Method for manufacturing a porous composite membrane
View Patent ↗Disclosed is a method for manufacturing a composite porous film having a stable film quality and a desired hollow shape by controlling the entrance of a film-forming resin solution into a hollow part of a hollow reinforcement support. The method is provided with a step of adhering a film-forming resin solution to the outer peripheral surface of the hollow reinforcement support and thereby forming a film intermediate, a step of adhering a coagulating liquid to the outer peripheral surface of the film intermediate, and a step of flowing the coagulating liquid along the outer peripheral surface of the film intermediate so that at least a part of the outermost interface of the coagulating liquid in the circumferential direction is a free surface and thereby coagulating the film-forming resin solution adhering to the outer peripheral surface of the hollow reinforcement support.
1. A method for manufacturing a porous composite membrane, the method comprising:
adhering a membrane-forming resin solution to an outside circumferential surface of a hollow reinforcing support body to obtain a membrane intermediate;
passing the membrane intermediate through a coagulating bath containing a coagulation solution of equal to or less than 500 mm in depth and adhering a coagulating solution to an outside circumference of the membrane intermediate with applying external pressure depending on the depth of the coagulation solution in the coagulating bath to the membrane-forming resin adhered to the outside circumferential surface of a hollow reinforcing support body; and
coagulating the membrane-forming resin solution as the coagulating solution flows along the outside circumferential surface of the membrane intermediate in such a way that at least a portion in a circumferential direction of an outermost boundary surface of the coagulating solution is treated as a free surface,
wherein a length of contact of the coagulation solution with the membrane intermediate is from 200 to 3000 mm.
2. The method of claim 1 , wherein, in the coagulating the membrane-forming resin solution, the membrane intermediate is transported in a vertical downward direction.
3. The method of claim 1 , wherein, in the coagulating the membrane-forming resin solution, the membrane intermediate is transferred in a direction inclined with respect to a vertical plane.
4. The method of claim 1 , wherein, in the adhering the coagulating solution to the outside circumference of the membrane intermediate, the coagulating solution is supplied from a portion of the circumferential direction, or from an entire circumference of the membrane intermediate.
5. The method of claim 1 , wherein the hollow reinforcing support body is a hollow knitting thread, a hollow twining thread, or a hollow fiber membrane.
6. The method of claim 1 , wherein a cross-sectional shape of the hollow reinforcing support body is annular.
7. The method of claim 1 , wherein the membrane-forming resin solution comprises a polysulfone resin, a polyacrylonitrile, a cellulose derivative, a fluoride resin, or copolymers of these resins, which could be partially-substituted, or mixtures thereof.
8. The method of claim 7 , wherein the membrane-forming resin solution comprises polysulfone, polyether sulfone, polyvinylidene fluoride, polyamide, polyester, polymethacrylate, or polyacrylate.
9. The method of claim 1 , wherein the membrane-forming resin solution is obtained by a process comprising dissolving from 10 mass % to 30 mass % of membrane-forming resin solution into a solvent.
10. The method of claim 1 , wherein the membrane-forming resin solution is obtained by a process comprising dissolving from 15 mass % to 25 mass % of membrane-forming resin solution into a solvent.
11. The method of claim 1 , wherein the membrane-forming resin solution comprises at least one additive selected from the group consisting of a hydrophilic polymer, water, alcohol, and an inorganic salt.
12. The method of claim 11 , wherein a concentration of the at least one additive in the membrane-forming resin solution is from 1 mass % to 20 mass %.
13. The method of claim 1 , wherein a viscosity of the membrane-forming resin solution is from 20,000 to 500,000 mPa·sec at 40° C.
14. The method of claim 1 , wherein the coagulating solution comprises water.
15. The method of claim 1 , further comprising removing unnecessary components remaining in the membrane after coagulating.