CN104284710B - The manufacture method of Porous hollow-fibre membrane and device for spinning - Google Patents
The manufacture method of Porous hollow-fibre membrane and device for spinning Download PDFInfo
- Publication number
- CN104284710B CN104284710B CN201380025020.8A CN201380025020A CN104284710B CN 104284710 B CN104284710 B CN 104284710B CN 201380025020 A CN201380025020 A CN 201380025020A CN 104284710 B CN104284710 B CN 104284710B
- Authority
- CN
- China
- Prior art keywords
- stock solution
- spinning
- masking
- porous hollow
- masking stock
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 197
- 239000012528 membrane Substances 0.000 title claims abstract description 176
- 238000009987 spinning Methods 0.000 title claims abstract description 109
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000011550 stock solution Substances 0.000 claims abstract description 390
- 230000000873 masking effect Effects 0.000 claims abstract description 328
- 238000007711 solidification Methods 0.000 claims abstract description 41
- 230000008023 solidification Effects 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 238000011144 upstream manufacturing Methods 0.000 claims description 113
- 210000000170 cell membrane Anatomy 0.000 claims description 63
- 239000003795 chemical substances by application Substances 0.000 claims description 41
- 239000002243 precursor Substances 0.000 claims description 37
- 239000011347 resin Substances 0.000 claims description 37
- 229920005989 resin Polymers 0.000 claims description 37
- 239000002904 solvent Substances 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 13
- 229920001600 hydrophobic polymer Polymers 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 235000012489 doughnuts Nutrition 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- 238000005336 cracking Methods 0.000 abstract description 25
- 230000001629 suppression Effects 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 230000002787 reinforcement Effects 0.000 description 22
- 239000002131 composite material Substances 0.000 description 16
- 238000005728 strengthening Methods 0.000 description 14
- 239000012530 fluid Substances 0.000 description 12
- 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
- 238000001035 drying Methods 0.000 description 9
- 230000005021 gait Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 238000004804 winding Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000009940 knitting Methods 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 230000008569 process Effects 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
- 239000000243 solution Substances 0.000 description 3
- -1 Amine imide Chemical class 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical group [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000000047 product Substances 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
- 239000013589 supplement Substances 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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000002202 Polyethylene glycol 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
- 238000013459 approach 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
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000000151 deposition Methods 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
- 230000003292 diminished effect Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 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
- 230000002349 favourable effect Effects 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
- 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
- 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
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 1
- 229920002647 polyamide 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
- 238000013139 quantization Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 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
- 238000003756 stirring Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 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
- 229920002554 vinyl polymer Polymers 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
Abstract
The purpose of the present invention is: even improve the occasion of spinning speed, it is possible to the Porous hollow-fibre membrane that suppression obtains produces the phenomenon of cracking.The manufacture method of a kind of Porous hollow-fibre membrane and the device for spinning (1) for this manufacture method, manufacture method has such spinning solidification operation: make masking stock solution be branched off into multiple and collaborate, the masking stock solution that will be formed with position, multiple interflow is supplied to spinning-nozzle (10), described masking stock solution branch is made in spinning-nozzle (10), make its be collaborate circularly after cylindric discharge, described masking stock solution is made to solidify with solidification liquid, make by formula t=V/Q (V: from the place forming initial position, interflow masking stock solution, volume (the cm of stock solution runner to the place at described masking stock solution interflow after branch in described spinning-nozzle3), Q: from the output (cm of described masking stock solution of the time per unit of spinning-nozzle (10)3/ the second).) ratio (t/T) of viscoelasticity relaxation time T of the time t that obtains and described masking stock solution is less than 1.
Description
Technical field
The present invention relates to the manufacture method of a kind of Porous hollow-fibre membrane.
The application based on March 16th, 2012 in the Patent 2012-060208 of Japanese publication CLAIM OF PRIORITY, and will
Its content quotation is at this.
Background technology
Due to the surging of the care for environmental pollution and the strengthening of restriction, use the mistake that separation property and compactedness etc. are excellent
The water of filter membrane processes noticeable.Filter membrane in processing as water, the multiple aperture plasma membrane layer that applicable use has hollow form is many
Hole matter hollow-fibre membrane (such as patent documentation 1).In the manufacture of Porous hollow-fibre membrane, such as, device for spinning pair is utilized
Masking stock solution carries out spinning, makes the solidification of this masking stock solution form Porous hollow-fibre membrane precursor with solidification liquid.Then, go
Except the solvent remained in formed Porous hollow-fibre membrane precursor, pore-creating agent, it is dried.Residual by fully removing
Stay the pore-creating agent in Porous hollow-fibre membrane precursor, thus obtain the Porous doughnut with abundant water permeability
Film.
As device for spinning, the most known spinning-nozzle 101 having shown in Fig. 5～7.Spinning-nozzle 101 has the 1st nozzle
111 and the 2nd nozzle 112.It addition, the inside of spinning-nozzle 101 has: the supporting mass making the reinforcement supporting mass of hollow form pass through leads to
Road 113；And make the stock solution runner 114 that the masking stock solution of formation multiple aperture plasma membrane layer circulates.Stock solution runner 114 has: be imported with
The introduction part 115 of described masking stock solution；Described masking stock solution is divided into two parts and make its be collaborate circularly branch interflow
Portion 116；And be cylindric figuration portion 117 by described masking stock solution figuration.Spinning-nozzle 101 supplies mouth 113a from supporting mass
Supply the reinforcement supporting mass of hollow form and derived from supporting mass export mouth 113b, former from resin supply mouth 114a supply masking
Liquid also cylindrically discharges it around described reinforcement supporting mass from outlet 114b.
In the spinning of the Porous hollow-fibre membrane carried out by spinning-nozzle 101, from the outlet of spinning-nozzle 101
The masking stock solution that 114b discharges, is coated on strengthening supporting mass of the hollow form simultaneously derived from supporting mass export mouth 113b
Side.
Patent document 1 discloses that such method: in the manufacture of Porous hollow-fibre membrane, make masking stock solution by from
Original fluid container, to the filter more than in the stock solution runner of spinning-nozzle set two, prevents fracture of wire and the product of reducing silk
Raw.
Patent document 2 discloses that such a device for spinning: in the manufacture device of Porous hollow-fibre membrane, make system
Before film stock solution flows into many ingots spinning base (Japanese: many yarn mouth gold), heat exchanger and silent oscillation blender are set, carry
The uniformity of high filate.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2009-50766 publication
Patent documentation 2: No. 4331579 publications of Japanese Patent Publication No.
But, in spinning-nozzle conventional as spinning-nozzle 101, especially when improving spinning speed so that with low one-tenth
When this and high production rate manufacture Porous hollow-fibre membrane, can shape being formed on the multiple aperture plasma membrane layer strengthened outside supporting mass
Become the starting point that ftractures vertically, sometimes produce cracking when obtained Porous hollow-fibre membrane is deformed into flat etc..Separately
Outward, as patent documentation 1 and 2, even if at the dress of the Porous hollow-fibre membrane employing filter and silent oscillation blender
In putting, it is difficult for fully suppressing to form the starting point ftractureed vertically on multiple aperture plasma membrane layer.
Summary of the invention
Invent problem to be solved
It is an object of the invention to, it is provided that the manufacture method of a kind of Porous hollow-fibre membrane and Porous hollow-fibre membrane
Device for spinning, even if improving the occasion of spinning speed, also can suppress to produce on obtained Porous hollow-fibre membrane to open
The phenomenon split.
For solving the means of problem
The manufacture method of the Porous hollow-fibre membrane of the present invention has following composition.
[1] manufacture method of a kind of Porous hollow-fibre membrane, this Porous hollow-fibre membrane have more than one layer many
Hole plasma membrane layer, this manufacture method have spinning solidification operation, this spinning solidification operation in, will containing film formative resin and this
The masking stock solution of the solvent of film formative resin is supplied to spinning-nozzle, make in this spinning-nozzle described masking stock solution branch,
And collaborate in circular, then discharge cylindric for described masking stock solution, make the solidification of described masking stock solution with solidification liquid and
Form Porous hollow-fibre membrane precursor,
In described spinning solidification operation, the masking stock solution of the outermost layer forming described multiple aperture plasma membrane layer to major general is supplying
Make described masking stock solution be branched off into multiple and collaborate again before being given to described spinning-nozzle, this is formed with position, multiple interflow
Masking stock solution is supplied to described spinning-nozzle,
The viscoelasticity of the masking stock solution making the time t obtained by following formula (1) and be formed with position, the plurality of interflow relaxes
The ratio (t/T) of time T is less than 1,
T=V/Q ... (1)
Wherein, in described formula (1), V and Q is expressed as follows the meaning:
V: from the place forming position, initial interflow the masking stock solution being formed with position, the plurality of interflow, to
In described spinning-nozzle after branch, the stock solution runner in place that the masking stock solution that is formed with position, the plurality of interflow is collaborated
Volume (cm3)；
Q: from time per unit, the masking stock solution that is formed with position, the plurality of interflow row of described spinning-nozzle
Output (cm3/ the second).
[2] manufacture method of the Porous hollow-fibre membrane as described in [1], it is thus achieved that Porous hollow-fibre membrane is described many
The external diameter of hole matter hollow-fibre membrane is 1～5mm, and the thickness of described multiple aperture plasma membrane layer is 50～500 μm.
[3] manufacture method of the Porous hollow-fibre membrane as described in [1] or [2], the reinforcement at hollow cylindrical supports
The outer circumferential side of body is coated with at least one masking stock solution and forms described Porous hollow-fibre membrane precursor.
[4] manufacture method of the Porous hollow-fibre membrane as according to any one of [1]～[3], solidifies in described spinning
In operation, the masking stock solution of more than two kinds was made to divide before the masking stock solution making more than two kinds is fed separately to described spinning-nozzle
Propping up into multiple and collaborate, the masking stock solution that will be formed with position, multiple interflow is fed separately to described spinning-nozzle, makes these
The respective described of masking stock solution is less than 1 than (t/T), and it is compound that these masking stock solutions carry out stacking.
[5] manufacture method of the Porous hollow-fibre membrane as according to any one of [1]～[4], described masking stock solution bag
Containing pore-creating agent.
[6] manufacture method of the Porous hollow-fibre membrane as described in [5], described pore-creating agent is hydrophilic pore-creating agent.
[7] manufacture method of the Porous hollow-fibre membrane as described in [5], described pore-creating agent is polyvinylpyrrolidone.
[8] manufacture method of the Porous hollow-fibre membrane as according to any one of [1]～[7], described film formative tree
Fat is hydrophobic polymer.
[9] manufacture method of the Porous hollow-fibre membrane as described in [8], described hydrophobic polymer is Kynoar
Resin.
The device for spinning of the Porous hollow-fibre membrane of the present invention has following composition.
[10] a kind of device for spinning, spins the masking stock solution of the multiple aperture plasma membrane layer forming Porous hollow-fibre membrane
Silk, this Porous hollow-fibre membrane has the multiple aperture plasma membrane layer of more than a layer, and this device for spinning has:
Upstream side branch merging part, this upstream side branch merging part at least makes the outermost of formation described multiple aperture plasma membrane layer
Masking stock solution is branched off into multiple and collaborates, makes the masking stock solution being formed with position, multiple interflow；
Spinning-nozzle, this spinning-nozzle has: make to be formed with the masking stock solution branch at position, the plurality of interflow and in circle
The downstream branch merging part collaborated annularly and will to make circular masking stock solution figuration be cylindric figuration portion；
And
Stock solution runner, described upstream side branch merging part and described downstream branch merging part are connected by this stock solution runner
Come,
Described upstream side branch merging part and described downstream branch merging part are configured to, following formula (1) the time t obtained
It is less than 1 with the ratio (t/T) of the viscoelasticity relaxation time T of the masking stock solution being formed with position, the plurality of interflow,
T=V/Q ... (1)
Wherein, in described formula (1), V and Q is expressed as follows the meaning:
V: from the place forming position, initial interflow the masking stock solution being formed with position, the plurality of interflow, to
In described spinning-nozzle after branch, the stock solution runner in place that the masking stock solution that is formed with position, the plurality of interflow is collaborated
Volume (cm3)；
Q: from time per unit, the masking stock solution that is formed with position, the plurality of interflow row of described spinning-nozzle
Output (cm3/ the second).
[11] device for spinning of the Porous hollow-fibre membrane as described in [10], described upstream side branch merging part is metal
Porous body.
[12] device for spinning of the Porous hollow-fibre membrane as described in [11], described metal porous body is many by metal sintering
Hole body is constituted.
[13] device for spinning of the Porous hollow-fibre membrane as described in [12], the nominal hole of described metal sintering porous body
Footpath is below more than 50 μm, 200 μm.
[14] device for spinning of the Porous hollow-fibre membrane as according to any one of [10]～[13], described upstream side divides
Propping up merging part is silent oscillation blender.
[15] device for spinning of the Porous hollow-fibre membrane as according to any one of [10]～[14], has: with formation
All masking stock solutions of the multiple aperture plasma membrane layer of more than two layers the most corresponding, multiple described upstream side branches merging part, described
Downstream branch merging part and described stock solution runner,
For each stock solution runner, make described to be each configured with each corresponding described upstream side than (t/T) less than 1 ground
Branch's merging part and described downstream branch merging part.
The effect of invention
Use the manufacture method of the Porous hollow-fibre membrane of the present invention, even if in the occasion improving spinning speed, it is possible to
Porous hollow-fibre membrane obtained by suppression produces the phenomenon of cracking.
It addition, use the device for spinning of the Porous hollow-fibre membrane of the present invention, even if improving the occasion of spinning speed,
Also the Porous hollow-fibre membrane that can suppress obtained produces 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 manufacturing device of the Porous hollow-fibre membrane representing the device for spinning with Fig. 1～3.
Fig. 5 is the top view representing conventional spinning-nozzle one example.
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 to represent the schematic configuration diagram that supporting mass manufactures device 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 passage
22,46,46A the 1st stock solution runner
24 the 1st introduction parts
26 the 1st downstream branch merging part
28 the 1st figuration portions
30,48,48A the 2nd stock solution 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
<device for spinning of Porous hollow-fibre membrane>
The device for spinning of the Porous hollow-fibre membrane of the present invention, both for the reinforcement supporting mass at hollow cylindrical
The outside of (below, " the reinforcement supporting mass of hollow cylindrical " being only called " reinforcement supporting mass ") is formed has multiple aperture plasma membrane layer
The device for spinning of Porous hollow-fibre membrane, it is possible to strengthen supporting mass for forming nothing, there is the multiple aperture plasma membrane of hollow form
The device for spinning of the Porous hollow-fibre membrane of layer.It addition, both for forming the porous of the multiple aperture plasma membrane layer with monolayer
The device for spinning of matter hollow-fibre membrane, it is possible to be the Porous hollow-fibre membrane for forming the multiple aperture plasma membrane layer with multilamellar
Device for spinning.
As strengthening supporting mass, the sennit of hollow cylindrical that the most useful various fibers are made, braid etc..It addition, both
Various raw material can be single use, it is possible to combine.The fibre used as sennit and the braid of hollow cylindrical
Dimension, if any synthetic fibers, semisynthetic fibre, regenerated fiber and natural fiber etc..Form as fiber, it is possible to be monofilament, many
A certain kind in silk and weaving silk.
The formation of the Porous hollow-fibre membrane precursor obtained for making masking stock solution solidify with solidification liquid, at least makes
By the masking stock solution after film formative resin is dissolved in the solvent of this film formative resin.Former for described masking
Liquid, preferably contains the pore-creating agent being made up of hydrophilic polymer etc. in the solvent dissolving in film formative resin, makees
Control for perforate assists.Pore-creating agent can be properly added according to required membrane structure.
As film formative resin, the common resin for forming Porous hollow-fibre membrane can be used, such as, have poly-
Sulphone resin, polyethersulfone resin, sulfonated polysulfone resin, polyvinylidene fluoride resin, polyacrylonitrile resin, polyimide resin, polyamides
Amine imide resin or polyesterimide resin etc..These can the most suitably select to use.It addition, after by spinning
When solvent in masking stock solution is replaced as non-solvent and makes it solidify, using the solidification liquid that water is main constituent that treatability is excellent
Occasion, as film formative resin, preferably use water be the hydrophobic polymer of non-solvent.Wherein excellent from drug resistance
From the perspective of, as film formative resin, preferably polyvinylidene fluoride resin.
It addition, the solvent of so-called film formative resin, refer to the amount of 20 DEG C of dissolving film formative resins be 5 mass % with
On.It addition, the non-solvent of so-called film formative resin, refer to that the amount of the film formative resin being dissolved in 20 DEG C of solvents is for being less than
0.1 mass %.
As pore-creating agent, as long as the formation on the vesicular structure of multiple aperture plasma membrane layer brings impact, it is possible to be any perforate
Agent, such as having Polyethylene Glycol is the unary alcohol of representative, di-alcohols, ternary alcohols or polyvinylpyrrolidone etc..Especially exist
The occasion that film formative resin is made up of hydrophobic polymer, because pore-creating agent remains in film, therefore permanently or temporarily gives hydrophilic
Property, can be readily formed can water flowing, in terms of this viewpoint, preferably use hydrophilic pore-creating agent.So-called pore-creating agent is hydrophilic
Property, refer to that the affinity with water is big, be soluble in water or the water capacity easily infiltrates the character come.
Other, when pore-creating agent to be removed, often using water is the cleanout fluid of main constituent, in this occasion, hydrophilic opens
Hole agent is suitable for use of water-soluble polymer.So-called water-soluble polymer, refer to be dissolved in the water when 25 DEG C 20 mass %
Above polymer.
They can the most suitably select to use, wherein in terms of thickening effect excellence, and preferably polyvinyl pyrrole
Alkanone.
As solvent, as long as described film formative resin and pore-creating agent can be dissolved, and without particular limitation of, such as there is diformazan
Base sulfoxide, N,N-dimethylacetamide, DMF and METHYLPYRROLIDONE etc..
It addition, for masking stock solution, do not hindering the scope of the control that is separated, as any composition, can comprise except
Other resin, additive and water etc. outside pore-creating agent.
Below, as device for spinning one example of the Porous hollow-fibre membrane of the present invention, now illustrate based on Fig. 1～3
The device for spinning 1 (hereinafter referred to as " device for spinning 1 ") of Porous hollow-fibre membrane, this device for spinning 1 is for manufacturing in reinforcement
Hold external side and be laminated with the Porous hollow-fibre membrane of two layers of multiple aperture plasma membrane layer.
Below, the multiple aperture plasma membrane layer of inner side is referred to as the 1st multiple aperture plasma membrane layer, the multiple aperture plasma membrane layer in outside is referred to as more than the 2nd
Hole plasma membrane layer.It addition, the masking stock solution forming the 1st multiple aperture plasma membrane layer is referred to as the 1st masking stock solution, the 2nd multiple aperture plasma membrane will be formed
The masking stock solution of layer is referred to as the 2nd masking stock solution.In this embodiment, the 2nd multiple aperture plasma membrane layer is the outermost layer of multiple aperture plasma membrane layer,
2nd masking stock solution is the outermost masking stock solution for forming multiple aperture plasma membrane layer.
Device for spinning 1 as shown in Figures 1 and 2, has: spin while masking stock solution is coated on the outside of reinforcement supporting mass
The spinning-nozzle 10 of silk；And it is located at the nozzle connection 12 of spinning-nozzle 10 upstream side.
(spinning-nozzle)
Spinning-nozzle 10 is as in figure 2 it is shown, have the 1st the most overlapping nozzle the 14, the 2nd nozzle the 16 and the 3rd nozzle 18.Spinning
It is formed on silk nozzle 10: make the supporting mass passage 20 that reinforcement supporting mass passes through；Make the 1st stock solution stream of the 1st masking stock solution circulation
Road 22；And make the 2nd stock solution runner 30 of the 2nd masking stock solution circulation.
The core of the through spinning-nozzle of supporting mass passage 20 10.
1st stock solution runner 22 has: import the 1st introduction part 24 of the 1st masking stock solution；Make the 1st masking stock solution branch and make
It is the 1st downstream branch merging part 26 collaborated circularly；And be the 1st cylindric tax by the 1st masking stock solution figuration
Shape portion 28.
It addition, the 2nd stock solution runner 30 has: import the 2nd introduction part 32 of the 2nd masking stock solution；The 2nd masking stock solution is made to divide
Propping up and making it is the 2nd downstream branch merging part 34 collaborated circularly；And be cylindric by the 2nd masking stock solution figuration
The 2nd figuration portion 36.
It addition, in this example, the 1st figuration portion 28 and the 2nd figuration portion 36 is utilized to be formed with composite part 38.That is, composite part
38 are thusly-formed: give shape by the 2nd masking stock solution come along merging part 34 circulation of the 2nd downstream branch, and make the 2nd
Film stock solution is layered in the outside of the 1st masking stock solution come along the circulation of the 1st figuration portion 28.
Supporting mass passage the 20, the 1st downstream branch merging part the 26, the 1st figuration portion the 28, the 2nd downstream branch merging part 34
And the 2nd figuration portion 36, its central shaft is the most consistent.
In spinning-nozzle 10, the 1st masking stock solution and the 2nd masking stock solution derive around from the supporting mass of supporting mass passage 20
Reinforcement supporting mass that mouthful 20a derives and cylindrically discharge from outlet 38a, and be coated on the periphery of described reinforcement supporting mass
Side.
The material of the 1st nozzle the 14, the 2nd nozzle the 16 and the 3rd nozzle 18, can use normally used conduct for manufacturing porous
The material of the spinning-nozzle of matter hollow-fibre membrane, in terms of the viewpoints such as thermostability, corrosion resistance and intensity, preferably stainless steel
(SUS)。
The cross sectional shape of supporting mass passage 20 is circular.
The diameter of supporting mass passage 20, it is possible to suitable according to the diameter strengthening supporting mass of the hollow cylindrical used
Set.
The cross sectional shape of the 1st introduction part 24 of the 1st stock solution runner 22, preferably circular.But, the 1st introduction part 24
Cross sectional shape is not limited to circle.
The diameter of the 1st introduction part 24 without particular limitation of.
1st downstream branch merging part 26, is to make the 1st masking stock solution branch come along the 1st introduction part 24 circulation and make
It is the part collaborated circularly.1st introduction part the 24 and the 1st downstream branch merging part 26, collaborates in the 1st downstream branch
One side's outer wall side connection in portion 26.
The cross sectional shape of the 1st downstream branch merging part 26 as it is shown on figure 3, be circular, the 1st downstream branch merging part
The center of 26 is consistent with the center of supporting mass passage 20.In the 1st downstream branch merging part 26, the 1st masking stock solution is led from the 1st
Enter side, portion 24 and be branched off into two tunnels arc-shaped circulation, and in circular the 1st joining part in the opposition side of the 1st introduction part 24
26a collaborates.
It addition, as in figure 2 it is shown, near the 1st figuration portion 28 in the 1st downstream branch merging part 26, it is possible to it is provided with and cuts
Oral area 26b.Give flow resistance by arranging notch 26b, thus can improve the 1st masking stock solution circumference discharge equal
Even property.
1st figuration portion 28, is the 1st masking stock solution that will flow into from the 1st downstream branch merging part 26, and figuration is and passes through
The part strengthening the concentrically ringed cylindrical shape of supporting mass of supporting mass passage 20.
The width (inwall and the distance of outer wall) in the 1st figuration portion 28, can be according to the thickness of the 1st multiple aperture plasma membrane layer formed
And suitably set.
It addition, the length (flow channel length) in the 1st figuration portion 28 without particular limitation of.
The cross sectional shape of the 2nd introduction part 32 of the 2nd stock solution runner 30, preferably circular.But, the 2nd introduction part 32
Cross sectional shape is not limited to circle.
The diameter of the 2nd introduction part 32 without particular limitation of.
2nd downstream branch merging part 34, is to make the 2nd masking stock solution branch come along the 2nd introduction part 32 circulation and make
It is the part collaborated circularly.
Cross sectional shape and the 1st downstream branch merging part 26 of the 2nd downstream branch merging part 34 are identical, are circular,
And the 2nd the center of downstream branch merging part 34 consistent with the center of supporting mass passage 20.In the 2nd downstream branch merging part 34
In, identical with the 1st downstream branch merging part 26, the 2nd masking stock solution is branched off into two tunnels arc-shaped stream from the 2nd introduction part 32 side
Logical, and collaborate in the opposition side of the 2nd introduction part 32 in circular.That is, in the 1st downstream branch merging part 26 and the 2nd
In downstream branch merging part 34, the 1st masking stock solution and the 2nd masking stock solution are fed into different positions branch, on the contrary
Side is collaborated.
It addition, near the 2nd figuration portion 36 in the 2nd downstream branch merging part 34, it is possible to because of with the 1st downstream branch
Reason that merging part 26 is same and notch 34a is set.
2nd figuration portion 36, is by the 2nd masking stock solution in the 2nd downstream branch merging part 34, and figuration is and passes through supporting
The part strengthening the concentrically ringed cylindrical shape of supporting mass of body passage 20.It addition, in this example, by the 1st figuration portion the 28 and the 2nd figuration
Portion 36 is formed with composite part 38.That is, in composite part 38, the while that in the 2nd figuration portion 36, figuration being the 2nd cylindric masking stock solution
Concentric circles ground stacking is compounded on the outside of the 1st masking stock solution come that circulates along the 1st figuration portion 28.In composite part 38,
By making each masking stock solution stacking be combined in nozzle interior, thus make the compound occasion phase of they stackings with at nozzle exterior
Ratio, the bond strength of each multiple aperture plasma membrane layer formed improves.It addition, the simplification of nozzle structure, simplified processing this respect
It is also advantageous.Even if it addition, made each masking stock solution stacking be combined by composite part 38, the most not because of molten in these solution
Agent phase counterdiffusion and harmful effect to each Porous layer structure.
The width (inwall and the distance of outer wall) of composite part 38, can be according to the thickness of the 2nd multiple aperture plasma membrane layer formed
Suitably set.
The spinning-nozzle of the device for spinning of the present invention is, enters the Porous hollow-fibre membrane with multi-layer porous plasma membrane layer
During the nozzle of row spinning, it is preferred that as the example illustrated, make while there is concentric circles each Porous of formation in downstream
The composite part of the masking stock solution composite laminate of film layer.
(nozzle connection)
Nozzle connection about 12 overlaps with the 1st joint the 40 and the 2nd joint 42, and the part at the 2nd joint 42 is built-in with: the
1 upstream side branch merging part the 50, the 1st upstream side branch merging part 50 makes the 1st masking stock solution be branched off into multiple and make it close again
Stream, makes the 1st masking stock solution form position, multiple interflow；And the 2nd upstream side branch merging part the 52, the 2nd upstream side branch
Merging part 52 makes the 2nd masking stock solution be branched off into multiple and make it collaborate again, makes the 2nd masking stock solution form position, multiple interflow.
More specifically now illustrate, nozzle connection 12 is respectively formed with: make the supporting mass passage that reinforcement supporting mass passes through
44；Make the 1st stock solution runner 46 of the 1st masking stock solution circulation；And make the 2nd stock solution runner 48 of the 2nd masking stock solution circulation, the
It is provided with the 1st upstream side branch merging part 50 on 1 stock solution runner 46, the 2nd stock solution runner 48 is provided with the 2nd upstream side branch
Merging part 52.
The supporting mass passage 44 of nozzle connection 12 connects with the supporting mass passage 20 of spinning-nozzle 10.It addition, nozzle connection
The 1st stock solution runner 46 of 12 connects with the 1st stock solution runner 22 of spinning-nozzle 10, the 2nd stock solution runner 48 of nozzle connection 12 with
2nd stock solution runner 30 of spinning-nozzle 10 connects.That is, the 1st upstream side branch merging part the 50 and the 1st downstream branch merging part
26, utilize the 1st introduction part 24 in the 1st stock solution runner 46 and the 1st stock solution runner 22 to link.It addition, the 2nd upstream side branch closes
Stream portion the 52 and the 2nd downstream branch merging part 34, utilizes the 2nd introduction part 32 in the 2nd stock solution runner the 48 and the 2nd stock solution runner 30
And link.
1st masking stock solution circulates along the 1st stock solution runner 46 of nozzle connection 12, and utilizes the 1st upstream side branch merging part
50 and be branched off into multiple, then make they interflow and after forming position, multiple interflow, flow into the 1st stock solution stream of spinning-nozzle 10
Road 22, is branched in the 1st downstream branch merging part 26, collaborates in circular.Equally, the 2nd masking stock solution connects along nozzle
The 2nd stock solution runner 48 of 12 circulates, and utilizes the 2nd upstream side branch merging part 52 to be branched off into multiple, then makes them close
Stream and after forming position, multiple interflow, flow into the 2nd stock solution runner 30 of spinning-nozzle 10, in the 2nd downstream branch merging part
It is branched in 34, collaborates in circular.
1st upstream side branch merging part 50, be make along the 1st stock solution runner 46 circulation the 1st masking stock solution be branched off into multiple,
And make they interflow form the part at position, multiple interflow.Here, the so-called merging part being formed in the 1st masking stock solution
Position, refers to carry out collaborating also between each the 1st masking stock solution when the 1st masking stock solution being branched is collaborated, after branch
The position of contact.It is being iteratively produced the occasion etc. at branch, interflow, may also be alternately between each position, interflow of multiple formation
's.
Film formative resin contained by 1st masking stock solution is it is contemplated that be macromolecule, and becomes and twine mutually in masking stock solution
Around state.But, at the position, interflow formed by making the masking stock solution of temporary transient branch collaborate, it is believed that film formative resin
Between be wound around mutually less, the state before branch to be returned to needs certain time.Accordingly it is contemplated that be, the 1st masking stock solution
By the 1st upstream side branch merging part 50, thus the position, interflow being wound around mutually less state between the 1st film formative resin
It is formed on masking stock solution on the whole.
1st upstream side branch merging part 50 is porous body in this example.Porous body has can be by the three of the 1st masking stock solution
Multiple holes of dimension.Therefore, by the 1st masking stock solution of porous body, repeatedly it is branched off into multiple due to three-dimensionality and closes again
Stream, therefore, forms position, multiple interflow according to the hole count of this porous body.
As porous body, such as have utilize sintering or welding, bonding way to obtain conjugant, coating and duplexer thereof,
Particle obturator etc., from the perspective of compressive resistance, corrosion resistance and bond strength, preferably sintered body.As porous body
Material, if any metal, pottery etc..As porous body, preferably metal porous body, from dimensional accuracy, yield and processing shape
From the perspective of the easiness of shape, preferably metal sintering porous body, is i.e. to be made up of the metal sinter employing metallic
Porous body.Owing to the 1st masking stock solution is by these upstream side branch merging part, therefore formed uniform in the 1st masking stock solution
Position, interflow.
If circulation area in porous body, the 1st masking stock solution is identical, then the least aperture opening ratio in the aperture of porous body is the highest,
The number at the position, interflow being formed in masking stock solution is increased by.It is it addition, even if the aperture of porous body is big occasion, described later
Than (t1//T1If) be less than 1 scope, then the circulation area of the 1st masking stock solution in porous body is done greatly, so that it may make to be formed at
The number at the position, interflow in the 1st masking stock solution increases.
Metal sintering porous body is to make the 1st passed through masking stock solution be branched off into multiple and collaborate, and if by aftermentioned
Ratio (t1//T1) make less than 1, then it is used as the metal sintering porous body in any aperture.Never supplement foreign body and gel content
And from the viewpoint of easily forming position, multiple interflow in the 1st masking stock solution, the nominal pore size of metal sintering porous body is preferable
It is below more than 50 μm, 200 μm, more than preferably 100 μm, below 150 μm.If described nominal pore size is more than 50 μm, then
Foreign body in 1st masking stock solution and gel content etc. are difficult to be added and easily suppression forms position, interflow in the 1st masking stock solution
Aperture portion be blocked for and make the phenomenon of function reduction.Further, since fill-in tails off, therefore, interpolation presses liter the short time
Probability the lowest, long spinning becomes easy.If described nominal pore size is below 200 μm, even if increasing the most not too much
Circulation area, also easily increases and is formed at the position, interflow in the 1st masking stock solution, and equipment will not too become big, therefore low cost
Aspect is favourable.It addition, easily by described later than (t1//T1) be made less than 1, additionally it is difficult to produce in metal sintering porous body
Raw delay portion, it is believed that the uniformity of the circumference of the 1st masking stock solution of spinning-nozzle interior cylindrical circulation is improved.
It addition, the 1st upstream side branch merging part 50, if the 1st masking stock solution can be branched off into multiple and makes it close again
Flow, formed in the 1st masking stock solution the parts at position, multiple interflow, be then not limited to porous body.Such as, the 1st upstream side branch
Merging part 50 may also be mechanical type or the homogenizer of ultrasonic type, blade mixer, long fibre or short fiber layers stack etc..Make
It is the 1st upstream side branch merging part 50, Sulzer agitator (Japanese: ス Le ザ ミ キ サ), stator tube stirrer
The silent oscillation blender such as (Japanese: ス テ タ チ ュ Block ミ キ サ) and static(al) formula agitator is the most preferable.
Mechanical homogenizer has: cylindrical portion, and the tip portion of this cylindrical portion has multiple otch；And at described circle
Carry out the swivel knife rotated in cylinder portion, enter the masking stock solution in described cylindrical portion, utilize the rotation of described swivel knife and from respectively
Individual otch is sent to outside, is thus branched into multiple, and then they collaborate the most again, is consequently formed corresponding with otch number
Position, multiple interflow.
The homogenizer of ultrasonic type is, makes vibrating elements vibration produce thick condensation wave, makes to be formed in fluid air pocket vacuum gas
Bubble.Masking stock solution utilizes the generation of the plurality of bubble to be repeatedly branched off into multiple, and masking stock solution utilizes the disappearance of these bubbles
And collaborate again, formed and produce, with bubble, the position, multiple interflow that number is corresponding.
Sulzer agitator, stator tube stirrer etc., inside there is the form with multiple hampering plate complex cross and
The runner being set as, masking stock solution is repeatedly branched off into multiple by this runner, then collaborates, and is formed and described hampering plate institute shape
Position, multiple interflow corresponding to disjunction quantity become.
Blade mixer has: cylindrical portion, and this cylindrical portion has the multiple blades prominent from the inside side of inwall；And rotation
Turning cylinder, this rotational circle cylinder rotates in described cylindrical portion, has the multiple blades highlighted laterally from outer wall, system
Film stock solution is by being repeatedly branched off into multiple between these blade and blades, and they collaborate again, be consequently formed with blade with
The position, multiple interflow that number of gaps between blade is corresponding.
Long fibre or short fiber layers stack are identical with porous body, and masking stock solution is branched off into repeatedly by three-dimensionality during its inside
Multiple, they collaborate again, are consequently formed the multiple interflow position corresponding with the disjunction quantity in each fiber.
Static(al) formula agitator is provided with multiple helical form hampering plate in runner, and masking stock solution is by branch repeatedly during this runner
Becoming multiple, they collaborate again, are consequently formed the multiple interflow position corresponding with the disjunction quantity that described hampering plate is formed.
As the 1st upstream side branch merging part 50, from being readily available the viewpoint of Porous hollow-fibre membrane being difficult to ftracture
See, in aforesaid parts, be also the homogenizer of metal sintering porous body, mechanical type or ultrasonic type, Sulzer agitator, fix
Finned pipe type agitator, blade mixer, long fibre or short fiber layers stack are preferable, from the easy shape the 1st masking stock solution of energy
The device this respect that become position, interflow, need not other power and complexity is seen, preferably metal sintering porous body, Sulzer stirs
Mix device, stator tube stirrer and fibrous layer stack.It addition, from can on the 1st masking stock solution multi-direction formed interflow position,
And be also difficult to produce because the runner obturation this respect of the 1st masking stock solution caused by filtration foreign body and gel content etc. is seen, Sulzer
Agitator, stator tube stirrer are more preferable.
1st upstream side branch merging part 50 is configured to, following formula (1A) the time t obtained1(the most sometimes it is only called " t1”)
Viscoelasticity relaxation time T with the 1st masking stock solution1(the most sometimes it is only called " T1") ratio (t1/T1) less than 1.
t1=V1/Q1…(1A)
And in described formula (1), V1And Q1It is expressed as follows the meaning.
V1: from the place forming initial position, interflow on the 1st masking stock solution, (the 1st masking stock solution flows into the 1st upstream side
The boundary face of the profile of branch's merging part 50), the place that the 1st masking stock solution after branch is collaborated to spinning-nozzle 10
Volume (the cm of the stock solution runner of (the 1st joining part 26a of the 1st downstream branch merging part 26)3)。
Q1: from the output (cm of the 1st masking stock solution of the time per unit of spinning-nozzle 103)。
V1In this example, being the volume after being added up to by three volumes, these three volume is: at the 1st of the 1st stock solution runner 46
Can the spatial volume of filling the 1st masking stock solution in the volume that profile is seen of upstream side branch merging part 50；1st stock solution runner
The volume of the downstream part of the 1st upstream side branch merging part 50 of 46；And the of the 1st stock solution runner 22 of spinning-nozzle 10
The volume of 1 introduction part the 24 and the 1st downstream branch merging part 26.
That is, time t1It is to be initially formed with collaborating position by the 1st upstream side branch merging part 50 from the 1st masking stock solution
Moment, to the 1st masking stock solution by the 1st downstream branch merging part 26 time in circular the moment collaborated.
So, the 1st upstream side branch merging part 50 is configured to, in the 1st masking stock solution by the 1st upstream side branch merging part 50
After originally forming position, interflow, with the viscoelasticity relaxation time T than the 1st masking stock solution1The short time and divide in the 1st downstream
Prop up merging part 26 to be collaborated, i.e. than (t1/T1) less than 1.
In the present invention, the viscoelasticity relaxation time T of masking stock solution can be obtained by method as follows: uses such as
AR2000 (TAinstruments company system, Φ 25mm parallel-plate) relaxes as determinator, the stress measuring masking stock solution,
The longitudinal axis takes the logarithm of stress, transverse axis takes the straight line portion of the mitigation situation curve after the real number of time t ', utilizes following formula (2) to enter
Row matching and obtain.
Log σ (t ' m)=-(t '/2.303T)+log (T) ... (2)
σ(t’m): minute t 'mIn stress
t’m: minute
T: the viscoelasticity relaxation time
Relax and be typically made up of 1 or multiple composition, but in the present invention, the one-tenth of maximum duration is divided into viscoelasticity and relaxes
Time T.The viscoelasticity relaxation time T of masking stock solution, preferably with the temperature of the masking stock solution in actual spinning to masking
The stress of stock solution relaxes the time being measured and obtain.
Additionally, it is also possible to the temperature different from the temperature of the masking stock solution of actual spinning and measure stress and relax, from advance
The viscoelasticity relaxation time first obtained-temperature conversion rule, the viscoelasticity obtaining the masking stock solution under the spinning temperature of reality delays
With time T.
In device for spinning 1, as it was previously stated, by the 1st upstream side branch merging part the 50 and the 1st downstream branch is collaborated
Portion 26 is configured to, described time t1Viscoelasticity relaxation time T with the 1st masking stock solution1Ratio (t1/T1) less than 1, thus in institute
In the Porous hollow-fibre membrane obtained, can suppress to be formed on the 1st multiple aperture plasma membrane layer formed by the 1st masking stock solution to open vertically
The starting point split.Therefore, the Porous hollow-fibre membrane being difficult to ftracture can be obtained.Although the reason obtaining this effect is the brightest
In vain, but can consider as follows.
The inventors of the present invention, conventional spinning-nozzle as the spinning-nozzle 101 illustrate Fig. 5～7 is carried out
Spinning in, especially on the occasion multiple aperture plasma membrane layer improving spinning speed, form the problem of the starting point ftractureed vertically, carry out
After detailed research, distinguish such situation: the starting point ftractureed vertically that is formed on multiple aperture plasma membrane layer, be formed at point
Prop up on the position suitable for joining part 116A that the masking stock solution after being divided into two tunnels in merging part 116 inside is collaborated.Recognized
For: mix the most smoothly in this joining part 116a masking stock solution, have film formative compared to the part beyond joining part 116a
It is wound around mutually, between resin, the tendency diminished.When masking stock solution is solidified liquid solidification, it was observed that such situation: interflow
The curdled appearance of part is different from the other parts beyond joining part, becomes and occasionally there are many length direction continuous print spaces
Such curdled appearance, therefore, it is it is contemplated that become, and waits load to become stress concentration point when producing flat, thus becomes formation
The starting point ftractureed vertically will be because of.
To this, in device for spinning 1, in nozzle connection 12, the 1st upstream side branch is utilized to close by the 1st masking stock solution
Stream portion 50 is branched off into multiple and collaborates, thus forms position, many interflow in the 1st masking stock solution.Further, the 1st upstream side divides
Merging part the 50 and the 1st downstream branch merging part 26 is configured to, from entering the 1st upstream side branch merging part 50 to arriving the
The required time of 1 joining part 26a, the most described time t1Viscoelasticity relaxation time T with the 1st masking stock solution1Ratio (t1/T1)
For less than 1.Thus, the position, interflow utilizing the 1st upstream side branch merging part 50 and be formed in the 1st masking stock solution is in the 1st system
Will not disappear in film stock solution, the 1st masking stock solution is fed into spinning-nozzle 10 when still suffering from many positions, interflow,
1st masking stock solution is branched in the 1st downstream branch merging part 26, even if also there is many all-round in circular interflow
Position, interflow.Therefore, in the position, interflow being previously formed is can be seen as at the position, interflow that the 1st joining part 26a is formed
Individual.Its result, circumference entirety exists for collaborating position, and film in the 1st masking stock solution is formed and is wrapped in mutually week between resin
To homogenized, curdled appearance homogenization, stress is disperseed simultaneously, therefore it is contemplated that be, the starting point that formation is ftractureed vertically
Phenomenon is inhibited.Therefore, it is considered, is also difficult on the hollow-fibre membrane after flat etc. power is applied to masking even if can obtain
The Porous hollow-fibre membrane of cracking.
As the aforementioned described in patent documentation 1, no matter employ filter to supplement the foreign body in masking stock solution and gel content, also
It is the uniformity utilizing silent oscillation blender to improve filate as described in Patent Document 2, is all difficult to suppress shape on multiple aperture plasma membrane layer
Become the phenomenon of starting point ftractureed vertically, it is contemplated that for by will be than (t1/T1) be made and it can be suppressed first less than 1.
In device for spinning 1, accordingly the 1st upstream side branch merging part the 50 and the 1st downstream is divided with the 1st masking stock solution
Prop up merging part 26 to be configured to, make time t1With viscoelasticity relaxation time T1Ratio (t1/T1) less than 1, it is preferred that with the 1st masking
1st upstream side branch merging part the 50 and the 1st downstream branch merging part 26 is configured to by stock solution accordingly, makes than (t1/T1) it is
Less than 0.6.
As in figure 2 it is shown, the 2nd upstream side branch merging part 52 is, make to be divided by the 2nd masking stock solution of the 2nd stock solution runner 48
For multiple and make it collaborate again, form the part at position, multiple interflow in the 2nd masking stock solution.
2nd upstream side branch merging part 52 is porous body in this example.If it addition, the 2nd upstream side branch merging part 52
The 2nd masking stock solution can be made to be branched off into multiple and make it collaborate again, make the 2nd masking stock solution form position, multiple interflow, then be not limited to
Porous body.It addition, the 1st upstream side branch merging part the 50 and the 2nd upstream side branch merging part 52, the most similar may also be different
Class, both same size may also be different size.As the 2nd upstream side branch merging part 52, such as, have and divide with the 1st upstream side
The alternate manner that merging part 50 is enumerated is identical.The preferred mode of the 2nd upstream side branch merging part 52 is divided with the 1st upstream side
The preferred mode propping up merging part 50 is identical.
2nd upstream side branch merging part 52 is configured to, following formula (1B) the time t obtained2(the most sometimes it is only called " t2”)
Viscoelasticity relaxation time T with the 2nd masking stock solution2(the most sometimes it is only called " T2") ratio (t2/T2) less than 1.
t2=V2/Q2…(1B)
And in described formula, V2And Q2It is expressed as follows the meaning.
V2: from the place forming initial position, interflow on the 2nd masking stock solution, (the 2nd masking stock solution flows into the 2nd upstream side
The boundary face of the profile of branch's merging part 52), the place that the 2nd masking stock solution after branch is collaborated to spinning-nozzle 10
Volume (the cm of the stock solution runner of (joining part of the 2nd downstream branch merging part 34)3)。
Q2: from the output (cm of the 2nd masking stock solution of the time per unit of spinning-nozzle 103)。
V2In this example, being the volume after being added up to by three volumes, these three volume is: at the 2nd of the 2nd stock solution runner 48
Can the spatial volume of filling the 2nd masking stock solution in the volume that profile is seen of upstream side branch merging part 52；2nd stock solution runner
The volume of the downstream part of the 2nd upstream side branch merging part 52 of 48；And the of the 2nd stock solution runner 30 of spinning-nozzle 10
The volume of 2 introduction part the 32 and the 2nd downstream branch merging part 34.
That is, time t2It is to be initially formed with collaborating position by the 2nd upstream side branch merging part 52 from the 2nd masking stock solution
Moment, to the 2nd masking stock solution by the 2nd downstream branch merging part 34 time in circular the moment collaborated.
So, the 2nd upstream side branch merging part 52 is configured to, and the 2nd masking stock solution is by the 2nd upstream side branch merging part 52
After just forming position, interflow, with the viscoelasticity relaxation time T than the 2nd masking stock solution2The short time and in the 2nd downstream branch
Merging part 34 is collaborated, i.e. than (t2/T2) 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 t2With
The viscoelasticity relaxation time T of the 2nd masking stock solution2Ratio (t2/T2) less than 1, thus at obtained Porous hollow-fibre membrane
In, can suppress to form, on the 2nd multiple aperture plasma membrane layer formed by the 2nd masking stock solution, the starting point ftractureed vertically.Therefore, difficulty can be obtained
Porous hollow-fibre membrane with cracking.Obtain the reason of this effect, it is contemplated that for the occasion phase with the 1st multiple aperture plasma membrane layer
With.
In device for spinning 1, accordingly the 2nd upstream side branch merging part the 52 and the 2nd downstream is divided with the 2nd masking stock solution
Prop up merging part 34 to be configured to, make time t2With viscoelasticity relaxation time T2Ratio (t2/T2) less than 1, it is preferred that with the 2nd masking
2nd upstream side branch merging part the 52 and the 2nd downstream branch merging part 34 is configured to by stock solution accordingly, makes than (t2/T2) it is
Less than 0.6.Identical with the 1st masking stock solution, it is contemplated that to be formed at masking stock solution for, the 2nd masking stock solution supplied there are
In position, many interflow states under, arrive the 2nd downstream branch merging part 34.Its result, it is contemplated that for, because depositing in circumference
Collaborate position in many, therefore being wound around mutually between film formative resin is homogenized, curdled appearance homogenization, and it is contemplated that
Concentrate for, stress and be avoided by, even if the power of flat grade is applied on the hollow-fibre membrane after masking, it is possible to obtain and be difficult to ftracture
Hollow-fibre membrane.
Using multiple masking stock solutions, carrying out composite laminate and made the occasion of multilamellar, it is preferred that opening with generation
The masking stock solution split configures upstream side branch merging part accordingly, it is preferred that with all masking stock solutions carrying out composite laminate
The upstream side branch of configuration accordingly merging part.Even if in masking monolayer occasion can being filmed without the multiple aperture plasma membrane layer ftractureed
The occasion of stock solution, makes when carrying out composite laminate together with can forming the masking stock solution of the multiple aperture plasma membrane layer that can produce cracking
During film, for using the layer that can form the masking stock solution of multiple aperture plasma membrane layer without cracking and formed, with the layer phase producing cracking
Same position the most also produces cracking.The cracking easness of Porous hollow-fibre membrane, is considered to be particularly susceptible by multiple aperture plasma membrane
The impact of the outermost layer cracking of layer, it is preferred that at least corresponding with for forming the outermost masking stock solution of multiple aperture plasma membrane layer
Ground configuration upstream side branch merging part.
In the figuration of many ingots, when masking stock solution being supplied to downstream branch merging part, divide along upstream side making it
After propping up merging part circulation, it is possible to distribution is supplied to multiple downstream branches merging part.In the figuration occasion of many ingots, from being supplied to respectively
The interflow uniformity at position formed in the masking stock solution of individual downstream branch merging part and being collaborated by upstream side branch
It is made short time this respect to the time arriving downstream branch merging part behind portion to see, it is preferred that the most independent as far as possible
Configure the upstream side branch merging part corresponding with each downstream branch merging part.
(acting on)
Below, the effect of device for spinning 1 is described.
In device for spinning 1, as in figure 2 it is shown, strengthen supporting mass to be fed into nozzle connection from supporting mass supply mouth 44a
The supporting mass passage 44 of 12, it addition, utilize the device of weight feed masking stock solution, respectively by former to the 1st masking stock solution and the 2nd masking
Liquid is supplied to the 1st stock solution runner the 46 and the 2nd stock solution runner 48 from stock solution supply mouth 46a, 48a.
Strengthen supporting mass respectively by supporting mass passage 44 and the supporting mass passage of spinning-nozzle 10 of nozzle connection 12
20 and be exported from supporting mass export mouth 20a.
1st masking stock solution circulates along the 1st stock solution runner 46, utilizes the 1st upstream side branch merging part 50 to be branched off into multiple
And collaborated again, after forming position, multiple interflow, flow into spinning-nozzle 10, in spinning-nozzle 10, flow through the 1st introduction part 24
Enter the 1st downstream branch merging part 26, carry out branch arc-shaped circulation in the 1st downstream branch merging part 26, with time described
Between t1With described viscoelasticity relaxation time T1Ratio (t1/T1) less than 1 condition be to be closed at the 1st joining part 26a circularly
Stream.Equally, the 2nd masking stock solution circulates along the 2nd stock solution runner 48, utilizes the 2nd upstream side branch merging part 52 to be branched off into multiple
And collaborate again, after forming position, multiple interflow, flow into spinning-nozzle 10, carry out branch also in the 2nd downstream branch merging part 34
Arc-shaped circulates, with described time t2With described viscoelasticity relaxation time T2Ratio (t2/T2) less than 1 condition be circularly
Interflow.Thus, it is contemplated that for, the 1st masking stock solution and the 2nd masking stock solution, there are be respectively formed in masking stock solution permitted
Collaborate in circular under the states at position, many interflow.Accordingly it is contemplated that be, because there is position, many interflow, therefore film in circumference
Form the winding mutually between resin homogenized, curdled appearance homogenization, and it is contemplated that be, stress is concentrated and is avoided by, the 1st
The phenomenon forming the starting point ftractureed vertically on porous layer and the 2nd porous layer is inhibited.
The 1st masking stock solution in 1st downstream branch merging part 26 and the 2nd system in the 2nd downstream branch merging part 34
Film stock solution, separately flows into the 1st figuration portion 28 and the 2nd figuration portion 36 and figuration is cylindrical shape.It addition, in this example, due to by the 1st
Figuration portion 36 of figuration portion the 28 and the 2nd forms composite part 38, and therefore, the 2nd masking stock solution figuration is cylindric, and concentric circles stratum
The folded outside being compounded in the 1st masking stock solution come along the circulation of the 1st figuration portion 28.
The 1st masking stock solution after stacking is compound and the 2nd masking stock solution, discharge from outlet 38a, and be coated on from supporting mass
The outer circumferential side strengthening supporting mass that export mouth 20a derives simultaneously.Then, make masking stock solution by making the gas containing moisture and system
In the container of film stock solution contact, make in the coagulating basin that masking stock solution contacts with solidification liquid, after making the solidification of masking stock solution, cleaned
Be dried, thus obtain Porous hollow-fibre membrane.
(other embodiment)
The device for spinning of the Porous hollow-fibre membrane of the present invention is not limited to aforementioned device for spinning 1.Such as, the present invention is many
The device for spinning of hole matter hollow-fibre membrane may also be the device for spinning 2 that Fig. 8 and Fig. 9 illustrates.For in Fig. 8 and Fig. 9 with Fig. 1 and
The part that Fig. 2 is identical, puts on same-sign and omits the description.Device for spinning 2 has and overlaps with the 1st joint 40A up and down, the 2nd connects
Head 41A and the nozzle connection 12A of the 3rd joint 42A, the 1st stock solution runner 46A and the 2nd system circulated in the 1st masking stock solution respectively
The 2nd joint 41A part in the 2nd stock solution runner 48A that film stock solution is circulated, configuration be made up of stator tube stirrer the
1 upstream side branch merging part 50A and the 2nd upstream side branch merging part 52A replace porous body, and in addition remaining fills with spinning
Put 1 identical.Stator tube stirrer had both configured single, it is possible to be that serial or parallel connection configuration is multiple.
It addition, the device for spinning of the present invention, it is possible to it is that porous body and stator tube stirrer order are differently connected
Configuration is used as the device etc. of upstream side branch merging part.
It addition, the device for spinning of the present invention, although from can be in terms of dual-purpose conventional spinning-nozzle this respect, such as aforementioned device for spinning
1 like that, the form after preferably being combined by the nozzle connection of spinning-nozzle and built-in upstream side branch merging part, but also
But the inside of the spinning-nozzles such as the introduction part of the stock solution runner in spinning-nozzle arranges the form of upstream side branch merging part.
It addition, the number that arranges of the upstream side branch merging part of the upstream side of the downstream branch merging part being located in spinning-nozzle is not limited to
One, it is possible to be more than two.
It addition, containing can to monolayer occasion without cracking the masking stock solution that is filmed of multiple aperture plasma membrane layer, make two kinds
The occasion that above masking stock solution stacking is compound, it is possible to do not configure with can be to monolayer occasion without the multiple aperture plasma membrane layer system ftractureed
The upstream side branch merging part that the masking stock solution of film is corresponding.But, if using the masking not configuring upstream side branch merging part former
Liquid and the multiple aperture plasma membrane layer that formed produces cracking, then be affected by, be provided with upstream side branch merging part and the multiple aperture plasma membrane that formed
Layer is also possible to produce cracking.Therefore, the starting point ftractureed vertically to easily suppress each layer to be formed, it is preferred that with all
Masking stock solution be arranged in correspondence with upstream side branch merging part.
It addition, the device for spinning of the present invention, it is possible to it is that spinning-nozzle does not has described composite part to answer in nozzle exterior stacking
Close each masking stock solution and masking stock solution is coated on the form strengthened outside supporting mass.It addition, the device for spinning of the present invention, both
But only one of which stock solution runner and formation have the device of the Porous hollow-fibre membrane of single layered porous plasma membrane layer, it is possible to be
There is the stock solution runner of more than three and there is each self-corresponding upstream side branch merging part and the dress of downstream branch merging part
Put.There is no supporting mass passage it addition, may also be and form the Porous hollow-fibre membrane only formed by hollow form multiple aperture plasma membrane layer
Device.
<manufacture method of Porous hollow-fibre membrane>
Porous hollow-fibre membrane, if make masking stock solution discharge from spinning-nozzle via downstream branch merging part,
And utilize non-solvent induction or heating consumers, the dispersion of non-dissolved matter and extraction etc. to form multiple aperture plasma membrane layer, then it is assumed that,
Even any external diameter and thickness are likely to produce the starting point of cracking, in the occasion of the masking stock solution using high viscosity, it is believed that
Its probability is the biggest.The present invention is relatively thin for the external diameter manufacturing the thickness relatively porous matter hollow-fibre membrane of multiple aperture plasma membrane layer
It is effective because of external force or deadweight for the Porous hollow-fibre membrane of easily flattening Deng, outward appearance, is 1 for obtaining external diameter
～for the Porous hollow-fibre membrane that the thickness of 5mm, multiple aperture plasma membrane layer is 50～500 μm more effectively.
It addition, the present invention for being coated on the reinforcement of hollow cylindrical by more than one masking stock solutions in spinning solidification operation
It is effective for there is outside the outer circumferential side of supporting mass, manufacture reinforcement supporting mass the Porous hollow-fibre membrane of multiple aperture plasma membrane layer
's.
Below, as manufacture method one example of the Porous hollow-fibre membrane of the present invention, now illustrate to use according to Fig. 4
There is the manufacture method manufacturing device 60 of described device for spinning 1.
Manufacturing device 60 as shown in Figure 4, have: device for spinning 1, this device for spinning 1 is by the 1st masking stock solution A and the 2nd masking
Stock solution B is spun to be coated on the outside of the reinforcement supporting mass C of hollow cylindrical；Solidification equipment 2, this solidification equipment 2 utilizes solidification
Liquid 2a and the 1st masking stock solution A and the solidification of the 2nd masking stock solution B after making by device for spinning 1 spinning and form Porous doughnut
Film precursor M '；Cleaning equipment 3, the solvent remained in Porous hollow-fibre membrane precursor M ' is given by this cleaning equipment 3
Remove；Eliminating equipment 4, the pore-creating agent remained in Porous hollow-fibre membrane precursor M ' is removed by this eliminating equipment 4
And obtain Porous hollow-fibre membrane M；Drying equipment 5, Porous hollow-fibre membrane M is dried by this drying equipment 5；And
Winding apparatus 6, Porous hollow-fibre membrane M is wound by this winding apparatus 6.Manufacture the Porous doughnut in device 60
The traveling of film precursor M ' and Porous hollow-fibre membrane M is limited by guiding parts 7.
The manufacture method of the Porous hollow-fibre membrane of this embodiment, have following spinning solidification operation, matting,
Removing step, drying process and rolling step.
Spinning solidification operation is: in device for spinning 1, make the 1st masking stock solution A and the 2nd masking stock solution B be branched off into many respectively
Individual and make it collaborate, each the 1st masking stock solution A and the 2nd masking stock solution B that will be formed with position, multiple interflow are supplied to spinning again
Nozzle 10 so that it is branch in spinning-nozzle 10, and with than (t1/T1) and than (t2/T2) be respectively less than 1 condition be annulus
Interflow, shape ground, to be coated on after the state strengthened outside supporting mass C discharges, utilize solidification equipment 2 and make the 1st masking stock solution A and
2nd masking stock solution B solidifies in solidification liquid 2a and forms Porous hollow-fibre membrane precursor M '.
Matting is: utilizes cleaning equipment 3 to be carried out Porous hollow-fibre membrane precursor M ', will remain in many
Solvent in the matter hollow-fibre membrane precursor M ' of hole is removed.
Removing step is: utilize eliminating equipment 4 to be given by the pore-creating agent remained in Porous hollow-fibre membrane precursor M '
To remove, it is thus achieved that Porous hollow-fibre membrane M.
Drying process is: utilize drying equipment 5 to be dried Porous hollow-fibre membrane M.
Rolling step is: utilize winding apparatus 6 to be wound by dried Porous hollow-fibre membrane M.
(spinning solidification operation)
In device for spinning 1, respectively the 1st masking stock solution A, the 2nd masking stock solution B and reinforcement supporting mass C are supplied to spinning
Device 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 respectively
Masking stock solution A and the 2nd masking stock solution B are branched off into multiple and make it collaborate again, and the 1st masking that will be formed with position, multiple interflow is former
Liquid A and the 2nd masking stock solution B are supplied to spinning-nozzle 10.Further, in the 1st downstream branch merging part the 26 and the 2nd downstream branch
In merging part 34, with than (t1/T1) and than (t2/T2) be respectively less than 1 condition make the 1st masking stock solution A and the 2nd masking respectively
Stock solution B branch, collaborates in circular, they gives composite laminate and cylindric discharges, to be coated on outside reinforcement supporting mass C
The state of side carries out spinning.Then, it is coated with the 1st masking stock solution A and the product of the 2nd masking stock solution B by strengthening outside supporting mass C
It is immersed in the solidification liquid 2a being contained in coagulating basin 2b, makes the 1st masking stock solution A and the solidification of the 2nd masking stock solution B, form Porous
Hollow-fibre membrane precursor M '.
Making the 1st masking stock solution A and the 2nd masking stock solution B be branched off into multiple and make it collaborate again, formed on them multiple
Behind position, interflow, with than (t1/T1) and than (t2/T2) be respectively less than 1 condition make these the 1st masking stock solution A and the 2nd maskings
Stock solution B is collaborated annularly in spinning-nozzle 10 inner circle, thus in the Porous hollow-fibre membrane M finally given, can suppress
1st multiple aperture plasma membrane layer and the 2nd multiple aperture plasma membrane layer form the phenomenon of the starting point ftractureed vertically.
Than (t1/T1) and than (t2/T2) preferred mode by aforementioned.
Described time t1With time t2Both can be identical, it is possible to different.It addition, described viscoelasticity relaxation time T1And viscoelasticity
Relaxation time T2Both can be identical, it is possible to different.It addition, than (t1/T1) and than (t2/T2) both can be identical, it is possible to different.
The temperature of the 1st masking stock solution A and the 2nd masking stock solution B preferably 20～100 DEG C.
In the present invention, by the temperature of masking stock solution when upstream side branch merging part and downstream branch merging part not
It is particularly limited to.Such as, the wet type in non-solvent induction is separated or the occasion of dry-and wet-type spinning, by upstream side, branch collaborates
The temperature of masking stock solution when portion and downstream branch merging part preferably less than 100 DEG C, preferably less than 90 DEG C.If should
Temperature is less than 100 DEG C, even if then in the occasion of the solidification liquid used with water as main constituent, solidification liquid is the most also difficult to boil
Rise, can more stably spinning.
It addition, in the present invention, from upstream side branch merging part to the masking stock solution by downstream branch merging part
Temperature, both alterable, it is possible to constant.In the occasion that the temperature of described masking stock solution is changed, it is possible to relax based on viscoelasticity
Time T is the shortest value and than (t/T) is being the position configuration upstream side branch merging part less than 1.But, if masking stock solution
Described variations in temperature, then it is assumed that the time being kept the position, interflow being formed in masking stock solution has an impact, the most preferably
It is that the described variations in temperature of masking stock solution controls the scope within 10 DEG C.
Solidification liquid 2a must be the solvent of insoluble film formative resin, and is the good solvent of pore-creating agent.As solidification liquid
2a, if any water, ethanol, methanol etc., or their mixture.Wherein, from the perspective of working environment, operational management, preferably
Solvent and the mixed liquor of water for masking stock solution.
The temperature of solidification liquid 2a preferably 20～100 DEG C.
It addition, the manufacture device 60 that Fig. 4 illustrates, it is between device for spinning 1 and solidification liquid 2a, to be provided with sky walk interval (gas
Gap) the form of dry-and wet-type spinning, but be not limited to this form, it is possible to use and be not provided with sky and walk interval, by direct for masking stock solution
The form of the wet spinning discharged in solidification liquid.
(matting)
For solidification operation in formed Porous hollow-fibre membrane precursor M ', remain solution state pore-creating agent or
Solvent.The film of Porous hollow-fibre membrane remains pore-creating agent, then can not give full play to water penetration.If it addition, pore-creating agent exists
In film solid, be the most also film mechanical strength decline reason.On the other hand, in removing step described later, when using oxidation
When agent carries out oxidation Decomposition (low molecule quantization) to pore-creating agent, if Porous hollow-fibre membrane precursor M ' remains solvent,
The most likely solvent and oxidant produce reaction.Therefore, in this embodiment, after solidification operation, will in matting
The solvent remained in Porous hollow-fibre membrane precursor M ' is removed, and then will remain in Porous in removing step
Pore-creating agent in hollow-fibre membrane precursor M ' is removed.
In matting, utilize cleaning equipment 3, with cleanout fluid 3a, Porous hollow-fibre membrane precursor M ' is carried out clearly
Wash, thus remove and remain in the solvent in Porous hollow-fibre membrane precursor M '.In Porous hollow-fibre membrane precursor M '
Solvent while moving to film diffusion into the surface inside film, mobile, from Porous to cleanout fluid 3a diffusion from film surface
Hollow fiber film precursor M ' is removed.
As cleanout fluid 3a, in terms of cleaning performance height this respect, preferably water.As the water used, if any from the beginning
Water, water for industrial use, river and well water etc..Additionally, it is possible to lived in they mixed ethanols, inorganic salts, oxidant and surface
Property agent etc. uses.It addition, as cleanout fluid 3a, it is possible to use the solvent contained by masking stock solution and the mixed liquor of water.But,
Use the occasion of this mixed liquor, below the concentration of solvent preferably 10 mass %.
The temperature of cleanout fluid 3a, the diffusion remaining in the solvent Porous hollow-fibre membrane precursor M ' from raising is moved
Speed this respect is seen, preferably more than 50 DEG C, preferably more than 80 DEG C.
It addition, in matting, although mainly the solvent in Porous hollow-fibre membrane precursor M ' is removed,
But by Porous hollow-fibre membrane precursor M ' is carried out, it is possible to by the part removal of pore-creating agent.
(removing step)
In removing step, utilize eliminating equipment 4 will remain in the perforate in Porous hollow-fibre membrane precursor M '
Agent is removed, it is thus achieved that Porous hollow-fibre membrane M.
As removing step, such as, can enumerate: Porous hollow-fibre membrane precursor M ' is immersed in containing oxidant
In medicinal liquid, after making Porous hollow-fibre membrane precursor M ' keep medicinal liquid, by Porous hollow-fibre membrane precursor M ' at gas
Heated in mutually and pore-creating agent carried out oxidation Decomposition, then, Porous hollow-fibre membrane precursor M ' is carried out and
The operation that the pore-creating agent that low molecule quantifies is removed.Thus, can obtain pore-creating agent remove after there is abundant water permeability
Porous hollow-fibre membrane M.
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 cheap etc. from the perspective of, preferably hypochlorite.As secondary
Chlorate, if any sodium hypochlorite, calcium hypochlorite etc., sodium hypochlorite is especially good.
From easily suppressing the oxidation Decomposition remaining in the pore-creating agent Porous hollow-fibre membrane precursor M ' in medicinal liquid
Carry out and suppress the pore-creating agent being shed in medicinal liquid to carry out oxidation Decomposition further and waste oxidant this respect and see, medicinal liquid
Temperature preferably less than 50 DEG C, preferably less than 30 DEG C.It addition, medicinal liquid to be controlled into from suppression the sides such as the cost of low temperature
Face is seen, the temperature of medicinal liquid preferably more than 0 DEG C, preferably more than 10 DEG C.
Maintain the heating of the Porous hollow-fibre membrane precursor M ' of medicinal liquid, the most under atmospheric pressure use heating
Fluid.
As adding hot fluid, from inhibited oxidation agent be dried, can carry out in terms of more effective resolution process this respect, preferably
It is the fluid using relative humidity high, i.e. heats under wet heat condition.In this occasion, the relative humidity adding hot fluid is preferable
Be more than 80%, preferably more than 90%, especially good near 100%.
In the occasion of continuous processing, from shortening in terms of process time this respect, heating-up temperature preferably more than 50 DEG C, more
Good is more than 80 DEG C.It addition, heating-up temperature is under atmospheric pressure state, preferably less than 100 DEG C.
As the method that the pore-creating agent that low molecule quantifies is removed, preferably to body before Porous hollow-fibre membrane
The method that body M ' is carried out.As cleaning method, it is not particularly limited, the cleaning side enumerated in aforementioned matting can be used
Method.
(drying process)
Utilize drying equipment 5 that Porous hollow-fibre membrane M is dried.
As the drying means of Porous hollow-fibre membrane M, the drying means as Porous hollow-fibre membrane can be used
And commonly used approach, such as there is the air drying methods etc. utilizing hot blast to be dried by Porous hollow-fibre membrane M.Tool
For body, such as, there is such method: in the device that hot blast can be made to circulate with the wind speed about many metres per second, make in Porous
Hollow fiber film M is back and forth continuously traveling for several times, is dried Porous hollow-fibre membrane M from outer circumferential side.
(rolling step)
Winding apparatus 6 is utilized to wind dried Porous hollow-fibre membrane M.
Use the manufacture method of the Porous hollow-fibre membrane of present invention mentioned above, even improve spinning speed
Occasion, due to can figuration masking stock solution equably, can suppress to be axially formed the starting point of cracking, therefore, can obtain and be difficult to out
The Porous hollow-fibre membrane split.
It addition, the manufacture method of the Porous hollow-fibre membrane of the present invention, it is not limited to use aforesaid manufacture device 60
Method.Such as, both single masking stock solution is used to manufacture the Porous hollow-fibre membrane with single multiple aperture plasma membrane layer
Method, it is possible to be to use the masking stock solution of more than three kinds to manufacture the Porous hollow fibre with more than three layers multiple aperture plasma membrane layers
The method of dimension film.
Embodiment
Below, describe the present invention in detail according to embodiment, but the present invention is not limited to following record.
(film cracking behavior validation test)
Between the head of digital micrometer (Mitutoyo company MDC-25MJ), the mensuration direction making micrometer is film
Radially clip Porous hollow-fibre membrane.With the external diameter of the Porous hollow-fibre membrane of uncompressed state as zero point, from this
Position rotates rotary shaft so that the indicated value of micrometer be negative, then makes mould contract, deforms until the instruction absolute value of micrometer
Arrive the diameter of the hollow bulb of film, the most with the naked eye confirm the generation of cracking, the indicated value of micrometer when record cracking produces.
In the occasion not finding that film ftractures, micrometer is temporarily unclamped, after making film rotate 45 °, again make it compress, become
Shape, confirms the generation of cracking, makes film rotate 45 ° every time, at most carries out four times and measures.
The external diameter of Porous hollow-fibre membrane is, circumference and the arbitrary position of head touching to each film before compression
Measured three times and made meansigma methods.Measure sample and be made as three about 1cm length.
The evaluation of cracking behavior is, observes many before instruction absolute value on micrometer arrives the diameter of film hollow bulb
The situation of hole matter hollow-fibre membrane cracking is provided as " × (bad) ", will not observe that the situation of cracking is provided as " (good when arriving
Good) ".
(viscoelasticity relaxation time mensuration)
For the masking stock solution after modulation, AR2000 (TAinstruments company system, Φ 25mm parallel-plate) is used to survey
The stress of customization film stock solution relaxes, and the longest value in the viscoelasticity relaxation time will obtained by formula (2) is provided as delaying into viscoelasticity
With time T.
(modulation of masking stock solution)
Mass ratio as shown in table 1 is such, by Kynoar A (Arkema company system, trade name: Kynar-301F),
Kynoar B (Arkema company system, trade name: Kynar-9000LD), Kynoar C (Arkema company system, commodity
Kynar-761A), Kynoar D (Arkema company system, trade name: Kynar-1015), polyvinylpyrrolidone name:
(catalyst company of Japan system, trade name: K-79), N,N-dimethylacetamide (DMAc) (サ system ソ Application Off ァ イ Application ケ ミ カ Le
Company's system) mixed, and be warmed to 60 DEG C and modulated masking stock solution (1)～(4).The viscoelastic of 32 DEG C of masking stock solution (1)
Property relaxation time T (1) be about 307 seconds.Viscoelasticity relaxation time T (2) of 32 DEG C of masking stock solution (2) is about 225 seconds.System
Viscoelasticity relaxation time T (3) of 32 DEG C of film stock solution (3) is about 54 seconds.When the viscoelasticity of 32 DEG C of masking stock solution (4) relaxes
Between T (4) be about 140 seconds.
[table 1]
[embodiment 1]
(strengthening the manufacture of supporting mass)
Use the supporting mass shown in Figure 10 to manufacture device 70, manufacture reinforcement supporting mass.
Supporting mass manufactures device 70 to be possessed: 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 being woven into by circular knitting machine 76 is carried out the rope feedway 80 of tractive；Centering
Empty shape sennit 78 carries out the heating mould 82 of heat treatment；The traction apparatus that hollow form sennit 78 after heat treatment is drawn
84；And using hollow form sennit 78 as the up-coiler 86 strengthening supporting mass and be 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
Five reels being wound with polyester fiber described in 5kg.As circular knitting machine 76, employ desk-top braiding machine (circle well fibre machine
Tool company system, knitting needle number: 12, pin size: 16 space, the circle diameter of main shaft: 8mm).As rope feedway 80 and traction
Device 84, employs Nelson roller.As heating mould 82, employ the mould of the stainless steel with firing equipment (once
Side internal diameter: 5mm, secondary side internal diameter: 2.5mm, length: 300mm).
The polyester fiber of pull-out on five bobbin winder brackets 72 is concentrated into one and does filamentation 74 and (add up to the fiber number to be
After 420dtex), circular knitting machine 76 compile circle and weave hollow form sennit 78, hollow form sennit 78 is passed through the heating of 190 DEG C
Mould 82, is wound on up-coiler as reinforcement supporting mass with winding speed 200m/hr using the hollow form sennit 78 after heat treatment
On 86.Persistently manufacture and strengthen supporting mass until bobbin winder bracket 72 is without polyester fiber.
The obtained external diameter strengthening supporting mass is approximately 2.55mm, and internal diameter is approximately 1.7mm.Constitute the hollow strengthening supporting mass
The number of turns of shape sennit 78 is, 12 weekly, and the maximum open width of mesh is approximately 0.1mm.The length strengthening supporting mass is
12000m。
(manufacture of Porous hollow-fibre membrane)
The device for spinning 1 using Fig. 1～3 to illustrate manufactures Porous hollow-fibre membrane.
As the 1st upstream side branch merging part the 50 and the 2nd upstream side branch merging part 52, (SMC is public to employ porous assembly
Department's system, sintering metal assembly ESKA-Z2802-120, aperture 120 μm).It addition, it is former to employ masking as the 1st masking stock solution
Liquid (1), employs masking stock solution (2) as the 2nd masking stock solution.1st masking stock solution is, with it from the row of spinning-nozzle 10
Output is about 0.083cm3The state of/second and be supplied to device for spinning 1.2nd masking stock solution is, with it from spinning-nozzle 10
Output, is about 0.097cm3The state of/second and be supplied to device for spinning 1.The 1st masking stock solution supplied and the 2nd masking stock solution
It is incubated into 32 DEG C.t1It is approximately 132 seconds, t2It is approximately 116 seconds, time t1Viscoelasticity relaxation time T with the 1st masking stock solution1Ratio
(t1/T1) it is 0.430, time t2Viscoelasticity relaxation time T with the 2nd masking stock solution2Ratio (t2/T2) it is 0.516.
Strengthen supporting mass and be supplied to the central part of spinning-nozzle 10, and make its gait of march divided with 5m/ advance.In spinning
Make the 1st masking stock solution and the 2nd masking stock solution stacking be combined in nozzle 10, be applied to strengthen supporting after discharging from spinning-nozzle 10
The outside of body and carry out stacking, be then passed in the air gap of 54mm, and be passed to be incubated into solidification liquid (8 matter of 74 DEG C
The mixed liquor of the water of the amount N,N-dimethylacetamide of % and 92 mass %) in and solidify, thus obtain Porous doughnut
Film 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 dipped in the aqueous sodium hypochlorite solution of 50000mg/L, then with the hot water of 98 DEG C carry out 15 minutes clean, with
110 DEG C of temperature are wound after being dried 10 minutes, it is thus achieved that Porous hollow-fibre membrane.
[embodiment 2,10～12]
Except the gait of march to reinforcement supporting mass, the 1st masking from spinning-nozzle 10 as shown in table 2 and table 3
Output, the time t of stock solution and the 2nd masking stock solution1, time t2, than (t1/T1) and than (t2/T2) change outside, remaining with
Embodiment 1 manufactures Porous hollow-fibre membrane in the same manner.
[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 arranged in series respectively
The stator tube stirrer (Mercury Supply Systems Corporation system, pattern: 005-031) of three grades and
The gait of march of supporting mass will be strengthened, from the 1st masking stock solution of spinning-nozzle 10 and the 2nd masking as shown in table 2 and table 3
The output of stock solution, time t1, time t2, than (t1/T1) and than (t2/T2) change outside, remaining is same as in Example 1ly
Manufacture Porous hollow-fibre membrane.
[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 arranged in series respectively
The stator tube stirrer (Mercury Supply Systems Corporation system, pattern: 005-031) of two grades and
As shown in table 2 like that will strengthen the gait of march of supporting mass, from the 1st masking stock solution of spinning-nozzle 10 and the 2nd masking stock solution
Output, time t1, time t2, than (t1/T1) and than (t2/T2) change outside, remaining manufactures same as in Example 1ly
Porous hollow-fibre membrane.
[embodiment 7,8]
Except being altered to the 1st upstream side branch merging part the 50 and the 2nd upstream side branch merging part 52 respectively configure one-level
Stator tube stirrer (Mercury Supply Systems Corporation system, pattern: 005-031) and such as table 2
As shown in will strengthen the gait of march of supporting mass, from the 1st masking stock solution of spinning-nozzle 10 and the discharge of the 2nd masking stock solution
Amount, time t1, time t2, than (t1/T1) and than (t2/T2) change outside, remaining manufactures Porous same as in Example 1ly
Hollow-fibre membrane.
[embodiment 9]
Except the 1st upstream side branch merging part 50 is altered to the stator tube stirrer of arranged in series three grades, (hydrargyrum supplies
Answer system Co., Ltd. system, pattern: 005-031), the 2nd upstream side branch merging part 52 is altered to configure one-level stator
Tube stirrer (hydrargyrum supply system Co., Ltd. system, pattern: 005-031) and the row of supporting mass will be strengthened the most like that
Enter speed, from the 1st masking stock solution of spinning-nozzle 10 and output, the time t of the 2nd masking stock solution1, time t2, than (t1/
T1) and than (t2/T2) change outside, remaining manufactures Porous hollow-fibre membrane same as in Example 1ly.
[embodiment 14]
(strengthening the manufacture of supporting mass)
In addition to using dance roller and replacing rope feedway 80, remaining uses identical with supporting mass manufacture device 70
Supporting mass manufactures device, it addition, (fiber number: 167dtex, single fiber dimension: 48fil add without curling except using a polyester fiber
Work) as silk outside, remaining manufactures same as in Example 1ly, and external diameter is about 1.47mm, internal diameter is about the reinforcement supporting mass of 0.91mm.
(manufacture of Porous hollow-fibre membrane)
Do not supply the 1st masking stock solution, the 2nd masking stock solution is altered to masking stock solution (4), be not provided with the 1st upstream side branch
Merging part 50, is altered to stator tube stirrer (the hydrargyrum supply system of arranged in series three grades by the 2nd upstream side branch merging part 52
System Co., Ltd. system, pattern: 005-031), and the gait of march of supporting mass will be strengthened, from spinning-nozzle the most like that
The 1st masking stock solution of 10 and output, the time t of the 2nd masking stock solution1, time t2, than (t1/T1) and than (t2/T2) become
More, in addition, remaining manufactures Porous hollow-fibre membrane same as in Example 1ly.
[comparative example 1]
(manufacture of hollow-fibre membrane)
It is not provided with the 1st upstream side branch merging part the 50 and the 2nd upstream side branch merging part 52, will add like that as shown in table 3
The gait of march of strong supporting mass, from the 1st masking stock solution of spinning-nozzle 10 and output, the time t of the 2nd masking stock solution1, time
Between t2, than (t1/T1) and than (t2/T2) change, in addition, remaining manufactures Porous hollow same as in Example 1ly
Fibrous membrane.
[comparative example 2]
Except as shown in table 3 like that by strengthen supporting mass gait of march, from spinning-nozzle 10 the 1st masking stock solution and
Output, the time t of the 2nd masking stock solution1, time t2, than (t1/T1) and than (t2/T2) change outside, remaining and embodiment
1 manufactures Porous hollow-fibre membrane in the same manner.
[comparative example 3]
2nd masking stock solution is altered to masking stock solution (3), by the 1st upstream side branch merging part the 50 and the 2nd upstream side branch
Merging part 52 be altered to respectively arranged in series three grades stator tube stirrer (hydrargyrum supply system Co., Ltd. system, pattern:
005-031), for another example as shown in table 3 by strengthen supporting mass gait of march, from spinning-nozzle 10 the 1st masking stock solution and
Output, the time t of the 2nd masking stock solution1, time t2, than (t1/T1) and than (t2/T2) change, in addition, remaining
Manufacture Porous hollow-fibre membrane same as in Example 1ly.
[table 2]
[table 3]
As shown in table 2 and table 3, the 1st masking stock solution and the 2nd masking stock solution both sides were made to be formed before being supplied to spinning-nozzle
Position, multiple interflow and will be than (t1/T1) and than (t2/T2) make in the embodiment 1～13 less than 1, do not observe that film ftractures.
It addition, only make the 2nd masking stock solution used by the outermost layer of formation multiple aperture plasma membrane layer form position, multiple interflow and will be than (t2/
T2) make in the embodiment 14 less than 1, do not observe that film ftractures yet.
On the other hand, in the comparative example 1 being not provided with position, upstream side branch interflow, it was observed that film cracking.It addition,
Than (t1/T1) and than (t2/T2) both sides are the comparative example 2 of more than 1, than (t2/T2) be more than 1 comparative example 3 in, also been observed
Film ftractures.
Claims (15)
1. a manufacture method for Porous hollow-fibre membrane, this Porous hollow-fibre membrane has the multiple aperture plasma membrane of more than a layer
Layer, this manufacture method has spinning solidification operation, in this spinning solidification operation, will be formed containing film formative resin and this film
The masking stock solution of the solvent of property resin is supplied to spinning-nozzle, makes described masking stock solution branch and in circle in this spinning-nozzle
Collaborate annularly, then discharge cylindric for described masking stock solution, make the solidification of described masking stock solution be formed many with solidification liquid
Hole matter hollow-fibre membrane precursor, the manufacture method of this Porous hollow-fibre membrane is characterised by,
In described spinning solidification operation, the masking stock solution of the outermost layer forming described multiple aperture plasma membrane layer to major general is being supplied to
Make described masking stock solution be branched off into multiple and collaborate again before described spinning-nozzle, this is formed with the masking at position, multiple interflow
Stock solution is supplied to described spinning-nozzle,
The viscoelasticity relaxation time T of the masking stock solution making the time t obtained by following formula (1) and be formed with position, the plurality of interflow
Ratio t/T less than 1,
T=V/Q ... (1)
Wherein, in described formula (1), V and Q is expressed as follows the meaning:
V: from the place forming initial position, interflow the masking stock solution being formed with position, the plurality of interflow, to described
In spinning-nozzle after branch, the appearance of the stock solution runner in place that the masking stock solution that is formed with position, the plurality of interflow is collaborated
Long-pending, its unit is cm3；
Q: from time per unit, the masking stock solution that is formed with position, the plurality of interflow discharge of described spinning-nozzle
Amount, its unit is cm3/ the second.
2. the manufacture method of Porous hollow-fibre membrane as claimed in claim 1, it is characterised in that obtain Porous hollow fine
Dimension film, the external diameter of described Porous hollow-fibre membrane is 1～5mm, and the thickness of described multiple aperture plasma membrane layer is 50～500 μm.
3. the manufacture method of Porous hollow-fibre membrane as claimed in claim 1 or 2, it is characterised in that at hollow cylindrical
Strengthen supporting mass outer circumferential side be coated with at least one masking stock solution and form described Porous hollow-fibre membrane precursor.
4. the manufacture method of Porous hollow-fibre membrane as claimed in claim 1, it is characterised in that solidify work in described spinning
In sequence, before the masking stock solution making more than two kinds is fed separately to described spinning-nozzle, make the masking stock solution branch of more than two kinds
Becoming multiple and collaborate, the masking stock solution that will be formed with position, multiple interflow is fed separately to described spinning-nozzle, makes these make
The respective described of film stock solution is less than 1 than t/T, and it is compound that these masking stock solutions carry out stacking.
5. the manufacture method of Porous hollow-fibre membrane as claimed in claim 1, it is characterised in that described masking stock solution comprises
Pore-creating agent.
6. the manufacture method of Porous hollow-fibre membrane as claimed in claim 5, it is characterised in that described pore-creating agent is hydrophilic
The pore-creating agent of property.
7. the manufacture method of Porous hollow-fibre membrane as claimed in claim 5, it is characterised in that described pore-creating agent is poly-second
Alkene pyrrolidone.
8. the manufacture method of Porous hollow-fibre membrane as claimed in claim 1, it is characterised in that described film formative resin
It it is hydrophobic polymer.
9. the manufacture method of Porous hollow-fibre membrane as claimed in claim 8, it is characterised in that described hydrophobic polymer
It it is polyvinylidene fluoride resin.
10. a device for spinning for Porous hollow-fibre membrane, to the multiple aperture plasma membrane layer forming Porous hollow-fibre membrane
Masking stock solution carries out spinning, and this Porous hollow-fibre membrane has the multiple aperture plasma membrane layer of more than a layer, this Porous doughnut
The device for spinning of film is characterised by having:
Upstream side branch merging part, this upstream side branch merging part at least makes the outermost masking of formation described multiple aperture plasma membrane layer
Stock solution is branched off into multiple and collaborates, makes the masking stock solution being formed with position, multiple interflow；
Spinning-nozzle, this spinning-nozzle has: make to be formed with the masking stock solution branch at position, the plurality of interflow and in circular
The downstream branch merging part at interflow, ground and will to make circular masking stock solution figuration be cylindric figuration portion；And
Stock solution runner, described upstream side branch merging part and described downstream branch merging part are coupled together by this stock solution runner,
Described upstream side branch merging part and described downstream branch merging part are configured to, following formula (1) the time t obtained and shape
The ratio t/T becoming to have the viscoelasticity relaxation time T of the masking stock solution at position, the plurality of 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 the place forming initial position, interflow the masking stock solution being formed with position, the plurality of interflow, to described
In spinning-nozzle after branch, the appearance of the stock solution runner in place that the masking stock solution that is formed with position, the plurality of interflow is collaborated
Long-pending, its unit is cm3；
Q: from time per unit, the masking stock solution that is formed with position, the plurality of interflow discharge of described spinning-nozzle
Amount, its unit is cm3/ the second.
The device for spinning of 11. Porous hollow-fibre membranes as claimed in claim 10, it is characterised 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 characterised in that described metal porous body
It is made up of metal sintering porous body.
The device for spinning of 13. Porous hollow-fibre membranes as claimed in claim 12, it is characterised in that described metal sintering is many
The nominal pore size of hole body is below more than 50 μm, 200 μm.
The device for spinning of the 14. Porous hollow-fibre membranes as according to any one of claim 10～13, it is characterised in that institute
Stating upstream side branch merging part is silent oscillation blender.
The device for spinning of 15. Porous hollow-fibre membranes as claimed in claim 10, it is characterised in that have: with formation two
All masking stock solutions of the multiple aperture plasma membrane layer that layer is above the most corresponding, multiple described upstream side branches merging part, described under
You Ce branch merging part and described stock solution runner,
For each stock solution runner, make described to be each configured with each corresponding described upstream side branch than t/T less than 1 ground and close
Stream portion and described downstream branch merging part.
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 CN104284710A (en) | 2015-01-14 |
| CN104284710B true CN104284710B (en) | 2016-11-30 |
Family
ID=
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104607053B (en) | Non-braided, textile-reinforced hollow fiber membrane | |
| US8752713B2 (en) | Hollow porous membrane and process for producing the same | |
| CN105063778B (en) | The manufacturing method of hollow-fibre membrane spinning-nozzle and hollow-fibre membrane | |
| CN103432916B (en) | Preparation method of enhanced hollow polyvinylidene fluoride fiber membrane | |
| CN102160967B (en) | Lining enhanced hollow fiber membrane tube and preparation device and preparation method thereof | |
| JP5834507B2 (en) | Method and apparatus for producing porous hollow fiber membrane | |
| CN104888621B (en) | A braided tube homogeneously-enhanced type polyvinylidene fluoride hollow fiber film and a preparing method thereof | |
| KR102171580B1 (en) | Method to make a yarn-reinforced hollow fibre membranes around a soluble core | |
| CN102365125B (en) | Non-braided reinforced hollow fibre membrane | |
| CN105797601A (en) | Reinforced hollow fiber composite membrane and preparation method thereof | |
| CN101439269A (en) | Method for preparing thermoplastic polyurethane elastic hollow fiber membrane | |
| JP5903780B2 (en) | Method and apparatus for producing porous hollow fiber membrane | |
| CN102824859B (en) | Method for preparing hollow fiber nanofiltration membrane by using thermally induced phase separation/interface cross linking synchronization method | |
| JP2009297642A (en) | Hollow fiber membrane for charge into hollow fiber | |
| CN108579461A (en) | Hollow porous membranes | |
| CN104284710B (en) | The manufacture method of Porous hollow-fibre membrane and device for spinning | |
| HU231006B1 (en) | Composite hollow fiber membrane and method for manufacturing same | |
| KR20130053930A (en) | Multi-layer hollow fiber membrane having high strength and excellent permeability and preparing method thereof | |
| CN103028330B (en) | Cotton-shaped enhancing hollow-fibre membrane of a kind of band and preparation method thereof | |
| CN104284710A (en) | Method and spinning device for producing porous hollow yarn membrane | |
| JP5790180B2 (en) | Method for producing porous hollow fiber membrane | |
| JP2012179603A (en) | Hollow porous membrane and method of manufacturing the same | |
| KR20170045454A (en) | Method of producing an ion-exchange fiber Plaited thread Micro chip filter | |
| KR20040038473A (en) | Hollow fiber membrane | |
| CN109012215A (en) | A kind of preparation method of graphene hydridization Kynoar liner coating film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Within Japan Tokyo Chiyoda pill 1 chome No. 1 Patentee after: MITSUBISHI CHEMICAL Corp. Address before: Within Japan Tokyo Chiyoda pill 1 chome No. 1 Patentee before: MITSUBISHI RAYON Co.,Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20161130 |