CN104284710A - Method and spinning device for producing porous hollow yarn membrane - Google Patents
Method and spinning device for producing porous hollow yarn membrane Download PDFInfo
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- CN104284710A CN104284710A CN201380025020.8A CN201380025020A CN104284710A CN 104284710 A CN104284710 A CN 104284710A CN 201380025020 A CN201380025020 A CN 201380025020A CN 104284710 A CN104284710 A CN 104284710A
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- spinning
- stoste
- masking stoste
- porous hollow
- fibre membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 186
- 238000009987 spinning Methods 0.000 title claims abstract description 113
- 238000000034 method Methods 0.000 title claims description 46
- 238000004519 manufacturing process Methods 0.000 claims abstract description 72
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 230000000873 masking effect Effects 0.000 claims description 330
- 239000000835 fiber Substances 0.000 claims description 203
- 238000011144 upstream manufacturing Methods 0.000 claims description 113
- 239000002243 precursor Substances 0.000 claims description 38
- 239000011347 resin Substances 0.000 claims description 38
- 229920005989 resin Polymers 0.000 claims description 38
- 239000003795 chemical substances by application Substances 0.000 claims description 37
- 230000002787 reinforcement Effects 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 30
- 230000015572 biosynthetic process Effects 0.000 claims description 22
- 238000007711 solidification Methods 0.000 claims description 20
- 230000008023 solidification Effects 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229920001600 hydrophobic polymer Polymers 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 238000005336 cracking Methods 0.000 abstract description 25
- 230000001112 coagulating effect Effects 0.000 abstract description 3
- 238000005345 coagulation Methods 0.000 abstract 1
- 230000015271 coagulation Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 238000004140 cleaning Methods 0.000 description 16
- 239000002131 composite material Substances 0.000 description 16
- 238000001035 drying Methods 0.000 description 15
- 239000012530 fluid Substances 0.000 description 12
- 238000009434 installation Methods 0.000 description 12
- 238000005728 strengthening Methods 0.000 description 11
- DSCFFEYYQKSRSV-FEPQRWDDSA-N (1s,2s,4s,5r)-6-methoxycyclohexane-1,2,3,4,5-pentol Chemical compound COC1[C@@H](O)[C@@H](O)C(O)[C@H](O)[C@H]1O DSCFFEYYQKSRSV-FEPQRWDDSA-N 0.000 description 10
- 230000005021 gait Effects 0.000 description 10
- 238000004804 winding Methods 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 6
- 238000009940 knitting Methods 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- -1 permanganate Chemical compound 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
- B01D69/085—Details relating to the spinneret
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
- B01D69/087—Details relating to the spinning process
- B01D69/0871—Fibre guidance after spinning through the manufacturing apparatus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0016—Coagulation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
- B01D69/081—Hollow fibre membranes characterised by the fibre diameter
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
- B01D69/087—Details relating to the spinning process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1213—Laminated layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/18—Pore-control agents or pore formers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/218—Additive materials
- B01D2323/2182—Organic additives
- B01D2323/21839—Polymeric additives
- B01D2323/2187—Polyvinylpyrolidone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/42—Details of membrane preparation apparatus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/04—Characteristic thickness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The purpose of the present invention is to control cracking of a porous hollow yarn membrane, even one produced under a high spinning speed. The method for producing a porous hollow yarn membrane of the present invention comprises a spinning and coagulation step wherein the membrane-producing liquor branches into multiple currents that merge back together; the membrane-producing liquid that has formed multiple merging sites is fed to a spinning nozzle (10); inside the spinning nozzle (10) the membrane-producing liquor branches, merges annularly, and then is extruded annularly; and the membrane-producing liquor is coagulated with a coagulating bath. The ratio (t/T) of the time t found by the formula t = V/Q (where V is the volume (cm3) of the liquor flow path, from the point where the first merging site is formed in the membrane-forming liquor to the point where the membrane-forming liquor that has branched merges inside the spinning nozzle, and Q is the amount extruded per time (cm3/second) of membrane-forming liquor from the spinning nozzle (10)) and the viscoelastic relaxation time T of the membrane-forming liquor is less than 1. Moreover, spinning device (1) is used for the production method.
Description
Technical field
The present invention relates to a kind of manufacture method of Porous hollow-fibre membrane.
The application based on March 16th, 2012 in No. 2012-060208, the Patent of Japanese publication and CLAIM OF PRIORITY, and by its content quotation at this.
Background technology
Due to the surging of the care for environmental pollution and the strengthening of restriction, use the water treatment of the filter membrane that separation property and compactedness etc. are excellent noticeable.As the filter membrane in water treatment, applicable use has the Porous hollow-fibre membrane (such as patent document 1) of the Porous rete of hollow form.In the manufacture of Porous hollow-fibre membrane, such as, utilize device for spinning to carry out spinning to masking stoste, with solidification liquid, this masking stoste solidified and form Porous hollow-fibre membrane precursor.Then, remove the solvent, the pore-creating agent that remain in formed Porous hollow-fibre membrane precursor, carry out drying.By fully removing the pore-creating agent remained in Porous hollow-fibre membrane precursor, thus obtain the Porous hollow-fibre membrane with abundant water permeability.
As device for spinning, such as, there will be a known the spinning-nozzle 101 shown in Fig. 5 ~ 7.Spinning-nozzle 101 has the 1st nozzle 111 and the 2nd nozzle 112.In addition, the inside of spinning-nozzle 101 has: make the supporting mass passage 113 that the reinforcement supporting mass of hollow form passes through; And the stoste runner 114 that the masking stoste of formation Porous rete is circulated.Stoste runner 114 has: the introduction part 115 being imported with described masking stoste; Described masking stoste is divided into two parts and makes it be branch's merging part 116 of collaborating circularly; And be cylindric figuration portion 117 by described masking stoste figuration.Spinning-nozzle 101 supplies the reinforcement supporting mass of hollow form from supporting mass supply port 113a and is derived from supporting mass export mouth 113b, supplies masking stoste and cylindrically discharged around described reinforcement supporting mass from outlet 114b from resin supply port 114a.
In the spinning of the Porous hollow-fibre membrane undertaken by spinning-nozzle 101, from the masking stoste that the outlet 114b of spinning-nozzle 101 discharges, be coated on the outside of the reinforcement supporting mass of the hollow form of simultaneously deriving from supporting mass export mouth 113b.
Patent document 1 discloses such method: in the manufacture of Porous hollow-fibre membrane, make masking stoste by stoste runner from original fluid container to spinning-nozzle set more than two filter, prevent the generation of fracture of wire and reducing silk.
Patent document 2 discloses so a kind of device for spinning: in the manufacturing installation of Porous hollow-fibre membrane, make before masking stoste flows into many ingots spinning base (Japanese: many Hammer Spinning yarn mouth gold), heat exchanger and silent oscillation blender are set, improve the uniformity of filate.
Prior art document
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2009-50766 publication
Patent document 2: Japanese Patent No. 4331579 publication
But, in the spinning-nozzle in the past that spinning-nozzle 101 is such, especially when improve spinning speed so as with low cost and high production rate manufactures Porous hollow-fibre membrane time, the starting point ftractureed vertically can be formed being formed on the Porous rete strengthened outside supporting mass, sometimes produce cracking when obtained Porous hollow-fibre membrane is deformed into flat etc.In addition, as patent document 1 and 2, even if in the device of Porous hollow-fibre membrane employing filter and silent oscillation blender, it is difficult for fully suppressing to form the starting point ftractureed vertically on Porous rete.
Summary of the invention
Invent problem to be solved
The object of the invention is to, a kind of manufacture method of Porous hollow-fibre membrane and the device for spinning of Porous hollow-fibre membrane are provided, even if improving the occasion of spinning speed, also can suppress the phenomenon obtained Porous hollow-fibre membrane producing cracking.
For solving the means of problem
The manufacture method of Porous hollow-fibre membrane of the present invention has following formation.
[1] a kind of manufacture method of Porous hollow-fibre membrane, this Porous hollow-fibre membrane has the Porous rete of more than one deck, this manufacture method has spinning and solidifies operation, solidify in operation in this spinning, the masking stoste of the solvent containing film formative resin and this film formative resin is supplied to spinning-nozzle, described masking stoste branch is made and in collaborating circularly in this spinning-nozzle, then discharge cylindric for described masking stoste, with solidification liquid, described masking stoste solidified and form Porous hollow-fibre membrane precursor
Solidify in operation in described spinning, the masking stoste forming the outermost layer of described Porous rete to major general made described masking stoste be branched off into multiple and collaborate before being supplied to described spinning-nozzle, the masking stoste this being formed with position, multiple interflow is supplied to described spinning-nozzle
The ratio (t/T) of viscoplasticity relaxation time T of the masking stoste making the time t that obtained by following formula (1) and be formed with position, described multiple interflow is less than 1,
t＝V/Q…(1)
Wherein, in described formula (1), V and Q is expressed as follows the meaning:
V: from formed the masking stoste being formed with position, described multiple interflow initial position, interflow place, to branch in described spinning-nozzle, the volume (cm of the stoste runner in place that the masking stoste that is formed with position, described multiple interflow is collaborated
3);
Q: from described spinning-nozzle time per unit, the discharge rate (cm of the masking stoste that is formed with position, described multiple interflow
3/ second).
The manufacture method of the Porous hollow-fibre membrane [2] as described in [1], obtain Porous hollow-fibre membrane, the external diameter of described Porous hollow-fibre membrane is 1 ~ 5mm, and the thickness of described Porous rete is 50 ~ 500 μm.
The manufacture method of the Porous hollow-fibre membrane [3] as described in [1] or [2], is coated with at least one masking stoste at the outer circumferential side of the reinforcement supporting mass of hollow cylindrical and forms described Porous hollow-fibre membrane precursor.
The manufacture method of the Porous hollow-fibre membrane [4] according to any one of [1] ~ [3], solidify in operation in described spinning, make the masking stoste of more than two kinds be supplied to described spinning-nozzle respectively before make the masking stoste of more than two kinds be branched off into multiple and collaborate again, the masking stoste being formed with position, multiple interflow is supplied to described spinning-nozzle respectively, make the respective described of these masking stostes be less than 1 than (t/T), and stacked compound is carried out to these masking stostes.
The manufacture method of the Porous hollow-fibre membrane [5] according to any one of [1] ~ [4], described masking stoste comprises pore-creating agent.
The manufacture method of the Porous hollow-fibre membrane [6] as described in [5], described pore-creating agent is hydrophilic pore-creating agent.
The manufacture method of the Porous hollow-fibre membrane [7] as described in [5], described pore-creating agent is polyvinylpyrrolidone.
The manufacture method of the Porous hollow-fibre membrane [8] according to any one of [1] ~ [7], described film formative resin is hydrophobic polymer.
The manufacture method of the Porous hollow-fibre membrane [9] as described in [8], described hydrophobic polymer is polyvinylidene fluoride resin.
The device for spinning of Porous hollow-fibre membrane of the present invention has following formation.
[10] device for spinning, carry out spinning to the masking stoste of the Porous rete forming Porous hollow-fibre membrane, this Porous hollow-fibre membrane has the Porous rete of more than one deck, and this device for spinning has:
Upstream side branch merging part, this upstream side branch merging part at least makes the outermost masking stoste of formation described Porous rete be branched off into multiple and collaborate, makes the masking stoste being formed with position, multiple interflow;
Spinning-nozzle, this spinning-nozzle has: make to be formed position, described multiple interflow masking stoste branch and in the downstream branch merging part of collaborating circularly and will to make circular masking stoste figuration be cylindric figuration portion; And
Stoste runner, described upstream side branch merging part and described downstream branch merging part couple together by this stoste runner,
Described upstream side branch merging part and described downstream branch merging part are configured to, and the ratio (t/T) of viscoplasticity relaxation time T of the time t obtained by following formula (1) and the masking stoste that is formed with position, described multiple interflow is less than 1,
t＝V/Q…(1)
Wherein, in described formula (1), V and Q is expressed as follows the meaning:
V: from formed the masking stoste being formed with position, described multiple interflow initial position, interflow place, to branch in described spinning-nozzle, the volume (cm of the stoste runner in place that the masking stoste that is formed with position, described multiple interflow is collaborated
3);
Q: from described spinning-nozzle time per unit, the discharge rate (cm of the masking stoste that is formed with position, described multiple interflow
3/ second).
The device for spinning of the Porous hollow-fibre membrane [11] as described in [10], described upstream side branch merging part is metal porous body.
The device for spinning of the Porous hollow-fibre membrane [12] as described in [11], described metal porous body is made up of metal sintering porous body.
The device for spinning of the Porous hollow-fibre membrane [13] as described in [12], the nominal pore size of described metal sintering porous body is more than 50 μm, less than 200 μm.
The device for spinning of the Porous hollow-fibre membrane [14] according to any one of [10] ~ [13], described upstream side branch merging part is silent oscillation blender.
The device for spinning of the Porous hollow-fibre membrane [15] according to any one of [10] ~ [14], have: with all masking stostes of the Porous rete of formation more than two layers corresponding, multiple described upstream side branches merging part, described downstream branch merging part and described stoste runner respectively
For each stoste runner, make describedly to be less than 1 ground than (t/T) and to be configured with upstream side branch merging part and described downstream branch merging part described in corresponding each respectively.
The effect of invention
Adopt the manufacture method of Porous hollow-fibre membrane of the present invention, even if in the occasion improving spinning speed, obtained Porous hollow-fibre membrane also can be suppressed to produce the phenomenon of cracking.
In addition, use the device for spinning of Porous hollow-fibre membrane of the present invention, even if in the occasion improving spinning speed, obtained Porous hollow-fibre membrane also can be suppressed to produce the phenomenon of cracking.
Accompanying drawing explanation
Fig. 1 is the top view of device for spinning one example representing Porous hollow-fibre membrane of the present invention.
Fig. 2 is the longitudinal section after using straight line I-I ' to be cut off by the device for spinning of Fig. 1.
Fig. 3 is the sectional elevation after using straight line II-II ' to be cut off by the device for spinning of Fig. 2.
Fig. 4 is the schematic view of the manufacturing installation of the Porous hollow-fibre membrane representing the device for spinning with Fig. 1 ~ 3.
Fig. 5 is the top view of spinning-nozzle one example represented in the past.
Fig. 6 is the sectional view after using straight line III-III ' to be cut off by the spinning-nozzle of Fig. 5.
Fig. 7 is the sectional view after using straight line IV-IV ' to be cut off by the spinning-nozzle of Fig. 6.
Fig. 8 is the top view of another example of device for spinning representing Porous hollow-fibre membrane of the present invention.
Fig. 9 is the longitudinal section after using straight line V-V ' to be cut off by the device for spinning of Fig. 8.
Figure 10 is the schematic configuration diagram representing supporting mass manufacturing installation one example.
Symbol description
1, the device for spinning of 2 Porous hollow-fibre membranes
10 spinning-nozzles
12,12A nozzle connection
20,44 supporting mass passages
22,46,46A the 1st stoste runner
24 the 1st introduction parts
26 the 1st downstream branch merging part
28 the 1st figuration portions
30,48,48A the 2nd stoste runner
32 the 2nd introduction parts
34 the 2nd downstream branch merging part
36 the 2nd figuration portions
38 composite parts
50,50A the 1st upstream side branch merging part
52,52A the 2nd upstream side branch merging part
Detailed description of the invention
The device for spinning > of < Porous hollow-fibre membrane
The device for spinning of Porous hollow-fibre membrane of the present invention, both for hollow cylindrical reinforcement supporting mass (below, " the reinforcement supporting mass of hollow cylindrical " is only called " reinforcement supporting mass ") outside formed there is the device for spinning of the Porous hollow-fibre membrane of Porous rete, may also be for the formation of without strengthen supporting mass, the device for spinning of the Porous hollow-fibre membrane of the Porous rete with hollow form.In addition, both for the formation of the device for spinning of Porous hollow-fibre membrane of Porous rete with individual layer, may also be the device for spinning of the Porous hollow-fibre membrane for the formation of the Porous rete with multilayer.
As reinforcement supporting mass, the sennit, braid etc. of the hollow cylindrical that such as useful various fiber is made.In addition, be both used alone various raw material, and may also be and combine.As the fiber that sennit and the braid of hollow cylindrical use, if any synthetic fibers, semisynthetic fibre, regenerated fiber and natural fiber etc.As the form of fiber, what may also be in monofilament, multifibres and weaving silk is a certain.
Solidify for making masking stoste with solidification liquid and the formation of the Porous hollow-fibre membrane precursor obtained, at least use the masking stoste after film formative resin dissolves is in the solvent of this film formative resin.For described masking stoste, be preferably the pore-creating agent be made up of hydrophilic polymer etc. containing dissolving in the solvent of film formative resin, the control being used as perforate is assisted.Pore-creating agent suitably can add according to required film structure.
As film formative resin, the common resin for the formation of Porous hollow-fibre membrane can be used, such as, have polysulfone resin, polyethersulfone resin, sulfonated polysulfone resin, polyvinylidene fluoride resin, polyacrylonitrile resin, polyimide resin, polyamide-imide resin or polyesterimide resin etc.These can as required and suitable choice for use.In addition, when the solvent in the masking stoste after spinning is replaced as non-solvent and makes it solidify, in the occasion of the solidification liquid that the water of use treatability excellence is principal component, as film formative resin, be preferably and use the hydrophobic polymer that water is non-solvent.Wherein from the aspect of drug resistance excellence, as film formative resin, be preferably polyvinylidene fluoride resin.
In addition, the solvent of so-called film formative resin, refers to that in the amount of 20 DEG C of dissolving film formative resins be more than 5 quality %.In addition, the non-solvent of so-called film formative resin, refers to that the amount of the film formative resin be dissolved in 20 DEG C of solvents is for being less than 0.1 quality %.
As pore-creating agent, as long as bring impact to the formation of the vesicular structure of Porous rete, may also be any pore-creating agent, such as, have polyethylene glycol to be the unary alcohol of representative, di-alcohols, ternary alcohols or polyvinylpyrrolidone etc.Especially in the occasion that film formative resin is made up of hydrophobic polymer, because pore-creating agent remains in film, therefore forever or temporarily give hydrophily, can easily be made can water flowing, and from then on viewpoint is seen to be preferably and used hydrophilic pore-creating agent.So-called pore-creating agent is hydrophily, refers to the compatibility of water large, is soluble in water or the water capacity easily infiltrates the character come.
Other, when removing pore-creating agent, often use the cleaning fluid that water is principal component, in this occasion, is also applicable to using water-soluble polymer in hydrophilic pore-creating agent.So-called water-soluble polymer, refers to the polymer of more than the 20 quality % that to be dissolved in the water 25 DEG C time.
They can as required and suitable choice for use, wherein from thickening effect excellence, is preferably polyvinylpyrrolidone.
As solvent, as long as described film formative resin and pore-creating agent can be dissolved, and without particular limitation of, such as there are dimethyl sulfoxide (DMSO), DMA, DMF and METHYLPYRROLIDONE etc.
In addition, for masking stoste, not hindering the scope being separated and controlling, as any composition, other resin, additive and water etc. except pore-creating agent can be comprised.
Below, as device for spinning one example of Porous hollow-fibre membrane of the present invention, the device for spinning 1 (hereinafter referred to " device for spinning 1 ") of Porous hollow-fibre membrane is now described based on Fig. 1 ~ 3, and this device for spinning 1 is for the manufacture of strengthening the Porous hollow-fibre membrane being laminated with two layers of Porous rete outside supporting mass.
, the Porous rete of inner side is called the 1st Porous rete below, the Porous rete in outside is called the 2nd Porous rete.In addition, the masking stoste of formation the 1st Porous rete is called the 1st masking stoste, the masking stoste of formation the 2nd Porous rete is called the 2nd masking stoste.In this embodiment, the 2nd Porous rete is the outermost layer of Porous rete, and the 2nd masking stoste is the outermost masking stoste for the formation of Porous rete.
Device for spinning 1 as shown in Figures 1 and 2, has: carry out spinning spinning-nozzle 10 with masking stoste being coated on the outside strengthening supporting mass; And be located at the nozzle connection 12 of spinning-nozzle 10 upstream side.
(spinning-nozzle)
Spinning-nozzle 10 as shown in Figure 2, has the 1st overlapping up and down nozzle 14, the 2nd nozzle 16 and the 3rd nozzle 18.Spinning-nozzle 10 is formed: make the supporting mass passage 20 that reinforcement supporting mass passes through; Make the 1st stoste runner 22 of the 1st masking stoste circulation; And make the 2nd stoste runner 30 of the 2nd masking stoste circulation.
The core of the through spinning-nozzle 10 of supporting mass passage 20.
1st stoste runner 22 has: the 1st introduction part 24 importing the 1st masking stoste; Make the 1st masking stoste branch and make it be the 1st downstream branch merging part 26 of collaborating circularly; And be the 1st cylindric figuration portion 28 by the 1st masking stoste figuration.
In addition, the 2nd stoste runner 30 has: the 2nd introduction part 32 importing the 2nd masking stoste; Make the 2nd masking stoste branch and make it be the 2nd downstream branch merging part 34 of collaborating circularly; And be the 2nd cylindric figuration portion 36 by the 2nd masking stoste figuration.
In addition, in this example, utilize the 1st figuration portion 28 and the 2nd figuration portion 36 and be formed with composite part 38.That is, composite part 38 is so formed: give shape by the 2nd masking stoste of coming that circulates along the 2nd downstream branch merging part 34, and the 2nd masking stoste is layered in the outside of the 1st masking stoste of coming that to circulate along the 1st figuration portion 28.
Supporting mass passage 20, the 1st downstream branch merging part the 26, the 1st figuration portion 28, the 2nd downstream branch merging part the 34 and the 2nd figuration portion 36, its central shaft is consistent respectively.
In spinning-nozzle 10, the reinforcement supporting mass that the 1st masking stoste and the 2nd masking stoste derive around the supporting mass export mouth 20a from supporting mass passage 20 and cylindrically discharging from outlet 38a, and be coated on the outer circumferential side of described reinforcement supporting mass.
The material of the 1st nozzle 14, the 2nd nozzle 16 and the 3rd nozzle 18, the normally used material as the spinning-nozzle for the manufacture of Porous hollow-fibre membrane can be used, from viewpoints such as heat resistance, corrosion resistance and intensity, be preferably stainless steel (SUS).
The cross sectional shape of supporting mass passage 20 is circular.
The diameter of supporting mass passage 20, also suitably can set according to the diameter of the reinforcement supporting mass of used hollow cylindrical.
The cross sectional shape of the 1st introduction part 24 of the 1st stoste runner 22, is preferably circle.But the cross sectional shape of the 1st introduction part 24 is not limited to circle.
The diameter of the 1st introduction part 24 without particular limitation of.
1st downstream branch merging part 26 makes to circulate the 1st masking stoste branch that comes make it be circular part of collaborating along the 1st introduction part 24.1st introduction part 24 and the 1st downstream branch merging part 26, be communicated with at side's outer wall side of the 1st downstream branch merging part 26.
The cross sectional shape of the 1st downstream branch merging part 26 as shown in Figure 3, is circular, and the center of the 1st downstream branch merging part 26 is consistent with the center of supporting mass passage 20.In the 1st downstream branch merging part 26, the 1st masking stoste is branched off into two tunnels from the 1st introduction part 24 side and arc-shaped circulation, and in collaborating at the 1st joining part 26a of the opposition side of the 1st introduction part 24 circularly.
In addition, as shown in Figure 2, near the 1st figuration portion 28 in the 1st downstream branch merging part 26, also notch 26b can be provided with.Give flow resistance by arranging notch 26b, thus the uniformity of discharging in circumference of the 1st masking stoste can be improved.
1st figuration portion 28 is the 1st masking stoste will flowed into from the 1st downstream branch merging part 26, and figuration is the part with the concentrically ringed cylindrical shape of reinforcement supporting mass by supporting mass passage 20.
The width (distance of inwall and outer wall) in the 1st figuration portion 28, suitably can set according to the thickness of the 1st formed Porous rete.
In addition, the 1st figuration portion 28 length (flow channel length) without particular limitation of.
The cross sectional shape of the 2nd introduction part 32 of the 2nd stoste runner 30, is preferably circle.But the cross sectional shape of the 2nd introduction part 32 is not limited to circle.
The diameter of the 2nd introduction part 32 without particular limitation of.
2nd downstream branch merging part 34 makes to circulate the 2nd masking stoste branch that comes make it be circular part of collaborating along the 2nd introduction part 32.
The cross sectional shape of the 2nd downstream branch merging part 34 is identical with the 1st downstream branch merging part 26, is circular, and the center of the 2nd downstream branch merging part 34 is consistent with the center of supporting mass passage 20.In the 2nd downstream branch merging part 34, identical with the 1st downstream branch merging part 26, the 2nd masking stoste is branched off into two tunnels from the 2nd introduction part 32 side and arc-shaped circulation, and in collaborating in the opposition side of the 2nd introduction part 32 circularly.That is, in the 1st downstream branch merging part the 26 and the 2nd downstream branch merging part 34, the 1st masking stoste and the 2nd masking stoste are fed into different positions and branch, collaborate in opposition side.
In addition, near the 2nd figuration portion 36 in the 2nd downstream branch merging part 34, also notch 34a can be set because of the reason same with the 1st downstream branch merging part 26.
2nd figuration portion 36 is by the 2nd masking stoste in the 2nd downstream branch merging part 34, and figuration is the part with the concentrically ringed cylindrical shape of reinforcement supporting mass by supporting mass passage 20.In addition, in this example, composite part 38 is formed with by the 1st figuration portion 28 and the 2nd figuration portion 36.That is, in composite part 38, the while that in the 2nd figuration portion 36, figuration being the 2nd cylindric masking stoste, stacked being compounded in concentric circles ground is circulated on the outside of the 1st masking stoste of coming along the 1st figuration portion 28.In composite part 38, by making the stacked compound of each masking stoste in nozzle interior, thus with make the occasion of their stacked compounds at nozzle exterior compared with, the bond strength of each Porous rete formed improves.In addition, the simplification of nozzle structure, simplified processing this respect are also favourable.In addition, even if make the stacked compound of each masking stoste by composite part 38, the harmful effect almost also not because of solvent phase counterdiffusion in these solution to each Porous layer structure.
The width (distance of inwall and outer wall) of composite part 38, suitably can set according to the thickness of the 2nd formed Porous rete.
The spinning-nozzle of device for spinning of the present invention is, when the nozzle of spinning is carried out to the Porous hollow-fibre membrane with multi-layer porous plasma membrane layer, be preferably, as the example illustrated, make while there is concentric circles the composite part of the masking stoste composite laminate of each Porous rete of formation in downstream.
(nozzle connection)
Nozzle connection about 12 overlap has the 1st joint 40 and the 2nd joint 42, be built-in with in the part of the 2nd joint 42: the 1st upstream side branch merging part 50,1st upstream side branch merging part 50 makes the 1st masking stoste be branched off into multiple and make it collaborate again, makes the 1st masking stoste form position, multiple interflow; And the 2nd upstream side branch merging part the 52,2nd upstream side branch merging part 52 make the 2nd masking stoste be branched off into multiple and make it collaborate again, make the 2nd masking stoste form position, multiple interflow.
Now further illustrate, nozzle connection 12 is formed respectively: make the supporting mass passage 44 that reinforcement supporting mass passes through; Make the 1st stoste runner 46 of the 1st masking stoste circulation; And make the 2nd stoste runner 48 of the 2nd masking stoste circulation, the 1st stoste runner 46 is provided with the 1st upstream side branch merging part 50, the 2nd stoste runner 48 is provided with the 2nd upstream side branch merging part 52.
The supporting mass passage 44 of nozzle connection 12 is communicated with the supporting mass passage 20 of spinning-nozzle 10.In addition, the 1st stoste runner 46 of nozzle connection 12 is communicated with the 1st stoste runner 22 of spinning-nozzle 10, and the 2nd stoste runner 48 of nozzle connection 12 is communicated with the 2nd stoste runner 30 of spinning-nozzle 10.That is, the 1st upstream side branch merging part the 50 and the 1st downstream branch merging part 26, utilizes the 1st introduction part 24 in the 1st stoste runner 46 and the 1st stoste runner 22 and links.In addition, the 2nd upstream side branch merging part the 52 and the 2nd downstream branch merging part 34, utilizes the 2nd introduction part 32 in the 2nd stoste runner 48 and the 2nd stoste runner 30 and links.
1st masking stoste circulates along the 1st stoste runner 46 of nozzle connection 12, and utilize the 1st upstream side branch merging part 50 and be branched off into multiple, then their interflow are made and after forming position, multiple interflow, flow into the 1st stoste runner 22 of spinning-nozzle 10, be branched in the 1st downstream branch merging part 26, collaborate in circular.Equally, 2nd masking stoste circulates along the 2nd stoste runner 48 of nozzle connection 12, and utilize the 2nd upstream side branch merging part 52 and be branched off into multiple, then their interflow are made and after forming position, multiple interflow, flow into the 2nd stoste runner 30 of spinning-nozzle 10, be branched in the 2nd downstream branch merging part 34, collaborate in circular.
1st upstream side branch merging part 50 makes the 1st masking stoste circulated along the 1st stoste runner 46 be branched off into multiple and make their interflow and form the part at position, multiple interflow.Here, the so-called position, interflow be formed in the 1st masking stoste, refers to and carries out collaborating and the position contacted between each the 1st masking stoste when the 1st masking stoste be branched is collaborated, after branch.Repeatedly producing the occasion etc. at branch, interflow, may also be alternately between each position, interflow of multiple formation.
Film formative resin contained by 1st masking stoste can consider it is macromolecule, and becomes the state be wound around mutually in masking stoste.But at the position, interflow formed by making the masking stoste interflow of temporary transient branch, think that the mutual winding between film formative resin is less, turn back to a point state of supporting the front needs certain hour.Therefore, can be thought of as, the 1st masking stoste is by the 1st upstream side branch merging part 50, thus the position, interflow of the less state of mutual winding between the 1st film formative resin is formed on masking stoste on the whole.
1st upstream side branch merging part 50 is porous body in this example.Porous body has multiple holes of the three-dimensional by the 1st masking stoste.Therefore, by the 1st masking stoste of porous body, due to repeatedly three-dimensionality and be branched off into multiple and collaborate again, therefore, position, multiple interflow is formed according to the hole count of this porous body.
As porous body, such as have utilize sintering or welding, conjugant that bonding way obtains, coating and duplexer, particle obturation etc., from compressive resistance, corrosion resistance and bond strength aspect, be preferably sintered body.As the material of porous body, if any metal, pottery etc.As porous body, being preferably metal porous body, from the easiness aspect of dimensional accuracy, output and machining shape, being more preferably metal sintering porous body, is namely the porous body be made up of the metal sinter employing metallic.Because the 1st masking stoste is by these upstream side branch merging part, therefore is formed in the 1st masking stoste and collaborate position uniformly.
If circulation area in porous body, the 1st masking stoste is identical, then the less aperture opening ratio in the aperture of porous body is higher, and the number being formed in the position, interflow in masking stoste just increases.In addition, even if the aperture of porous body is large occasion, described later than (t
1//T
1if) be less than 1 scope, then the circulation area of the 1st masking stoste in porous body is done greatly, the number at the position, interflow be formed in the 1st masking stoste just can be made to increase.
Metal sintering porous body makes the 1st passed through masking stoste be branched off into multiple and collaborate, and if by described later than (t
1//T
1) make and be less than 1, then also can use the metal sintering porous body in any aperture.Never supplement foreign matter and gel content and the easy viewpoint forming position, multiple interflow in the 1st masking stoste is seen, the nominal pore size of metal sintering porous body is preferably more than 50 μm, less than 200 μm, is more preferably more than 100 μm, less than 150 μm.If described nominal pore size is more than 50 μm, then the foreign matter in the 1st masking stoste and gel content etc. are difficult to be added and easily suppress the aperture portion forming position, interflow in the 1st masking stoste to be made the phenomenon of function reduction by obturation.In addition, because fill-in tails off, therefore, it is just low that short time interpolation presses the possibility risen, and long spinning becomes easy.If described nominal pore size is less than 200 μm, even if then increase circulation area not too much, also easily increase the position, interflow be formed in the 1st masking stoste, equipment can not too become large, and therefore low cost aspect is favourable.In addition, easily by described later than (t
1//T
1) be made and be less than 1, be difficult in addition produce delay portion in metal sintering porous body, can think that the uniformity of circumference of the 1st masking stoste that spinning-nozzle interior cylindrical circulates is improved.
In addition, the 1st upstream side branch merging part 50, if can be branched off into multiple by the 1st masking stoste and make it collaborate again, form the parts at position, multiple interflow in the 1st masking stoste, is then not limited to porous body.Such as, the 1st upstream side branch merging part 50 may also be the homogenizer of mechanical type or ultrasonic type, blade mixer, long fibre or short fiber duplexer etc.As the 1st upstream side branch merging part 50, the silent oscillation blenders such as Sulzer agitator (Japanese: ス ル ザ ー ミ キ サ ー), stator tube stirrer (Japanese: ス テ ー タ チ ュ ー Block ミ キ サ ー) and static(al) formula agitator are also better.
Mechanical homogenizer has: cylindrical portion, and the tip portion of this cylindrical portion has multiple otch; And in described cylindrical portion, carry out the rotating knife that rotates, enter the masking stoste in described cylindrical portion, utilize the rotation of described rotating knife and be sent to outside from each otch, being branched into multiple thus, then they collaborate mutually again, form the position, multiple interflow corresponding with otch number thus.
The homogenizer of ultrasonic type is, makes vibrating elements vibrate and produce thick condensation wave, makes to form air pocket bubbles of vacuum in fluid.Masking stoste utilizes the generation of the plurality of bubble and is repeatedly branched off into multiple, and masking stoste utilizes the disappearance of these bubbles and collaborates, is formed and produces position, multiple interflow corresponding to number with bubble.
Sulzer agitator, stator tube stirrer etc., inside has the runner be set as with the form of multiple hampering plate complex cross, masking stoste is branched off into multiple by this runner repeatedly, then collaborates, and forms the multiple interflow position corresponding with the disjunction quantity that described hampering plate is formed.
Blade mixer has: cylindrical portion, and this cylindrical portion has from inwall multiple blades outstanding to the inside; And rotational circle cylindrical shell, this rotational circle cylindrical shell rotates in described cylindrical portion, have from outer wall multiple blades outstanding laterally, masking stoste is by being repeatedly branched off into multiple between these blade and blades, they collaborate again, form the multiple interflow position corresponding with the number of gaps between blade with blade thus.
Long fibre or short fiber duplexer identical with porous body, three-dimensionalityly when masking stoste is inner by it be repeatedly branched off into multiple, they collaborate again, form the multiple interflow position corresponding with the disjunction quantity in each fiber thus.
Static(al) formula agitator is provided with multiple helical form hampering plate in runner, and masking stoste is multiple by being repeatedly branched off into during this runner, and they collaborate again, forms the multiple interflow position corresponding with the disjunction quantity that described hampering plate is formed thus.
As the 1st upstream side branch merging part 50, from easily obtaining the viewpoint being difficult to the Porous hollow-fibre membrane ftractureed, in aforesaid parts, also be that the homogenizer of metal sintering porous body, mechanical type or ultrasonic type, Sulzer agitator, stator tube stirrer, blade mixer, long fibre or short fiber duplexer are better, from easily forming position, interflow the 1st masking stoste, not need, viewed from the device this respect of other power and complexity, to be more preferably metal sintering porous body, Sulzer agitator, stator tube stirrer and fibre lay-up body.In addition, from multi-directionly on the 1st masking stoste can form position, interflow and be also difficult to produce viewed from the inaccessible this respect of runner because of the 1st caused masking stoste such as filtering foreign matter and gel content, Sulzer agitator, stator tube stirrer are better.
1st upstream side branch merging part 50 is configured to, the time t obtained by following formula (1A)
1(be sometimes only called " t below
1") and the viscoplasticity relaxation time T of the 1st masking stoste
1(be sometimes only called " T below
1") ratio (t
1/ T
1) be less than 1.
t
1＝V
1/Q
1…(1A)
And in described formula (1), V
1and Q
1be expressed as follows the meaning.
V
1: from the place (the 1st masking stoste flows into the boundary face of the most profile of the 1st upstream side branch merging part 50) forming initial position, interflow in the 1st masking stoste, the volume (cm of the stoste runner in the place (the 1st joining part 26a of the 1st downstream branch merging part 26) that the 1st masking stoste to spinning-nozzle 10 after branch is collaborated
3).
Q
1: from the discharge rate (cm of the 1st masking stoste of the time per unit of spinning-nozzle 10
3).
V
1in this example, be the volume after three volumes being added up to, these three volumes are: can the spatial volume of filling the 1st masking stoste in the volume that the most profile of the 1st upstream side branch merging part 50 of the 1st stoste runner 46 is seen; The volume of the downstream part of the 1st upstream side branch merging part 50 of the 1st stoste runner 46; And the volume of the 1st introduction part 24 of the 1st stoste runner 22 of spinning-nozzle 10 and the 1st downstream branch merging part 26.
That is, time t
1be from the 1st masking stoste by the 1st upstream side branch merging part 50 be formed at first position, interflow moment, to the 1st masking stoste by the time of the 1st downstream branch merging part 26 in circular the moment of collaborating.
So, the 1st upstream side branch merging part 50 is configured to, after the 1st masking stoste forms position, interflow at first by the 1st upstream side branch merging part 50, with the viscoplasticity relaxation time T than the 1st masking stoste
1short time and being collaborated in the 1st downstream branch merging part 26, that is, than (t
1/ T
1) be less than 1.
In the present invention, the viscoplasticity relaxation time T of masking stoste obtains by method as follows: use such as AR2000 (TAinstruments Inc., Φ 25mm parallel-plate) as determinator, the stress measuring masking stoste relaxes, to the straight line portion that the longitudinal axis gets the logarithm of stress, transverse axis gets the mitigation situation curve after the real number of time t ', following formula (2) is utilized to carry out matching and obtain.
logσ(t’m)＝-(t’/2.303T)+log(T)…(2)
σ (t '
m): minute t '
min stress
T '
m: minute
T: viscoplasticity relaxation time
Relax and be generally made up of 1 or multiple composition, but in the present invention, the one-tenth of maximum duration is divided into viscoplasticity relaxation time T.The viscoplasticity relaxation time T of masking stoste, is preferably to relax the stress of masking stoste with the temperature of the masking stoste in the spinning of reality and measures and time of obtaining.
In addition, also can measure stress by the different temperature of the temperature of the masking stoste of the spinning from reality and relax, from obtain in advance viscoplasticity relaxation time-temperature conversion rule, obtain the viscoplasticity relaxation time T of the masking stoste under actual spinning temperature.
In device for spinning 1, as previously mentioned, by the 1st upstream side branch merging part the 50 and the 1st downstream branch merging part 26 is configured to, described time t
1with the viscoplasticity relaxation time T of the 1st masking stoste
1ratio (t
1/ T
1) being less than 1, thus in obtained Porous hollow-fibre membrane, can suppress the 1st Porous rete that formed by the 1st masking stoste forms the starting point ftractureed vertically.Therefore, the Porous hollow-fibre membrane being difficult to ftracture can be obtained.Although the reason obtaining this effect is not necessarily understood, can consider as follows.
Inventors of the present invention, on the occasion Porous rete improving spinning speed, the problem of the starting point ftractureed vertically is formed in the spinning that the spinning-nozzle in the past such to the illustrative spinning-nozzle in Fig. 5 ~ 7 101 carries out, especially, after being studied in detail, distinguish such situation: be formed in the starting point ftractureed vertically on Porous rete, be formed on the suitable position of joining part 116A that the masking stoste after being divided into two tunnels in branch's merging part 116 inside collaborates.Be considered to: do not mix smoothly, compared to the tendency that the part beyond joining part 116a has the mutual winding between film formative resin to diminish in this joining part 116a masking stoste.When masking stoste be solidified liquid solidify time, observed such situation: the curdled appearance of joining part is different from the other parts beyond joining part, become and sometimes there is the such curdled appearance in many length direction continuous print spaces, therefore, it can be considered to, become stress concentration point flat grade during load generation, thus become the essential factor of the starting point that formation is ftractureed vertically.
To this, in device for spinning 1, in nozzle connection 12, utilize the 1st upstream side branch merging part 50 be branched off into multiple and collaborate again by the 1st masking stoste, thus form position, many interflow in the 1st masking stoste.Further, the 1st upstream side branch merging part the 50 and the 1st downstream branch merging part 26 is configured to, from the required time, the i.e. described time t that enter the 1st upstream side branch merging part 50 to arrival the 1st joining part 26a
1with the viscoplasticity relaxation time T of the 1st masking stoste
1ratio (t
1/ T
1) for being less than 1.Thus, utilize the 1st upstream side branch merging part 50 and the position, interflow be formed in the 1st masking stoste can not disappear in the 1st masking stoste, 1st masking stoste is fed into spinning-nozzle 10 under the state that still there is position, many interflow, 1st masking stoste is branched in the 1st downstream branch merging part 26, even if in collaborating also there is position, many interflow all-round circularly.Therefore, one in the visual position, interflow as previously having been formed, position, interflow that the 1st joining part 26a is formed.Its result, just there is position, interflow in circumferential entirety, being wrapped in mutually between the film formation resin in the 1st masking stoste is circumferential homogenized, curdled appearance homogenising, stress is disperseed simultaneously, therefore can be thought of as, and the phenomenon forming the starting point ftractureed vertically is inhibited.Therefore, be considered to, though can obtain flat etc. power be applied to masking after hollow-fibre membrane on be also difficult to ftracture Porous hollow-fibre membrane.
Described in patent document 1 as the aforementioned, filter no matter is utilized to come foreign matter in supplementary masking stoste and gel content, still utilize silent oscillation blender to improve the uniformity of filate as described in Patent Document 2, all be difficult to the phenomenon suppressing Porous rete to be formed the starting point ftractureed vertically, can be thought of as by will than (t
1/ T
1) be made and be less than 1 and can suppress it first.
In device for spinning 1, accordingly the 1st upstream side branch merging part the 50 and the 1st downstream branch merging part 26 is configured to the 1st masking stoste, makes time t
1with viscoplasticity relaxation time T
1ratio (t
1/ T
1) be less than 1, be preferably, accordingly the 1st upstream side branch merging part the 50 and the 1st downstream branch merging part 26 be configured to the 1st masking stoste, make than (t
1/ T
1) be less than 0.6.
As shown in Figure 2, the 2nd upstream side branch merging part 52 is, makes to branch into multiple by the 2nd masking stoste of the 2nd stoste runner 48 and makes it collaborate again, in the 2nd masking stoste, form the part at position, multiple interflow.
2nd upstream side branch merging part 52 is porous body in this example.In addition, as long as the 2nd upstream side branch merging part 52 can make the 2nd masking stoste be branched off into multiple and make it collaborate again, makes the 2nd masking stoste form position, multiple interflow, then porous body is not limited to.In addition, the 1st upstream side branch merging part the 50 and the 2nd upstream side branch merging part 52, both similarly may also be inhomogeneity, and both same size may also be different size.As the 2nd upstream side branch merging part 52, such as, have identical with the alternate manner that the 1st upstream side branch merging part 50 is enumerated.The preferred mode of the 2nd upstream side branch merging part 52 is identical with the preferred mode of the 1st upstream side branch merging part 50.
2nd upstream side branch merging part 52 is configured to, the time t obtained by following formula (1B)
2(be sometimes only called " t below
2") and the viscoplasticity relaxation time T of the 2nd masking stoste
2(be sometimes only called " T below
2") ratio (t
2/ T
2) be less than 1.
t
2＝V
2/Q
2…(1B)
And in described formula, V
2and Q
2be expressed as follows the meaning.
V
2: from the place (the 2nd masking stoste flows into the boundary face of the most profile of the 2nd upstream side branch merging part 52) forming initial position, interflow in the 2nd masking stoste, the volume (cm of the stoste runner in the place (joining part of the 2nd downstream branch merging part 34) that the 2nd masking stoste to spinning-nozzle 10 after branch is collaborated
3).
Q
2: from the discharge rate (cm of the 2nd masking stoste of the time per unit of spinning-nozzle 10
3).
V
2in this example, be the volume after three volumes being added up to, these three volumes are: can the spatial volume of filling the 2nd masking stoste in the volume that the most profile of the 2nd upstream side branch merging part 52 of the 2nd stoste runner 48 is seen; The volume of the downstream part of the 2nd upstream side branch merging part 52 of the 2nd stoste runner 48; And the volume of the 2nd introduction part 32 of the 2nd stoste runner 30 of spinning-nozzle 10 and the 2nd downstream branch merging part 34.
That is, time t
2be from the 2nd masking stoste by the 2nd upstream side branch merging part 52 be formed at first position, interflow moment, to the 2nd masking stoste by the time of the 2nd downstream branch merging part 34 in circular the moment of collaborating.
So, the 2nd upstream side branch merging part 52 is configured to, after the 2nd masking stoste forms position, interflow at first by the 2nd upstream side branch merging part 52, with the viscoplasticity relaxation time T than the 2nd masking stoste
2short time and being collaborated in the 2nd downstream branch merging part 34, that is, than (t
2/ T
2) be less than 1.
By the 2nd upstream side branch merging part the 52 and the 2nd downstream branch merging part 34 is configured to, described time t
2with the viscoplasticity relaxation time T of the 2nd masking stoste
2ratio (t
2/ T
2) being less than 1, thus in obtained Porous hollow-fibre membrane, can suppress the 2nd Porous rete that formed by the 2nd masking stoste forms the starting point ftractureed vertically.Therefore, the Porous hollow-fibre membrane being difficult to ftracture can be obtained.Obtain the reason of this effect, can be thought of as identical with the occasion of the 1st Porous rete.
In device for spinning 1, accordingly the 2nd upstream side branch merging part the 52 and the 2nd downstream branch merging part 34 is configured to the 2nd masking stoste, makes time t
2with viscoplasticity relaxation time T
2ratio (t
2/ T
2) be less than 1, be preferably, accordingly the 2nd upstream side branch merging part the 52 and the 2nd downstream branch merging part 34 be configured to the 2nd masking stoste, make than (t
2/ T
2) be less than 0.6.Identical with the 1st masking stoste, can be thought of as, the 2nd masking stoste supplied, under the state having the position, many interflow be formed in masking stoste, arrives the 2nd downstream branch merging part 34.Its result, can be thought of as, because there is position, many interflow in circumference, therefore mutual winding between film formative resin is homogenized, curdled appearance homogenising, and can be thought of as, stress is concentrated and is avoided, even if the power of flat grade is applied on the hollow-fibre membrane after masking, the hollow-fibre membrane being difficult to ftracture also can be obtained.
Use multiple masking stoste, carrying out composite laminate and made the occasion of multilayer, be preferably, the masking stoste ftractureed with generation configures upstream side branch merging part accordingly, is more preferably, configures upstream side branch merging part accordingly with all masking stostes of carrying out composite laminate.Even if in the occasion of masking stoste that can be filmed without the Porous rete of cracking individual layer occasion, when being filmed when carrying out composite laminate together with can forming the masking stoste of the Porous rete that can produce cracking, for using the layer that can be formed and be formed without the masking stoste of the Porous rete of cracking, sometimes also produce cracking in the position identical with the layer that generation is ftractureed.The cracking easness of Porous hollow-fibre membrane, is considered to, especially easily by the impact that the outermost layer of Porous rete ftractures, be preferably, at least configures upstream side branch merging part accordingly with the outermost masking stoste for the formation of Porous rete.
In the figuration of many ingots, when masking stoste being supplied to downstream branch merging part, making it after the merging part circulation of upstream side branch, also can distributing and being supplied to multiple downstream branches merging part.In the figuration occasion of many ingots, from be supplied to the position, interflow formed the masking stoste of each downstream branch merging part uniformity and by by being made viewed from short time this respect to the time arriving downstream branch merging part after upstream side branch merging part as far as possible, be preferably, the upstream side branch merging part that respective separate configurations is corresponding with each downstream branch merging part respectively.
(effect)
Below, the effect of device for spinning 1 is described.
In device for spinning 1, as shown in Figure 2, strengthen supporting mass is fed into nozzle connection 12 supporting mass passage 44 from supporting mass supply port 44a, in addition, utilize the device of weight feed masking stoste, respectively the 1st masking stoste and the 2nd masking stoste are supplied to the 1st stoste runner 46 and the 2nd stoste runner 48 from stoste supply port 46a, 48a.
Strengthen supporting mass to be exported from supporting mass export mouth 20a respectively by the supporting mass passage 44 of nozzle connection 12 and the supporting mass passage 20 of spinning-nozzle 10.
1st masking stoste circulates along the 1st stoste runner 46, utilize the 1st upstream side branch merging part 50 and be branched off into multiple and collaborated again, after forming position, multiple interflow, flow into spinning-nozzle 10, in spinning-nozzle 10, flow into the 1st downstream branch merging part 26 through the 1st introduction part 24, carry out branch and arc-shaped circulation, with described time t in the 1st downstream branch merging part 26
1with described viscoplasticity relaxation time T
1ratio (t
1/ T
1) condition that is less than 1 collaborated at the 1st joining part 26a circularly.Equally, the 2nd masking stoste circulates along the 2nd stoste runner 48, utilizes the 2nd upstream side branch merging part 52 and is branched off into multiple and collaborates, after forming position, multiple interflow, flow into spinning-nozzle 10, carry out branch and arc-shaped circulation, with described time t in the 2nd downstream branch merging part 34
2with described viscoplasticity relaxation time T
2ratio (t
2/ T
2) condition that is less than 1 is collaborate circularly.Thus, can be thought of as, the 1st masking stoste and the 2nd masking stoste, in collaborating circularly under the state having the position, many interflow be respectively formed in masking stoste.Therefore, can be thought of as, because there is position, many interflow in circumference, therefore the mutual winding that film is formed between resin is homogenized, curdled appearance homogenising, and can be thought of as, stress is concentrated and is avoided, and the phenomenon that the 1st porous layer and the 2nd porous layer are formed the starting point ftractureed vertically is inhibited.
The 2nd masking stoste in the 1st masking stoste in 1st downstream branch merging part 26 and the 2nd downstream branch merging part 34, flows into the 1st figuration portion 28 and the 2nd figuration portion 36 respectively and figuration be cylindrical shape.In addition, in this example, owing to forming composite part 38 by the 1st figuration portion 28 and the 2nd figuration portion 36, therefore, the 2nd masking stoste figuration is cylindric, and the stacked outside being compounded in the 1st masking stoste of coming that to circulate along the 1st figuration portion 28, concentric circles ground.
The 1st masking stoste after stacked compound and the 2nd masking stoste, discharge from outlet 38a, and be coated on the outer circumferential side of the reinforcement supporting mass of simultaneously deriving from supporting mass export mouth 20a.Then, make masking stoste by the container that makes the gas containing moisture and contact with masking stoste, in the coagulating basin that makes masking stoste contact with solidification liquid, after making masking stoste solidify, through cleaning and dry etc., thus obtain Porous hollow-fibre membrane.
(other embodiment)
The device for spinning of Porous hollow-fibre membrane of the present invention is not limited to aforementioned device for spinning 1.Such as, the device for spinning of Porous hollow-fibre membrane of the present invention may also be the illustrative device for spinning 2 of Fig. 8 and Fig. 9.For the part identical with Fig. 1 and Fig. 2 in Fig. 8 and Fig. 9, put on same-sign and omit the description.Device for spinning 2 has the nozzle connection 12A that upper and lower overlap has the 1st joint 40A, the 2nd joint 41A and the 3rd joint 42A, the 2nd joint 41A part in the 2nd stoste runner 48A that the 1st stoste runner 46A circulated in the 1st masking stoste respectively and the 2nd masking stoste circulate, the 1st upstream side branch merging part 50A that configuration is made up of stator tube stirrer and the 2nd upstream side branch merging part 52A is to replace porous body, and in addition all the other are identical with device for spinning 1.Stator tube stirrer had both configured single, may also be serial or parallel connection configuration multiple.
In addition, device for spinning of the present invention, may also be by porous body and stator tube stirrer order differently arranged in series be used as the device etc. of upstream side branch merging part.
In addition, device for spinning of the present invention, although from can dual-purpose spinning-nozzle this respect in the past, as aforementioned device for spinning 1, be preferably the form after being combined by the nozzle connection of spinning-nozzle and built-in upstream side branch merging part, but the inside that may also be the spinning-nozzles such as the introduction part of the stoste runner in spinning-nozzle arranges the form of upstream side branch merging part.In addition, the number that arranges being located at the upstream side branch merging part of the upstream side of the downstream branch merging part in spinning-nozzle is not limited to one, may also be more than two.
In addition, containing can to individual layer occasion without cracking the masking stoste that is filmed of Porous rete, the occasion that makes the stacked compound of masking stoste of more than two kinds, also can not configure the upstream side branch merging part corresponding with the masking stoste that can be filmed without the Porous rete ftractureed individual layer occasion.But the masking stoste not configuring upstream side branch merging part if use and the Porous rete that formed produces cracking, then affect by it, be provided with upstream side branch merging part and the Porous rete that formed also likely produces cracking.Therefore, in order to easily suppress each layer to form the starting point ftractureed vertically, be more preferably, upstream side branch merging part is set accordingly with all masking stoste.
In addition, device for spinning of the present invention, may also be spinning-nozzle does not have described composite part and is coated on the form strengthened outside supporting mass in each masking stoste of the stacked compound of nozzle exterior and by masking stoste.In addition, device for spinning of the present invention, both only had a stoste runner and formed the device with the Porous hollow-fibre membrane of single layered porous plasma membrane layer, and may also be the stoste runner with more than three and there is the device of each self-corresponding upstream side branch merging part and downstream branch merging part.In addition, may also be and there is no supporting mass passage and form the device of Porous hollow-fibre membrane only formed by hollow form Porous rete.
The manufacture method > of < Porous hollow-fibre membrane
Porous hollow-fibre membrane, if make masking stoste discharge from spinning-nozzle and utilize non-solvent to induce or heating consumers, the dispersion of non-dissolved matter and extraction etc. and form Porous rete via downstream branch merging part, then think, even any external diameter and thickness all likely produce the starting point of cracking, in the occasion of the masking stoste of use high viscosity, think that its possibility is large especially.The present invention is effective for manufacturing the thickness grade thinner relative to the external diameter of Porous hollow-fibre membrane of Porous rete, outward appearance because of external force or deadweight the Porous hollow-fibre membrane of easily flattening, and for obtaining that external diameter is 1 ~ 5mm, the thickness of Porous rete is more effective the Porous hollow-fibre membrane of 50 ~ 500 μm.
In addition, the present invention for spinning solidify in operation, more than one masking stostes are coated on the reinforcement supporting mass of hollow cylindrical outer circumferential side, to manufacture the Porous hollow-fibre membrane strengthening having Porous rete outside supporting mass be effective.
Below, as manufacture method one example of Porous hollow-fibre membrane of the present invention, the manufacture method using and have the manufacturing installation 60 of described device for spinning 1 is now described according to Fig. 4.
Manufacturing installation 60 as shown in Figure 4, has: device for spinning 1, and the 1st masking stoste A and the 2nd masking stoste B is spun to the outside of the reinforcement supporting mass C being coated on hollow cylindrical by this device for spinning 1; Solidification equipment 2, this solidification equipment 2 utilizes solidification liquid 2a and makes the 1st masking stoste A after by device for spinning 1 spinning and the 2nd masking stoste B solidify and form Porous hollow-fibre membrane precursor M '; Cleaning equipment 3, the solvent remained in Porous hollow-fibre membrane precursor M ' is removed by this cleaning equipment 3; Eliminating equipment 4, the pore-creating agent remained in Porous hollow-fibre membrane precursor M ' is removed and is obtained Porous hollow-fibre membrane M by this eliminating equipment 4; Drying equipment 5, this drying equipment 5 couples of Porous hollow-fibre membrane M carry out drying; And winding apparatus 6, Porous hollow-fibre membrane M is reeled by this winding apparatus 6.Advancing of Porous hollow-fibre membrane precursor M ' in manufacturing installation 60 and Porous hollow-fibre membrane M is limited by guiding parts 7.
The manufacture method of the Porous hollow-fibre membrane of this embodiment, has following spinning and solidifies operation, matting, removing step, drying process and rolling step.
Operation is solidified in spinning: in device for spinning 1, the 1st masking stoste A and the 2nd masking stoste B is made to be branched off into multiple and to make it collaborate again respectively, each the 1st masking stoste A and the 2nd masking stoste B of being formed with position, multiple interflow are supplied to spinning-nozzle 10, make its branch in spinning-nozzle 10, and with than (t
1/ T
1) and than (t
2/ T
2) to be respectively the condition being less than 1 be collaborate circularly, after discharging with the state be coated on outside reinforcement supporting mass C, utilize solidification equipment 2 and make the 1st masking stoste A and the 2nd masking stoste B solidify in solidification liquid 2a and form Porous hollow-fibre membrane precursor M '.
Matting is: utilize cleaning equipment 3 couples of Porous hollow-fibre membrane precursor M ' to clean, removed by the solvent remained in Porous hollow-fibre membrane precursor M '.
Removing step is: utilize eliminating equipment 4 to be removed by the pore-creating agent remained in Porous hollow-fibre membrane precursor M ', obtains Porous hollow-fibre membrane M.
Drying process is: utilize drying equipment 5 couples of Porous hollow-fibre membrane M to carry out drying.
Rolling step is: utilize winding apparatus 6 to be reeled by dried Porous hollow-fibre membrane M.
(operation is solidified in spinning)
In device for spinning 1, respectively the 1st masking stoste A, the 2nd masking stoste B and reinforcement supporting mass C are supplied to device for spinning 1.In the 1st upstream side branch merging part the 50 and the 2nd upstream side branch merging part 52 of nozzle connection 12, make the 1st masking stoste A and the 2nd masking stoste B be branched off into multiple and make it collaborate again respectively, the 1st masking stoste A and the 2nd masking stoste B that are formed with position, multiple interflow are supplied to spinning-nozzle 10.Further, in the 1st downstream branch merging part the 26 and the 2nd downstream branch merging part 34, with than (t
1/ T
1) and than (t
2/ T
2) be respectively the condition being less than 1 and make the 1st masking stoste A and the 2nd masking stoste B branch respectively, collaborate in circular, they given composite laminate and cylindricly to discharge, carrying out spinning to be coated on the state strengthened outside supporting mass C.Then, the product strengthening being coated with outside supporting mass C the 1st masking stoste A and the 2nd masking stoste B is immersed in and is contained in the solidification liquid 2a of coagulating basin 2b, the 1st masking stoste A and the 2nd masking stoste B is solidified, form Porous hollow-fibre membrane precursor M '.
Be branched off into multiple making the 1st masking stoste A and the 2nd masking stoste B and after making it collaborate again, form position, multiple interflow on them, with than (t
1/ T
1) and than (t
2/ T
2) be respectively the condition being less than 1 these the 1st masking stoste A and the 2nd masking stoste B are collaborated annularly in spinning-nozzle 10 inner circle, thus in the Porous hollow-fibre membrane M finally obtained, the phenomenon forming the starting point ftractureed vertically at the 1st Porous rete and the 2nd Porous rete can be suppressed.
Than (t
1/ T
1) and than (t
2/ T
2) preferred mode by aforementioned.
Described time t
1with time t
2both can be identical, also can be different.In addition, described viscoplasticity relaxation time T
1with viscoplasticity relaxation time T
2both can be identical, also can be different.In addition, than (t
1/ T
1) and than (t
2/ T
2) both can be identical, also can be different.
The temperature of the 1st masking stoste A and the 2nd masking stoste B is preferably 20 ~ 100 DEG C.
In the present invention, by the temperature of masking stoste when upstream side branch merging part and downstream branch merging part without particular limitation of.Such as, the wet type in non-solvent induction is separated or the occasion of dry-and wet-type spinning, be preferably less than 100 DEG C by the temperature of masking stoste when upstream side branch merging part and downstream branch merging part, be more preferably less than 90 DEG C.If this temperature is less than 100 DEG C, even if then in the occasion using with water the solidification liquid being principal component, solidification liquid is also difficult to boiling at ambient pressure, can more stably spinning.
In addition, in the present invention, from upstream side branch merging part to the temperature of the masking stoste by downstream branch merging part, both alterable, also can be constant.Carrying out the occasion changed in the temperature of described masking stoste, can be also the shortest value and than (t/T) the position configuration upstream side branch merging part for being less than 1 based on viscoplasticity relaxation time T.But if the described variations in temperature of masking stoste, then thinking has impact to the time that the position, interflow be formed in masking stoste keeps, the described variations in temperature being therefore preferably masking stoste controls the scope within 10 DEG C.
Solidification liquid 2a must be the solvent of not dissolving film formative resin, and is the good solvent of pore-creating agent.As solidification liquid 2a, if any water, ethanol, methyl alcohol etc., or their mixture.Wherein, from operating environment, operational management aspect, be preferably the mixed liquor of solvent for masking stoste and water.
The temperature of solidification liquid 2a is preferably 20 ~ 100 DEG C.
In addition, the illustrative manufacturing installation 60 of Fig. 4, between device for spinning 1 and solidification liquid 2a, be provided with the form that sky walks the dry-and wet-type spinning in interval (air gap), but be not limited to this form, also can adopt the form of wet spinning sky not being set and walking interval, masking stoste directly discharged in solidification liquid.
(matting)
For solidifying the Porous hollow-fibre membrane precursor M ' formed in operation, remain pore-creating agent or the solvent of solution state.Remain pore-creating agent in the film of Porous hollow-fibre membrane, then can not give full play to water penetration.In addition, if pore-creating agent is solid in film, then it is also the reason that the mechanical strength of film declines.On the other hand, in removing step described later, when using oxidant to carry out oxidation Decomposition (low molecule quantification) to pore-creating agent, if remain solvent in Porous hollow-fibre membrane precursor M ', then likely solvent and oxidant produce reaction.Therefore, in this embodiment, after solidifying operation, in matting, the solvent remained in Porous hollow-fibre membrane precursor M ' is removed, then in removing step, the pore-creating agent remained in Porous hollow-fibre membrane precursor M ' is removed.
In matting, utilize cleaning equipment 3, with cleaning fluid 3a, Porous hollow-fibre membrane precursor M ' is cleaned, remove the solvent remained in Porous hollow-fibre membrane precursor M ' thus.Solvent in Porous hollow-fibre membrane precursor M ', inner while film diffusion into the surface movement from film, spread to cleaning fluid 3a mobile from film surface, is removed from Porous hollow-fibre membrane precursor M '.
As cleaning fluid 3a, from cleaning performance height this respect, be preferably water.As used water, if any running water, water for industrial use, river and well water etc.In addition, also can use for their mixed ethanols, inorganic salts, oxidant and surfactant etc.In addition, as cleaning fluid 3a, the mixed liquor of solvent contained by masking stoste and water also can be used.But using the occasion of this mixed liquor, the concentration of solvent is preferably below 10 quality %.
The temperature of cleaning fluid 3a, remains in viewed from the diffusion translational speed this respect of the solvent Porous hollow-fibre membrane precursor M ' from raising, is preferably more than 50 DEG C, is more preferably more than 80 DEG C.
In addition, in matting, although mainly the solvent in Porous hollow-fibre membrane precursor M ' is removed, by cleaning Porous hollow-fibre membrane precursor M ', also a part for pore-creating agent can be removed.
(removing step)
In removing step, utilize eliminating equipment 4 and the pore-creating agent remained in Porous hollow-fibre membrane precursor M ' is removed, obtaining Porous hollow-fibre membrane M.
As removing step, such as can exemplify: Porous hollow-fibre membrane precursor M ' is immersed in the liquid containing oxidant, after making Porous hollow-fibre membrane precursor M ' keep liquid, Porous hollow-fibre membrane precursor M ' is heated in the gas phase and oxidation Decomposition is carried out to pore-creating agent, then, Porous hollow-fibre membrane precursor M ' is cleaned and the operation removed of pore-creating agent that low molecule is quantized.Thus, the Porous hollow-fibre membrane M with abundant water permeability after pore-creating agent removal can be obtained.
As oxidant, if any hypochlorite, ozone, hydrogen peroxide, permanganate, bichromate and persulfate etc.Wherein, strong from oxidizing force, decomposability is excellent, operability is excellent and the aspect such as cheap, is preferably hypochlorite.As hypochlorite, if any clorox, calcium hypochlorite etc., clorox is good especially.
Carry out in liquid from easily suppressing the oxidation Decomposition of the pore-creating agent remained in Porous hollow-fibre membrane precursor M ' and suppress the pore-creating agent be shed in liquid to carry out oxidation Decomposition further and waste viewed from oxidant this respect, the temperature of liquid is preferably less than 50 DEG C, is more preferably less than 30 DEG C.In addition, from suppression, liquid is controlled to the aspects such as the cost of low temperature, the temperature of liquid is preferably more than 0 DEG C, is more preferably more than 10 DEG C.
Maintain the heating of the Porous hollow-fibre membrane precursor M ' of liquid, be preferably under atmospheric pressure use and add hot fluid.
As adding hot fluid, from suppressing the drying of oxidant, more effective resolution process this respect can being carried out, being preferably the fluid using relative humidity high, namely heating under wet heat condition.In this occasion, the relative humidity adding hot fluid is preferably more than 80%, is more preferably more than 90%, good especially near 100%.
In processed continuously occasion, from shortening processing time this respect, heating-up temperature is preferably more than 50 DEG C, is more preferably more than 80 DEG C.In addition, heating-up temperature, under atmospheric pressure state, is preferably less than 100 DEG C.
As the method that the pore-creating agent quantized by low molecule is removed, be preferably the method that Porous hollow-fibre membrane precursor M ' is cleaned.As cleaning method, be not particularly limited, the cleaning method enumerated in aforementioned matting can be adopted.
(drying process)
Drying equipment 5 couples of Porous hollow-fibre membrane M are utilized to carry out drying.
As the drying means of Porous hollow-fibre membrane M, the drying means of Porous hollow-fibre membrane and normally used method can be used as, such as, have and utilize hot blast Porous hollow-fibre membrane M to be given dry air drying methods etc.Specifically, such as, there is such method: hot blast can be made with in the device of the wind speed circulation about every number of seconds rice, Porous hollow-fibre membrane M is back and forth continuously traveling for several times, from outer circumferential side, drying is carried out to Porous hollow-fibre membrane M.
(rolling step)
Utilize winding apparatus 6 and the dried Porous hollow-fibre membrane M that reels.
Adopt the manufacture method of Porous hollow-fibre membrane of the present invention described above, even improve the occasion of spinning speed, due to can figuration masking stoste equably, the starting point forming cracking vertically can be suppressed, therefore, the Porous hollow-fibre membrane being difficult to ftracture can be obtained.
In addition, the manufacture method of Porous hollow-fibre membrane of the present invention, is not limited to the method using aforesaid manufacturing installation 60.Such as, both used single masking stoste to manufacture the method for the Porous hollow-fibre membrane with single Porous rete, the masking stoste that may also be use more than three kinds manufactures the method for the Porous hollow-fibre membrane with more than three layers Porous retes.
Embodiment
, describe the present invention in detail according to embodiment below, but the present invention is not limited to record below.
(validation test of film cracking behavior)
Between the head of digital micrometer (Mitutoyo Inc. MDC-25MJ), make the mensuration direction of micrometer be film radially clip Porous hollow-fibre membrane.With the external diameter of the Porous hollow-fibre membrane of uncompressed state for zero point, rotating rotating shaft is negative from this position to make the indicated value of micrometer, then make mould contract, be out of shape until the instruction absolute value of micrometer arrives the diameter of the hollow bulb of film, with the naked eye confirm the generation of ftractureing, the indicated value of micrometer when record cracking produces simultaneously.
Not finding the occasion that film ftractures, micrometer temporarily being unclamped, after making film rotate 45 °, again making it compress, be out of shape, confirm the generation of cracking, make film rotate 45 ° at every turn, carry out at most four times and measure.
The external diameter of Porous hollow-fibre membrane is, the arbitrary position that circumference and the head of each film are before compression touched is given to mensuration three times and makes mean value.Measuring sample is make three about 1cm length.
The evaluation of cracking behavior is, the situation observing Porous hollow-fibre membrane cracking before the absolute value of instruction on micrometer is arrived the diameter of film hollow bulb establishes work " × (bad) ", establishes the situation not observing cracking when arriving as " 〇 (well) ".
(viscoplasticity relaxation time mensuration)
For the masking stoste after modulation, the stress using AR2000 (TAinstruments Inc., Φ 25mm parallel-plate) to measure masking stoste relaxes, and establishes the longest value in the viscoplasticity relaxation time obtained by formula (2) as viscoplasticity relaxation time T.
(modulation of masking stoste)
Mass ratio as shown in table 1 is such, by Kynoar A (Arkema Inc., trade name: Kynar-301F), Kynoar B (Arkema Inc., trade name: Kynar-9000LD), Kynoar C (Arkema Inc., trade name: Kynar-761A), Kynoar D (Arkema Inc., trade name: Kynar-1015), polyvinylpyrrolidone (Japanese catalyst Inc., trade name: K-79), N, N-dimethylacetylamide (DMAc) (サ system ソ Application Off ァ イ Application ケ ミ カ Le Inc.) is mixed, and be warmed to 60 DEG C and modulated masking stoste (1) ~ (4).The viscoplasticity relaxation time T (1) of 32 DEG C of masking stoste (1) is approximately 307 seconds.The viscoplasticity relaxation time T (2) of 32 DEG C of masking stoste (2) is approximately 225 seconds.The viscoplasticity relaxation time T (3) of 32 DEG C of masking stoste (3) is approximately 54 seconds.The viscoplasticity relaxation time T (4) of 32 DEG C of masking stoste (4) is approximately 140 seconds.
[table 1]
[embodiment 1]
(strengthening the manufacture of supporting mass)
Use the supporting mass manufacturing installation 70 shown in Figure 10, manufacture reinforcement supporting mass.
Supporting mass manufacturing installation 70 possesses: bobbin winder bracket 72; The silk 74 pulled out from bobbin winder bracket 72 is compiled round circular knitting machine 76; With some tension, the hollow form sennit 78 be woven into by circular knitting machine 76 is carried out to the rope feedway 80 of tractive; To the heating mould 82 that hollow form sennit 78 is heat-treated; To the draw-gear 84 that the hollow form sennit 78 after heat treatment draws; And using hollow form sennit 78 as strengthening supporting mass and the up-coiler 86 that is wound on bobbin winder bracket.
Use polyester fiber (fiber number: 84dtex, single fiber dimension: 36, false twist yarn) as silk.As bobbin winder bracket 72, prepare the reel that five are wound with polyester fiber described in 5kg.As circular knitting machine 76, employ desk-top braiding machine (Yuan Jing fibre machinery Inc., knitting needle number: 12, pin size: 16 space, the circle diameter of main shaft: 8mm).As rope feedway 80 and draw-gear 84, employ Nelson roller.As heating mould 82, employ the mould (primary side internal diameter: 5mm, secondary side internal diameter: 2.5mm, length: 300mm) of the stainless steel with firing equipment.
The polyester fiber pulled out from five bobbin winder brackets 72 is concentrated into one and after making silk 74 (total fiber number is 420dtex), compile circle by circular knitting machine 76 and weave hollow form sennit 78, by the heating mould 82 of hollow form sennit 78 by 190 DEG C, the hollow form sennit 78 after heat treatment is wound on up-coiler 86 as reinforcement supporting mass with winding speed 200m/hr.Continue to manufacture and strengthen supporting mass until bobbin winder bracket 72 is without polyester fiber.
The external diameter of the reinforcement supporting mass obtained is about 2.55mm, and internal diameter is about 1.7mm.The number of turns forming the hollow form sennit 78 strengthening supporting mass is that 12 weekly, the maximum open width of mesh is about 0.1mm.The length strengthening supporting mass is 12000m.
(manufacture of Porous hollow-fibre membrane)
The illustrative device for spinning 1 in Fig. 1 ~ 3 is used to manufacture Porous hollow-fibre membrane.
As the 1st upstream side branch merging part the 50 and the 2nd upstream side branch merging part 52, employ porous assembly (SMC Inc., sintering metal assembly ESKA-Z2802-120,120 μm, aperture).In addition, employ masking stoste (1) as the 1st masking stoste, employ masking stoste (2) as the 2nd masking stoste.1st masking stoste is, is about 0.083cm with its discharge rate from spinning-nozzle 10
3the state of/second and be supplied to device for spinning 1.2nd masking stoste is, is about 0.097cm with its discharge rate from spinning-nozzle 10
3the state of/second and be supplied to device for spinning 1.The 1st masking stoste supplied and the 2nd masking stoste are incubated into 32 DEG C.T
1about 132 seconds, t
2about 116 seconds, time t
1with the viscoplasticity relaxation time T of the 1st masking stoste
1ratio (t
1/ T
1) be 0.430, time t
2with the viscoplasticity relaxation time T of the 2nd masking stoste
2ratio (t
2/ T
2) be 0.516.
Strengthen the central part that supporting mass is supplied to spinning-nozzle 10, and its gait of march of dividing with 5m/ is advanced.The 1st masking stoste and the stacked compound of the 2nd masking stoste is made in spinning-nozzle 10, after discharging from spinning-nozzle 10, be applied to the outside strengthening supporting mass and carry out stacked, then make it by the air gap of 54mm, and make it pass through to be incubated into the solidification liquid (N of 8 quality % of 74 DEG C, the mixed liquor of the water of N-dimethylacetylamide and 92 quality %) in and solidify, thus obtain Porous hollow-fibre membrane precursor.
Then, obtained Porous hollow-fibre membrane precursor is carried out in the hot water of 98 DEG C the desolventizing of 1 minute, then be impregnated in the aqueous sodium hypochlorite solution of 50000mg/L, cleaning in 15 minutes is carried out again with the hot water of 98 DEG C, reel after being dried 10 minutes by 110 DEG C of temperature, obtain Porous hollow-fibre membrane.
[embodiment 2,10 ~ 12]
Except as shown in table 2 and table 3 to strengthen supporting mass gait of march, from the 1st masking stoste of spinning-nozzle 10 and discharge rate, the time t of the 2nd masking stoste
1, time t
2, than (t
1/ T
1) and than (t
2/ T
2) change outside, all the other manufacture Porous hollow-fibre membrane identically with embodiment 1.
[embodiment 3,4,13]
Except the 1st upstream side branch merging part the 50 and the 2nd upstream side branch merging part 52 is altered to respectively arranged in series three grades stator tube stirrer (Mercury Supply Systems Corporation system, pattern: 005-031) and as shown in table 2 and table 3 by strengthen supporting mass gait of march, from the 1st masking stoste of spinning-nozzle 10 and discharge rate, the time t of the 2nd masking stoste
1, time t
2, than (t
1/ T
1) and than (t
2/ T
2) change outside, all the other manufacture Porous hollow-fibre membrane identically with embodiment 1.
[embodiment 5,6]
Except the 1st upstream side branch merging part the 50 and the 2nd upstream side branch merging part 52 is altered to respectively arranged in series secondary stator tube stirrer (Mercury Supply Systems Corporation system, pattern: 005-031) and as shown in table 2 like that by strengthen supporting mass gait of march, from the 1st masking stoste of spinning-nozzle 10 and discharge rate, the time t of the 2nd masking stoste
1, time t
2, than (t
1/ T
1) and than (t
2/ T
2) change outside, all the other manufacture Porous hollow-fibre membrane identically with embodiment 1.
[embodiment 7,8]
Except the 1st upstream side branch merging part the 50 and the 2nd upstream side branch merging part 52 is altered to respectively configuration one-level stator tube stirrer (Mercury Supply Systems Corporation system, pattern: 005-031) and as shown in table 2 like that by strengthen supporting mass gait of march, from the 1st masking stoste of spinning-nozzle 10 and discharge rate, the time t of the 2nd masking stoste
1, time t
2, than (t
1/ T
1) and than (t
2/ T
2) change outside, all the other manufacture Porous hollow-fibre membrane identically with embodiment 1.
[embodiment 9]
Except the 1st upstream side branch merging part 50 being altered to stator tube stirrer (mercury supply system Co., Ltd. system of arranged in series three grades, pattern: 005-031), the 2nd upstream side branch merging part 52 is altered to configuration one-level stator tube stirrer (mercury supply system Co., Ltd. system, pattern: 005-031) and as shown in table 3 like that by strengthen supporting mass gait of march, from the 1st masking stoste of spinning-nozzle 10 and discharge rate, the time t of the 2nd masking stoste
1, time t
2, than (t
1/ T
1) and than (t
2/ T
2) change outside, all the other manufacture Porous hollow-fibre membrane identically with embodiment 1.
[embodiment 14]
(strengthening the manufacture of supporting mass)
Except using dance roller and replacing rope feedway 80, all the other use the supporting mass manufacturing installation identical with supporting mass manufacturing installation 70, in addition, except using a polyester fiber (fiber number: 167dtex, single fiber dimension: 48fil, without stample fiber) as outside silk, all the other manufacture the reinforcement supporting mass that external diameter is about 1.47mm, internal diameter is about 0.91mm identically with embodiment 1.
(manufacture of Porous hollow-fibre membrane)
Do not supply the 1st masking stoste, 2nd masking stoste is altered to masking stoste (4), 1st upstream side branch merging part 50 is not set, 2nd upstream side branch merging part 52 is altered to stator tube stirrer (mercury supply system Co., Ltd. system of arranged in series three grades, pattern: 005-031), and as shown in table 3 such by the gait of march of reinforcement supporting mass, from the 1st masking stoste of spinning-nozzle 10 and discharge rate, the time t of the 2nd masking stoste
1, time t
2, than (t
1/ T
1) and than (t
2/ T
2) change, in addition, all the other manufacture Porous hollow-fibre membrane identically with embodiment 1.
[comparative example 1]
(manufacture of hollow-fibre membrane)
1st upstream side branch merging part the 50 and the 2nd upstream side branch merging part 52 is not set, as shown in table 3 such by the gait of march of reinforcement supporting mass, from the 1st masking stoste of spinning-nozzle 10 and discharge rate, the time t of the 2nd masking stoste
1, time t
2, than (t
1/ T
1) and than (t
2/ T
2) change, in addition, all the other manufacture Porous hollow-fibre membrane identically with embodiment 1.
[comparative example 2]
Except as shown in table 3 such by the gait of march of reinforcement supporting mass, from the 1st masking stoste of spinning-nozzle 10 and discharge rate, the time t of the 2nd masking stoste
1, time t
2, than (t
1/ T
1) and than (t
2/ T
2) change outside, all the other manufacture Porous hollow-fibre membrane identically with embodiment 1.
[comparative example 3]
2nd masking stoste is altered to masking stoste (3), 1st upstream side branch merging part the 50 and the 2nd upstream side branch merging part 52 is altered to respectively stator tube stirrer (mercury supply system Co., Ltd. system of arranged in series three grades, pattern: 005-031), more as shown in table 3 such by the gait of march of reinforcement supporting mass, from the 1st masking stoste of spinning-nozzle 10 and discharge rate, the time t of the 2nd masking stoste
1, time t
2, than (t
1/ T
1) and than (t
2/ T
2) change, in addition, all the other manufacture Porous hollow-fibre membrane identically with embodiment 1.
[table 2]
[table 3]
As shown in table 2 and table 3, before being supplied to spinning-nozzle, the 1st masking stoste and the 2nd masking stoste both sides are made to form position, multiple interflow and will than (t
1/ T
1) and than (t
2/ T
2) make and be less than in the embodiment 1 ~ 13 of 1, do not observe film cracking.In addition, position, multiple interflow is formed in the 2nd masking stoste only making the outermost layer of formation Porous rete used and will than (t
2/ T
2) make and be less than in the embodiment 14 of 1, do not observe film cracking yet.
On the other hand, in the comparative example 1 not being provided with position, upstream side branch interflow, observed film cracking.In addition, than (t
1/ T
1) and than (t
2/ T
2) both sides be more than 1 comparative example 2, than (t
2/ T
2) be in the comparative example 3 of more than 1, also been observed film cracking.
Claims (15)
1. the manufacture method of a Porous hollow-fibre membrane, this Porous hollow-fibre membrane has the Porous rete of more than one deck, this manufacture method has spinning and solidifies operation, solidify in operation in this spinning, the masking stoste of the solvent containing film formative resin and this film formative resin is supplied to spinning-nozzle, described masking stoste branch is made in this spinning-nozzle, and in collaborating circularly, then discharge cylindric for described masking stoste, with solidification liquid, described masking stoste solidified and form Porous hollow-fibre membrane precursor, the feature of the manufacture method of this Porous hollow-fibre membrane is,
Solidify in operation in described spinning, the masking stoste forming the outermost layer of described Porous rete to major general made described masking stoste be branched off into multiple and collaborate before being supplied to described spinning-nozzle, the masking stoste this being formed with position, multiple interflow is supplied to described spinning-nozzle
The ratio (t/T) of viscoplasticity relaxation time T of the masking stoste making the time t that obtained by following formula (1) and be formed with position, described multiple interflow is less than 1,
t＝V/Q …(1)
Wherein, in described formula (1), V and Q is expressed as follows the meaning:
V: from formed the masking stoste being formed with position, described multiple interflow initial position, interflow place, to branch in described spinning-nozzle, the volume (cm of the stoste runner in place that the masking stoste that is formed with position, described multiple interflow is collaborated
3);
Q: from described spinning-nozzle time per unit, the discharge rate (cm of the masking stoste that is formed with position, described multiple interflow
3/ second).
2. the manufacture method of Porous hollow-fibre membrane as claimed in claim 1, is characterized in that, obtain Porous hollow-fibre membrane, the external diameter of described Porous hollow-fibre membrane is 1 ~ 5mm, and the thickness of described Porous rete is 50 ~ 500 μm.
3. the manufacture method of Porous hollow-fibre membrane as claimed in claim 1 or 2, is characterized in that, is coated with at least one masking stoste and forms described Porous hollow-fibre membrane precursor at the outer circumferential side of the reinforcement supporting mass of hollow cylindrical.
4. the manufacture method of the Porous hollow-fibre membrane according to any one of claims 1 to 3, it is characterized in that, solidify in operation in described spinning, make the masking stoste of more than two kinds be supplied to described spinning-nozzle respectively before make the masking stoste of more than two kinds be branched off into multiple and collaborate again, the masking stoste being formed with position, multiple interflow is supplied to described spinning-nozzle respectively, make the respective described of these masking stostes be less than 1 than (t/T), and stacked compound is carried out to these masking stostes.
5. the manufacture method of the Porous hollow-fibre membrane according to any one of Claims 1 to 4, is characterized in that, described masking stoste comprises pore-creating agent.
6. the manufacture method of Porous hollow-fibre membrane as claimed in claim 5, it is characterized in that, described pore-creating agent is hydrophilic pore-creating agent.
7. the manufacture method of Porous hollow-fibre membrane as claimed in claim 5, it is characterized in that, described pore-creating agent is polyvinylpyrrolidone.
8. the manufacture method of the Porous hollow-fibre membrane according to any one of claim 1 ~ 7, is characterized in that, described film formative resin is hydrophobic polymer.
9. the manufacture method of Porous hollow-fibre membrane as claimed in claim 8, it is characterized in that, described hydrophobic polymer is polyvinylidene fluoride resin.
10. a device for spinning, carry out spinning to the masking stoste of the Porous rete forming Porous hollow-fibre membrane, this Porous hollow-fibre membrane has the Porous rete of more than one deck, and the feature of this device for spinning is to have:
Upstream side branch merging part, this upstream side branch merging part at least makes the outermost masking stoste of formation described Porous rete be branched off into multiple and collaborate, makes the masking stoste being formed with position, multiple interflow;
Spinning-nozzle, this spinning-nozzle has: make to be formed position, described multiple interflow masking stoste branch and in the downstream branch merging part of collaborating circularly and will to make circular masking stoste figuration be cylindric figuration portion; And
Stoste runner, described upstream side branch merging part and described downstream branch merging part couple together by this stoste runner,
Described upstream side branch merging part and described downstream branch merging part are configured to, and the ratio (t/T) of viscoplasticity relaxation time T of the time t obtained by following formula (1) and the masking stoste that is formed with position, described multiple interflow is less than 1,
t＝V/Q …(1)
Wherein, in described formula (1), V and Q is expressed as follows the meaning:
V: from formed the masking stoste being formed with position, described multiple interflow initial position, interflow place, to branch in described spinning-nozzle, the volume (cm of the stoste runner in place that the masking stoste that is formed with position, described multiple interflow is collaborated
3);
Q: from described spinning-nozzle time per unit, the discharge rate (cm of the masking stoste that is formed with position, described multiple interflow
3/ second).
The device for spinning of 11. Porous hollow-fibre membranes as claimed in claim 10, is characterized in that, described upstream side branch merging part is metal porous body.
The device for spinning of 12. Porous hollow-fibre membranes as claimed in claim 11, it is characterized in that, described metal porous body is made up of metal sintering porous body.
The device for spinning of 13. Porous hollow-fibre membranes as claimed in claim 12, is characterized in that, the nominal pore size of described metal sintering porous body is more than 50 μm, less than 200 μm.
The device for spinning of 14. Porous hollow-fibre membranes according to any one of claim 10 ~ 13, it is characterized in that, described upstream side branch merging part is silent oscillation blender.
The device for spinning of 15. Porous hollow-fibre membranes according to any one of claim 10 ~ 14, it is characterized in that, have: with all masking stostes of the Porous rete of formation more than two layers corresponding, multiple described upstream side branches merging part, described downstream branch merging part and described stoste runner respectively
For each stoste runner, make describedly to be less than 1 ground than (t/T) and to be configured with upstream side branch merging part and described downstream branch merging part described in corresponding each respectively.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012060208 | 2012-03-16 | ||
| JP2012-060208 | 2012-03-16 | ||
| PCT/JP2013/057422 WO2013137438A1 (en) | 2012-03-16 | 2013-03-15 | Method and spinning device for producing porous hollow yarn membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104284710A true CN104284710A (en) | 2015-01-14 |
| CN104284710B CN104284710B (en) | 2016-11-30 |
Family
ID=
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|---|---|---|---|---|
| CN113842786A (en) * | 2014-01-30 | 2021-12-28 | 三菱化学株式会社 | Method for producing hollow fiber membrane and nozzle for spinning hollow fiber membrane |
| CN116571098A (en) * | 2023-05-23 | 2023-08-11 | 山东仁丰特种材料股份有限公司 | Hydrogen separation membrane and preparation method thereof |
| US11883131B2 (en) | 2006-06-09 | 2024-01-30 | St. Jude Medical International Holding S.À R.L. | Triaxial fiber optic force sensing catheter |
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| JP2009050766A (en) * | 2007-08-24 | 2009-03-12 | Toyobo Co Ltd | Method of manufacturing hollow fiber membrane |
| JP2012040461A (en) * | 2010-08-13 | 2012-03-01 | Asahi Kasei Chemicals Corp | Method for manufacturing porous hollow fiber membrane, porous hollow fiber membrane, module using porous hollow fiber membrane, filter using porous hollow fiber membrane, and water-treating method using porous hollow fiber membrane |
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|---|---|---|---|---|
| CN101282780A (en) * | 2005-10-13 | 2008-10-08 | 旭化成化学株式会社 | Porous multilayered hollow-fiber membrane and process for producing the same |
| JP2009050766A (en) * | 2007-08-24 | 2009-03-12 | Toyobo Co Ltd | Method of manufacturing hollow fiber membrane |
| JP2012040461A (en) * | 2010-08-13 | 2012-03-01 | Asahi Kasei Chemicals Corp | Method for manufacturing porous hollow fiber membrane, porous hollow fiber membrane, module using porous hollow fiber membrane, filter using porous hollow fiber membrane, and water-treating method using porous hollow fiber membrane |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US11883131B2 (en) | 2006-06-09 | 2024-01-30 | St. Jude Medical International Holding S.À R.L. | Triaxial fiber optic force sensing catheter |
| CN113842786A (en) * | 2014-01-30 | 2021-12-28 | 三菱化学株式会社 | Method for producing hollow fiber membrane and nozzle for spinning hollow fiber membrane |
| CN116571098A (en) * | 2023-05-23 | 2023-08-11 | 山东仁丰特种材料股份有限公司 | Hydrogen separation membrane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101789368B1 (en) | 2017-10-23 |
| JP5741871B2 (en) | 2015-07-01 |
| JPWO2013137438A1 (en) | 2015-08-03 |
| WO2013137438A1 (en) | 2013-09-19 |
| KR20140142288A (en) | 2014-12-11 |
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