic oxide film above the inflection point 30 of the cross-sectional shape of the micropore 16c and eliminate the deformed portion 20 above the micropore 16c, the anodic oxide film formed in the step (1) is used. May be removed in step (4).
As will be described later, when the step (3) and the step (4) are repeated twice or more, the deformed portion 30 is eliminated in the anodized film 14d after the step (4) is performed, and the cross-sectional shape of the micropore 16d Since the whole has a substantially straight pipe shape, a new micropore is formed above the micropore formed in step (3) (hereinafter referred to as “step (3 ′)”) following step (4). A deformed part occurs in Therefore, in the step (4) (hereinafter referred to as “step (4 ′)” in this paragraph) to be performed following the step (3 ′), a new upper portion of the micropore formed in the step (3 ′) is added. It is necessary to remove the deformed part. Therefore, in step (4 ′), it is necessary to remove the anodized film above the inflection point of the micropore formed in step (3 ′).

  In the step (4), the process for removing the anodic oxide film above the inflection point of the cross-sectional shape of the micropore 16c may be a polishing process such as mechanical polishing, chemical polishing, and electrolytic polishing. However, as in the step (2), a treatment for dissolving the anodized film using an acid or an alkali is preferable. In this case, as shown in FIG. 1D, an anodic oxide film 14d having a thickness smaller than that of the anodic oxide film 14c shown in FIG. 1C is formed.

  In the step (4), when the anodized film is partially dissolved using acid or alkali, the dissolved amount of the anodized film is not particularly limited, and the total amount of the anodized film is not limited. It is preferable that it is 0.01-30 mass%, and it is more preferable that it is 0.1-15 mass%. When the dissolution amount is in the above range, the irregular portion of the surface arrangement of the anodized film can be dissolved, and the regularity of the arrangement of the micropores can be increased. Moreover, when performing a process (3) and a process (4) repeatedly 2 times or more, the starting point of the anodizing process in the process (3) implemented next can be left.

It is preferable to repeat the step (3) and the step (4) twice because the regularity of the pore arrangement is high, more preferably 3 times or more, and more preferably 4 times or more. Is more preferable.
When the above steps are repeated twice or more, the conditions of each step (3) and step (4) may be the same or different. From the viewpoint of improving the degree of ordering, the step (3) is preferably performed by changing the voltage every time. In this case, it is more preferable to gradually change to a high voltage condition from the viewpoint of improving the degree of ordering.

In the state shown in FIG. 1D, the average pore density is preferably 50 to 1500 / μm ² , and the area ratio occupied by the micropores is preferably 20 to 50%.

  FIG. 2 is a partial cross-sectional view showing a state after the anodizing treatment (A). As shown in FIG. 2, an anodic oxide film 14 having micropores 16 is formed on the surface of the aluminum substrate 12.

[Separation (B)]
The separation treatment (B) is a treatment for removing the aluminum substrate after the anodizing treatment (A) and separating the oxide film from the aluminum substrate.
The aluminum substrate is removed by dissolving the aluminum substrate 12 from the state shown in FIG. FIG. 3 is a partial cross-sectional view showing a state after the separation process (B), and shows a fine structure made of the anodic oxide film 14 having the micropores 16.
Therefore, in the aluminum removal treatment, a treatment solution that does not dissolve alumina but dissolves aluminum is used.

The treatment liquid is not particularly limited as long as it does not dissolve alumina and dissolves aluminum. For example, an aqueous solution such as mercury chloride, bromine / methanol mixture, bromine / ethanol mixture, aqua regia, hydrochloric acid / copper chloride mixture, etc. Etc.
As a density | concentration, 0.01-10 mol / L is preferable and 0.05-5 mol / L is more preferable.
As processing temperature, -10 degreeC-80 degreeC are preferable, and 0 degreeC-60 degreeC is preferable.

  The separation process (B) is performed by contacting with the above-described processing liquid. 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, and more preferably 1 minute to 3 hours.

  The thickness of the anodized film after the separation treatment (B) is preferably 1 to 1000 μm, and more preferably 10 to 500 μm.

  After the separation treatment (B), the anodized film 14 is preferably washed with water before the penetration treatment (C) described later. In order to suppress changes in the pore diameter of the micropores 16 due to hydration, the water washing treatment is preferably performed at 30 ° C. or lower.

[Penetration treatment (C)]
The penetration treatment (C) is a treatment for penetrating the micropores of the oxide film separated by the separation treatment (B).
In the penetration process (C), the anodic oxide film 14 having the micropores 16 shown in FIG. 3 is immersed in an acid aqueous solution or an alkali aqueous solution to partially dissolve the anodic oxide film 14. Thereby, the anodic oxide film 14 at the bottom of the micropore 16 is removed, and the micropore 16 penetrates (a micropore through hole 18 is formed). FIG. 4 is a partial cross-sectional perspective view showing a state after the penetration treatment (C), and shows a microstructure formed of the anodized film 14 having the micropore through-holes 18.
In FIG. 4, all the micropores existing in the anodic oxide film 14 are micropore through holes 18, but all the micropores existing in the anodic oxide film do not penetrate by the penetration treatment (C). Also good. However, it is preferable that 70% of the micropores existing in the anodized film penetrate through the penetration treatment (C).

When an acid aqueous solution is used for the penetration treatment (C), 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. The concentration of the acid aqueous solution is preferably 1 to 10% by mass. The temperature of the acid aqueous solution is preferably 25 to 40 ° C.
When an aqueous alkali solution is used for the penetration treatment (C), 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.
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 120 minutes, more preferably 10 to 90 minutes, and still more preferably 15 to 60 minutes.

  The film thickness of the anodized film after the penetration treatment (C) is preferably 1-1000 μm, and more preferably 10-500 μm.

  After the penetration treatment (C), the anodic oxide film 14 is washed with water. In order to suppress a change in the pore diameter of the micropore through hole 18 due to hydration, the water washing treatment is preferably performed at 30 ° C. or lower.

In the present invention, the separation process (B) and the penetration process (C) described above may be a method of performing these processes simultaneously.
Specifically, the portion below the anodized film 14 shown in FIG. 2, that is, the portion on the aluminum substrate 12 side in the anodized film 14 is physically removed using a cutting process using a laser or the like or various polishing processes. A method of forming the anodic oxide film 14 having the micropore through holes 18 shown in FIG. 4 is preferably exemplified.

[Heat treatment (D)]
The heat treatment (D) is a treatment in which the oxide film that has penetrated the micropores by the penetration treatment (C) is heated at a temperature of 100 ° C. or higher while applying a load of 0.5 g / cm ² or more.
By performing such heat treatment, the resulting porous alumina membrane filter using the microstructure of the present invention is excellent in filtration flow rate and flatness.
This is because the residual stress in the oxide film generated by performing the above-described processes (particularly, the separation process (B)) is relaxed by heating, and the film shape is reconstructed by the load. This is probably because a fine oxide film microstructure was formed.

Here, the load is preferably 1.0 g / cm ² or more, more preferably 1.5 g / cm ² or more, still more preferably 5.0 g / cm ² or more. It is particularly preferably 0 g / cm ² or more.
The upper limit of the load is not particularly limited because it depends on the thickness of the oxide film, but is preferably 1000 g / cm ² or less from the viewpoint of preventing damage to the film itself.

In the present invention, the method of applying the load is preferably a method in which an oxide film is sandwiched and pressed by a flat material that does not change its shape at the temperature in the heat treatment.
By applying a load by this method, the obtained porous alumina membrane filter using the microstructure of the present invention has a more excellent flatness. This is considered to be because the reconstruction of the film shape due to the load described above easily proceeds.
Here, specific examples of the flat material that does not change its shape at the temperature in the heat treatment include a stainless steel plate, a titanium plate, a nickel plate, and a magnesium plate.

On the other hand, the heating temperature (heating temperature) is preferably 200 ° C. or higher, more preferably 250 ° C. or higher, and further preferably 300 ° C. or higher.
However, if the heating temperature is too high, the thermal deformation property of the oxide film (alumina) itself is affected, and the flatness may be lowered. Therefore, the heating temperature is preferably 1500 ° C. or less, and 1000 ° C. or less. It is more preferable that the temperature is 800 ° C. or lower.

The heating time (heating time) is preferably 1 minute or more, more preferably 10 minutes or more, and further preferably 30 minutes or more. When the heating time is 1 minute or longer, the residual stress in the oxide film described above is sufficiently relaxed, and the flatness of the porous alumina membrane filter using the resulting fine structure becomes better.
The upper limit of the heating time is preferably 10 hours or less, more preferably 7 hours or less, and even more preferably 5 hours or less. Heating for more than 10 hours is not preferable because it does not contribute to improvement of the flatness of the porous alumina membrane filter using the resulting fine structure, and damage to the oxide film itself may occur.

In this invention, the aspect which cools the oxide film after the said heating rapidly is preferable.
Specific examples of the cooling method include a method in which the heated oxide film (fine structure) is directly poured into water or the like.

<Protection treatment>
In the present invention, after the penetration treatment (C) and before the heat treatment (D), it is preferable to perform a protection treatment for forming a protective film that prevents hydration on the surface of the oxide film.
In the protection treatment, the porous alumina membrane filter composed of the anodic oxide film 14 having the micropore through-hole 18 shown in FIG. 4 is covered over the entire surface of the anodic oxide film 14 including the inside of the micropore through-hole 18. A protective film that prevents hydration of the oxide film is formed.

  Examples of the protective film include an inorganic protective film containing at least one selected from the group consisting of Zr element and Si element, or an organic protective film containing a water-insoluble polymer.

(Inorganic protective film)
The formation of the protective film containing the Zr element is not particularly limited, but, for example, a method in which the protective film is directly immersed in an aqueous solution in which a zirconium compound is dissolved is generally used. From the viewpoint of the robustness / stability of the protective film It is preferable to use an aqueous solution in which a phosphorus compound is dissolved together.

  Zirconium compounds include zirconium, fluoride fluoride, sodium fluoride zirconate, calcium fluoride zirconate, zirconium fluoride, zirconium chloride, zirconium oxychloride, zirconium oxynitrate, zirconium sulfate, zirconium ethoxide, zirconium propoxide, zirconium Butoxide, zirconium acetylacetonate, tetrachlorobis (tetrahydrofuran) zirconium, bis (methylcyclopentadienyl) zirconium dichloride, dicyclopentadienylzirconium dichloride, ethylenebis (indenyl) zirconium (IV) dichloride, etc. can be used. Sodium fluorinated zirconate is preferred. Moreover, as a density | concentration, 0.01-10 wt% is preferable from a viewpoint of the uniformity of a protective film thickness, and 0.05-5 wt% is more preferable.

  As the phosphorus compound, phosphoric acid, sodium phosphate, calcium phosphate, sodium hydrogen phosphate, calcium hydrogen phosphate and the like can be used, and sodium hydrogen phosphate is particularly preferable. Moreover, as a density | concentration, 0.1-20 wt% is preferable from a viewpoint of the uniformity of a protective film thickness, and 0.5-10 wt% is more preferable.

Moreover, since the function which prevents the hydration of the anodic oxide film of the protective film formed improves, it is preferable to include tannic acid in the aqueous solution in which the zirconium compound is dissolved in the immersion treatment. In this case, the concentration of tannic acid in the aqueous solution is preferably 0.05 to 10 wt%, and more preferably 0.1 to 5 wt%.
Moreover, as processing temperature, 0-120 degreeC is preferable and 20-100 degreeC is more preferable.

The formation of the protective film containing Si element is not particularly limited, but, for example, a method in which the protective film is directly immersed in an aqueous solution in which an alkali metal silicate is dissolved is generally used.
The aqueous solution of the alkali metal silicate is composed of a ratio of silicon oxide SiO ₂ and alkali metal oxide M ₂ O (generally expressed as a molar ratio of [SiO ₂ ] / [M ₂ O]) and concentration. It is possible to adjust the protective film thickness. Here, as M, sodium and potassium are particularly preferably used.
As a molar ratio, [SiO ₂ ] / [M ₂ O] is preferably 0.1 to 5.0, and more preferably 0.5 to 3.0. The content of SiO _2, preferably from 0.1 to 20 mass%, 0.5 to 10 mass% is more preferable.

(Organic protective film)
As the organic protective film, a method in which only the solvent is volatilized by heat treatment after being directly immersed in an organic solvent in which a water-insoluble polymer is dissolved is preferable.

Examples of the water-insoluble polymer include polyvinylidene chloride, poly (meth) acrylonitrile, polysulfone, polyvinyl chloride, polyethylene, polycarbonate, polystyrene, polyamide, cellophane and the like.
Examples of the organic solvent include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxyethane. , Methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ-butyrolactone, toluene, and the like. As a density | concentration, 0.1-50 wt% is preferable and 1-30 wt% is more preferable.
Moreover, as heating temperature at the time of solvent volatilization, 30-300 degreeC is preferable and 50-200 degreeC is more preferable.

  After the protective film formation treatment, the thickness of the protective film is preferably 1 to 50 nm, and more preferably 5 to 25 nm.

A fine structure (hereinafter referred to as “the fine structure of the present invention”) obtained by the method for producing a fine structure of the present invention, which is subjected to each treatment described above, and a porous alumina membrane filter (hereinafter referred to as “the present invention”) using the same. The porous alumina membrane filter ”) has good flatness.
In the present invention, the smoothness is evaluated by “warp”, but this warp may be a warp in the length direction of the fine structure (porous alumina membrane filter) or a warp in the width direction. Also good.
Here, “warp” can be measured by a surface roughness meter or a micromap meter, but a linear unevenness (μm) having a width of 10 mm was measured at an arbitrary position of 10 or more on the surface of the oxide film. The average value calculated the difference between the minimum and maximum values.

In the microstructure of the present invention and the porous alumina membrane filter of the present invention, the warpage per 10 mm width on the surface of the oxide film is 20 μm or less, and the smoothness is extremely excellent.
In addition, when the load in the heat treatment (D) is 1.0 g / cm ² or more, the heating temperature is 200 ° C. or more, and the heating time is 1 minute or more, the warpage per 10 mm width is 15 μm or less, and the smoothness Is better.
Furthermore, when the load in the heat treatment (D) is 1.5 g / cm ² or more, the heating temperature is 250 ° C. or more, and the heating time is 10 minutes or more, the warpage per 10 mm width is 10 μm or less, and the smoothness Is even better.

The microstructure of the present invention and the porous alumina membrane filter of the present invention are related to the micropores present in the oxide film, and the pore diameter dispersion is preferably within 3% of the average diameter in the range of 1 μm ^2. Is more preferable. As described above, the average pore diameter and the dispersion can be obtained by the following equations, respectively.
When the pore diameter dispersion is within 3% of the average diameter, the pressure resistance of the porous alumina membrane filter using the fine structure is improved, and the filtration flow rate becomes better.
Average diameter: μ _x = (1 / n) ΣXi
Dispersion: σ ² = (1 / n) (ΣXi ² ) −μ _x ²
Dispersion / average diameter = σ / μ _x ≦ 0.03
Here, Xi is the pore diameter of one micropore measured in the range of 1 μm ² .

The microstructure according to the present invention and the porous alumina membrane filter according to the present invention preferably have a degree of ordering defined by the following formula (1) of 50% or more and 70% or more with respect to the micropores present in the oxide film. It is more preferable that it is 80% or more.
When the degree of ordering of the micropores is 50% or more, the pressure resistance of the porous alumina membrane filter using the fine structure is improved, and the filtration flow rate becomes better.

  Ordering degree (%) = B / A × 100 (1)

  In the above formula (1), A represents the total number of micropores in the measurement range. B is centered on the center of gravity of one micropore, and when a circle with the shortest radius inscribed in the edge of another micropore is drawn, the center of gravity of the micropore other than the one micropore is placed inside the circle. This represents the number in the measurement range of the one micropore to be included.

Here, FIG. 5 is an explanatory diagram of a method for calculating the degree of ordering of pores. The above formula (1) will be described more specifically with reference to FIG.
The micropore 1 shown in FIG. 5A draws a circle 3 (inscribed in the micropore 2) having the shortest radius and centering on the center of gravity of the micropore 1 and inscribed in the edge of another micropore. In this case, the center of the circle 3 includes six centroids of micropores other than the micropore 1. Therefore, the micropore 1 is included in B.
The micropore 4 shown in FIG. 5 (B) draws a circle 6 (inscribed in the micropore 5) having the shortest radius and centering on the center of gravity of the micropore 4 and inscribed in the edge of the other micropore. In this case, the center of gravity of the micropores other than the micropores 4 is included inside the circle 6. Therefore, the micropore 4 is not included in B.
In addition, the micropore 7 shown in FIG. 5B is centered on the center of gravity of the micropore 7 and has the shortest radius 9 inscribed in the edge of another micropore (inscribed in the micropore 8). Is drawn, the circle 9 includes seven centroids of micropores other than the micropore 7. Therefore, the micropore 7 is not included in B.

  As described above, the fine structure of the present invention is suitable as a porous alumina membrane filter due to the flatness of the oxide film surface, but the micropores of the oxide film carry organic compounds, inorganic compounds, metal fine particles, and the like. You can also.

  The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these.

Example 1
1. Production of microstructure (porous alumina membrane filter) (1) Electropolishing treatment Anodizing a high purity aluminum substrate (manufactured by Sumitomo Light Metal Co., Ltd., purity 99.99 mass%, thickness 0.4 mm) in an area of 10 cm square After being cut as possible, an electropolishing treatment was performed using an electropolishing liquid having the following composition under conditions of a voltage of 25 V, a liquid temperature of 65 ° C., and a liquid flow rate of 3.0 m / min.
The cathode was a carbon electrode, and GP0110-30R (manufactured by Takasago Seisakusho) was used as the power source. The flow rate of the electrolytic solution was measured using a vortex flow monitor FLM22-10PCW (manufactured by AS ONE).

<Electrolytic polishing liquid composition>
-660 mL of 85% phosphoric acid (reagent manufactured by Wako Pure Chemical Industries, Ltd.)
・ Pure water 160mL
・ Sulfuric acid 150mL
・ Ethylene glycol 30mL

(2) Anodizing treatment The electropolished sample obtained above was subjected to 0.30 mol / L sulfuric acid electrolytic solution for 1 hour under conditions of a voltage of 25 V, a liquid temperature of 15 ° C., and a liquid flow rate of 3.0 m / min. Anodized. Further, the anodized sample was immersed in a mixed solution of 0.5 mol / L phosphoric acid for 20 minutes at 40 ° C. for film removal.
After these treatments were repeated four times in this order, re-anodization treatment was performed for 5 hours with an electrolyte of 0.30 mol / L sulfuric acid under conditions of a voltage of 25 V, a liquid temperature of 15 ° C., and a liquid flow rate of 3.0 m / min. Further, the micropores 16 are formed in a straight tubular and honeycomb shape on the surface of the aluminum substrate 12 by performing a film removal treatment by dipping for 20 minutes at 40 ° C. using a mixed aqueous solution of 0.5 mol / L phosphoric acid. Arranged anodic oxide films 14 were formed (see FIG. 1D and FIG. 2).

  In both the anodic oxidation treatment and the re-anodic oxidation treatment, the cathode was a stainless electrode, and the power supply was GP0110-30R (manufactured by Takasago Seisakusho). In addition, NeoCool BD36 (manufactured by Yamato Kagaku Co.) was used as the cooling device, and Pear Stirrer PS-100 (manufactured by EYELA) was used as the stirring and heating device. The flow rate of the electrolyte was measured using a vortex flow monitor FLM22-10PCW (manufactured by AS ONE).

(3) Separation treatment The sample after the anodization treatment obtained above is immersed in a 2 mol / L mercury chloride aqueous solution at 20 ° C. for 3 hours to dissolve and remove the aluminum substrate 12, thereby removing micropores. The sample which consists of the anodic oxide film 14 which has 16 was produced (refer FIG. 3).

(4) Penetration treatment The sample after the separation treatment obtained above is immersed in 30% at 30 ° C. using 5% by mass phosphoric acid to thereby remove the anodic oxide film 12 having the micropore through-holes 16. (See FIG. 4).

(5) Heat treatment The sample after the penetration treatment obtained above was sandwiched between stainless plates, and subjected to heat treatment at a temperature of 400 ° C. for 1 hour with a load of 2.0 g / cm ² applied. The microstructure sample of Example 1 was produced.

(Example 2)
A microstructure sample of Example 2 was produced in the same manner as in Example 1 except that the heat treatment load was 10.0 g / cm ² .

(Example 3)
A microstructure sample of Example 3 was produced in the same manner as in Example 1 except that the heat treatment load was 0.6 g / cm ² .

Example 4
The microstructure of Example 4 was obtained in the same manner as in Example 1 except that the electrolyte used in the micropore formation process by anodization was an electrolyte of 0.50 mol / L oxalic acid and the voltage was 40V. A body sample was prepared.

(Example 5)
The electrolyte used in the micropore formation process by anodizing is 0.30 mol / L phosphoric acid, the voltage is 195 V, and the concentration of the phosphoric acid mixed aqueous solution used in the film removal process is 1.0 mol / L. A microstructure sample of Example 5 was produced in the same manner as in Example 1 except that.

(Example 6)
A microstructure sample of Example 6 was produced in the same manner as in Example 1 except that the heat treatment time was 30 minutes.

(Example 7)
A microstructure sample of Example 7 was produced in the same manner as in Example 1 except that the heat treatment time was 10 hours.

(Example 8)
A microstructure sample of Example 8 was produced in the same manner as in Example 1 except that the heat treatment temperature was 100 ° C.

(Comparative Example 1)
A microstructure sample of Comparative Example 1 was produced in the same manner as in Example 1 except that the heat treatment was omitted.

(Comparative Example 2)
A microstructure sample of Comparative Example 2 was produced in the same manner as in Example 4 except that the heat treatment was omitted.

(Comparative Example 3)
A microstructure sample of Comparative Example 3 was produced in the same manner as in Example 5 except that the heat treatment was omitted.

(Comparative Example 4)
A microstructure sample of Comparative Example 4 was produced in the same manner as in Example 1 except that the temperature of the heat treatment was 150 ° C., the heating time was 5 minutes, and the load was 0.1 g / cm ² .

(Comparative Example 5)
A microstructure sample of Comparative Example 5 was produced in the same manner as in Example 1 except that the temperature of the heat treatment was 50 ° C., the heating time was 5 minutes, and the load was 0.5 g / cm ² .

2. Shape analysis of microstructure (porous alumina membrane filter) For the microstructure samples prepared in Examples 1-8 and Comparative Examples 1-5, select 10 arbitrary locations on the anodized film surface, and for each location, The amount of warpage per 10 mm width was measured using a surface roughness meter Surfcom (Aclaytech), and the average value was calculated. The results are shown in Table 1.

Moreover, the surface diameters (magnification 20000 times) of the microstructure samples prepared in Examples 1 to 8 and Comparative Examples 1 to 5 were photographed with FE-SEM, and the average diameter of the micropores existing in the 1 μm × 1 μm visual field. And the dispersion of the pore diameter was determined by the following formula, and the dispersion / average diameter was determined. The results are shown in Table 1.
Average diameter: μ _x = (1 / n) ΣXi
Dispersion: σ ² = (1 / n) (ΣXi ² ) −μ _x ²
Dispersion / average diameter = σ / μ _x
Here, Xi is the pore diameter of one micropore measured in the range of 1 μm ² .

Furthermore, the degree of ordering defined by the following formula (1) was determined using 300 arbitrary micropores. As a result, the degree of ordering was 90%.
Ordering degree (%) = B / A × 100 (1)
In the above formula (1), A represents the total number of micropores in the measurement range. B is centered on the center of gravity of one micropore, and when a circle with the shortest radius inscribed in the edge of another micropore is drawn, the center of gravity of the micropore other than the one micropore is placed inside the circle. This represents the number in the measurement range of the one micropore to be included.

3. Filtration characteristics as a porous alumina membrane filter The filtration characteristics as a porous alumina membrane filter of the microstructure samples prepared in Examples 1 to 8 and Comparative Examples 1 to 5 were evaluated.
Specifically, the filtration flow rate of 20 ° C. pure water with a driving pressure of 1.0 kgf · cm cm ⁻² and a filtration time of 0 to 100 minutes was determined. It can be said that the larger the value, the better the filtering characteristics as a filter. The results are shown in Table 1.

As shown in Table 1, all of the microstructure samples of Examples 1 to 8 produced by performing heat treatment under a predetermined load are excellent in flatness and filtered as porous alumina membrane filters. It was found that the flow rate was as good as 100 ml / cm ² or more.
On the other hand, the microstructure sample of Comparative Examples 1 to 3 produced without heat treatment and Comparative Example 4 produced by heat treatment in a state of less than a predetermined load and a state of less than a predetermined temperature It was found that all of the microstructure samples of Comparative Example 5 produced by performing the heat treatment in were warped and inferior in flatness.

FIG. 1 is a schematic end view of an aluminum substrate and an anodized film formed on the aluminum substrate. FIG. 2 is a partial cross-sectional view showing a state after the anodizing treatment (A). FIG. 3 is a partial cross-sectional view showing a state after the separation process (B). FIG. 4 is a partial cross-sectional view showing a state after the penetration process (C). FIG. 5 is an explanatory diagram of a method for calculating the degree of ordering of pores.

Explanation of symbols

1, 2, 4, 5, 7, 8 Micropore 3, 6, 9 Circle 12, 12a, 12b, Aluminum substrate 14, 14a, 14b, 14c, 14d Anodized film 16, 16a, 16b, 16c, 16d Micropore 18: Micropore through hole 20 Deformed portion 30 Inflection point

Claims (5)

Anodizing to form an oxide film having micropores by anodizing an aluminum substrate;
A separation treatment for removing the aluminum substrate after the anodizing treatment and separating the oxide film from the aluminum substrate;
A penetration treatment for penetrating the micropores of the oxide film separated by the separation treatment;
A heat treatment in which the oxide film penetrating the micropores by the penetration treatment is heated at a temperature of 100 ° C. or higher while applying a load of 0.5 g / cm ² or more;
A method for producing a fine structure, in which a fine structure having micropores on the surface is obtained by applying at least in this order.   The manufacturing method of the fine structure according to claim 1, wherein the method of applying the load in the heat treatment is a method of sandwiching and pressing the oxide film with a flat material that does not change in shape at the temperature in the heat treatment. Method.   A fine structure obtained by the method for producing a fine structure according to claim 1.   The microstructure according to claim 3, wherein the pore diameter dispersion of the micropores is within 3% of the average diameter, and the warpage per 10 mm width is 20 μm or less.   A porous alumina membrane filter using the fine structure according to claim 3 or 4.

Images