CN101664645B - Composite porous membrane and method of manufacturing the membrane - Google Patents
Composite porous membrane and method of manufacturing the membrane Download PDFInfo
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- CN101664645B CN101664645B CN2009101777219A CN200910177721A CN101664645B CN 101664645 B CN101664645 B CN 101664645B CN 2009101777219 A CN2009101777219 A CN 2009101777219A CN 200910177721 A CN200910177721 A CN 200910177721A CN 101664645 B CN101664645 B CN 101664645B
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Abstract
An object of the present invention is to provide a composite porous membrane, which has not only excellent filtration capacity, but also excellent adhesion between a porous membrane and a braid and mechanical properties, and a method for producing the composite porous membrane. The present invention relates to a composite porous membrane comprising a braid, and a membrane material; wherein the membrane material comprises a first porous layer comprising a dense layer which is arranged on the outer surface of the braid, and a second porous layer comprising a dense layer which is arranged on the first porous layer, and a method for producing the composite porous membrane.
Description
The present invention divides an application for following application.
Denomination of invention: composite porous film and manufacturing approach thereof
The applying date: on November 10th, 2003
Application number: 200380102726.6 (PCT/JP2003/014262)
Technical field
The present invention relates to smart filter membrane of a kind of conduct or milipore filter, be used for compound many (little) pore membranes and the manufacturing approach thereof of water treatment.
Background technology
In recent years, because the reinforcement of the surging and regulation of the care of environmental pollution, the water treatment of membrane filtration method that has the filter membrane of excellent separation completeness and miniaturization etc. by employing is just gazed at.On the purposes of this type of water treatment, require filter membrane not only to have good stalling characteristic and through performance, also require to have than higher in the past mechanical properties.
Up to now, as the good filter membrane of through performance, the filter membrane of system such as the polysulfones that known with good grounds wet type or dry-and wet-type spinning method are produced, polyacrylonitrile, cellulose acetate, Kynoar.These filter membranes are that Polymer Solution is done after the microphase-separated, said Polymer Solution is solidified in non-solvent form, and have compacted zone and supporting layer, and have porous and asymmetrical structure.
In above-mentioned filter membrane material, because polyvinylidene fluoride resin has excellent resistance rerum natura, hear resistance, so suitable as separation membrane material.Yet,, exist the problem of bad mechanical strength by the filter membrane that the Kynoar hollow fiber membrane that is proposed up to now constitutes.
The filter membrane that is improved as intensity, existing people propose with the hollow cotton rope imbed fully perforated membrane in the porous matter pellicle (with reference to Japan Patent clear 52-081076 communique is disclosed, Japan Patent discloses clear 52-082682 communique and Japan Patent discloses clear 52-120288 communique).Yet this perforated membrane is imbedded in the porous matter pellicle in the porous matter pellicle owing to cotton rope fully, so there is the low problem of water permeability.
On the other hand, in order to improve water permeability, the someone proposes the diffusion barrier (with reference to No. 5472607 communique of United States Patent (USP)) that hollow cotton rope surface is provided with perforated membrane.Yet, therefore exist the easy problem of peeling off of perforated membrane from cotton rope because this diffusion barrier only is configured on the surface of cotton rope.
The present invention In view of the foregoing accomplishes, and the objective of the invention is to: provide not only to have excellent through performance, and have excellent perforated membrane and the cementability between the cotton rope, composite porous film that its mechanical properties is also good and manufacturing approach thereof.
Summary of the invention
Promptly; The present invention provides a kind of compound many (little) pore membrane; Said composite porous film has cotton rope and film material, it is characterized in that, said film material has first porous layer and second porous layer; Said first porous layer has the compacted zone that is adjacent to the cotton rope outer surface, and said second porous layer has the compacted zone that is adjacent to said first porous layer.
Composite porous film of the present invention preferably is coated in the film material on the cotton rope and the porous matter hollow fiber membrane that forms.In the water treatment purposes, the liquid phase that once filters side that film is seen through flows to face.Because this face stream makes the film vibration, is pulled, so composite porous film of the present invention need have sufficient mechanical.Because cotton rope is being born said mechanical strength, so composite porous film of the present invention has good mechanical strength.
Therefore composite porous film of the present invention can improve the durability of film owing to dispose the compacted zone that has more than 2 layers.
In addition; The present invention provides the manufacturing approach of composite porous film; On cotton rope, applying preparation liquid with annular nozzle; After making it in solidification liquid, to solidify formation first porous layer, use the surface applied preparation liquid of annular nozzle again, make it in solidification liquid, to solidify formation second porous layer at this first porous layer.
Description of drawings
The cutaway view of annular nozzle one example for the manufacturing that is used for composite porous film of the present invention shown in Figure 1.
The specific embodiment
Below preferable example of the present invention is described.
Composite porous film of the present invention; Said composite porous film has cotton rope and film material; It is characterized in that; Said film material has first porous layer and second porous layer, and said first porous layer has the compacted zone that is adjacent to the cotton rope outer surface, and said second porous layer has the compacted zone that is adjacent to said first porous layer.
At first describe with regard to the cotton rope that is used for composite porous film of the present invention.
The cotton rope that uses in the present invention, the silk thread that it constituted are preferably any one of composite filament, monofilament, weaving spun yarn.In addition, the cross sectional shape of silk thread any one of circular cross-section, hollow structure, odd-shaped cross section preferably.
Use the occasion of composite filament at cotton rope, if use the composite filament of silk number as 30-200, then excellent intensity and permeability are preferential to be used because of having.If the silk number is discontented with 30, then because withstand voltage routed ability is low, unsatisfactory.If silk outnumbers 200, then reduce owing to existing because of internal diameter dwindles the water permeability that causes, also undesirable.
As the raw material of cotton rope, can be used alone or in combination synthetic fibers, semisynthetic fibre, regenerated fiber, natural fiber or inorfil.
As synthetic fibers, the polyamide-based various fibers of nylon 6, nylon 66, aromatic polyamide etc. can be arranged for example; The various fibers of the polyester system of PETG, polybutylene terephthalate (PBT), PLA, polyethylene glycol acid; The various fibers of the acrylic acid series of polyacrylonitrile etc.; The various fibers of the polyolefin of polyethylene and polypropylene etc.; The various fibers of polyethenol series; The various fibers of Vingon system; Polyvinyl chloride fiber; The various fibers of polyurethane series; The phenol series fiber; The fluorine series fiber that constitutes by Kynoar and polytetrafluoroethylene (PTFE) etc.; And the various fibers of polyalkylene p-hydroxybenzoate system etc.
As semisynthetic fibre, the various fibers of cellulose-based derivatives class as raw material such as cellulose diacetate, triacetate cellulose, keratan, shitosan (キ ト サ Application) can be arranged for example; And be called as protein-based various fibers of Promix (プ ロ ミ Star Network ス) etc.
As regenerated fiber, can have for example: the cellulose-based various regenerated fibers that utilize rayon spinning method and copper-ammonia spin processes or organic solvent method to obtain specifically, have staple fibre, cuprammonium staple fibre, koplon etc.
As natural fiber, that can give an example has flax, a jute etc.
As inorfil, that can give an example has glass fibre, carbon fiber, various metallic fibers etc.
In these fibers,, better be by at least a fiber that constitutes in polyester fiber, acrylic fiber, vinylal fibre, Fypro, the polyolefine fiber from the good viewpoint of resistance rerum natura.In addition, good especially is polyester fiber, acrylic fiber.
From the durability of raising film and the viewpoint of cementability, the fiber number of cotton rope is the scope of 500-1200dtx (dtex) preferably.If the discontented 500dtx of the fiber number of cotton rope, then the withstand voltage routed ability owing to film reduces, so unsatisfactory.On the other hand,, then possibly reduce, greater than 1200dtx like the fiber number of cotton rope so also undesirable because of the internal diameter downsizing causes water permeability.
In addition, from the durability that improves film and the viewpoint of water permeability, the silk thread number of cotton rope preferably 8～50.If the silk thread number deficiency 8 of cotton rope is then because withstand voltage routed ability is low unsatisfactory.In addition, if the silk thread number of cotton rope greater than 50, then possibly cause that water permeability reduces because of internal diameter dwindles, so also undesirable.
The cilium number of cotton rope is preferably at every meter below 15.If the number of cilium more than 15 every meter, then disperses to apply bad part easily, this part makes bacterium and the suspended solid of coliform etc. see through easily, and practicality is undesirable.The cilium number is preferably at every meter below 10, is more preferably below 5.
Moreover; Cilium described herein is meant; The fiber that constitutes cotton rope because of the foreign matter fibrous or other shapes of separating state that fibre or fracture fly out from cotton rope, also refer to constitute beyond the fiber of cotton rope adheres on the cotton rope, is in the state of giving prominence to from the cotton rope surface in braiding processing.
From improve with respect to the film of cotton rope resinous impregnation rate, the hot water shrinkage of cotton rope better is below 5%.The hot water shrinkage is better below 4%, and best is below 3%.If the hot water shrinkage surpasses 5%, then in the hot water matting as an operation of manufacturing process, cotton rope shrinks in hot-tub significantly.If cotton rope shrinks, first porous layer of then impregnation (soaking suction) in cotton rope shrinks too.On the other hand, like following detailed description ground, because second porous layer and not exclusively bonding with first porous layer can not shrink significantly.Thus, the gap enlargement between first porous layer and second porous layer, because this big gap, and make resin be difficult to impregnation (soaking suction).
The cotton rope feeding tension brings influence can for the stability of film making process and the impregnation property of fixing resin.In order to improve this situation, preferably the cotton rope feeding tension is made as 1kPa～30kPa.If the cotton rope feeding tension is less than 1kPa, then in manufacturing process, exists cotton rope and take place easily from the tendency of the fault of guide groove disengaging etc.If the cotton rope feeding tension surpasses 30kPa, though then cotton rope and first porous layer exist the tendency that the degree that attenuates increases, the distortion of second porous layer not quite.Therefore exist the tendency that the gap between first porous layer and second porous layer enlarges easily.The cotton rope feeding tension is preferably at 3kPa～25kPa, is more preferably, at 5kPa～20kPa.Also have, the cotton rope feeding tension can the position till cotton rope is directed to annular nozzle on, try to achieve through the pressure that uses mensurations cotton rope generation such as tensometer.
As cotton rope, can use as with 96 monofilaments of polyester fiber of 8.6dtx (デ シ テ Star Network ス), promptly amount to 830dtx (デ シ テ Star Network ス), 16, the speed with 10 rev/mins in braiding machine is woven into the cotton rope that the hollow line rope form is made.
Secondly, the film material is described.
The film material has first porous layer and second porous layer, and first porous layer has the compacted zone that is adjacent to the cotton rope outer surface, and second porous layer has the compacted zone that is adjacent to said first porous layer.
See that from realizing viewpoints such as sufficient strainability said film material preferably has a plurality of holes that are communicated to other surfaces from a surface.The hole that is arranged on the film material also can be hole that directly connects or the hole that enters into inner mesh configuration.
From improving resistance rerum natura and stable on heating viewpoint, the film material is preferably formed by fluorine resin.Kynoar is especially good.Also have, contain weight average molecular weight 100,000～1, the Kynoar (B) of 000,000 Kynoar (A) and weight average molecular weight 10,000～500,000, the mass ratio of (A)/(B) are that 0.5～10 Kynoar is better.(A)/(B) mass ratio is that 1～3 Kynoar is better.By such mass ratio, can adjust the aperture of film easily.
The thickness of film material, if its thickness is blocked up, then water penetration is with low; On the other hand; If its thickness is thin excessively, damaged danger is then arranged, so the thickness of the outer surface of cotton rope till promptly from the inner surface of film material to the outmost surface of film material is preferably the scope of 200 μ m～500 μ m.
First porous layer and second porous layer bond together as if the inner surface of first porous layer with the outer surface and second porous layer, then improve as compound porous film strength.Yet, if engage fully, because the water penetration reduction, so be preferably, for the area 100% at both interfaces, bonding 1～50%.
From having water permeability simultaneously and making the viewpoint of the aperture control that block divides (Japanese: divide picture aperture system imperial), first porous layer preferably has the compacted zone that average pore size is 0.2～1 mu m range.Also have, said second porous layer preferably has the compacted zone that average pore size is 0.1～0.8 mu m range.
The thickness of above-mentioned compacted zone is preferably the scope of 50nm～50 μ m, and the scope of 200nm～30 μ m is better, and best is the scope at 500nm～10 μ m.
Also have, from having water permeability simultaneously and make the viewpoint of the aperture control that block divides, any one deck in best first porous layer and second porous layer or two-layer, the inboard of playing 0.1～50 μ m on the film surface has compacted zone.Do not have the film of compacted zone having 0.1 μ m part from the film surface; Because of from the impact of outside or receive in the film making process the easy damaged of occasion of bonding etc. the troublesome operations between the film; So it is undesirable; Though have compacted zone from the inboard more than the outermost position 50 μ m on the other hand, film properties does not reduce yet, has compacted zone just enough in the inboard that needs only on the practicality more than 50 μ m.
In order to improve water penetration, any one deck in first porous layer and second porous layer or two-layer preferably has from the compacted zone side and begins the supporting layer that increases gradually to the cotton rope aperture.The thickening film thickness relies on and adopts such apsacline structure, even also can be guaranteed high water-permeability.
The big space that in above-mentioned supporting layer, also can contain aperture with 50 μ m～150 μ m.The aperture of the supporting layer except that big space better is the scope of 0.1 μ m～50 μ m, and the scope of 0.3 μ m～30 μ m is better, and best is the scope of 0.5 μ m～20 μ m.
Also have, in the average pore size that becomes on each layer outermost locations, in first porous layer, the scope of 1～5 μ m preferably, in second porous layer, the scope of 0.8～2 μ m preferably.
Have, the outermost position that becomes each porous layer described herein is meant the position at the interface that becomes first porous layer and second porous layer at first porous layer again; At second porous layer, second porous layer is that outermost occasion is meant that it becomes the position of outmost surface, the occasion that also has other porous layer around second porous layer be meant and its layer between the position at interface.
Below, describe with regard to composite porous film with above-mentioned cotton rope and above-mentioned film material.
The thickness that composite porous film is whole is considered water penetration, withstand voltage routed intensity, preferably 600～1200 μ m.Also have, reduce if cross the membrane area of thick then unit volume, if cross detailed rules and regulations because the footpath of hollow bulb becomes meticulous, the water flowing resistance increases on the other hand, so the external diameter of composite porous film 2000～5000 μ m preferably, internal diameter is 700～3000 μ m.
From realizing the viewpoint of sufficient strainability, the water permeability of composite porous film (WF) is 50 (m preferably
3/ m
2/ h/MPa) or more than.If through performance less than 50 (m
3/ m
2/ h/MPa) then strainability low, be difficult to use.Though to the strainability no maximum, as long as 400 (m are arranged on practicality
3/ m
2/ h/MPa) just enough.
The pressure in bubbles point (BP) of composite porous film is preferably more than 50 (kPa).If pressure in bubbles puts not enough 50kPa, the seeing through of bacterium, suspended solid of coliform etc. then taken place, unsatisfactory on practicality.
From having water permeability simultaneously and make the viewpoint of the aperture control that block divides, the water flowing of composite porous film break press preferably 200kPa or more than.Press not enough 200kPa if the water flowing of perforated membrane is broken, then produce the seeing through of bacterium, suspended solid of coliform etc., unsatisfactory on practicality.Press no maximum though water flowing broken, as long as in fact there is 1000kPa just enough.
From have simultaneously water permeability with and make the viewpoint of the aperture control that block divides, when composite porous film being carried out continuous water flowing with 200kPa, the durable time preferably 150 hours or more than.If durable deficiency of time 150 hours, then produce the seeing through of bacterium, suspended solid of coliform etc., and impracticable.Though to durable time no maximum, as long as there in fact have 10000 hours to be just enough.Have, the durable time described herein is meant the time of the performance of dividing at the block that carries out keeping composite porous film before the water flowing and had again.
Durability times when in addition, applying the pressure of 400kPa repeatedly is preferably more than 100 times.If the durability times less than of 400kPa 100 times, the seeing through of bacterium, suspended solid of coliform etc. then taken place, unsatisfactory on practicality.Though to the durability times no maximum, as long as in fact have 10,000 times just enough.Also have, durability times described herein is meant the number of times of the performance that the block before exerting pressure at first, keeping composite porous film and had is divided.
Below, the manufacturing approach that just has the composite porous film of above-mentioned characteristic describes.
Preferably adopt so-called dry-and wet-type spin processes.Promptly preferably, after annular nozzle is discharged preparation liquid,,, form the film material of porous matter shape thus through being solidified the liquid dipping with after the fixed time placement film (Japanese: sky is walked).At first make cotton rope pass through annular nozzle in the time of the system film and on cotton rope, apply preparation liquid then.
The manufacturing approach of composite porous film of the present invention is so a kind of method; Promptly on cotton rope, apply preparation liquid with annular nozzle; After making it in solidification liquid, to solidify formation first porous layer; With the surface applied preparation liquid of annular nozzle, make it in solidification liquid, to solidify formation second porous layer at this first porous layer.
At first, on cotton rope, in formation first porous layer, on cotton rope, apply very thin being prone to and contain first preparation liquid that is dipped in the cotton rope, afterwards, on cotton rope, apply the suitable second denseer preparation liquid of concentration porous layer, ratio first preparation liquid that forms.First preparation liquid and second preparation liquid through using above-mentioned variable concentrations can make it contain in the major part that is dipped in cotton rope, improve film material peeling off from cotton rope.
If consider impregnation property to cotton rope, form the concentration of the polymer of the film material in first preparation liquid, be preferably below 12%, be more preferably below 10%, best is below 7%.Through making concentration like this, first preparation liquid is prone to contain and is dipped in the cotton rope.In addition, when making film forming, because it is identical with polymer concentration degree in first preparation liquid to occupy the polymer concentration of the film material in the space of cotton rope, so the water penetration of the film can keep very high filtration the time.Have again, the film material is attached on the cotton rope with enough intensity.
Identical with first preparation liquid, second preparation liquid also uses will be as the preparation liquid of polymer dissolution in solvent of film material.When making composite porous film,, preferably use to have identical or be higher than the polymer solution of the polymer concentration of above-mentioned first preparation liquid in order to obtain being difficult to form the mechanical strength of void layer.Specifically, the polymer concentration that forms the film material in second preparation liquid is made as more than 12%, is more preferably the scope more than 15%.In order to improve through flow, polymer concentration is to be no more than 25% scope for well usually.
As the solvent of first and second preparation liquid organic solvent preferably.ジ メ チ Le ア セ ト ア ミ De), dimethyl sulfoxide (DMSO) etc. as what organic solvent used N arranged, N dimethyl formamide, dimethylacetylamide (Japanese:.Wherein dimethylacetylamide is better on high this aspect of permeable flow of the porous plastid that obtains.
In addition, be separated from each other the additive of usefulness, in preparation liquid, preferably dissolve the hydrophilic polymer of the unit alcohol system, dihydroxylic alcohols system, trihydroxylic alcohol system, polyvinylpyrrolidone etc. of polyethylene glycol representative simultaneously as control.The concentration limit of hydrophilic polymer better is 1 quality %, and 5 quality % are better.In addition, the upper limit of concentration of hydrophilic polymer better is 20 quality %, and 12 quality % are better.
If the temperature of the above-mentioned preparation liquid when nozzle sprays is less than 20 ℃, then because preparation liquid maybe the low temperature gelation, so undesirable.On the other hand, if the temperature of above-mentioned preparation liquid more than 40 ℃, then is difficult to control the aperture, the seeing through of bacterium, suspended solid of coliform etc. takes place in its result, and practicality is undesirable.So preferably 20～40 ℃ of temperature of preparation liquid.
Then, the preparation liquid sky that is coated on the cotton rope is walked after, rely on impregnated in to form first porous layer in the solidification liquid.
If be below 0.01 second standing time, then strainability reduces and undesirable.Though standing time no maximum, as long as there have 4 seconds on the practicality to be just enough.So preferably 0.01～4 second standing time.
As solidification liquid, preferably use to contain the aqueous solution that is useful on the solvent in the preparation liquid.Though also depend on employed solvent species, in the occasion of for example using dimethylacetylamide as the solvent of preparation liquid, the concentration of the dimethylacetylamide in the solidification liquid preferably 1～50%.
From improving the intensity of machinery, the temperature of solidification liquid is advisable with low.Yet, if the undue temperature that reduces solidification liquid,,, be more preferably more than 50 ℃, 85 ℃ or following scope so select usually below 90 ℃ because the permeable flow of the film that makes reduces.
After solidifying, be preferably in cleaning solvent in 60 ℃～100 ℃ the hot water.This rinse bath temperature does not effectively take place to be set as high temperature in the scope of heat fusing between first porous layer as far as possible.From then on viewpoint is seen, the rinse bath temperature is preferably more than 60 ℃.
The most handy hypochlorous acid etc. carries out the soup cleaning after hot water cleans.Using the occasion of aqueous sodium hypochlorite solution, its concentration preferably 10～120,000mg/L.When the concentration deficiency 10mg/L of aqueous sodium hypochlorite solution, because the permeable flow reduction of the film that makes, so undesirable.Though to the concentration no maximum of aqueous sodium hypochlorite solution, in fact need only 120,000mg/L is just enough.
Then, preferably soup being cleaned film afterwards cleans in 60 ℃～100 ℃ hot water.Afterwards, preferably with more than 60 ℃ less than 100 ℃ temperature range, oven dry is more than 1 minute, less than 24 hours.60 ℃ less than because oven dry long, production cost of processing time rises, so unfavorable on commercial production.More than 100 ℃, owing to baking operation film excessive shrinkage, maybe small be full of cracks take place on the film surface, so undesirable.
Film after the oven dry preferably twists in bobbin or box (casket) frame (Japanese: カ セ).If twist on the box frame, then because of monomer (エ レ メ Application ト) handling ease, so desirable.
As previously mentioned, because if the fully bonding then water penetration of first porous layer and second porous layer reduces, institute thinks and prevents this phenomenon, is preferably in to form second porous layer before at the surface attachment of first porous layer solution of dissolving film material not.
As the solution of dissolving film material not, the preferred aqueous solution that contains the solvent that is useful on preparation liquid that uses.For example, in the occasion of using dimethylacetylamide as the solvent of preparation liquid, the concentration of the dimethylacetylamide in the solution of dissolving film material preferably 1～50%.As the solution of other desirable not dissolving film materials, preferred with an organic solvent, the mixture of organic solvent and water or in the former, to have added glycerine etc. be the solution of the additive of principal component.
On the surface of first porous layer, apply second preparation liquid then and form second preparation liquid.In the formation of second preparation liquid, need not the first rare preparation liquid of working concentration.
State in the manufacturing approach the preferred annular nozzle that uses the structure that for example in Fig. 1, shows on the implementation.First distributing nozzle 9 that this annular nozzle assembles by distribution plate 10, in abutting connection with distribution plate 10, also have in abutting connection with 9 assemblings of first distributing nozzle, second distributing nozzle, 8 these 3 members of constituting the tubular nozzle leading section and constitute.
First distributing nozzle 9 is that cross sectional shape is roughly T word shape, flat shape is the member of disc-shape.The heart is formed with outstanding tube 13 outstanding in above-mentioned second distributing nozzle 8 therein.The inside of this outstanding tube 13 is hollow bulbs, and this hollow bulb is communicated with above-mentioned pipeline 1, forms cotton rope path 10 0.If first distributing nozzle 9 and distribution plate 10 are overlapped into concentric shape, then form cotton rope path 10 0 therein at heart.
First distributing nozzle 9 has hollow bulb that is communicated in first supply port 6 and the hollow bulb that is communicated in second supply port 7 respectively around cotton rope path 10 0.
Be overlapped into concentric occasion at the distribution plate 10 and first distributing nozzle 9, in these, form ditch, be communicated in the first liquid pool portion 11 of first supply port 6 with formation.Be overlapped into concentric occasion at these in addition, also form narrow annular channel in the whole perisporium scope of cotton rope path 10 0 so that first outlet 2 forms.This first outlet 2 is communicated with the above-mentioned first liquid pool portion 11.Also have, the said first liquid pool portion 11 is communicated with first outlet 2.
The distribution plate 10 and first distributing nozzle 9 are overlapped into concentric shape, if to first supply port, 6 feed fluids, the liquid that then is supplied to can be stored in the first liquid pool portion 11, discharges liquid from first outlet 2 to cotton rope path 10 0 then.
Second distributing nozzle 8 also is discoid member, and its center has the second liquid pool portion 12 to form, and also is formed with the hollow bulb that is communicated with the second liquid pool portion 12.This hollow bulb is situated between by the hollow bulb that is communicated in second supply port 7, in first distributing nozzle 9, forms, and is communicated in above-mentioned second supply port 7.Through around first distributing nozzle 9, forming with overlapping second distributing nozzle 8 of concentric circles and first distributing nozzle, 9, the second liquid pool portions 12.Specifically, the space that forms on the end face that is provided with outstanding annulus 13 by first distributing nozzle 9, by the outstanding tube 13 and second distributing nozzle 8 becomes the second liquid pool portion 12.The above-mentioned second liquid pool portion 12 forms to the leading portion direction of the outstanding tube 13 of first distributing nozzle 9 and dwindles its sectional area.That is, the inwall of second distributing nozzle 8 is towards the slowly bulging of outstanding annulus 13.
Also have, in the leading portion portion of the second liquid pool portion 12, be formed with second aspis 3.Promptly form second outlet 3 by the outer wall of the leading section of giving prominence to tube 13 and the inwall of second distributing nozzle 8.
Especially, the front end face of outstanding annulus 13, i.e. the front end face 110 of cotton rope path 10 0 cans be compared to the front end face 5 of second outlet 3 most, and promptly the front end face 5 of second distributing nozzle 8 more is positioned at the inboard of annular nozzle.
In other words, the front end face of outstanding annulus 13, promptly the cotton rope path 10 0, and with the front end face 5 of second outlet 3, promptly the distance 4 between the front end face 5 of second distributing nozzle 8 (to call liquid sealing length in the following text) is preferably 0.5～150mm.(Japanese: liquid シ one Le) lower limit of length is more preferably more than the 0.6mm liquid sealing, and best is more than 0.8mm.In the occasion of liquid sealing curtailment 0.5mm, second preparation liquid that is coated on the surface of first porous layer is discharged under the situation of almost not having the film pressure of being coated with.For this reason, even the external diameter of the film that forms at first porous layer has thin part, second porous layer also can be discharged from by same diameter.Very big space might take place in its result between first porous layer and second porous layer.From being coated with the viewpoint of film pressure, the upper limit of liquid sealing length do not have not Xian Ding, but if the long tendency that is difficult to make annular nozzle that then exists.So the upper limit of liquid sealing length is preferably below 150mm.Be more preferably, the upper limit of liquid sealing length is below 100mm, and best is below the 50mm.
The actual occasion of using composite porous film of the present invention in water treatment; Though in order to separate the fixed component that once filters side and secondary filter side and use common synthetic resin etc.; But if on composite porous film, form this type of gap, then resin gets into the gap, the shipwreck that should handle increases to contain the possibility that is dipped in the whole composite porous film.If liquid sealing length is made as suitable length, then there is the tendency of (Japanese: コ one テ イ Application グ) pressure increase of filming of the preparation liquid that is discharged from.So form the situation in very big gap in can preventing between first porous layer and second porous layer.
As described above; If in the state that distribution plate 10, first distributing nozzle 9 and second distributing nozzle 8 are overlaped with concentric shape to second supply port, 7 feed fluids; The hollow bulb that the liquid that then is supplied to can form through hollow bulb, first distributing nozzle 9 and second distributing nozzle 8 by first distributing nozzle 9 is stored in the second liquid pool portion 12, discharges to cotton rope path 10 0 from second outlet 3 then.
Desire uses the annular nozzle of this class formation to make composite porous film, at first supplies with cotton rope from pipeline 1 to cotton rope passage 1.Supply with first preparation liquid from first supply port 6 to the first liquid pool portion 11.Supply with second preparation liquid from second supply port 7 to the second liquid pool portion 12.
When pipeline 1 was supplied with cotton rope, promptly the limit was moved the cotton rope limit and is discharged first preparation liquid from first outlet 2 in the cotton rope path 10, makes it impregnation in cotton rope, contained from second outlet, 3 discharges, second preparation liquid to be dipped into the cotton rope.
Then, as discussed previously, the cotton rope that has flooded first and second preparation liquid is immersed in the solidification liquid, clean, dry, reel with hot water and soup.
Then, supply with the solution that does not dissolve above-mentioned film material, discharge the not solution of dissolving film material, on the surface of first porous layer, apply said solution from first outlet to first supply port 6.
Afterwards, will supply with and be stored in second preparation liquid the second liquid pool portion 12, from 3 discharges of second outlet, be coated on the surface of first porous layer once more from second supply port 7.
In above-mentioned explanation, although the composite porous film that clear film material is made up of first porous layer and second porous layer, but in the present invention,, multi-layer porous matter layer also has no relations even further being set on second porous layer.This occasion is as long as with as the order that on first porous layer, forms second porous layer, form multi-ply construction and both can.
Test Example
Below be the basis with the experimental example, just the present invention describes in more detail.
Method with shown in following has been measured each physics value.
In addition, " % " expression quality % that is used for containing ratio, concentration mark.
< maximum diameter of hole (μ m) (pressure in bubbles point method) >
According to JIS K 3832 standards, ethanol is measured as measuring medium.
< hot water shrinkage >
To in 90 ℃ hot water, flood 30 minutes with the cotton rope that the length of about 1m is cut off, measure the length before and after handling, from obtaining with following formula.
Hot water shrinkage (%)=(the cotton rope length after the cotton rope length-hot water treatment before handling) cotton rope length * 100 before ÷ handles
Experimental example 1
Use Kynoar A (manufacturing of ア ト Off イ Na ジ ヤ パ Application, trade name カ イ Na one 301F) Kynoar B (manufacturing of ア ト Off イ Na ジ ヤ パ Application, trade name カ イ Na one 9000LD), polyvinylpyrrolidone (ISP manufactured, trade name K-90), N; The N-dimethylacetylamide has been prepared the preparation liquid 1 and 2 with composition shown in the table 1.
Table 1
| Form | First preparation liquid | Second preparation |
| Kynoar A | ||
| 3 |
12 quality | |
| Kynoar B | ||
| 2 |
8 | |
| Polyvinylpyrrolidone | ||
| 2 |
10 quality % | |
| N, the N-dimethylacetylamide | 93 quality % | 70 quality % |
| Fluid temperature | 50℃ | 60℃ |
| Kynoar concentration in the liquid | 12 quality % | 20 quality % |
In the pipeline 1 of the external diameter 2.5mm of the annular nozzle that Fig. 1 of 30 ℃ of insulations shows, internal diameter 2.4mm, import polyester composite filament single fiber cotton rope (composite filament; Total decitex 830/96 monofilament, 16 (Japanese: beat Chi)), discharge first preparation liquid from first outlet 2, discharge second preparation liquid from second outlet 3.The cotton rope of coated first and second preparation liquid imports by N, and is that N-dimethylacetylamide 5 mass parts and water 95 mass parts form, in the solidification liquid of 80 ℃ of degree insulations, on cotton rope, forms first porous layer.
The cotton rope that will have first porous layer carries out impregnated in the aqueous sodium hypochlorite solution of 50000mg/L after 1 minute desolventizing in 98 ℃ hot water.Afterwards, in 90 ℃ hot water, cleaned 10 minutes, the up-coiler that is used in 90 ℃ of oven dry in 10 minutes is reeled.The cilium number that adheres to or imbed in the cotton rope is one every meter.The hot water shrinkage 1% of cotton rope.The feeding tension of cotton rope is 9.8kPa.
Then; Import cotton rope in the pipeline 1 of the external diameter 2.7mm that Fig. 1 of insulation shows in 30 ℃, the annular nozzle that internal diameter 2.6mm forms with first porous layer; This first outlet is discharged the glycerine (with light aphrodisiac industry system one-level) as solidified inside liquid, discharges second preparation liquid from second outlet 3.On first porous layer, apply second preparation liquid thus.The cotton rope that obtains is imported by N, and N-dimethylacetylamide 5 quality %, water 95 quality % form, spend in the solidification liquid of insulation 80, obtain composite porous film.Composite porous film is carried out in 98 ℃ hot water after 1 minute desolventizing, impregnated in the aqueous sodium hypochlorite solution of 50000mg/L after, in 90 ℃ hot water, cleaned 10 minutes, the up-coiler that is used in 90 ℃ of oven dry in 10 minutes is reeled.
Outer warp/the internal diameter of the composite porous film of gained is that about 2.8/1.1m, film thickness are that 900 μ m, through performance are 100m
3/ m
2/ h/Mpa, water flowing break that to press for 500kPa, in the durability times of 400kPa be 1000 times, be 2000 hours in the durable time of continuous water flowing of 200kPa.
Experimental example 2
After obtaining having the composite porous film of first porous layer, do not clean, dry, and except the annular nozzle that uses external diameter 8mm, internal diameter 2.7mm, the long 1.0mm of liquid sealing, other obtain composite porous film as experimental example 1.
Outer warp/the internal diameter of resulting composite porous film is that about 2.8/1.2mm, thickness are that the thickness of 800 μ m, the resin bed from the cotton rope to the surface is that 400 μ m, pressure in bubbles point 180kPa, through performance are 110m
3/ m
2/ h/Mpa, water flowing break that to press for 520kPa, in the durability times of 400kPa be 1300 times, be 3000 hours in the durable time of continuous water flowing of 200kPa.
Utilize possibility on the industry
Composite porous film of the present invention has the mechanical properties of the filtering material that do not have up to now and the adhesive strength between the cotton rope etc.So,, can improve the quality of filtrating even in the too harsh service condition of various water treatments that are difficult to up to now membrane filter technique filter, separate etc., also can use.In addition, because through performance is high,, realize the miniaturization of equipment so can reduce the use membrane area.
In addition, manufacturing method according to the invention can be made easily and has above-mentioned composite porous film with superior characteristic.
Claims (6)
1. the manufacturing approach of a composite porous film; It is characterized in that; On cotton rope, apply preparation liquid with annular nozzle, make it in solidification liquid, to solidify form first porous layer after, with the surface applied preparation liquid of annular nozzle at this first porous layer; Make it in solidification liquid, to solidify formation second porous layer
Said annular nozzle has: the cotton rope passage that lets said cotton rope pass through; First outlet at whole all wall openings of this cotton rope passage; And outlet one side and this cotton rope passage that are positioned at said cotton rope passage be concentric circles and be configured in second outlet of the periphery of this cotton rope passage,
After supplying with first preparation liquid and be coated on said cotton rope from said first outlet, second preparation liquid of supplying with than the said first preparation liquid higher concentration from second outlet is coated on said cotton rope, forms first porous layer.
2. the manufacturing approach of a composite porous film; It is characterized in that; On cotton rope, apply preparation liquid with annular nozzle, make it in solidification liquid, to solidify form first porous layer after, with the surface applied preparation liquid of annular nozzle at this first porous layer; Make it in solidification liquid, to solidify formation second porous layer
Said annular nozzle has: the cotton rope passage that lets said cotton rope pass through; First outlet at whole all wall openings of this cotton rope passage; And outlet one side and this cotton rope passage that are positioned at said cotton rope passage be concentric circles and be configured in second outlet of the periphery of this cotton rope passage,
After forming said first porous layer, from the undissolved solution of the said first outlet delivery film material, be coated on the surface of said first porous layer after, discharge said second preparation liquid from said second outlet and apply.
3. the manufacturing approach of a composite porous film; It is characterized in that; On cotton rope, apply preparation liquid with annular nozzle, make it in solidification liquid, to solidify form first porous layer after, with the surface applied preparation liquid of annular nozzle at this first porous layer; Make it in solidification liquid, to solidify formation second porous layer
Said annular nozzle has: the cotton rope passage that lets said cotton rope pass through; First outlet at whole all wall openings of this cotton rope passage; And outlet one side and this cotton rope passage that are positioned at said cotton rope passage be concentric circles and be configured in second outlet of the periphery of this cotton rope passage,
Said cotton rope passage front end face is positioned at the inboard of annular nozzle than the said second outlet front end face, and the distance between said cotton rope passage front end face and the said second outlet front end face is the scope of 0.5～150mm.
4. the manufacturing approach of composite porous film as claimed in claim 3; It is characterized in that; In forming said first porous layer and said second porous layer, behind at least one layer, composite porous film impregnated in the aqueous sodium hypochlorite solution, carry out drying after the reusable heat washing is clean.
5. the manufacturing approach of composite porous film as claimed in claim 3 is characterized in that, said preparation liquid contains weight average molecular weight 100; Inferior ethene A and weight average molecular weight 10 are fluoridized in 000～1,000,000 gather; Inferior ethene B is fluoridized in 000～500,000 gather, and the mass ratio of A/B is 0.5～10.
6. the manufacturing approach of composite porous film as claimed in claim 3 is characterized in that, using every 1m cilium number is 15 or following cotton rope.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002-328085 | 2002-11-12 | ||
| JP2002328085 | 2002-11-12 | ||
| JP2002328085 | 2002-11-12 | ||
| JP2003194892 | 2003-07-10 | ||
| JP2003194892 | 2003-07-10 | ||
| JP2003-194892 | 2003-07-10 |
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| CN200380102726A Division CN100591410C (en) | 2002-11-12 | 2003-11-10 | Composite porous membrane |
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| CN101664645A CN101664645A (en) | 2010-03-10 |
| CN101664645B true CN101664645B (en) | 2012-06-27 |
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| CN2009101777219A Expired - Fee Related CN101664645B (en) | 2002-11-12 | 2003-11-10 | Composite porous membrane and method of manufacturing the membrane |
| CN200380102726A Expired - Fee Related CN100591410C (en) | 2002-11-12 | 2003-11-10 | Composite porous membrane |
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| US20100108599A1 (en) * | 2008-11-03 | 2010-05-06 | Kristof Vizvardi | Filtration membrane with tubular support |
| WO2011010690A1 (en) * | 2009-07-22 | 2011-01-27 | 三菱レイヨン株式会社 | Process for producing porous film |
| CN104117289B (en) * | 2014-07-29 | 2017-07-11 | 枫科(北京)膜技术有限公司 | One kind enhancing composite support hollow-fibre membrane and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1113165A (en) * | 1994-03-31 | 1995-12-13 | 珀美阿有限公司 | Precess for producing composite membranes |
| US5914039A (en) * | 1997-07-01 | 1999-06-22 | Zenon Environmental Inc. | Filtration membrane with calcined α-alumina particles therein |
| CN1304329A (en) * | 1998-06-05 | 2001-07-18 | 科克梅姆布莱尼系统公司 | High performance composite membrane |
-
2003
- 2003-11-10 CN CN2009101777219A patent/CN101664645B/en not_active Expired - Fee Related
- 2003-11-10 CN CN200380102726A patent/CN100591410C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1113165A (en) * | 1994-03-31 | 1995-12-13 | 珀美阿有限公司 | Precess for producing composite membranes |
| US5914039A (en) * | 1997-07-01 | 1999-06-22 | Zenon Environmental Inc. | Filtration membrane with calcined α-alumina particles therein |
| CN1304329A (en) * | 1998-06-05 | 2001-07-18 | 科克梅姆布莱尼系统公司 | High performance composite membrane |
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| CN1711128A (en) | 2005-12-21 |
| CN100591410C (en) | 2010-02-24 |
| CN101664645A (en) | 2010-03-10 |
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