Highly durable porous PVDF film, method of producing the same and washing method and filtration method using the same

• US 8,931,647 B2
• Filed: 04/16/2007
• Issued: 01/13/2015
• Est. Priority Date: 04/19/2006
• Status: Active Grant

• Current Assignee: Asahi Kasei Kabushiki Kaisha (Asahi Kasei Corporation)
• Original Assignee: Asahi Kasei Chemicals Corporation (Asahi Kasei Corporation)
• Inventors: Shiki, Satoshi, Ohya, Hiroyoshi, Kubota, Noboru, Hattori, Makiko
• Primary Examiner(s): ZALASKY, KATHERINE M
• Application Number:
  US12/297,580
• Publication Number:
  US 20090101600A1
• Time in Patent Office: 2,829 Days
• Field of Search: 210/500.36, 210/500.23, 210/649, 210/636
• US Class Current: 210/500.42
• CPC Class Codes: B01D 2323/02 Hydrophilization
• CPC Class Codes: B01D 2325/30 Chemical resistance
• CPC Class Codes: B01D 2325/34 Molecular weight or degree of polymerisation
• CPC Class Codes: B01D 67/0011 Casting solutions therefor
• CPC Class Codes: B01D 69/02 characterised by their properties
• CPC Class Codes: B01D 69/08 Hollow fibre membranes manufacture of hollow fibres D01D5/24, D01F1/08
• CPC Class Codes: B01D 71/34 Polyvinylidene fluoride
• CPC Class Codes: C08J 2327/16 Homopolymers or copolymers of vinylidene fluoride
• CPC Class Codes: C08J 5/18 Manufacture of films or sheets
• CPC Class Codes: Y10T 428/24595 and varying density

Abstract

The present invention provides a PVDF porous film and method for producing it, which has high water permeability and high chemical resistance to washing chemicals and the like that has been difficult to realize with conventional polymer porous films, and which can be used over a prolonged period of time, and a method of producing the same and the like. Namely, the present invention provides a porous film in which the degree of crystallization of the PVDF resin is 50% or more but not more than 90%, and the product of the degree of crystallization of the PVDF resin and the specific surface area of the film is 300 (%·m²/g) or more but not more than 2000 (%·m²/g).

Claims

1. A porous film comprising a polymer component having a polyvinylidene fluoride (PVDF), resin as a main component thereof,

wherein the degree of crystallization of the PVDF resin in the film is 50% or more but not more than 90%, and

the product of the degree of crystallization of the PVDF resin in the film and a specific surface area of the film is 300 (%·

m²/g) or more but not more than 2000 (%·

m²/g).

2. The porous film according to claim 1, wherein a total amount of β

-type crystal and γ

-type crystal in a crystalline portion of the PVDF resin is 30% or less based on a total amount of the crystalline portion of the PVDF resin.

3. The porous film according to claim 1, wherein polyethylene glycol having a weight average molecular weight of 20,000 or more but not more than 300,000 is contained as the polymer component at 0.01 parts by weight or more but not more than 3 parts by weight based on 100 parts by weight of the PVDF resin.

4. The porous film according to claim 1, wherein the PVDF resin has an intramolecular irregular sequence ratio as determined by ¹⁹F-NMR measurement of 8.8% or more but less than 30.0%.

5. The porous film according to claim 1, wherein the porous film has a film structure of a hollow fiber membrane.

6. The porous film according to claim 1, wherein the porous film has a film structure in which a backbone of the polymer component forms a mesh-like network and pores are provided therein, and the thickness of the backbone of the polymer component increases continuously or in a stepwise manner to at least ⅕

the film thickness from the side of the top and bottom film surfaces having the greatest density.

7. A method for washing a porous film, comprising contacting the porous film according to claim 1 with an alkaline solution.

8. A filtering method, comprising contacting the porous film according to claim 1 with an aqueous solution and an alkaline solution alternately at least one time.

9. A method for producing a porous film comprising:

producing a porous film having a polyvinylidene fluoride (PVDF) resin as a main component thereof by extruding, from a molding nozzle, a film-forming solution which at least comprises a hydrophobic polymer component having a PVDF resin as a main component thereof, a hydrophilic polymer component and a common solvent for both the hydrophobic and hydrophilic polymer components, and solidifying the film-forming solution in a solution having water as a main component thereof, wherein polyethylene glycol having a weight average molecular eight of 20,000 or more but not more than 150,000 is used as the hydrophilic polymer component,

wherein the degree of crystallization of the PVDF resin in the film is 50% or more but not more than 90% and

the product of the degree of crystallization of the PVDF resin in the film and a specific surface area of the film is 300 (%·

m²/g) or more but not more than 2000 (%·

m²/g).

10. The method for producing a porous film according to claim 9, wherein a PVDF resin having an intramolecular irregular sequence ratio as determined by ¹⁹F-NMR measurement of 8.8% or more but less than 30.0% is used as the PVDF resin.

11. The method for producing a porous film according to claim 9, wherein the film-forming solution contains 20% by weight or more but not more than 35% by weight of the hydrophobic polymer component, and 8% by weight or more but not more than 30% by weight of the hydrophilic polymer component.

12. The method for producing a porous film according to claim 9, wherein the temperature of the solution for solidifying the film-forming solution (Tb°

C.) satisfies the relationship of Td+5≦

Tb≦

Td+30 and the e relationship of Td≦

Tc≦

Tb with respect to the temperature of the film-forming solution (Td°

C.) and the cloud point temperature of the film-forming solution (Tc°

C.).

13. The method for producing a porous film according to claim 9, wherein the molding nozzle is a double-tube nozzle, and a porous film having a hollow fiber membrane structure is produced by extruding the film-forming solution from the molding nozzle together with a hollowing agent, and solidifying the same in a solution having water as a main component thereof.

14. The method for producing a porous film according to claim 9, wherein the film-forming solution contains at least dimethylacetoamide as the common solvent.