JP6353330B2 - Filtration membrane for capturing fine particles and method for producing the same, porous membrane and method for producing the same - Google Patents

Description

  The present invention relates to a filtration membrane for capturing fine particles in water to be treated, and more particularly to a filtration membrane for capturing fine particles used for measuring the number of fine particles contained in ultrapure water, a solvent, or a chemical for semiconductor production. . The present invention also relates to a porous membrane having fine communication holes.

  Currently, ultrapure water and chemicals used in semiconductor manufacturing processes or fine particles in chemicals are managed with a particle size of 50 to 100 nm. However, in recent years, along with the high integration of semiconductor devices, the line width of devices has become finer, so that it has been required to manage with a smaller particle size of about 10 nm.

  Fine particles in ultrapure water can be evaluated by online methods using laser scattering and sound waves, ultrapure water filtered through a fine particle capture membrane, and fine particles captured on the membrane using an optical microscope or scanning electron microscope. There is a direct microscopic method to measure. An anodic oxide film is used as the microscopic particle capturing film for the direct spectroscopic method. However, since the anodized film has low water resistance, it is necessary to perform a baking process after the anodizing process (Patent Document 1).

  For example, FIG. 1 of Patent Document 2 shows a film having a different diameter structure, and the example describes that the minimum pore size is about 20 nm. Moreover, as a commercially available anodic oxide film, a film having a minimum pore diameter of up to 20 nm is commercially available.

JP 2007-70126 A JP-A-2-218422

  However, at present, there is no anodic oxide film having a smaller pore diameter. Therefore, development of an anodic oxide film having an average pore diameter of 20 nm or less that can meet the recent demand for management of fine particles having a smaller particle diameter is desired.

  Therefore, the present invention provides a particulate trapping filtration membrane obtained by forming communication holes by anodization, and providing a particulate trapping filtration membrane having an average pore size smaller than that of the prior art and a method for producing the same. Another object of the present invention is to provide a porous film obtained by forming communication holes by anodic oxidation, and having a smaller average pore diameter than conventional ones and a method for producing the same.

Such a problem is solved by the following invention.
That is, the present invention (1) is a particulate trapping filtration membrane obtained by forming communication holes by anodic oxidation of an aluminum material,
A small hole diameter portion in which a communication hole opening on one surface of the filtration membrane is formed;
An intermediate hole portion in which a communication hole of the small hole diameter portion is connected and a communication hole having a diameter larger than the diameter of the communication hole of the small hole diameter portion is formed;
A large hole diameter portion in which the communication hole of the intermediate hole portion is connected, the diameter is larger than the diameter of the communication hole of the intermediate hole portion, and a communication hole opened on the other surface of the filtration membrane is formed;
Have
In the small pore diameter portion, communication holes having an average pore diameter of 4 to 20 nm are formed from one surface of the filtration membrane to a position of 400 to 1000 nm,
The total thickness of the filtration membrane Ri 15~50μm der,
Ultra-pure water, fine supplement film Der Rukoto of solvent or liquid chemical,
A filtration membrane for capturing fine particles characterized by the above is provided.

In addition, the present invention (2) includes a first anodizing step for obtaining an anodized aluminum material (1) by anodizing an aluminum material to form a communication hole for a large hole diameter portion in the aluminum material,
By anodizing the anodized aluminum material (1), the anodized aluminum material (1) is connected to the communicating hole for the large hole diameter portion and has a diameter smaller than that of the communicating hole for the large hole diameter portion. A second anodizing step of forming an anodized aluminum material (2) by forming a communicating hole for the part;
By anodizing the anodized aluminum material (2), the anodized aluminum material (2) is connected to the communication hole for the intermediate hole and has a smaller diameter than the communication hole for the intermediate hole. A third anodizing step of forming an anodized aluminum material (3) by forming a communicating hole for the part;
A peeling and etching step of peeling the anodized part from the anodized aluminum material (3), and then etching the peeled part to obtain an anodized part;
A firing step of obtaining a filtration membrane for capturing fine particles by firing the anodized portion at 800 to 1200 ° C .;
Have
In the third anodic oxidation step, communication holes having an average pore diameter of 4 to 20 nm are formed in the thickness direction from 400 to 1000 nm.
And from the first anodizing step to the third anodizing step, the total thickness of the portion where the communicating holes are formed by anodization is 15 to 50 μm,
A method for producing a filtration membrane for capturing fine particles is provided.

  ADVANTAGE OF THE INVENTION According to this invention, it is a filtration membrane for fine particle capture | acquisition obtained by forming a communicating hole by anodic oxidation, and can provide the filtration membrane for fine particle capture | acquisition with a smaller average pore diameter than before, and its manufacturing method. Moreover, according to this invention, it is a porous membrane obtained by forming a communicating hole by anodic oxidation, and can provide the porous membrane with a smaller average pore diameter than before, and its manufacturing method.

FIG. 3 is an enlarged view of a portion surrounded by a dotted line indicated by reference numeral 40 in FIG. 2. It is a typical end view of a form example of a filtration membrane for capturing particulates of the present invention. It is an enlarged view of the part enclosed with the dotted line shown with the code | symbol 39 in FIG. It is a conceptual diagram which shows an anodizing process. It is a typical end view which shows a mode that an aluminum material is anodized. It is a typical end view which shows a mode that an aluminum material is anodized. It is a typical end view which shows a mode that an aluminum material is anodized. It is a typical end view which shows a mode that an aluminum material is anodized. It is a typical end view of one surface vicinity of the example of the form of the filtration membrane for particulate capture of the present invention. It is a schematic diagram of one surface of the form example of the filtration membrane for fine particle capturing of the present invention. It is a typical end view of one surface vicinity of the example of the form of the filtration membrane for particulate capture of the present invention. It is a typical end view of one surface vicinity of the example of the form of the filtration membrane for particulate capture of the present invention. 2 is a SEM image of a cross section of the filtration membrane for capturing fine particles of Example 1. FIG. 2 is a SEM image of the surface on the small pore diameter side of the filtration membrane for capturing fine particles of Example 1. FIG.

  With reference to FIGS. 1-5, the filtration membrane for fine particle capture | acquisition of this invention and its manufacturing method are demonstrated. 1 is an enlarged view of a portion surrounded by a dotted line indicated by reference numeral 40 in FIG. 2, and is an enlarged view of the vicinity of one surface of the filtration membrane. FIG. 2 is a schematic view of an embodiment of the filtration membrane for capturing fine particles of the present invention, and is an end view when cut perpendicularly to the surface of the filtration membrane. FIG. 3 is an enlarged view of a portion surrounded by a dotted line indicated by reference numeral 39 in FIG. 2, and is an enlarged view of the vicinity of the other surface of the filtration membrane. FIG. 4 is a conceptual diagram showing an anodic oxidation process. FIG. 5 is a schematic view showing an aluminum material being anodized, and is an end view when cut perpendicular to the surface of the filtration membrane.

  As shown in FIGS. 1 to 3, the particulate trapping filtration membrane 1 has a small pore diameter portion 2 in which communication pores having an average pore diameter of 4 to 20 nm are formed, and a diameter larger than the diameter of the communication pores of the small pore diameter portion. It has the intermediate hole part 3 in which the communication hole is formed, and the large hole diameter part 4 in which the communication hole larger than the communication hole of the intermediate hole part 3 is formed. The total thickness of the small-diameter hole portion 2, the intermediate hole portion 3, and the large-pore diameter portion 4, that is, the total film thickness of the particulate trapping filtration membrane 1 is 50 μm or less. In addition, as shown in FIG.1 and FIG.3, although the small hole diameter part 2, the intermediate | middle hole part 3, and the large hole diameter part 4 of the filtration membrane 1 for particulate capture | acquisition have formed the communicating hole, in FIG. For convenience, the communicating holes are not described, and only the positions where the small hole diameter part 2, the intermediate hole part 3 and the large hole diameter part exist are indicated by hatching. 2 are portions of the small hole diameter portion 2, the intermediate hole portion 3 and the large hole diameter portion 4 of the particulate trapping filtration membrane 1. In practice, the hatched portion in FIG. The small hole diameter part 2, the intermediate hole part 3, and the large hole diameter part 4 are continuous in both the left and right directions.

  The small hole diameter portion 2 is formed on one surface 5 side of the fine particle capturing filtration membrane 1, and the opening 7 of the communication hole 8 of the small hole diameter portion 2 is opened on one surface 5 of the filtration membrane. The large pore diameter portion 4 is formed on the other surface 6 side of the particulate trapping filtration membrane 1, and the opening 11 of the communication hole 10 of the large pore diameter portion 4 is opened on one surface 6 of the filtration membrane. The intermediate hole portion 3 is formed between the small hole diameter portion 2 and the large hole diameter portion 4, the communication hole 8 of the small hole diameter portion 2 is connected to the communication hole 9 of the intermediate hole portion 3, and the intermediate hole portion The three communication holes 9 are connected to the communication hole 10 of the large hole diameter portion 4. Therefore, the communication hole 8 of the small hole diameter portion 2, the communication hole 9 of the intermediate hole portion 3, and the communication hole 10 of the large hole diameter portion 4 are continuous from one surface 5 to the other surface 6 of the filtration membrane 1 for capturing particles. A communication hole is formed.

  A plurality of communication holes 8 of the small hole diameter portion 2 are connected to the communication holes 9 of the intermediate hole portion 3, and a plurality of communication holes 9 of the intermediate hole portion 3 are connected to the communication holes 10 of the large hole diameter portion 4. Yes.

  Since the skeleton of the particulate trapping filtration membrane 1 is obtained by anodizing an aluminum material, then peeling the anodized portion from the aluminum material, then etching the surface, and then firing, Consists of aluminum. That is, the communication hole 8 of the small hole diameter portion 2, the communication hole 9 of the intermediate hole portion 3, and the communication hole 10 of the large hole diameter portion 4 are formed by aluminum oxide walls 12a, 12b and 12c.

  And the to-be-processed water 21 such as ultrapure water is supplied into the filtration membrane from one surface 5 side of the particulate trapping filtration membrane 1, passes through the communication hole in the filtration membrane, and then passed through the filtration membrane 1. From the other surface 6 side, the treated water 22 is discharged out of the filtration membrane. At this time, fine particles in the water to be treated 21 such as ultrapure water are captured on one surface 5 of the fine particle capturing filtration membrane 1.

  Such communication holes of the particulate trapping filtration membrane 1 are formed by anodic oxidation as shown in FIG. In anodization, an aluminum material 23 and a counter electrode material 24 made of a material such as aluminum, copper, nickel, or platinum are immersed in the electrolytic solution 25 so that a direct current flows from the aluminum material 23 to the counter electrode material 24. This is done by applying a DC power supply 26.

  The anodic oxidation in the production of the particulate trapping filtration membrane 1 includes anodization (FIG. 5 (A)) for forming the communication hole 101 for the large pore diameter portion with respect to the aluminum material 23, and for the intermediate pore portion. Anodization for forming the communication hole 91 (FIG. 5B) and anodization for forming the small hole diameter communication hole 81 (FIG. 5C) are performed in three stages. Note that the communication hole 101 for the large hole diameter part, the communication hole 91 for the intermediate hole part, and the communication hole 81 for the small hole diameter part are communicated with the large hole diameter part 4 of the particulate trapping filtration membrane 1 through firing. These are communication holes which are the hole 10, the communication hole 9 of the intermediate hole portion 3, and the communication hole 8 of the small hole diameter portion 2.

  First, in the anodic oxidation for forming the large hole diameter communication hole 101 shown in FIG. 5A, the large hole diameter communication hole 101 is formed from the surface of the aluminum material 23 by anodic oxidation. An anodized aluminum material (1) 31 is obtained. Next, in the anodic oxidation for forming the communication hole 91 for the intermediate hole shown in FIG. 5 (B), it is intermediate from the end of the communication hole 101 formed in the anodized aluminum material (1) 31 by anodic oxidation. The hole 91 is formed to obtain the anodized aluminum material (2) 32. Next, in the anodic oxidation for forming the small hole diameter portion communication hole 81 shown in FIG. 5C, anodization is performed from the end of the communication hole 91 formed in the anodized aluminum material (2) 32. A communicating hole 81 for the hole diameter portion is formed to obtain the anodized aluminum material (3) 33. In addition, the formation of the communication hole 101, the communication hole 91, and the communication hole 81 is appropriately selected according to an anodic oxidation condition such as a voltage to be applied, a current to be applied, an application time, and a type of electrolyte as described later. Is done. In FIG. 5, the portion denoted by reference numeral 401, the portion denoted by reference numeral 301, and the portion denoted by reference numeral 201 are subjected to firing until the large pore diameter portion 4, the intermediate pore portion 3, and the small pore portion of the particulate trapping filtration membrane 1, respectively. It is a part which becomes the hole diameter part 2, and is a part corresponding to the large hole diameter part 4, the part corresponding to the intermediate hole part 3, and the part corresponding to the small hole diameter part 2, respectively.

  After performing the three-stage anodization as described above, the anodized portion 34 is peeled off from the aluminum material portion 35 of the anodized aluminum material (3) 33 obtained, and then the surface of the obtained anodized portion 34 is etched. Processing is performed to obtain the anodized portion 34 shown in FIG.

  Next, the anodized portion 34 obtained by performing the etching treatment is baked at 800 to 1200 ° C., thereby obtaining the particulate capturing filter membrane 1.

  As described above, the particulate trapping filtration membrane 1 is a particulate trapping filtration membrane obtained by forming communication holes by anodization of an aluminum material.

The filtration membrane for capturing fine particles of the present invention is a filtration membrane for capturing fine particles obtained by forming a communication hole by anodization of an aluminum material,
A small hole diameter portion in which a communication hole opening on one surface of the filtration membrane is formed;
An intermediate hole portion in which a communication hole of the small hole diameter portion is connected and a communication hole having a diameter larger than the diameter of the communication hole of the small hole diameter portion is formed;
A large hole diameter portion in which the communication hole of the intermediate hole portion is connected, the diameter is larger than the diameter of the communication hole of the intermediate hole portion, and a communication hole opened on the other surface of the filtration membrane is formed;
Have
In the small pore diameter portion, a communication hole having an average pore diameter of 4 to 20 nm is formed from one surface of the filtration membrane to a position of at least 400 nm,
The total membrane thickness of the filtration membrane is 50 μm or less,
Is a filtration membrane for capturing fine particles.

  The aluminum material according to the filtration membrane for capturing particulates of the present invention is a raw material for producing the filtration membrane for capturing particulates of the present invention, and is an anodized material. The aluminum material according to the filtration membrane for capturing fine particles of the present invention is a material mainly made of aluminum, and is not particularly limited. However, since a large amount of impurities contained in aluminum tends to cause defects during production, The purity is preferably 98.5% by mass or more, particularly preferably 99.0% by mass or more.

  The filtration membrane for capturing fine particles of the present invention is a filtration membrane for capturing fine particles obtained by forming communication holes by anodizing an aluminum material, and more specifically, anodizing the aluminum material to form communication holes. Then, the anodized portion is peeled from the aluminum material, then the anodized portion is subjected to surface etching treatment, and then the anodized portion is baked to obtain a particulate trapping filtration membrane. In the filtration membrane for capturing fine particles of the present invention, the communication hole of the small hole diameter part, the communication hole of the intermediate hole part and the communication hole of the large hole diameter part are first applied voltage, current to be applied, application time, type of electrolyte, etc. The anodization with the selected anodic oxidation conditions was performed to form, in order, a communication hole for the large hole diameter portion, a communication hole for the intermediate hole portion, and a communication hole for the small hole diameter portion in the aluminum material. It can be obtained by peeling off the oxidized portion, etching the anodic oxidized portion, and baking.

  The fine particle capturing filtration membrane of the present invention has a small hole diameter portion in which a communication hole having an average pore diameter of 4 to 20 nm is formed, and a communication hole of the small hole diameter portion is connected and the diameter of the communication hole having a small hole diameter portion. An intermediate hole portion in which a larger communication hole is formed, and a large hole diameter portion in which the communication hole of the intermediate hole portion is connected and a communication hole having a diameter larger than that of the communication hole of the intermediate hole portion is formed. The small hole diameter communication hole, the intermediate hole communication hole, and the large hole diameter communication hole extend in a direction substantially perpendicular to one and the other surfaces of the particulate trapping filtration membrane, that is, in the thickness direction of the filtration membrane. ing.

  The small pore diameter portion is formed on one surface side of the fine particle capturing filtration membrane of the present invention, and the communication hole of the small pore diameter portion opens on one surface of the fine particle capturing filtration membrane of the present invention. The large pore diameter portion is formed on the other surface side of the fine particle capturing filtration membrane of the present invention, and the communication hole of the large pore diameter portion opens on the other surface of the fine particle capturing filtration membrane of the present invention. The intermediate hole portion is formed between the small hole diameter portion and the large hole diameter portion, the communication hole of the intermediate hole portion is connected to the communication hole of the small hole diameter portion, and the communication hole of the intermediate hole portion is the communication hole of the large hole diameter portion. It is connected to. Therefore, the water to be treated passes through the small pore diameter communication hole, the intermediate hole communication hole, and the large pore diameter communication hole in this order from one surface to the other surface of the filtration membrane for capturing fine particles of the present invention. The continuous hole which can be formed is formed.

  The communication hole of the intermediate hole part may be connected to only one communication hole of the small hole diameter part or may be connected to a plurality of communication holes of the small hole diameter part. Further, only one communication hole of the intermediate hole portion may be connected to the communication hole of the large hole diameter portion, or a plurality of communication holes of the intermediate hole portion may be connected. In the fine particle capturing filtration membrane of the present invention, a plurality of communication holes of the small hole diameter portion are connected to the communication hole of the intermediate hole portion, and a plurality of communication holes of the intermediate hole portion are connected to the communication hole of the large hole diameter portion. In other words, a plurality of communication holes of the intermediate hole portion extend from the end of one communication hole of the large hole diameter portion, and the communication of the small hole diameter portion extends from the end of the one communication hole of the intermediate hole portion. The structure in which a plurality of holes extend allows the small pore diameter communication holes to be densely provided on one surface of the particulate trapping filtration membrane, which facilitates the passage of treated water.

  In the small pore diameter portion of the filtration membrane for capturing fine particles of the present invention, there is a communication pore having an average pore diameter of 4 to 20 nm, preferably 8 to 20 nm, particularly preferably 9 to 15 nm, and more preferably 9 to 12 nm. It is formed from the one surface of this to the position of at least 400 nm. That is, in the small pore diameter portion, pores having an average pore diameter of 4 to 20 nm, preferably 8 to 20 nm, particularly preferably 9 to 15 nm, more preferably 9 to 12 nm are located at least 400 nm from at least one surface of the filtration membrane. Is continuous. In other words, the average pore diameter is 4 to 20 nm, preferably 8 to 20 nm, particularly preferably 9 to 15 nm, and more preferably 9 to 12 nm. When the average pore diameter of the communication holes in the small pore diameter portion is within the above range, excellent performance is exhibited as a filtration membrane for capturing fine particles used in direct spectroscopic methods. Further, when the thickness of the small hole diameter portion is 400 nm or more, the communication holes in the small hole diameter portion of the anodized portion obtained by anodic oxidation, peeling and etching are less damaged. Further, the small pore diameter portion has an average pore diameter of 4 to 20 nm, preferably 8 to 20 nm, particularly preferably 9 to 15 nm, more preferably 9 to 12 nm, at a position 1000 nm from one surface of the filtration membrane. In other words, it is preferable that the thickness of the small hole diameter portion is 1000 nm or less because the permeate flow rate due to pressure loss does not become too low when the water to be treated is passed. The thickness of the small hole diameter portion is preferably 400 to 1000 nm, particularly preferably 400 to 700 nm.

  The average pore diameter of the communication holes in the entire small pore diameter portion is 4 to 20 nm, preferably 8 to 20 nm, particularly preferably 9 to 15 nm, and more preferably 9 to 12 nm. When the average pore diameter of the communicating holes in the entire small pore diameter portion is in the above range, excellent performance is exhibited as a filtration membrane for capturing fine particles used in direct spectroscopic methods.

  In the present invention, for example, the confirmation that a communication hole having an average pore diameter of 4 to 20 nm is formed from one surface of the filtration membrane to a position of at least 400 nm is obtained by cutting the filtration membrane for capturing fine particles in the thickness direction. The cross section is observed with a scanning electron microscope, and is performed based on the obtained SEM image. A specific confirmation method will be described with reference to FIG. Moreover, in this invention, the average hole diameter of the communicating hole of the whole small hole diameter part is calculated | required as follows. FIG. 6 is a schematic SEM image 40 of a cross section in the vicinity of the surface of the fine particle capturing filtration membrane. First, in the SEM image 40, a straight line 41a is drawn in parallel with one surface of the filtration membrane at the position of the surface of the filtration membrane in the portion of the small hole diameter portion 2, and then overlaps with each communication hole 8 in the straight line 41a. For each of the portions, the lengths are measured, the lengths are averaged, the average value is calculated, and the average pore diameter of the communication holes at the position of the surface of the filtration membrane of the small pore diameter portion 2 is obtained. Next, a straight line 41b is drawn in parallel with one surface of the filtration membrane in the vicinity of the position connected to the communication hole 9 of the intermediate hole part 3 in the small hole diameter part 2, and then each communication hole 8 in the straight line 41b. For each of the overlapping portions, the lengths are measured, the lengths are averaged, the average value is calculated, and the hole diameter of the communication hole in the vicinity of the position connected to the communication hole 9 of the intermediate hole portion 3 is calculated. Find the average. Next, a straight line 41c is drawn parallel to one surface of the filtration membrane in the vicinity of the middle position between the surface of the filtration membrane and the vicinity of the position connected to the communication hole 9 of the intermediate hole portion 3, and then, among the straight lines 41c, The length of each of the portions overlapping each communication hole 8 is measured, the lengths are averaged, the average value is calculated, and the surface of the filtration membrane of the small hole diameter portion 2 communicates with the intermediate hole portion 3. The average of the hole diameters of the communication holes near the intermediate position with the vicinity of the position connected to the hole is obtained. And the average of the hole diameter of the communication hole of the position of the surface of the filtration membrane of the small hole diameter part 2, and the hole diameter of the communication hole near the position connected to the communication hole 9 of the intermediate hole part 3 of the small hole diameter part 2, If any of the average pore diameters of the communication holes near the intermediate position between the surface of the filtration membrane of the small hole diameter part 2 and the vicinity of the position connected to the communication hole 9 of the intermediate hole part 3 is in the range of 4 to 20 nm, From one surface of the filtration membrane to the position in the vicinity of the position connected to the communication hole 9 of the intermediate hole portion 3, it is determined that a communication hole having an average pore diameter of 4 to 20 nm is formed. And if the distance from the straight line 41a to the straight line 41b is 400 nm or more, it will be judged that the communicating hole with an average hole diameter of 4-20 nm is formed from the one surface of the filtration membrane to the position of at least 400 nm. Further, the total area (total area A) of the communication holes 8 existing in the portion delimited by the straight line 41a and the straight line 41b, and the communication existing in the portion delimited by the straight line 41a and the straight line 41b. The number of holes 8 (the number of communicating holes B) and the distance (distance C) between the straight line 41a and the straight line 41b are measured. Then, the value calculated by the formula “average hole diameter of communication holes in the entire small hole diameter portion = (A / (B × C))” is the average hole diameter of the communication holes in the entire small hole diameter portion.

  The relative standard deviation in the hole diameter distribution of the communication holes in the small hole diameter portion is preferably 40% or less, particularly preferably 35% or less. The relative standard deviation in the pore size distribution of the communicating holes in the small pore diameter portion is preferably in the above range, so that it is easy to accurately capture fine particles having a target particle size.

  In the present invention, the relative standard deviation in the pore size distribution of the communicating holes of the small pore diameter portion is obtained by observing a cross section of the fine particle capturing filtration membrane in the thickness direction with a scanning electron microscope as follows. It is determined based on the image. A specific method will be described with reference to FIG. First, in the SEM image 40 shown in FIG. 6, a straight line 41 a is connected to the communication hole 9 of the intermediate hole portion 3 at the position of the surface of the filtration membrane in the portion of the small hole diameter portion 2 in parallel with one surface of the filtration membrane. A straight line 41b is drawn in the vicinity of the position, and a straight line 41c is drawn in the vicinity of the intermediate position between the surface of the filtration membrane and the vicinity of the position connected to the communication hole 9 of the intermediate hole portion 3, and each of the straight lines 41a, 41b and 41c The length of each portion overlapping the communication hole 8 is measured. Next, a relative standard deviation is calculated from the average value and standard deviation of these measured values.

  The open area ratio of the small pore diameter communication holes on one surface of the fine particle capturing filtration membrane of the present invention is preferably 10 to 50%, particularly preferably 15 to 50%. When the open area ratio of the small pore diameter communication hole on one surface of the fine particle capturing filtration membrane is in the above range, a larger amount of permeated water is obtained, and the pressure resistance is maintained, so that the damage is reduced. This is preferable.

  In the present invention, the opening ratio of the small pore diameter communication hole on one surface of the fine particle capturing filtration membrane is as follows: the surface on the side where the small pore diameter communication hole of the fine particle capturing filtration membrane is open Is observed with a scanning electron microscope and obtained based on the obtained SEM image. First, the total area of the opening 7 of the communication hole of the small hole diameter part in the SEM image shown in FIG. 7 is measured. Next, the ratio of the total area of the opening 7 to the area of the measurement visual field is calculated, and the value is set as the opening ratio of the communication hole of the small hole diameter portion on one surface of the fine particle capturing filtration membrane. FIG. 7 is a schematic diagram of an SEM image of one surface of the filtration membrane for capturing fine particles.

  In the filtration membrane for capturing microparticles of the present invention, the proportion of communication holes in the small hole diameter portion (area ratio = ((area of communication holes / area of small hole diameter)) × 100 in the SEM image of the cross section observed with a scanning electron microscope. ) Is preferably 10% to 60%, particularly preferably 20% to 50%, and the permeation rate of the communication hole in the small pore diameter portion in the SEM image of the cross-section of the filtration membrane for capturing fine particles is within the above range. This is preferable in that the amount of water increases.

  In the present invention, the existence ratio (area ratio) of communication holes in the small pore diameter portion in the SEM image of the cross section of the filtration membrane for capturing fine particles is obtained as follows. First, in the SEM image 40 shown in FIG. 8, a straight line 41 d is formed parallel to one surface of the filtration membrane at a position on one surface of the filtration membrane, and a straight line 41 e in the vicinity of the position connected to the communication hole of the intermediate hole portion 3. To measure the area of the small hole diameter portion 2 between the straight line 41d and the straight line 41e, that is, the area of the rectangles 42a, 42b, 42c, and 42d. Next, the total area of the communication holes 8 of the small hole diameter portion 2 existing in the rectangles 42a, 42b, 42c, and 42d is obtained. Next, the ratio of the total area of the communication holes 8 of the small-diameter portion 2 existing in the rectangles 42a, 42b, 42c, 42d to the areas of the rectangles 42a, 42b, 42c, 42d is calculated, and the value is used for capturing particles. It is set as the existence ratio (area ratio) of the communication hole in the small hole diameter part in the SEM image of the cross section of the filtration membrane. FIG. 8 is a schematic SEM image 40 of a cross section in the vicinity of the surface of the same fine particle capturing filtration membrane as FIG.

  The intermediate hole portion may have a communication hole having the same hole diameter from the vicinity of the position where the communication hole of the small hole diameter portion is connected to the vicinity of the position where the communication hole of the large hole diameter portion is connected, or the small hole diameter portion. A communication hole having a larger hole diameter may be formed from the vicinity of the position where the communication hole is connected to the vicinity of the position where the communication hole is connected to the communication hole of the large hole diameter portion. And the hole diameter of the communicating hole of an intermediate | middle hole part becomes like this. Preferably it is 10-1000 nm, Most preferably, it is 20-100 nm. Moreover, the thickness of the intermediate hole is preferably 50 to 1000 nm, particularly preferably 50 to 800 nm.

  In the present invention, for example, confirmation that the pore diameter of the intermediate hole portion is 10 to 1000 nm is obtained by observing a cross section of the fine particle capturing filtration membrane in the thickness direction with a scanning electron microscope, as shown below. This is performed based on the SEM image. A specific confirmation method will be described with reference to FIG. First, in the SEM image 40 in FIG. 9, a straight line 43 a is formed in the vicinity of the position where the communication hole 8 of the small hole diameter portion 2 of the intermediate hole portion 3 is connected in parallel with one surface of the filtration membrane, and the intermediate rear portion 3. The straight line 43b is located in the vicinity of the position connected to the communication hole 10 of the large hole diameter portion 4, and the position near the position where the communication hole 8 of the small hole diameter portion 2 is connected to the communication hole 10 of the large hole diameter portion 4. A straight line 43c is drawn in the vicinity of an intermediate position with the vicinity, and then the length of each of the portions of the straight lines 43a, 43b, and 43c that overlap with the communication holes 9 is measured. And if all of those length exists in the range of 10-1000 nm, it will be judged that the hole diameter of an intermediate | middle hole part is 10-1000 nm. FIG. 9 is a schematic SEM image 40 of a cross section in the vicinity of the surface of the same fine particle capturing filtration membrane as FIG.

  In the large hole diameter portion, a communication hole having the same hole diameter is formed from the vicinity of the position where the communication hole of the intermediate hole portion is connected to the other surface of the filtration membrane, or the communication hole of the intermediate hole portion is not provided. A communication hole having a larger pore diameter may be formed from the vicinity of the connected position to the other surface of the filtration membrane. And the hole diameter of the communicating hole of a large hole diameter part becomes like this. Preferably it is 20-2000 nm, Most preferably, it is 30-2000 nm.

  In the present invention, for example, to confirm that the pore diameter of the communicating hole of the large pore diameter portion is 20 to 2000 nm, as shown below, a cross section of the fine particle capturing filter membrane cut in the thickness direction is observed with a scanning electron microscope. And based on the obtained SEM image. First, an SEM image is obtained in which the measurement field of view extends from the position connected to the communication hole of the intermediate hole portion of the large hole diameter portion to the position of the other surface of the filtration membrane. Next, in the SEM image, in the vicinity of the position where the straight hole X is connected to the position of the other surface of the filtration membrane in parallel with the other surface of the filtration membrane and the communication hole of the intermediate hole portion of the large pore diameter portion 4 is connected A straight line Z is drawn in the vicinity of the intermediate position between the other surface of the filtration membrane and the vicinity of the position where the communication hole of the intermediate hole portion of the large pore diameter portion 4 is connected, and then the straight lines X, Y and Z Of these, the length of each portion of the large-diameter portion that overlaps each communication hole is measured. And if all of those length exists in the range of 20-2000 nm, it will be judged that the hole diameter of a large hole diameter part is 20-2000 nm.

  The average pore diameter of the communication holes of the entire large pore diameter portion is preferably 30 to 1000 nm, particularly preferably 50 to 1000 nm.

  In the present invention, as shown below, the average pore diameter of the communication holes of the entire large pore diameter portion is based on the SEM image obtained by observing a cross-section of the particulate trapping filtration membrane in the thickness direction with a scanning electron microscope. Done. In addition, although the measuring object differs in the method of calculating | requiring the average hole diameter of the communicating hole of the whole large hole diameter part shown below, it is the same as that of the average hole diameter of the communicating hole of the whole small hole diameter part mentioned above. First, an SEM image is obtained in which the measurement field of view extends from the position connected to the communication hole of the intermediate hole portion of the large hole diameter portion to the position of the other surface of the filtration membrane. Next, in the SEM image, a straight line X is connected to the position of the surface of the filtration membrane at the large pore diameter portion in parallel with the other surface of the filtration membrane, and the communication hole of the intermediate hole portion at the large pore diameter portion is connected. A straight line Y is drawn near the position. Next, the total area (total area A) of the communication holes existing in the part delimited by the straight line X and the straight line Y, the communication hole existing in the part delimited by the straight line X and the straight line Y And the distance (distance C) between the straight line X and the straight line Y are measured. Then, the value calculated by the formula “average pore diameter of communication holes in the entire large hole diameter portion = (A / (B × C))” is the average hole diameter of the communication holes in the entire large hole diameter portion.

  In the filtration membrane for collecting fine particles of the present invention, the ratio of the average pore diameter of the entire large pore diameter portion to the average pore diameter of the communication pores of the entire small pore diameter portion (average pore diameter of the entire large pore diameter portion / total pore diameter portion The average pore diameter of the communication holes) is preferably 3 to 100, particularly preferably 4 to 50, and further preferably 4 to 20. The ratio of the average hole diameter of the communication holes of the entire large hole diameter portion to the average hole diameter of the communication holes of the entire small hole diameter portion is preferable because it is resistant to stress and difficult to break.

  The thickness of the large pore diameter portion is preferably 10 to 50 μm, particularly preferably 20 to 40 μm.

  The total film thickness of the filtration membrane for capturing fine particles of the present invention is 50 μm or less, preferably 20 to 50 μm, particularly preferably 20 to 35 μm. When the total film thickness of the particulate trapping filtration membrane is within the above range, the anodized portion is less damaged when the anodized portion obtained by anodizing, peeling and etching is baked.

  The fine particle capturing filtration membrane of the present invention is a fine particle capturing filtration membrane obtained by forming a communication hole by anodization of an aluminum material, and more specifically, an aluminum material is anodized to form a communication hole, Next, since the anodized portion is peeled off from the aluminum material, and then the anodized portion is subjected to surface etching treatment, and then the anodized portion is baked, the particulate capturing filter of the present invention is obtained. The walls of the membrane skeleton, in other words, the small hole diameter communication hole, the intermediate hole communication hole, and the large hole diameter communication hole are made of aluminum oxide.

  In addition, when the communication hole of the intermediate hole portion and the communication hole of the large hole diameter portion in the filtration membrane for capturing fine particles of the present invention are extracted at random, and the pore diameters are compared, There exists a thing with a part whose hole diameter is larger than the communicating hole of a hole diameter part. On the other hand, a series of large-pore diameter communication holes and intermediate-hole communication holes and small-hole diameter portions forming a continuous flow path from one surface side to the other surface side in the filtration membrane for capturing fine particles of the present invention When the pore diameters are compared, the filtration membrane for capturing particulates of the present invention is a filtration membrane for capturing particulates obtained by forming a communication hole by anodization of an aluminum material. The communication hole is connected to a communication hole of an intermediate hole portion having a smaller hole diameter, and the communication hole of the intermediate hole portion is connected to a communication hole of a small hole diameter portion having a smaller hole diameter.

  The filtration membrane for capturing fine particles of the present invention is suitably used as a fine particle capturing membrane for evaluating fine particles by direct spectroscopic methods such as ultrapure water, solvents, chemical solutions, etc. used in semiconductor production. The filtration membrane for capturing fine particles of the present invention is also used for capturing fine particles in gases, aerosols and other fluids, and for separating and capturing proteins and DNA.

  The fine particle capturing filtration membrane of the present invention is preferably produced by the following method for producing a fine particle measurement filtration membrane of the present invention.

The method for producing a filtration membrane for fine particle measurement according to the present invention includes a first anode for obtaining an anodized aluminum material (1) by anodizing an aluminum material to form a communicating hole for a large pore diameter portion in the aluminum material. An oxidation process;
By anodizing the anodized aluminum material (1), the anodized aluminum material (1) is connected to the communicating hole for the large hole diameter portion and has a diameter smaller than that of the communicating hole for the large hole diameter portion. A second anodizing step of forming an anodized aluminum material (2) by forming a communicating hole for the part;
By anodizing the anodized aluminum material (2), the anodized aluminum material (2) is connected to the communication hole for the intermediate hole and has a smaller diameter than the communication hole for the intermediate hole. A third anodizing step of forming an anodized aluminum material (3) by forming a communicating hole for the part;
Peeling and etching step of removing the anodized part from the anodized aluminum material (3) and then etching the peeled part to obtain an anodized part;
A firing step of obtaining a filtration membrane for capturing fine particles by firing the anodized portion at 800 to 1200 ° C .;
Have
In the third anodic oxidation step, a communication hole having an average pore diameter of 4 to 20 nm is formed in a thickness direction of 400 nm or more,
And, from the first anodizing step to the third anodizing step, the total thickness of the portion where the communicating holes are formed by anodizing is 50 μm or less,
Is a method for producing a filtration membrane for capturing fine particles.

  In the first anodizing step according to the method for producing a microparticle-capturing filtration membrane of the present invention, the aluminum material is anodized to form communication holes for large-diameter portions in the aluminum material, and the anodized aluminum material (1 ). The communication hole for the large pore diameter portion is a communication hole that becomes a communication hole for the large pore diameter portion in the filtration membrane for capturing fine particles obtained through the firing step.

  The aluminum material related to the first anodizing step is a material to be anodized in the first anodizing step and is a material mainly made of aluminum, and is not particularly limited, but when there are many impurities contained in the aluminum Since defects are likely to occur during production, the purity of the aluminum material is preferably 98.5% by mass or more, particularly preferably 99.0% by mass or more.

  Moreover, in the first anodizing step, the surface of the aluminum material to be anodized is preferably subjected to degreasing treatment and smoothing treatment in advance. The method for performing the degreasing treatment is not particularly limited as long as it is a method capable of removing organic substances and oils and fats existing on the surface of the aluminum material. For example, the aluminum material is made of acetone, ethanol, methanol, IPA (isopropyl alcohol). Examples thereof include a method of immersing in an organic solvent such as irradiating ultrasonic waves and a method of heating (annealing). The method for performing the smoothing treatment is not particularly limited as long as the surface of the aluminum material can be smoothed. Examples thereof include electrolytic polishing, chemical polishing, and mechanical polishing. Examples of the electrolytic solution for electropolishing include phosphoric acid and ethanol containing perchloric acid. Examples of chemical polishing include a method using a mixed acid of phosphoric acid and nitric acid, a method using a mixed acid of phosphoric acid and sulfuric acid, and the like.

  In the first anodizing step, the anodizing conditions for anodizing the aluminum material are appropriately selected according to the communicating holes of the large pore diameter portion in the particulate trapping filtration membrane to be obtained, and the desired large pore diameter The voltage to be applied, the current to be energized, the application time, the type of the electrolytic solution, and the like are appropriately selected so that the communication hole of the part is formed. As anodizing conditions in the first anodizing step, for example, 50 to 200 V in an electrolytic solution such as an aqueous solution of oxalic acid having a concentration of 0.5 to 30% by mass, an aqueous solution of phosphoric acid, an aqueous solution of chromic acid, or a mixed acid aqueous solution thereof. Conditions are mentioned. At this time, a method using a constant voltage, a method using a constant current, or a method of changing both voltage and current may be used.

  In the first anodizing step, the hole diameter of the large hole diameter portion formed in the aluminum material by anodization is preferably 20 to 2000 nm, particularly preferably 30 to 2000 nm. The average pore diameter of the communication holes of the entire portion corresponding to the large pore diameter portion is preferably 30 to 1000 nm, particularly preferably 50 to 1000 nm, and the thickness of the portion corresponding to the large pore diameter portion is preferably 10 to 50 μm, particularly Preferably it is 20-40 micrometers.

  Then, by performing the first anodizing step, a communication hole is formed in the thickness direction from the surface of the aluminum material, and a communication hole for a large hole diameter portion extending in the thickness direction from the surface of the aluminum material is formed in the aluminum material. An anodized aluminum material (1) is obtained.

  In the second anodizing step according to the method for producing a filtration membrane for capturing fine particles of the present invention, the anodized aluminum material (1) is anodized to form a communication hole for the intermediate hole portion in the anodized aluminum material (1). In this step, an anodized aluminum material (2) is obtained. In addition, the communication hole for intermediate | middle hole parts is a communication hole used as the communication hole of the intermediate | middle hole part in the filtration membrane for fine particle acquisition obtained through a baking process.

  In the second anodizing step, the anodizing conditions for anodizing the anodized aluminum material (1) are appropriately selected according to the communication hole of the intermediate hole portion in the particulate trapping filtration membrane to be obtained, The voltage to be applied, the current to be applied, the application time, the type of the electrolyte, and the like are appropriately selected so that the target communication hole of the intermediate hole is formed. The anodic oxidation conditions in the second anodizing step may be any conditions as long as a communication hole having a diameter smaller than that of the large hole diameter portion is formed. For example, an aqueous oxalic acid solution having a concentration of 0.5 to 30% by mass, In electrolyte solution, such as phosphoric acid aqueous solution, chromic acid aqueous solution, or those mixed acid aqueous solution, 50-200V, Preferably the conditions with a voltage lower than the voltage of 1st anodizing conditions are mentioned. At this time, a method using a constant voltage, a method using a constant current, or a method of changing both voltage and current may be used.

  In the second anodic oxidation step, the communication hole for the intermediate hole part formed in the anodized aluminum material (1) by anodic oxidation has a hole diameter of the communication hole for the intermediate hole part of preferably 10 to 1000 nm, particularly preferably. It is 20-100 nm, The thickness of the part corresponding to an intermediate | middle hole part becomes like this. Preferably it is 50-1000 nm, Most preferably, it is 50-800 nm.

  And by performing a 2nd anodizing process, the communicating hole whose hole diameter is smaller than the communicating hole for large-diameter parts in the thickness direction from the edge part of the communicating hole for large-diameter parts in the anodized aluminum material (1). The anodized aluminum material (1) is formed with a communication hole for an intermediate hole extending in the thickness direction from the end of the large hole diameter communication hole of the anodized aluminum material (1). A material (2) is obtained.

  In the third anodizing step according to the method for producing a particulate trapping filtration membrane of the present invention, the anodized aluminum material (2) is anodized so that a small hole diameter communicating hole is formed in the anodized aluminum material (2). In this step, an anodized aluminum material (3) is obtained. In addition, the communication hole for small hole diameter parts is a communication hole which becomes a communication hole of the small hole diameter part in the filtration membrane for fine particle capture | acquisition obtained through a baking process.

  In the third anodizing step, the anodizing conditions for anodizing the anodized aluminum material (2) are appropriately selected according to the communication holes of the small pore diameter portion in the filter membrane for capturing fine particles to be obtained, The voltage to be applied, the current to be energized, the application time, the type of the electrolyte, and the like are appropriately selected so that the desired communication hole having a small hole diameter is formed. As anodizing conditions in the third anodizing step, the average pore diameter is 4 to 20 nm, preferably 8 to 20 nm, particularly preferably 9 to 15 nm, more preferably 9 to 12 nm, and 400 nm or more in the thickness direction, preferably May be any condition as long as a communication hole communicating with 400 to 1000 nm, particularly preferably 400 to 700 nm is formed. Examples thereof include 5 to 30 V in a sulfuric acid aqueous solution electrolyte. At this time, a method using a constant voltage, a method using a constant current, or a method of changing both voltage and current may be used.

  In the third anodizing step, a small pore diameter portion having an average pore diameter of 4 to 20 nm, preferably 8 to 20 nm, particularly preferably 9 to 15 nm, and more preferably 9 to 12 nm in the anodized aluminum material (2) by anodization. The communication hole for use is formed in a thickness direction of 400 nm or more, preferably 400 to 1000 nm, particularly preferably 400 to 700 nm. When the average pore diameter of the communication holes for the small pore diameter portion is within the above range, a particulate trapping filtration membrane exhibiting excellent performance can be obtained as a particulate trapping membrane used in the direct spectroscopic method. Moreover, when the thickness of the part corresponding to the small hole diameter part is 400 nm or more, the breakage of the communication hole in the part corresponding to the small hole diameter part of the anodized part obtained by performing the peeling step is reduced. Moreover, it is preferable that the thickness of the part corresponding to the small pore diameter part is 1000 nm or less in that a filtration membrane for trapping fine particles can be obtained in which the permeate flow rate due to pressure loss is not too low when water to be treated is passed.

  In the third anodic oxidation step, the communication hole for the small hole diameter portion formed in the anodized aluminum material (2) by anodic oxidation has an average hole diameter of 4 to 20 nm of the communication holes of the entire portion corresponding to the small hole diameter part, Preferably it is 8-20 nm, Especially preferably, it is 9-15 nm, More preferably, it is 9-12 nm, The relative standard deviation in the hole diameter distribution of the communicating hole for small hole diameter parts becomes like this. Preferably it is 40% or less, Most preferably, it is 35% or less The existence ratio (area ratio) of the communicating holes in the portion corresponding to the small hole diameter portion in the SEM image of the cross section is preferably 10 to 60%, particularly preferably 20 to 50%.

  And by performing a 3rd anodizing process, the communicating hole whose hole diameter is smaller than the communicating hole for intermediate holes in the thickness direction from the edge part of the communicating hole for intermediate holes in the anodized aluminum material (2). The anodized aluminum material (2) is formed with a small hole diameter communication hole extending in the thickness direction from the end of the intermediate hole communication hole of the anodized aluminum material (2). A material (3) is obtained.

  In the first anodizing step, the second anodizing step, and the third anodizing step, depending on the shape of each communicating hole of the small pore diameter portion, the intermediate pore portion, and the large pore diameter portion in the filter membrane for capturing fine particles to be obtained Each anodizing in the first anodizing step, the second anodizing step and the third anodizing step so that the communication holes of the small hole diameter part, the intermediate hole part and the large hole diameter part of the desired shape are formed. The conditions, that is, the voltage to be applied, the current to be energized, the application time, the type of electrolyte, etc. are adjusted.

  Also, in both the first anodizing step, the second anodizing step or both the first anodizing step and the second anodizing step, the anodized aluminum material after the anodization is treated with a phosphoric acid aqueous solution, a chromic acid aqueous solution, It is also possible to perform a treatment for expanding the pore diameter of the communicating hole corresponding to the large pore diameter portion or the medium pore diameter portion by immersing in an aqueous solution of oxalic acid aqueous solution, sulfuric acid aqueous solution, mixed acid aqueous solution thereof, sodium hydroxide aqueous solution or the like. .

  In addition, the first anodizing step to the third anodizing step are performed so that the total thickness of the portion where the communication holes are formed is 50 μm or less, preferably 20 to 50 μm, particularly preferably 20 to 35 μm. Each anodizing condition in the one anodizing process, the second anodizing process, and the third anodizing process is adjusted. In the first anodizing step to the third anodizing step, the entire thickness of the portion where the communication holes are formed is in the above range, so that when the anodized portion is fired in the firing step, the anodized portion is damaged. Less.

  The peeling and etching step according to the method for producing a filtration membrane for capturing fine particles of the present invention is performed by peeling an anodized part from the anodized aluminum material (3), and then etching the surface of the peeled part. This is a step of obtaining an anodized portion.

  In the peeling and etching step, the method for peeling the anodized portion from the anodized aluminum material (3) is not particularly limited, and examples thereof include solution immersion, a reverse current method, and electropolishing. The solution immersion is performed by immersing the anodized aluminum material (3) in an aqueous copper sulfate solution, hydrochloric acid or the like, and is a method with little physical damage, although it takes a long time for peeling. The reverse current method is a method in which the current at the time of anodizing is reversed and the anodized portion can be quickly peeled off from the anodized aluminum material (3). The electrolytic polishing is performed by applying voltage to the anodized aluminum material (3) in a perchloric acid-containing ethanol solution or a perchloric acid-containing diacetone solution. It is a method which can peel.

  In the stripping and etching step, the method for etching the surface of the stripped anodized portion is not particularly limited, but for example, a method of immersing in a solution such as oxalic acid, phosphoric acid, chromic acid, sulfuric acid, alkaline aqueous solution, etc. , Etc.

  Then, by performing an etching process, the surface of the part peeled off from the aluminum material is etched to form a communication hole for the large hole diameter part, a communication hole for the intermediate hole part, and a communication hole for the small hole diameter part, As a result, an anodized portion which is a penetrating film penetrating therethrough is obtained.

  The firing step according to the method for producing a particulate trapping filtration membrane of the present invention is a step of obtaining a particulate trapping filtration membrane by firing an anodized portion.

  In the firing step, the firing temperature when firing the anodized portion is 800 to 1200 ° C, preferably 800 to 1000 ° C. In the firing step, the firing time when firing the anodized portion is preferably 10 hours or less, particularly preferably 1 to 5 hours. In the firing step, the firing atmosphere when firing the anodized portion is an oxidizing atmosphere such as air or oxygen gas.

  Since the communication holes of the filtration membrane for capturing fine particles of the present invention are formed by anodization from the large pore diameter portion to the small pore diameter portion, that is, by anodic oxidation, first, the communication holes for the large pore diameter portion are formed in the aluminum material. Next, a communication hole for the intermediate hole is formed from the end of the communication hole for the large hole diameter part, and then a communication hole for the small hole diameter part is formed from the end of the communication hole for the intermediate hole part. Since they are formed in the order of formation, all the communication holes from one surface side of the filtration membrane to the other surface side are connected.

The porous film of the present invention is a porous film obtained by forming communication holes by anodization of an aluminum material,
A small hole diameter portion in which a communication hole opening on one surface of the porous membrane is formed;
An intermediate hole portion in which a communication hole of the small hole diameter portion is connected and a communication hole having a diameter larger than the diameter of the communication hole of the small hole diameter portion is formed;
A large hole diameter portion in which the communication hole of the intermediate hole portion is connected, the diameter is larger than the diameter of the communication hole of the intermediate hole portion, and a communication hole is formed in the other surface of the porous membrane;
Have
In the small pore diameter portion, a communication hole having an average pore diameter of 4 to 20 nm is formed from one surface of the porous membrane to a position of at least 400 nm,
The total thickness of the porous membrane is 50 μm or less,
Is a porous film characterized by

  The aluminum material, anodizing, communication hole, small hole diameter part, intermediate hole part and large hole diameter part relating to the porous membrane of the present invention are the aluminum material, anodizing, communication hole, and the fine particle capturing filtration membrane of the present invention, The same as the small hole diameter part, the intermediate hole part and the large hole diameter part.

  As the use of the porous membrane of the present invention, in addition to the filtration membrane for capturing fine particles, an enzyme carrier for immobilizing an enzyme with an enzyme electrode or the like, a carbon material, a template for semiconductor wiring, a solvent or a solvent in a trace amount. Examples include an addition filter for addition.

The method for producing a porous membrane of the present invention comprises a first anodizing step in which an aluminum material is anodized to form a communicating hole for a large pore diameter portion in the aluminum material to obtain an anodized aluminum material (1). When,
By anodizing the anodized aluminum material (1), the anodized aluminum material (1) is connected to the communicating hole for the large hole diameter portion and has a diameter smaller than that of the communicating hole for the large hole diameter portion. A second anodizing step of forming an anodized aluminum material (2) by forming a communicating hole for the part;
By anodizing the anodized aluminum material (2), the anodized aluminum material (2) is connected to the communication hole for the intermediate hole and has a smaller diameter than the communication hole for the intermediate hole. A third anodizing step of forming an anodized aluminum material (3) by forming a communicating hole for the part;
A peeling and etching step of peeling the anodized part from the anodized aluminum material (3), and then etching the peeled part to obtain an anodized part;
A firing step of firing the anodized part at 800 to 1200 ° C. to obtain a porous film;
Have
In the third anodic oxidation step, a communication hole having an average pore diameter of 4 to 20 nm is formed in a thickness direction of 400 nm or more,
And the total thickness of the portion where the communicating holes are formed by anodization from the first anodizing step to the third anodizing step is 50 μm or less,
Is a method for producing a porous membrane.

  Aluminum material, anodization, large hole diameter communication hole, anodized aluminum material (1), first anodization step, intermediate hole communication hole, anodized aluminum according to the porous membrane manufacturing method of the present invention The material (2), the second anodizing step, the communication hole for the small hole diameter portion, the anodized aluminum material (3), the third anodizing step, the peeling and etching step, and the firing step are for capturing fine particles of the present invention. Aluminum material, anodizing, communication hole for large pore diameter part, anodized aluminum material (1), first anodizing step, communication hole for intermediate hole part, anodized aluminum material (2) The second anodizing step, the small hole diameter communicating hole, the anodized aluminum material (3), the third anodizing step, the peeling and etching step, and the firing step are the same.

  The method for producing a porous membrane of the present invention includes an enzyme carrier, a carbon material, a semiconductor wiring template, a solvent or a solvent for immobilizing an enzyme with an enzyme electrode or the like in addition to the production of the filtration membrane for capturing fine particles. It is used to form a porous film on the surface of a base material by manufacturing a porous film used for an addition filter for adding each one or the like, or by performing surface treatment to make it difficult to peel off the coating.

  Hereinafter, the present invention will be described in detail based on examples. However, the present invention is not limited to the following examples.

Example 1
・ Manufacture of filtration membrane for capturing fine particles <Preparation of anodized aluminum plate>
Five aluminum plates with a purity of 98.5% by mass were prepared. Next, the aluminum plate was ultrasonically irradiated in acetone for 30 minutes, and electropolished in a 10% by weight perchloric acid-containing ethanol solution at 20 V for 15 minutes to prepare an anodized aluminum plate.
In addition, among the prepared aluminum plates for anodization, one sheet was subjected to the peeling process and used for observing the breakage of the small hole diameter portion, and the remaining four sheets were subjected to the firing process.
<First anodizing process>
The aluminum plate material for anodization obtained above was anodized under a constant voltage of 100 V at a bath temperature of 5 ° C. using an 1.8 mass% oxalic acid aqueous solution as an electrolyte.
<Second anodizing process>
Subsequently, 1.8 mass% oxalic acid aqueous solution was used as the electrolytic solution, and the voltage was gradually decreased at a bath temperature of 5 ° C. to perform anodic oxidation for 5 minutes.
<Third anodizing process>
Next, anodic oxidation was performed in a 20% by mass sulfuric acid aqueous solution at a bath temperature of 5 ° C. and a voltage of 9.5 V for 3 minutes.
<Peeling and etching process>
Next, the anodized portion was peeled off by electropolishing. Next, the obtained anodized portion was washed with ultrapure water and then immersed in a 20% by mass sulfuric acid aqueous solution to etch the surface to form a penetrating film. Subsequently, it was washed with ultrapure water.
<Baking process>
Next, firing was performed at 1000 ° C. in an air atmosphere to obtain a filtration membrane for capturing fine particles.

-Analysis of the structure of the fine particle capturing filtration membrane The cross section of the obtained fine particle capturing filtration membrane and the surface of the small pore diameter side were observed with a scanning electron microscope, and the structure was determined from the obtained SEM image. Moreover, the SEM image of the obtained cross section is shown in FIG. 10, and the SEM image of the surface is shown in FIG.
<Small hole diameter part>
The thickness of the small hole diameter portion was 400 nm. Moreover, the average of the hole diameter of the surface of a small hole diameter part and 200 nm and 400 nm position was 10 nm, 10 nm, and 10 nm, respectively. Moreover, the average hole diameter of the communication hole of the whole small hole diameter part was 10 nm. The relative standard deviation in the hole diameter distribution of the communication holes was 30%. Further, the opening ratio of the communication hole of the small hole diameter portion was 17%. Further, the existence ratio of the communication holes in the small hole diameter portion was 37%.
<Intermediate hole>
The hole diameter of the communication hole of the intermediate hole portion was 23 to 40 nm. The hole diameter of the communication hole of the intermediate hole portion is a hole diameter in the vicinity of the intermediate position in the thickness direction of the intermediate hole portion. The same applies to the diameter of the communication hole of the intermediate hole portion.
<Large hole diameter part>
The hole diameter of the communication hole in the large hole diameter portion was 27 to 102 nm. Moreover, the average hole diameter of the communication hole of the whole large hole diameter part was 58 nm.
<Total thickness of filtration membrane>
The total film thickness of the filtration membrane was 22 μm.

-Observation of the damage state of the small hole diameter part after peeling and an etching process The surface by the side of the small hole diameter part of the anodized part after peeling and an etching process was observed with the scanning electron microscope. Next, the ratio of the area of the damaged portion to the area of the observation field was obtained from the obtained SEM image. As a result, the ratio of the area of the damaged portion to the area of the observation field was 1.5%.

-Sintering success rate in firing process For each of the four anodic oxidized portions that were fired, if they were not damaged by firing, the firing was successful and the firing success rate was determined. The term “breakage” refers to a case where a crack occurs in the film or a case where the film breaks. As a result, the firing success rate was 100%.

(Example 2)
A filtration membrane for capturing fine particles was obtained in the same manner as in Example 1 except that the anodic oxidation time in the third anodizing step was 5 minutes.

・ Analysis of the structure of filtration membrane for capturing fine particles <Small pore size>
The thickness of the small hole diameter portion was 600 nm. Moreover, the average of the hole diameter of the surface of a small hole diameter part and a 300 nm and 600 nm position was 10 nm, 10 nm, and 10 nm, respectively. Moreover, the average hole diameter of the communication hole of the whole small hole diameter part was 10 nm. The relative standard deviation in the pore size distribution of the communication holes was 39%. Further, the opening ratio of the communication hole of the small hole diameter portion was 19%. The proportion of communication holes in the small hole diameter portion was 23%.
<Intermediate hole>
The hole diameter of the communication hole of the intermediate hole portion was 25 to 50 nm.
<Large hole diameter part>
The hole diameter of the communication hole in the large hole diameter portion was 40 to 144 nm. Moreover, the average hole diameter of the communication hole of the whole large hole diameter part was 77 nm.
<Total thickness of filtration membrane>
The total film thickness of the filtration membrane was 23 μm.

・ Observation of damage condition of small hole diameter part after peeling and etching process The ratio of the area of the broken part to the area of the observation field on the surface of the small hole diameter part of the anodized part after peeling and etching process is 1 %.

(Example 3)
A filtration membrane for capturing fine particles was obtained in the same manner as in Example 1 except that the anodic oxidation time in the third anodizing step was 10 minutes.

・ Analysis of the structure of filtration membrane for capturing fine particles <Small pore size>
The thickness of the small hole diameter portion was 1000 nm. Moreover, the average of the hole diameter of the surface of a small hole diameter part, 500 nm, and 1000 nm position was 14 nm, 14 nm, and 14 nm, respectively. Moreover, the average hole diameter of the communication hole of the whole small hole diameter part was 14 nm. Moreover, the relative standard deviation in the hole diameter distribution of the communication holes was 29%. Further, the opening ratio of the communication hole of the small hole diameter portion was 30%. Further, the existence ratio of the communication holes in the small hole diameter portion was 37%.
<Intermediate hole>
The hole diameter of the communication hole of the intermediate hole portion was 28 to 52 nm.
<Large hole diameter part>
The hole diameter of the communication hole in the large hole diameter portion was 48 to 135 nm. Moreover, the average hole diameter of the communication hole of the whole large hole diameter part was 75 nm.
<Total thickness of filtration membrane>
The total film thickness of the filtration membrane was 25 μm.

・ Observation of damage condition of small hole diameter part after peeling and etching process The ratio of the area of the broken part to the area of the observation field on the surface of the small hole diameter part of the anodized part after peeling and etching process is 1 %.

(Comparative Example 1)
A filtration membrane for capturing fine particles was obtained in the same manner as in Example 1 except that the anodic oxidation time in the third anodizing step was 2 minutes.

・ Analysis of the structure of filtration membrane for capturing fine particles <Small pore size>
The thickness of the small hole diameter portion was 200 nm. Moreover, the average of the hole diameter of the surface of a small hole diameter part and a 100 nm and 200 nm position was 10 nm, 10 nm, and 10 nm, respectively. Moreover, the average hole diameter of the communication hole of the whole small hole diameter part was 10 nm. Moreover, the relative standard deviation in the hole diameter distribution of the communication holes was 27%. Further, the opening ratio of the communication hole of the small hole diameter portion was 17%. In addition, the existence ratio of communication holes in the small hole diameter portion was 30%.
<Intermediate hole>
The hole diameter of the communication hole of the intermediate hole portion was 7 to 31 nm.
<Large hole diameter part>
The hole diameter of the communication hole in the large hole diameter portion was 21 to 78 nm. Moreover, the average hole diameter of the communication hole of the whole large hole diameter part was 50 nm.
<Total thickness of filtration membrane>
The total film thickness of the filtration membrane was 25 μm.

・ Observation of damage state of small hole diameter part after peeling and etching process The ratio of the area of the broken part to the area of the observation field on the surface of the small hole diameter part of the anodized part after peeling and etching process is 30 %Met.

Example 4
A filtration membrane for capturing fine particles was obtained in the same manner as in Example 1 except that the anodic oxidation time in the first anodizing step was made longer than that in Example 1.

-Successful firing rate in firing step When the successful firing rate in the firing step was determined, the successful firing rate was 100%.

-Analysis of the total film thickness of the anodized part after a peeling process The total film thickness of the anodized part after a peeling process was 40 micrometers.
・ Analysis of the structure of filtration membrane for capturing fine particles <Small pore size>
The thickness of the small hole diameter portion was 400 nm. Moreover, the average of the hole diameter of the surface of a small hole diameter part and 200 nm and 400 nm position was 10 nm, 10 nm, and 10 nm, respectively. Moreover, the average hole diameter of the communication hole of the whole small hole diameter part was 10 nm. The relative standard deviation in the hole diameter distribution of the communication holes was 30%. Further, the opening ratio of the communication hole of the small hole diameter portion was 20%. The proportion of communication holes in the small hole diameter portion was 36%.
<Intermediate hole>
The hole diameter of the communication hole of the intermediate hole portion was 15 to 55 nm.
<Large hole diameter part>
The hole diameter of the communication hole in the large hole diameter portion was 20 to 81 nm. Moreover, the average hole diameter of the communication hole of the whole large hole diameter part was 50 nm.
<Total thickness of filtration membrane>
The total film thickness of the filtration membrane was 40 μm.

(Example 5)
A filtration membrane for capturing fine particles was obtained in the same manner as in Example 1 except that the anodic oxidation time in the first anodizing step was made longer than that in Example 4.

-Successful firing rate in firing step When the successful firing rate in the firing step was determined, the successful firing rate was 75%.

-Analysis of the total film thickness of the anodized part after a peeling process The total film thickness of the anodized part after a peeling process was 50 micrometers.
・ Analysis of the structure of filtration membrane for capturing fine particles <Small pore size>
The thickness of the small hole diameter portion was 400 nm. Moreover, the average of the hole diameter of the surface of a small hole diameter part and 200 nm and 400 nm position was 10 nm, 10 nm, and 10 nm, respectively. Moreover, the average hole diameter of the communication hole of the whole small hole diameter part was 10 nm. The relative standard deviation in the hole diameter distribution of the communication holes was 37%. Further, the opening ratio of the communication hole of the small hole diameter portion was 20%. The proportion of communication holes in the small hole diameter portion was 36%.
<Intermediate hole>
The hole diameter of the communication hole of the intermediate hole portion was 22 to 48 nm.
<Large hole diameter part>
The hole diameter of the communication hole in the large hole diameter portion was 27 to 66 nm. Moreover, the average hole diameter of the communication hole of the whole large hole diameter part was 50 nm.
<Total thickness of filtration membrane>
The total film thickness of the filtration membrane was 50 μm.

(Comparative Example 2)
A filtration membrane for capturing fine particles was obtained in the same manner as in Example 1 except that the anodic oxidation time in the first anodizing step was made longer than that in Example 5.

-Successful firing rate in firing step When the successful firing rate in the firing step was determined, the successful firing rate was 0%.

-Analysis of the total film thickness of the anodized part after peeling and an etching process The total film thickness of the anodized part after a peeling and etching process was 60 micrometers.
・ Analysis of the structure of the filter membrane for capturing fine particles Since it was completely damaged in the firing process, a filter membrane for capturing fine particles could not be obtained.

(Example 6)
In the second anodic oxidation step, the voltage was gradually lowered for 2 minutes to perform anodic oxidation, and then immersed in a 1.8 wt% oxalic acid solution for 4 hours to obtain the obtained anodized aluminum material. In the same manner as in Example 1 except that the third anodizing step was performed, a filtration membrane for capturing fine particles was obtained.

・ Analysis of the structure of filtration membrane for capturing fine particles <Small pore size>
The thickness of the small hole diameter portion was 400 nm. Moreover, the average of the hole diameter of the surface of a small hole diameter part and 200 nm and 400 nm position was 10 nm, 10 nm, and 10 nm, respectively. Moreover, the average hole diameter of the communication hole of the whole small hole diameter part was 10 nm. The relative standard deviation in the hole diameter distribution of the communication holes was 36%. Further, the opening ratio of the communication hole of the small hole diameter portion was 25%. The proportion of communication holes in the small hole diameter portion was 38%.
<Intermediate hole>
The hole diameter of the communication hole of the intermediate hole portion was 16 to 72 nm.
<Large hole diameter part>
The hole diameter of the communication hole of the large hole diameter portion was 31 to 120 nm. Moreover, the average hole diameter of the communication hole of the whole large hole diameter part was 80 nm.
<Total thickness of filtration membrane>
The total film thickness of the filtration membrane was 24 μm.

-Observation of the damage state of the small hole diameter part after peeling and an etching process The surface by the side of the small hole diameter part of the anodized part after peeling and an etching process was observed with the scanning electron microscope. Next, the ratio of the area of the damaged portion to the area of the observation field was obtained from the obtained SEM image. As a result, the ratio of the area of the damaged portion to the area of the observation field was 0.1%.

-Successful firing rate in firing step When the successful firing rate in the firing step was determined, the successful firing rate was 100%.

(Example 7)
-Manufacture of filtration membrane for capturing particulates A filtration membrane for capturing particulates is obtained in the same manner as in Example 6 except that in the third anodizing step, the voltage is set to 20 V instead of 9.5 V. It was.

・ Analysis of the structure of filtration membrane for capturing fine particles <Small pore size>
The thickness of the small hole diameter portion was 1000 nm. Moreover, the average of the hole diameter of the surface of a small hole diameter part and 500 nm and 1000 nm position was 20 nm, 20 nm, and 20 nm, respectively. Moreover, the average hole diameter of the communication hole of the whole small hole diameter part was 20 nm. The relative standard deviation in the hole diameter distribution of the communication holes was 21%. Further, the opening ratio of the communication hole of the small hole diameter portion was 26%. The proportion of communication holes in the small hole diameter portion was 36%.
<Intermediate hole>
The hole diameter of the communication hole of the intermediate hole portion was 40 to 80 nm.
<Large hole diameter part>
The hole diameter of the communication hole of the large hole diameter portion was 51 to 139 nm. Moreover, the average hole diameter of the communicating hole of the whole large hole diameter part was 91 nm.
<Total thickness of filtration membrane>
The total film thickness of the filtration membrane was 24 μm.
(Example 8)
In the first anodizing step, after anodizing, the substrate is immersed in a 1.8 wt% oxalic acid solution for 4 hours, and the resulting anodized aluminum material is used to perform the third anodizing step. Except that, a filtration membrane for capturing fine particles was obtained in the same manner as in Example 7.

・ Analysis of the structure of filtration membrane for capturing fine particles <Small pore size>
The thickness of the small hole diameter portion was 1000 nm. The averages of the pore diameters at the surface of the small pore diameter portion and at the positions of 500 nm and 1000 nm were 20 nm, 20 nm and 20 nm, respectively. Moreover, the average hole diameter of the communication hole of the whole small hole diameter part was 20 nm. The relative standard deviation in the hole diameter distribution of the communication holes was 28%. Further, the opening ratio of the communication hole of the small hole diameter portion was 20%. The proportion of communication holes in the small hole diameter portion was 56%.
<Intermediate hole>
The hole diameter of the communication hole of the intermediate hole portion was 40 to 80 nm.
<Large hole diameter part>
The hole diameter of the communication hole in the large hole diameter portion was 62 to 136 nm. Moreover, the average hole diameter of the communication hole of the whole large hole diameter part was 90 nm.
<Total thickness of filtration membrane>
The total film thickness of the filtration membrane was 25 μm.

-Observation of the damage state of the small hole diameter part after peeling and an etching process The surface by the side of the small hole diameter part of the anodized part after peeling and an etching process was observed with the scanning electron microscope. Next, the ratio of the area of the damaged portion to the area of the observation field was obtained from the obtained SEM image. As a result, the ratio of the area of the damaged portion to the area of the observation field was 0.1%.

-Successful firing rate in firing step When the successful firing rate in the firing step was determined, the successful firing rate was 100%.

DESCRIPTION OF SYMBOLS 1 Filtration membrane for particulate capture 2 Small pore diameter part 3 Middle pore part 4 Large pore diameter part 5 One surface of filtration membrane 6 Other surface of filtration membrane 7 Small pore diameter communication hole opening 8 Small pore diameter communication hole 9 Middle Hole 10 communicating hole 11 Large hole diameter communicating hole 11 Large hole diameter communicating hole 12 Wall, skeleton 21 Water to be treated 22 Treated water 23 Aluminum material 24 Counter electrode material 25 Electrolytic solution 26 DC power source 31 Anodized aluminum material (1)
32 Anodized aluminum material (2)
33 Anodized aluminum (3)
34 Anodized portion 35 Aluminum material portion 81 Communication hole 91 for small hole diameter portion Communication hole 101 for intermediate hole portion Communication hole 201 for large hole diameter portion 301 Corresponding to small hole diameter portion 301 Portion corresponding to intermediate hole portion Large Portion corresponding to the hole diameter

Claims (6)

A filtration membrane for capturing fine particles obtained by forming communication holes by anodization of an aluminum material,
A small hole diameter portion in which a communication hole opening on one surface of the filtration membrane is formed;
An intermediate hole portion in which a communication hole of the small hole diameter portion is connected and a communication hole having a diameter larger than the diameter of the communication hole of the small hole diameter portion is formed;
A large hole diameter portion in which the communication hole of the intermediate hole portion is connected, the diameter is larger than the diameter of the communication hole of the intermediate hole portion, and a communication hole opened on the other surface of the filtration membrane is formed;
Have
In the small pore diameter portion, communication holes having an average pore diameter of 4 to 20 nm are formed from one surface of the filtration membrane to a position of 400 to 1000 nm,
The total thickness of the filtration membrane Ri 15~50μm der,
Ultra-pure water, fine supplement film Der Rukoto of solvent or liquid chemical,
A filter membrane for capturing fine particles.   The communication hole of the intermediate hole portion is connected to a plurality of communication holes of the small hole diameter portion, and the communication hole of the large hole diameter portion is connected to a plurality of communication holes of the intermediate hole portion. The filtration membrane for capturing fine particles according to 1.   The filtration membrane for trapping fine particles according to claim 1 or 2, wherein a relative standard deviation in the pore size distribution of the communication holes of the small pore diameter portion is 40% or less.   The filtration membrane for capturing particulates according to any one of claims 1 to 3, wherein the aperture ratio of the communication hole of the small pore diameter portion on one surface of the filtration membrane is 10 to 50%.   The fine particle trapping filtration according to any one of claims 1 to 4, wherein in the SEM image of the cross section obtained by observation with a scanning electron microscope, the proportion of the communicating holes in the small hole diameter portion is 10 to 60%. film. A first anodizing step for obtaining an anodized aluminum material (1) by anodizing the aluminum material to form a communicating hole for a large-diameter portion in the aluminum material;
By anodizing the anodized aluminum material (1), the anodized aluminum material (1) is connected to the communicating hole for the large hole diameter portion and has a diameter smaller than that of the communicating hole for the large hole diameter portion. A second anodizing step of forming an anodized aluminum material (2) by forming a communicating hole for the part;
By anodizing the anodized aluminum material (2), the anodized aluminum material (2) is connected to the communication hole for the intermediate hole and has a smaller diameter than the communication hole for the intermediate hole. A third anodizing step of forming an anodized aluminum material (3) by forming a communicating hole for the part;
A peeling and etching step of peeling the anodized part from the anodized aluminum material (3), and then etching the peeled part to obtain an anodized part;
A firing step of obtaining a filtration membrane for capturing fine particles by firing the anodized portion at 800 to 1200 ° C .;
Have
In the third anodic oxidation step, communication holes having an average pore diameter of 4 to 20 nm are formed in the thickness direction from 400 to 1000 nm,
And from the first anodizing step to the third anodizing step, the total thickness of the portion where the communicating holes are formed by anodization is 15 to 50 μm,
A method for producing a fine particle capturing filtration membrane.