KR20080038385A - Porous polymer membrane, method for producing same, and method for manufacturing stamper used for production of same - Google Patents

Abstract

Pores of an anodized porous alumina having a porous surface structure are filled with a material and then the anodized porous alumina is dissolved and removed, thereby forming a stamper which is made of the material and has a reverse structure of the surface structure of the alumina. By transferring the reverse structure of the stamper to a polymer, there is produced a porous polymer membrane having the surface structure of the alumina. Consequently, a large-sized porous polymer membrane having a surface structure, wherein pores of a uniform size are formed orthogonal to the membrane surface, can be produced without requiring a complicated process.

Description

POROUS POLYMER MEMBRANE, METHOD FOR PRODUCING SAME, AND METHOD FOR MANUFACTURING STAMPER USED FOR PRODUCTION OF SAME

The present invention relates to a porous polymer membrane and a method for manufacturing the same, and in particular, a method for producing a porous polymer membrane in which a fine concavo-convex structure, for example, a porous structure or a hole array structure, is transferred to a surface using a stamper, and manufactured by the method. The present invention relates to a porous polymer membrane having a concave-convex structure, for example, a porous structure or a hole array structure, and a method for producing a stamper used in the production of the porous polymer membrane.

This application claims priority based on Patent Application No. 2005-245702 filed with Japan Patent Office on August 26, 2005 and Patent Application 2006-059103 filed with Japan Patent Office on March 6, 2006 , Use the content here.

BACKGROUND ART Polymer films having fine uneven structures on the surface of sub-micron to nanometer scales are expected to be applied to various fields such as water- and oil-repellent films and anti-reflection films. Until now, various methods have been studied on the method of forming a fine concavo-convex pattern on the surface of the polymer film. Among them, the concave-convex pattern corresponding to the geometrical structure of the mold by mechanically pressing a mold having a fine concavo-convex pattern on the surface of the polymer. Nano imprinting method that can form a on the surface of a sample attracts attention (for example, nonpatent literature 1). According to this method, since it is possible to form a large-area regular structure with a high throughput, it can be expected as a method for manufacturing various nanodevices. However, since electron beam lithography is usually used for the production of molds used for nanoimprint, these methods have a problem in that it is difficult to produce large uneven patterns of 100 nm or less in large area. . Non-Patent Document 1: S. Y. Chou, P. R. Krauss, and J. Renstrom, Science, 272, 85 (1996)

Disclosure of the Invention

Problems to be Solved by the Invention

The present invention provides a porous material in which pores are arranged in a self-organizing structure in order to solve the above problems when producing a polymer film having a concave-convex structure, for example, a porous structure or a hole array structure, on the surface of which various applications are expected. For example, the result of earnestly examining about the means of easily obtaining a porous polymer membrane using the stamper which has the inverted structure of the said hole array structure manufactured using the hole array structure which anodized porous alumina has as a template was made.

SUMMARY OF THE INVENTION An object of the present invention is to provide a porous structure in which pores of uniform size are orthogonal to the membrane surface, i.e., a porous polymer membrane having a hole array structure on its surface, without having to go through a complicated process, and a method thereof, and a method thereof. It is to provide a porous polymer membrane produced by. Moreover, the manufacturing method of the stamper suitable for use for the manufacture, especially the manufacturing method of the metal stamper which has a high aspect ratio uneven structure (uneven | corrugated pattern), and the polymer film which has a hole array structure through which each pore penetrated (So-called through-hole membrane).

Means to solve the problem

In order to achieve the above object, the method for producing a porous polymer membrane according to the present invention is made of the material by filling the material in the pores of the anodic oxidation porous alumina having a porous surface structure, and by dissolving and removing the anodic oxidation porous alumina And producing a stamper having an inverted structure of the surface structure and transferring the inverted structure of the stamper to a polymer, thereby producing a polymer film having the surface structure. That is, a porous polymer membrane having the above-described surface structure of anodized porous alumina is obtained by using a stamper produced using anodized porous alumina as a template and transferring the unevenness of the surface of the stamper to the polymer membrane.

In order to obtain the stamper used in the present invention, a metal, a metal oxide, a semiconductor, or the like is filled in the pores of the anodized porous alumina, and then the mold, that is, the alumina is dissolved and removed. As a material of the stamper thus produced, that is, a material to be filled in the pores of the anodized porous alumina and the surface thereof, metal is preferable, and nickel, gold and platinum are more preferable.

In the method according to the present invention, a stamper manufactured by using anodized porous alumina having a pore whose pore size is continuously changed by repeatedly performing anodization and pore size expansion may be used. In this way, when a porous alumina having a pore whose pore size is continuously changed by anodic oxidation and pore size expansion treatment is used as a mold, it is possible to produce a stamper having a continuously changed protruding diameter in the pore depth direction. Therefore, it is possible to fabricate the porous surface structure, that is, the hole array structure, in which the pore diameter is changed linearly or curvedly on the surface of the polymer membrane. The hole array structure on the surface of the polymer membrane formed at this time can be controlled by changing the production conditions of the anodized porous alumina serving as a template during stamper fabrication.

Moreover, various conditions can be employ | adopted as the manufacturing conditions of a stamper, especially the manufacturing conditions of the anodic oxidation porous alumina as a mold for stamper manufacture. For example, a stamper produced by using anodic oxidation porous alumina as a template using oxalic acid as an electrolyte, or sulfuric acid as an electrolyte, and anodized using 10 V to 30 V in chemical conversion voltage. You may use the stamper which made the porous alumina as a template, or the stamper which used phosphoric acid as the electrolyte solution and made the anodized porous alumina produced by chemical conversion voltage 180V-200V as a template.

In addition, in the manufacture of a stamper, the regular pore arrangement of the porous alumina pore bottom obtained by performing anodization for a long time at a constant voltage under appropriate conditions and dissolving and removing the bare metal part and the bottom of the film of the sample is performed. By using this, a stamper in which protrusions are regularly arranged can be obtained. By using the stamper thus produced, it is possible to form a hole array structure in which pores of uniform size are regularly arranged on the surface of the polymer film.

In addition, even after anodic oxidation for a long time at a constant voltage, by using the anodic oxidation porous alumina produced by removing the oxide film and then anodizing under the same conditions as a template, a stamper having a high protrusion arrangement regularity can be obtained. Can be. Using such a stamper, it is also possible to obtain a porous polymer membrane having a hole array structure in which pores are arranged regularly.

In addition, prior to the anodic oxidation, a fine pit may be formed on the surface of aluminum, and a stamper may be produced using anodic oxidation porous alumina produced as a starting point of pore generation during anodization as a template. According to this method, it is possible to produce anodized porous alumina having an arbitrary arrangement. Using the stamper produced by using this as a mold, a porous polymer membrane having a hole array structure having an arbitrary pore array on its surface can be obtained.

In addition, by using a stamper made of anodized porous alumina in which the pore wall expansion time is controlled and the proportion of the pore wall portion is controlled as a template, a polymer membrane having a hole array structure having a small proportion of the pore wall portion at the surface side can be obtained. You can also get For example, the ratio of the pore wall portion on the surface side of the hole array structure formed on the surface of the polymer membrane (that is, the sum of the area of the upper surface of the pore wall to the area of the region surrounded by the outer edge of the polymer membrane) is 30% or less, It is possible to produce a porous polymer membrane which is preferably 20% or less, more preferably 10% or less, even more preferably 5% or less. The pore cross-sectional shape at the surface side of the hole array structure formed on the surface of the polymer film may be triangular, square or hexagonal, for example, by enlarging the pore diameter to the limit. Such a porous polymer membrane is effective because the porosity on the surface of a sample increases, so that the proportion of the flat pore wall portion is small, thereby improving antireflection characteristics and water / oil repellent characteristics.

By using the stamper produced by such a method, a porous polymer membrane having a hole array structure on its surface can be produced by a method of transferring the inverted structure of the various stampers. For example, a thermal imprint method using a thermoplastic resin as a polymer material for transferring the reverse structure of the stamper, or an optical imprint using a photocuring resin (particularly an ultraviolet curable resin) as a polymer material for transferring the reverse structure of the stamper. In addition to the method, a solution in which a polymer is dissolved is cast on a stamper, the solvent is dried, the stamper is peeled off, and a method such as a casting method of a polymer solution in which the reverse structure of the stamper is transferred to the polymer, It is possible to produce the same hole array structure on the surface of the polymer membrane as the anodized porous alumina used as the starting structure.

Moreover, this invention also provides the manufacturing method of the metal stamper of especially high aspect ratio suitable for use for manufacture of said porous polymer membrane. That is, the method for producing a stamper according to the present invention is a method for producing a stamper whose material is metal, and when the metal is filled by electrolytic deposition into the pores of the anodic oxide porous alumina as a mold, the surface of the mold An ion-beam sputter apparatus is used to coat the metal and provide a conductive layer. In this way, in particular, it is possible to easily manufacture a metal stamper having a high aspect ratio.

In the manufacturing method of this stamper, when providing a conductive layer to the mold surface, it is preferable to perform ion beam sputtering on the conditions which the vacuum degree of the sample chamber of an ion beam sputtering apparatus is 3 * 10 <^-4> Pa-1 * 10 <^-5> Pa. . By thus optimizing the sputtering conditions, a preferred conductive layer is reliably provided.

By transferring the inverted structure of the stamper produced by this method to a polymer, it is possible to easily produce a porous polymer membrane having respective pores of a shape corresponding to a stamper having a high aspect ratio.

The present invention also provides a method for producing a porous polymer membrane, in particular a through hole membrane. In other words, the method for producing a porous polymer membrane according to the present invention comprises filling the material in pores of the anodized porous alumina having a porous surface structure and dissolving and removing the anodized porous alumina. A stamper having a structure is fabricated, and the stamper is provided on a layer of a polymer and a base substrate, and the stamper until the convex tip of the inverted structure reaches or contacts the surface of the base substrate via the polymer. The pores were penetrated by applying a load to the inverted structure to transfer the polymer to produce a polymer film having the surface structure, and peeling the polymer film from the base substrate (including dissolving and removing the base substrate). Membrane having a modified surface structure (hole array structure) It is prepared. By this method, in particular, the through-hole membrane can be easily manufactured.

In the method for producing a porous polymer membrane having a hole array structure in which each of the pores is penetrated, at least as a base substrate, a substrate made of a polymer, for example, a substrate in which a polymer substrate or a solution in which a polymer is dissolved is cast, glass, or the like. The base substrate which superposed | polymerized the monomer on the board | substrate and formed the polymer film on the surface, and the multilayer base substrate etc. which the outermost surface consists of a polymer film may be used. Moreover, at least the surface may use the base substrate which consists of thermoplastic resins, and you may make it load a stamper under a heating condition.

The present invention also provides a porous polymer membrane prepared using the above method.

Effects of the Invention

According to the porous polymer membrane and the manufacturing method thereof according to the present invention, a porous polymer membrane having a hole array structure in which a large number of pores orthogonal to the membrane surface are uniformly and largely arranged in a uniform and fine size is complicated. It is possible to manufacture simply and efficiently without going through one process.

According to the present invention, a porous polymer membrane having a hole array structure in which each pore is penetrated can be easily manufactured.

Moreover, according to this invention, the high aspect ratio stamper suitable for use in manufacture of these porous polymer membranes can also be provided.

1 is a process flowchart showing an example of a manufacturing process of a stamper.

Fig. 2 is a process flow diagram showing an example of a manufacturing process of a stamper made of anodized porous alumina having pores whose pore size is continuously changed.

3 is a process flowchart showing an example of a process for producing a porous polymer membrane by thermal imprint.

4 is a process flowchart showing an example of a process for producing a porous polymer membrane by photoimprint.

Fig. 5 is a process flow diagram showing an example of the manufacturing process of the porous polymer membrane by the solution cast on the stamper.

6 is a process flowchart showing an example of a through hole membrane fabrication process.

FIG. 7: is a figure which shows the observation result by the electron microscope of the surface of the polymethyl methacrylate porous film produced by thermal imprint (pore period 200nm).

FIG. 8: is a figure which shows the observation result by the electron microscope of the surface of the acrylic resin porous film produced by optical imprint (pore period 200nm).

FIG. 9 is a diagram showing an observation result by an electron microscope of a cross section of an acrylic resin porous membrane produced by optical imprint (pore cycle 200 nm).

It is a figure which shows the observation result by the electron microscope of the surface of the fluororesin porous membrane produced by the casting method (pore period 500 nm).

FIG. 11 is a view showing an observation result by an electron microscope of a high aspect ratio metal stamper prepared in Example 5. FIG.

12 is a view showing an observation result by an electron microscope of the through-hole membrane prepared in Example 6.

<Description of the code>

1: aluminum

2: anodized porous alumina

3: filling material layer

4: stamper

5: Anodized porous alumina with pores with varying pore size continuously

6: thermoplastic resin

7: substrate

8: porous polymer membrane

9: photocurable monomer

10: polymer membrane after polymerization

11: dissolved polymer solution

12: polymer membrane after solvent drying

21: substrate

22: polymer layer

23: base substrate

24: photocurable resin layer

25: stamper

26: through hole membrane

31: stamper

32: through hole membrane

Implement the invention  Best form for

EMBODIMENT OF THE INVENTION Below, the porous polymer membrane which concerns on this invention, its manufacturing method, and the manufacturing method of the stamper used for the manufacture are demonstrated in detail, referring drawings.

Fig. 1 shows an example of a method for producing a stamper made of anodized porous alumina used in the present invention as a template. After anodizing aluminum (1) in an acidic bath to produce anodized porous alumina (2), this is used as a mold to fill a material into the pores and the surface thereof (material filling layer (3)). . Thereafter, only the aluminum and alumina portions are selectively dissolved away. As a substance to be filled, a metal, a metal oxide, a semiconductor, etc. can be used. For example, a metal stamper 4 can be produced by forming a conductive thin film on the surface of the anodized porous alumina 2 by a sputtering method or a vapor deposition method, and then electrolytically depositing a metal using this as an electrode. .

In the present invention, as shown in Fig. 2, the anodic oxidation porous alumina 5 having pores whose pore size is continuously changed linearly or curvedly by combining the anodic oxidation and the enlarging process of the pores by etching. And using this as a mold, a stamper 4 having a desired projection shape can be obtained.

Various imprint methods can be used for the production of a porous polymer membrane having a hole array structure in which pores of uniform pore diameter are arranged on the surface. 3 shows a method for producing the porous polymer membrane 8 by thermal imprinting. A thermoplastic resin 6 is provided on the substrate 7 as a polymer material for transferring the structure of the stamper 4, and the stamper 4 is pressed against the thermoplastic resin 6 under a temperature condition equal to or higher than the glass transition point. Then, by cooling to a temperature below the glass transition point and peeling the stamper 4, it is possible to obtain the porous polymer membrane 8 to which the fine concavo-convex structure on the surface of the stamper has been transferred.

In addition, as shown in FIG. 4, after the ultraviolet curable (photocurable) monomer 9 is dripped on the board | substrate 7, as a ultraviolet curable resin as a polymeric material which transfers the structure of the stamper 4, the stamper 4 is carried out. ) Is irradiated with ultraviolet light, and the post-curing stamper 4 is peeled off to obtain the polymer film 10 after polymerization, so that the optical imprint method for transferring the structure of the stamper 4 can also be used.

In addition to these imprint methods, as shown in Fig. 5, the polymer solution 11 dissolved in a suitable solvent is cast on the stamper 4, and after the solvent is dried (polymer membrane 12 after solvent drying), the polymer membrane is removed. The method of peeling and manufacturing the porous polymer film 8 can also be used.

According to the present invention, it is possible to produce a porous polymer membrane having a hole array structure in which the pores of uniform size on a submicron to nanometer scale are regularly arranged. In addition, when the method of the present invention is carried out on a polymer film having a thin film thickness, it is possible to obtain a through-hole membrane through which pores pass.

An example of the manufacturing method of a through hole membrane is shown in FIG. The photocurable resin layer 24 is provided, for example on the base substrate 23 which consists of the board | substrate 21 and the polymer layer 22, and the top part of the convex part of the stamper 25 is the photocurable resin layer from above. The stamper 25 is loaded by applying a load to the stamper 25 until it reaches the inside of the base substrate 23 slightly past the position of the surface of the base substrate 23 via the 24, and transfers the surface structure of the stamper 25. After peeling off (25), by peeling from the base substrate 23 or performing an operation equivalent thereto, for example, the base substrate 23 is dissolved and removed (in this case, the polymer layer 22 is dissolved and removed). ), The through hole membrane 26 can be obtained.

Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited by these Examples.

Example 1 [Preparation of Porous Polymer Membrane Using a Stamper Made of Anodic Oxidized Porous Alumina as a Template]

An aluminum plate having a purity of 99.99% was subjected to an electropolishing treatment in a perchloric acid and ethanol mixed solution (volume ratio 1: 4). In the oxalic acid aqueous solution which adjusted the mirrored aluminum plate to the density | concentration of 0.3 M, after carrying out anodizing for 15 hours at 40 degreeC of direct current at the bath temperature of 17 degreeC, the oxide layer was dissolved and removed once again, and again Anodization was carried out for 90 seconds under the same conditions to form anodized porous alumina having a pore depth of 150 nm. Then, the sample was immersed in 5 weight% phosphoric acid aqueous solution for 30 minutes, the pore size expansion process was performed, and the pore size was adjusted to 70 nm. This surface was coated with 50 nm of Pt-Pd using a sputtering apparatus, and then Ni electrolytic precipitation was performed. Thereafter, the mold was dissolved and removed with an aqueous sodium hydroxide solution to obtain a stamper having a regular protrusion arrangement on the surface. Using the obtained Ni stamper, an imprint process was performed on the surface of the polymethyl methacrylate resin formed on the Si substrate under a heating condition of 180 ° C., thereby obtaining a polymer film having a hole array structure in which pores were regularly arranged. lost.

Example 2 [Production of Polymethyl methacrylate (PMMA) Porous Membrane by Thermal Imprint Method Using a Stamper with a Controlled Projection Shape]

On the surface of an aluminum plate with a purity of 99.99%, a SiC mold having a structure in which protrusions were regularly arranged at 200 nm intervals was pressed to form a fine concavo-convex pattern on the surface. The aluminum plate subjected to the texturing treatment was subjected to anodization for 2 seconds in a oxalic acid aqueous solution adjusted to a concentration of 0.05 M under a condition of a direct current of 80 V at a bath temperature of 17 ° C. Then, it was immersed in 10 weight% phosphoric acid aqueous solution for 25 minutes, and the pore enlargement process was performed. This operation was repeated five times to obtain a porous alumina having tapered pores having a pore period of 200 nm, a pore opening of 200 nm, a bottom portion of 50 nm, and a hole depth of 300 nm. Ni surface electrolytic precipitation was carried out after 50 nm of Pt-Pd was coated on this surface using a sputtering apparatus. Thereafter, the mold was dissolved and removed to obtain a stamper having a regular protrusion arrangement on the surface. Using the obtained Ni stamper, an imprint process was performed on the surface of the polymethyl methacrylate resin formed on the Si substrate under a heating condition of 180 ° C., thereby obtaining a polymer film having a hole array structure in which pores were regularly arranged. lost. In FIG. 7, the electron micrograph (drawing observed with the electron microscope) of the surface of the polymethyl methacrylate porous film (porous polymer film 8) produced by thermal imprint is shown.

Example 3 [ Preparation of Acrylic Porous Membrane by Optical Imprint Method Using a Stamper with a Controlled Projection Shape]

Ultraviolet irradiation was performed in the state which pressed the Ni stamper produced by the method similar to Example 2 on the acrylic monomer dripped on the glass substrate. After the monomer was cured, a porous acrylic resin film was produced on the substrate by peeling the stamper. The electron micrograph (drawing observed with the electron microscope) of the surface of the produced acrylic resin porous film (porous polymer membrane 8) is shown in FIG. 8, and the cross-sectional electron micrograph (drawing observed with the electron microscope) is shown in FIG.

Example 4 [ Preparation of Fluorine Resin Porous Membrane by the Cast Method Using a Stamper with a Controlled Projection Shape]

On the surface of an aluminum plate with a purity of 99.99%, a SiC mold having a structure in which protrusions were regularly arranged at 500 nm intervals was pressed to form a fine concavo-convex pattern on the surface. The aluminum plate subjected to the texturing treatment was subjected to anodization for 10 seconds in a phosphoric acid aqueous solution adjusted to a concentration of 0.1 M at a bath temperature of 0 deg. Then, it was immersed in 10 weight% phosphoric acid aqueous solution for 25 minutes, and the pore enlargement process was performed. This operation was repeated five times to obtain a porous alumina having tapered pores having a pore period of 500 nm, a pore opening of 400 nm, a bottom of 150 nm, and a hole depth of 800 nm. Ni surface electrolytic precipitation was carried out after 50 nm of Pt-Pd was coated on this surface using a sputtering apparatus. Thereafter, the mold was dissolved and removed to obtain a stamper having a regular array of protrusions on the surface. The fluorine solution which melt | dissolved the fluororesin on the produced stamper was dripped, and the stamper was peeled off, and the porous fluororesin film was produced. An electron micrograph (drawing observed with an electron microscope) of the surface of the produced fluororesin porous membrane (porous polymer membrane 8) is shown in FIG.

Example 5 [Production of High Aspect Ratio Metal Stamper]

An aluminum plate having a purity of 99.99% was subjected to an electropolishing treatment in a perchloric acid and ethanol mixed solution (volume ratio 1: 4). A mold made of SiC having a structure in which protrusions were regularly arranged at 500 nm intervals was pressed on the mirrored aluminum plate, thereby forming a fine concavo-convex pattern on the surface. In the phosphoric acid aqueous solution adjusted to the concentration of 0.1 M, anodization was performed for 14 minutes under the conditions of 200 V of direct current at the bath temperature of 0 degreeC. Then, the sample was immersed in 10 weight% phosphoric acid aqueous solution for 30 minutes, the pore size expansion process was performed, and the pore size was adjusted to 300 nm. On this surface, 50 nm of Pt was coated using an ion beam sputtering apparatus, and Ni electrolytic precipitation was performed. Thereafter, the mold was dissolved and removed to obtain a stamper having a regular protrusion arrangement on the surface. The produced Ni stamper 31 is shown in FIG.

Example 6 Fabrication of Through Hole Membrane

Photocurable resin was dripped on the Ni stamper produced by the method similar to Example 5, and was defoamed under reduced pressure conditions. The stamper was pressed on the glass substrate which cast PMMA, and ultraviolet irradiation was performed, applying a load. After the resin was completely cured by light irradiation, the Ni stamper was peeled off. The sample was immersed in acetone, and only the PMMA layer was dissolved and removed to obtain a polymer through hole membrane. The fabricated through hole membrane 32 is shown in Figs. 12A and 12B.

Claims (24)

By filling a material into the pores of the anodized porous alumina having a porous surface structure, and dissolving and removing the anodized porous alumina, to produce a stamper made of the material and having a reverse structure of the surface structure, A method of producing a porous polymer membrane, wherein the polymer structure having the surface structure is produced by transferring the inverted structure of the stamper to a polymer. The method of claim 1, Method for producing a porous polymer membrane wherein the material is a metal. The method of claim 2, Method for producing a porous polymer membrane wherein the metal is any one of nickel, gold, platinum. The method of claim 1, A method for producing a porous polymer membrane having pores in which the anodic oxidation porous alumina is continuously changed in pore size by repeatedly performing anodization and pore size expansion. The method of claim 1, A method for producing a porous polymer membrane, wherein the anodic oxidation porous alumina uses oxalic acid as an electrolyte and is produced at a chemical conversion voltage of 30 V to 40 V. The method of claim 1, The anodic oxidation porous alumina is a method for producing a porous polymer membrane produced using a sulfuric acid as an electrolyte, at a chemical conversion voltage of 10V to 30V. The method of claim 1, The anodic oxidation porous alumina is a method for producing a porous polymer membrane produced using a phosphoric acid as an electrolyte solution at a chemical conversion voltage of 180V to 20OV. The method of claim 1, After the anodic oxidation porous alumina is subjected to anodization at a constant voltage, the oxide film is dissolved and removed once, and then subjected to anodization under the same conditions. The method of claim 1, A method for producing a porous polymer membrane, wherein the anodic oxidation porous alumina is formed by forming a fine pit on the surface of aluminum before anodizing and anodizing the pit as a starting point of pore generation. The method of claim 1, A method for producing a porous polymer membrane, wherein the proportion of the pore wall portion on the surface side of the surface structure of the polymer membrane is 30% or less. The method of claim 10, A method for producing a porous polymer membrane, wherein the proportion of the pore wall portion on the surface side of the surface structure of the polymer membrane is 20% or less. The method of claim 11, A method for producing a porous polymer membrane, wherein a proportion of the pore wall portion on the surface side of the surface structure of the polymer membrane is 10% or less. The method of claim 12, A method for producing a porous polymer membrane, wherein a proportion of the pore wall portion on the surface side of the surface structure of the polymer membrane is 5% or less. The method of claim 1, A method for producing a porous polymer membrane, wherein the pore cross-sectional shape at the surface side of the surface structure of the polymer membrane is triangular, square, or hexagonal. The method of claim 1, The polymer is a method of producing a porous polymer membrane is a thermoplastic resin. The method of claim 1, The polymer is a method of producing a porous polymer membrane is a photocurable resin. The method of claim 1, A method for producing a porous polymer membrane, wherein the solution in which the polymer is dissolved is cast on the stamper, the solvent is dried, and the stamper is peeled off to transfer the surface structure of the stamper to the polymer. A method for producing a stamper, wherein a metal is coated on a surface of the anodized porous alumina by using an ion beam sputtering device and a conductive layer is provided when the metal is filled into pores of the anodized porous alumina. The method of claim 18, A method for producing a stamper, wherein the ion beam sputtering is carried out under the condition that the degree of vacuum is 3 × 10 ⁻⁴ Pa to 1 × 10 ⁻⁵ Pa when the conductive layer is applied to the surface of the anodized porous alumina. The manufacturing method of the porous polymer membrane which transfers the surface structure of the stamper manufactured by the manufacturing method of the stamper of Claim 18 to a polymer. Filling a material into pores of the anodized porous alumina having a porous surface structure, and dissolving and removing the anodized porous alumina to produce a stamper made of the material and having an inverted structure of the surface structure, The stamper is installed on a layer of a polymer and a base substrate, and a load is applied to the stamper until the ball neck end of the inverted structure contacts or reaches the surface of the base substrate through the polymer. By transferring to the polymer to produce a polymer film having the surface structure, A method for producing a porous polymer membrane, wherein the polymer membrane is peeled from the base substrate to produce a polymer membrane having a surface structure through which pores are penetrated. The method of claim 21, The base substrate is a method for producing a porous polymer membrane at least the surface of the polymer. The method of claim 22, The polymer is a thermoplastic resin, and a method for producing a porous polymer membrane is applied to the stamper under heating conditions. The porous polymer membrane manufactured using the method of any one of Claims 1-17 and 20-23.

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