JP3466734B2 - Vinylidene fluoride resin porous membrane and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a porous membrane used as a microfiltration membrane for drugs or bacteria, or a porous membrane used as a separator for batteries. The present invention relates to a vinylidene fluoride resin porous membrane having an asymmetric structure with different pore diameters, excellent mechanical strength such as stress at break and elongation at break, and a narrow pore diameter distribution width, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, synthetic resin porous membranes have been used in various fields as separation membranes for gas separation, gas-liquid separation, solid-liquid separation, etc., or as insulating materials, heat insulating materials, sound insulation materials, heat insulating materials, etc. ing. Of these, the following properties that affect the separation function are required especially when used as a separation membrane. First, it has a suitable porosity for the purpose of separating the porous membrane, has a uniform pore size distribution for the purpose of improving the separation accuracy, and has an optimum pore size for the separation target. Desired. Further, as the properties of the membrane constituent material, chemical resistance, weather resistance, heat resistance, strength and the like with respect to the characteristics of the separation target are required. Furthermore, sufficient elongation at break, stress at break, etc. are required as mechanical strength when the porous membrane is used. At present, vinylidene fluoride-based resins are excellent in weather resistance, chemical resistance, heat resistance, strength, etc., and their application to these porous membranes for separation is being investigated.
However, while the vinylidene fluoride resin has the above-mentioned excellent properties, it is non-adhesive and has low compatibility, so that the moldability is not always good. Further, in the development of a porous membrane, a high porosity and a narrow pore size distribution were pursued for the purpose of improving the separation performance, and satisfactory mechanical strength was not obtained. For this reason, in order to replenish the strength, when used as a filtration membrane, the support membrane is superposed on the porous membrane to enhance the mechanical properties and used. In addition, when used in a battery separator, since the porous film is used by being wound around a core material, sufficient elongation at break and elongation at break that can withstand the winding step during battery production. It is desired to have mechanical properties such as stress. In addition, when used as a battery separator, it has a narrow distribution pore size that can block the fine powder of the active material used for the electrode and the high efficiency of the electrolytic solution that is performed after winding the porous membrane around the core material. A good impregnation property is desired. Further, when it is used as a microfiltration membrane, it is desired to maintain high filterability for a long period of time. Japanese Patent Laid-Open No. 3-2
Japanese Patent No. 15535 describes a method of mixing polyvinylidene fluoride resin with an organic liquid such as diethyl phthalate and hydrophobic silica as an inorganic fine powder, and extracting the organic liquid and the hydrophobic silica after melt molding. The porous membrane obtained by this method has relatively high mechanical strength.
However, this porous membrane has a relatively uniform average pore size on both sides of the membrane and is not a porous membrane having an asymmetric structure as provided by the present invention. Highly efficient impregnation of liquid or high permeability over a long period when used as a microfiltration membrane cannot be expected. Furthermore, since an aqueous alkali solution is used to extract the hydrophobic silica, the vinylidene fluoride resin is likely to deteriorate.

The object of the present invention is to have a highly efficient impregnation property of an electrolytic solution when it is used in a battery separator, a high permeability for a long period of time when it is used as a microfiltration membrane, and an elongation at break and It is an object of the present invention to provide a vinylidene fluoride-based resin porous membrane having an asymmetric structure having excellent mechanical strength such as stress at break and a method for producing the same.

[0004]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of these circumstances and found that a vinylidene fluoride resin having a specific inherent viscosity and a specific plasticizer are used to form a film by melt extrusion molding. , When subjected to a specific post-treatment, the efficiency of impregnation of the electrolytic solution when used in a battery separator and the long-term permeability when used as a microfiltration membrane are excellent, and further stress at break and elongation at break It was found that an asymmetric vinylidene fluoride resin porous membrane excellent in mechanical properties such as degree is produced, and the present invention has been completed.

[0005] That is, according to the present invention, the inherent viscosity of the vinylidene fluoride resin forming the porous membrane is 1.3~15.0 (dl / g), satisfies the following formula (A) , P1 is 0.89 μm or less, a vinylidene fluoride resin porous membrane is provided.

(A) 4.0 <P ₁ / P ₂ ≦ 10.0 {P ₁ is a single-sided electron microscope having a large average pore size.
Measured average pore size (μm), P ₂ is the electron on the other surface
It is the average pore diameter (μm) measured by a microscope . }

According to the present invention, the vinylidene fluoride resin porous material has a ratio P ₄ / P _{3 of} the pore diameter P ₄ measured by the bubble point method to the pore diameter P ₃ measured by the half dry method is 2.0 or less. A quality membrane is provided.

According to the invention, the porous membrane is empty.
Considering the porosity φ, the stress at break Tb (MP
Convert the product of a) and elongation at break Eb (%) to 0% porosity.
The above-mentioned vinylidene fluoride-based resin porous film is provided.

(B) [Tb × Eb / (100−φ)] × 100 ≧ 1000 {φ is the porosity (volume%), Tb is the stress at break (MP
a) and Eb are elongation at break (%). }

According to the present invention, 30 to 250 parts by weight of aliphatic polyester as a plasticizer is added to 100 parts by weight of vinylidene fluoride resin having an inherent viscosity of 1.4 to 15.0 (dl / g). Part was added, and the obtained composition was extruded.
Manufacture of a vinylidene fluoride-based resin porous film satisfying the following formula (A), characterized in that the film is formed by cooling with a chill roll at ℃ or below and air-cooling on the other side to form a film. A method is provided.

(A) 4.0 <P ₁ / P ₂ ≦ 10.0 {P ₁ has a large average pore diameter The average pore diameter on one surface (μ
m) and P ₂ are the average pore diameter (μm) on the other surface. }

Further, according to the present invention, 30 to 250 parts by weight of a fatty polyester as a plasticizer is added to 100 parts by weight of a vinylidene fluoride resin having an inherent viscosity of 1.4 to 15.0 (dl / g). And 1 to 50 parts by weight of a good solvent of vinylidene fluoride resin is added, and the obtained composition is extruded.
A vinylidene fluoride-based resin porous material satisfying the following formula (A), characterized in that it is cooled with a chill roll at ℃ or below, and the other side is air-cooled to form a film, and then a plasticizer and a good solvent are extracted from the film. A method of making a membrane is provided.

(A) 4.0 <P ₁ / P ₂ ≦ 10.0 {P ₁ has a large average pore diameter The average pore diameter on one surface (μ
m) and P ₂ are the average pore diameter (μm) on the other surface. }

Further, according to the present invention, there is provided the above-mentioned method for producing a vinylidene fluoride resin porous membrane, characterized in that the porous membrane after extraction is dried while preventing the shrinkage of the porous membrane.

Further, according to the present invention, there is provided the above-mentioned method for producing a vinylidene fluoride-based resin porous membrane, which comprises drying the porous membrane after extraction without fixing the porous membrane and then stretching. Provided. Hereinafter, the present invention will be described in detail.

The vinylidene fluoride resin used in the present invention is a vinylidene fluoride homopolymer, a copolymer containing vinylidene fluoride as a constituent unit in an amount of 70 mol% or more, or a mixture of these polymers. can do. Examples of the monomer copolymerized with vinylidene fluoride include tetrafluoroethylene, hexafluoropropylene, trifluoroethylene, trifluorochloroethylene, vinyl fluoride, and the like, and one or more of these may be used. Can be used. Further, the inherent viscosity of the vinylidene fluoride resin as a raw material is 1.4 to 15.0 (dl /
g), preferably 1.5 to 10.0 (dl
/ G), more preferably 1.6 to 8.0 (dl / g)
Is. If the inherent viscosity of the vinylidene fluoride resin as a raw material is within this range, a porous film having sufficient mechanical strength such as elongation at break, stress at break, etc. of the resulting porous film is formed, and the pore size is also reduced. A uniform porous film is formed. The inherent viscosity in the present invention is 0.4 g / d using dimethylformamide as a solvent.
It is a value measured under the conditions of 1 and temperature of 30 ° C. Further, if the inherent viscosity of the vinylidene fluoride resin as a raw material is in the above range, the inherent viscosity of the vinylidene fluoride resin constituting the obtained porous film of the present invention is almost the same as that of the raw material, and 1.3 to It is in the range of 15 (dl / g). The vinylidene fluoride resin contains an antioxidant,
An antistatic agent, a lubricant, a surfactant and the like can be appropriately added as needed.

The plasticizer used in the present invention is a plasticizer for vinylidene fluoride resins, such as adipic acid-propylene glycol, adipic acid-1,3.
-Adipic acid-based polyester such as butylene glycol-based, sebacic acid-propylene glycol-based, sebacic acid-1,3-butylene glycol-based sebacic acid-based polyester, azelaic acid-propylene glycol-based, azelaic acid-1,3 An aliphatic polyester plasticizer composed of an aliphatic dibasic acid such as an azelaic acid-based polyester such as butylene glycol-based polyester and glycol is exemplified, but particularly adipic acid-based from the viewpoint of compatibility with vinylidene fluoride-based resin. Polyester is preferred. Further, the compounding amount of the plasticizer is 3 with respect to 100 parts by weight of the vinylidene fluoride resin.
The amount is 0 to 250 parts by weight, preferably 40 to 170 parts by weight, and more preferably 50 to 120 parts by weight.

In the present invention, it is preferable to use a good solvent of vinylidene fluoride resin in combination with the plasticizer. This makes it possible to obtain a porous membrane having a narrower pore size distribution width represented by the ratio P ₄ / P ₃ . The good solvent for the vinylidene fluoride resin is a solvent capable of dissolving the vinylidene fluoride resin in any temperature range within the range of 20 to 250 ° C., for example, N-methylpyrrolidone, dimethylformamide, dimethylacetamide. , Dimethyl sulfoxide, methyl ethyl ketone, acetone, tetrahydrofuran, dioxane, ethyl acetate, propylene carbonate, cyclohexane, methyl isobutyl ketone, dimethyl phthalate, etc.
-Methylpyrrolidone is preferred. The mixing ratio of the good solvent is 1 to 100 parts by weight of vinylidene fluoride resin.
It is preferable to use 50 parts by weight, more preferably 10 parts by weight.
˜35 parts by weight.

The method for producing the vinylidene fluoride resin porous membrane of the present invention is as follows: a vinylidene fluoride resin is added with a plasticizer or a good solvent, and then a plasticizer or a good solvent is added. To extract. As the film forming method, a general melt extrusion molding method of vinylidene fluoride resin can be adopted. The melting temperature of the resin composition during molding is preferably 170 to 250 ° C, more preferably 180 to 240 ° C. For extrusion, a T-die is preferably used to form a film having a thickness of 10 to 300 μm, more preferably 20 to 100 μm. At that time, it is preferable to cool one side of the extruded film in a molten state by a chill roll at 150 ° C. or lower, preferably 30 to 100 ° C., and air-cool the other side. The air cooling at that time may be performed using an air knife or the like. By rapidly cooling one surface as compared with the other surface in this manner, an asymmetric vinylidene fluoride resin porous membrane can be obtained through extraction described later.

The solvent for extracting the plasticizer or the good solvent from the film obtained above is not particularly limited as long as it does not dissolve the vinylidene fluoride resin and can dissolve the plasticizer and the good solvent. . Examples include alcohols such as methanol and isopropyl alcohol, and examples of chlorinated hydrocarbons such as methylene chloride and 1,1,1-trichloroethane.

The above extraction method using a solvent is carried out at a temperature of 10 to 1
It is left in an extraction solvent at 50 ° C, preferably 15 to 100 ° C, more preferably 20 to 50 ° C. Moreover, it is possible to accelerate the extraction by applying appropriate vibration. After extracting the plasticizer or good solvent, the temperature is 50 to 150 for drying the porous membrane.
Heat treatment is performed at 0 ° C. for 0.5 to 360 minutes. During the drying, the periphery of the porous membrane is held by a mold or the like to prevent shrinkage during drying, or after performing the extraction and drying without fixing the porous membrane, the shrinkage during drying is performed. It is preferable to stretch the film uniaxially or biaxially to the extent that wrinkles are removed.

Thus, the vinylidene fluoride resin porous membrane of the present invention is obtained, but it may be further uniaxially or biaxially stretched in order to improve the mechanical strength. Stretching is 1.
It is preferably 5 to 3 times. The porous film stretched in this manner also satisfies the above formula (A) and is the vinylidene fluoride resin porous film of the present invention.

The porous membrane of the present invention thus obtained generally has a porosity of 20 to 80%, preferably 25 to 6
0%, film thickness 10-300 μm, preferably 10-300 μm
It is in the range of 100 μm, the pore diameter P ₃ measured by the half dry method is 0.01 to 10 μm, and the ratio P ₄ / P ₃ of the pore diameter P ₄ measured by the bubble point method is 2.0 or less, more preferably 1 It is less than or equal to 8. Since the ratio P ₄ / P ₃ is small as described above, that is, the pore size distribution width is narrow, a highly accurate separation function is achieved as a separation membrane. Membranes with P ₄ of 10.0 μm or less are suitable for microfiltration membranes, and P ₃ of 0.01 to 2.0 μm.
The film of m can be used for a battery separator and the like. The porous membrane of the present invention obtained as described above satisfies the following expression (A), and particularly preferably also satisfies the following expression (B). At that time, more preferably, the value on the left side of the formula (B) is in the range of 5,000 to 50,000.

(A) 4.0 <P ₁ / P ₂ ≦ 10.0 {P ₁ has a large average pore diameter The average pore diameter on one surface (μ
m) and P ₂ are the average pore diameter (μm) on the other surface. } (B) [Tb × Eb / (100−φ)] × 100 ≧ 1
000 {φ is porosity (volume%), Tb is stress at break (MP
a) and Eb are elongation at break (%). }

Therefore, the through hole diameter has a sufficient mechanical strength to withstand winding operation around the electrode when it is used for the battery separator, and has a narrow distribution width capable of blocking fine powder of the active material. And has an asymmetric structure in which the average pore diameter on one side is larger than the average pore diameter on the other surface, and therefore has the characteristic that the electrolytic solution after winding is easily impregnated. When used as a microfiltration membrane, it has a sufficient separation function and exhibits high permeability over a long period of time.

[0021]

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited thereto. The measurements in Examples and Comparative Examples were based on the following methods.

(Measurement Method) [1. Stress at Break and Elongation at Break] Using a tensile strength / elongation measuring machine (Tensilon RTM-100 type, manufactured by Orientec Co., Ltd.), a vinylidene fluoride-based resin porous flat membrane was formed to have a width of 10 mm and a length of 100 mm. A cut test piece was used. This test piece has a chuck distance of 50 mm and a pulling speed of 25 mm.
The strength at break and the amount of elongation to break were measured under the condition of / min, and the stress at break and the elongation at break were determined from the following formulas.

## EQU10 ## Stress at break (MPa) = [(strength at break Kg
f) / cross-sectional area of test piece before tension (cm ² )] × 0.09
81, elongation at break (%) = [elongation to break (displacement) (m
m) / 50 (mm)] × 100

[2. Porosity] PMI Porosimeter (P
The pore volume using mercury was measured by using Orous Materials), and the porosity was calculated from the following formula. The maximum pressure during measurement is 20,000 PSI (1,40
6 kg / cm ² ).

[Equation 11] Porosity (%) = (pore volume / porous membrane volume) × 100

[3. Pore diameter P ₃ ] Pore diameter P ₃ is measured area 2
It was determined by a half-dry method using ethanol based on ASTM F-316-86 using a 0 mmφ test piece.

[4. Pore diameter P ₄ ] Pore diameter P ₄ is measured area 2
It was determined by a bubble point method using an ethanol based on ASTM F-316-86 using a 0 mmφ test piece.

[5. Average pore size P ₁ , P ₂ ] The surface of the porous membrane was observed by a scanning electron microscope photograph, and the average of the major axis and the minor axis of 100 openings was weighted averaged.

Example 1 An inherent viscosity of 1.6
(Dl / g) polyvinylidene fluoride resin "PVDF"
After mixing 50 parts by weight of an adipic acid-based polyester plasticizer (PN-640, manufactured by Asahi Denka Kogyo Co., Ltd.) with 100 parts by weight of KF # 1600 (Kureha Chemical Industry Co., Ltd.) with a Hensyl mixer, a temperature of 240 was used. It was melt extruded at 0 ° C. and pelletized. Width of the obtained pellets 350 mm,
With a melt extruder equipped with a T die with a lip clearance of 1.4 mm, melt extrude into a film with a thickness of 50 μm at a temperature of 240 ° C., and continuously cool one surface with a chill roll at a temperature of 60 ° C. while cooling the other surface with an air knife. The formed film was molded. The formed film is cut into 200 mm squares and vibrated in methylene chloride at room temperature for 10 minutes.
It was immersed for a minute to extract the plasticizer, and dried and heat-treated at 100 ° C. for 30 minutes while holding the four sides with a mold to prevent shrinkage, to obtain a vinylidene fluoride resin porous membrane. The resulting inherent viscosity of polyvinylidene fluoride resin constituting the vinylidene fluoride resin porous membrane, the porosity of the porous membrane, the average pore diameter P ₁ to P _2, pore size P ₃ to P _4, and at break The stress and the elongation at break were measured. The results are shown in Table-1. Where P ₁ is the average pore size of the surface cooled by the chill roll,
P ₂ is the average pore diameter of the surface cooled by the air knife.

Example 2 An inherent viscosity of 1.6
(Dl / g) polyvinylidene fluoride resin "PVDF"
(Kureha Chemical Industry Co., Ltd., KF # 1600) 50 parts by weight and adipic acid polyester plasticizer (Asahi Denka Co., Ltd., PN-640) 50 parts by weight and N.
After mixing 17 parts by weight of methylpyrrolidone with a Hensyl mixer, the mixture was melt extruded at a temperature of 240 ° C. and pelletized. The obtained pellets were melt-extruded with a T-die having a width of 350 mm and a lip clearance of 1.4 mm,
A film having a thickness of 50 μm was melt-extruded at a temperature of 240 ° C., one surface was cooled by a chill roll at a temperature of 60 ° C., and the other surface was air-cooled at room temperature to form a continuous film. The formed continuous film is immersed in methylene chloride at room temperature for 10 minutes while applying ultrasonic waves to continuously extract the plasticizer and good solvent, and the resulting porous film is not fixed while applying hot air at 50 ° C. After drying and winding, it was uniaxially stretched 1.5 times between metal rolls at 30 ° C at a line speed of 1 m / min, and heat-treated for 2 minutes on the metal rolls at 100 ° C to obtain continuous vinylidene fluoride. A porous resin film was obtained. Obtained polyvinylidene fluoride resin porous film constituting polyvinylidene fluoride resin inherent viscosity, porosity of the porous film, average pore diameters P _{1 to} P ₂ , pore diameters P _{3 to} P ₄ , and stress at break The elongation at break was measured. The results are shown in Table-1
Shown in. Here, P ₁ is the average pore size of the surface cooled by the chill roll, and P ₂ is the average pore size of the surface cooled by air.

Example 3 An inherent viscosity of 1.6
(Dl / g) polyvinylidene fluoride resin "PVDF"
(Kureha Chemical Industry Co., Ltd., KF # 1600) 100 parts by weight, adipic acid polyester plasticizer (Asahi Denka Kogyo Co., Ltd., PN-150) 117 parts by weight and N-methylpyrrolidone 17 parts by weight are added to the hensyl mixer. After mixing at −, the mixture was melt extruded at a temperature of 200 ° C. and pelletized. The obtained pellets were melt-extruded with a T-die having a width of 350 mm and a lip clearance of 1.4 mm,
A film having a thickness of 50 μm was melt-extruded at a temperature of 180 ° C., and a continuous film was formed while cooling one surface with a chill roll at a temperature of 60 ° C. and the other surface with an air knife. The extraction of the plasticizer and the good solvent, and the heat treatment for drying were conducted in Example
A vinylidene fluoride resin porous membrane was obtained in the same manner as in. With respect to the obtained vinylidene fluoride resin porous membrane, the film properties and mechanical properties were measured by the same measurement method as in Example 1. The results are shown in Table-1. Here, P ₁ is the average pore diameter of the surface cooled by the chill roll, and P ₂ is the average pore diameter of the surface cooled by the air knife.

(Comparative Example 1) Commercially available vinylidene fluoride resin porous membrane made by Millipore Durapore GVHP0001
0 was used to measure the same property items as in Examples 1 to 3. The results are shown in Table-1.

[0031]

[Table 1]

(Results) According to the method for producing a vinylidene fluoride resin porous membrane of the present invention, sufficient stress at break,
An asymmetric porous membrane having elongation at break was obtained. Even when compared with the conventional product (Comparative Example 1) obtained by a method other than the melt extrusion molding according to the present invention, the pore size distribution width was comparable to the conventional product in use.

[0033]

According to the method for producing a vinylidene fluoride resin porous membrane of the present invention, a porous membrane having excellent mechanical strength such as stress at break and elongation at break can be obtained. Moreover, since the obtained porous membrane has a narrow pore size distribution width, it is possible to perform separation with higher accuracy. Further, since the vinylidene fluoride resin porous membrane according to the present invention has high mechanical strength, it does not need to be supported by a reinforcing material or the like, and is extremely useful in production and use. Further, since it is an asymmetric type porous membrane having different average pore diameters on both sides, high permeability can be maintained for a long period of time, and the impregnation efficiency of the electrolytic solution when used as a battery separator is good.

─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Hiroshi Sato 21 No. 21 Kamigamasato, Tamari-son, Shinji-gun, Ibaraki 138 (56) References JP-A-63-296940 (JP, A) JP-A-52-51465 (JP) , A) JP-A-3-215535 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08J 9/00-9/42

Claims (7)

(57) [Claims] 1. The inherent viscosity of the vinylidene fluoride resin forming the porous film is 1.3 to 15.0 (dl).
/ G), which satisfies the following expression (A), and P1 is 0.89μ.
A vinylidene fluoride-based resin porous membrane having a thickness of m or less . (A) 4.0 <P ₁ / P ₂ ≦ 10.0 {P ₁ is a single-sided electron microscope having a large average pore size.
Measured average pore size (μm), P ₂ is the electron on the other surface
It is the average pore diameter (μm) measured by a microscope . } 2. A ratio P ₄ / P of the pore diameter P ₄ measured by the bubble point method to the pore diameter P ₃ measured by the half dry method.
_{3. The} vinylidene fluoride resin porous membrane according to claim 1, wherein ₃ is 2.0 or less. 3. Considering the porosity φ of the porous membrane,
Stress at break Tb (MPa) and elongation at break Eb of porous film
The value obtained by converting the product of (%) into a porosity of 0% satisfies the following expression (B): The vinylidene fluoride resin porous membrane according to claim 1 or 2, wherein (B) [Tb × Eb / (100−φ)] × 100 ≧ 1000 {φ is the porosity (volume%), Tb is the stress at break (MP
a) and Eb are elongation at break (%). } 4. The inherent viscosity is 1.4 to 15.0.
30 to 30 parts by weight of aliphatic polyester as a plasticizer with respect to 100 parts by weight of vinylidene fluoride resin (dl / g).
250 parts by weight of the composition obtained was extruded, and one side of the molten film extruded was cooled with a chill roll at a temperature of 150 ° C. or lower, and the other side was air-cooled to form a film, and then a plasticizer was extracted from the film. A method for producing a vinylidene fluoride-based resin porous membrane satisfying the following formula (A): ## EQU00003 ## (A) 4.0 <P ₁ / P ₂ ≦ 10.0 {P ₁ is a single-sided electron microscope having a large average pore size.
Measured average pore size (μm), P ₂ is the electron on the other surface
It is the average pore diameter (μm) measured by a microscope . } 5. The inherent viscosity is 1.4 to 15.0.
To 100 parts by weight of vinylidene fluoride resin (dl / g), 30 to 2 of fatty polyester as a plasticizer is used.
50 parts by weight and 1 of good solvent of vinylidene fluoride resin
-50 parts by weight is added, and the obtained composition is extruded, and one side of the molten film is cooled with a chill roll at a temperature of 150 ° C or lower, and the other side is air-cooled to form a film, and then a plasticizer and a good solvent are added. Is extracted from the film. A method for producing a vinylidene fluoride resin porous membrane satisfying the following formula (A): (A) 4.0 <P ₁ / P ₂ ≦ 10.0 {P ₁ is a single-sided electron microscope having a large average pore size.
Measured average pore size (μm), P ₂ is the electron on the other surface
It is the average pore diameter (μm) measured by a microscope . } 6. The porous membrane after extraction is dried while preventing shrinkage of the porous membrane.
A method for producing a vinylidene fluoride resin porous membrane as described. 7. The method for producing a vinylidene fluoride resin porous membrane according to claim 4, wherein the porous membrane after extraction is dried without fixing the porous membrane, and then stretched. .