JPS6164304A - Production of hollow yarn composite membrane - Google Patents

Abstract

PURPOSE:To form a hollow yarn composite membrane not having a defect such as the formation of a minute flaw or a non-uniform membrane thickness, by guiding a hollow yarn into an atmosphere, in which a solution of a polymer material having separation function is atomized, to form a membrane to the outer periphery of said hollow yarn. CONSTITUTION:A prous hollow yarn with an outer diameter of 200-500mum, a surface area standard void ratio of 30-80% and an average pore size of 0.1-0.3mum is used as a support. A polymer membrane forming material having separation function such as poly(4-methylpentene-1) is dissolved in an org. solvent and the resulting solution 8 is used to generate an atomized atmosphere 9 by an ultrasonic vibrator 5 or an air gun. The concn. of the solution is pref. 1-3wt.% and the size of liquid droplet is 3mum or less and the density thereof is 10<7>-10<9>/cm<3>. The support hollow yarn 2 is passed through said atmosphere at 0.15-0.6m/sec for 30sec-2min and dried under heating at 20-60 deg.C for 30 sec-2min. The membrane thickness is 0.3-1mum.

Description

[Detailed Description of the Invention] [Industrial Utilization] The invention relates to a method for producing a polyester fiber, specifically a porous hollow fiber support and an outer periphery of the support. /c first cover? An improved method for manufacturing a six-hollow fiber composite membrane consisting of a thin film of a functional polymeric material is described below.In the specification of the present application, this hollow fiber composite membrane is It is also called a hollow fiber with a synthetic membrane.

′:! :8MBBWrh Shime Yozukun E66Δ and City/
2Dark 14 people in various fields, such as ultrafiltration membranes, reverse! '2 Advantageous as a permeable membrane, body decoration, etc.; τ can be used.

[Conventional technology]

When using - as a separation membrane, the separation selectivity and permeation amount of the membrane become issues. In particular, the amount of permeation is a major factor that determines the success or failure of a membrane in practical use.

The permeability is generally inversely proportional to the film thickness if the film is non-porous. Therefore, in order to make the film thickness as thin as possible, a composite film in which an ultra-thin film is combined with a porous support has been proposed and is now widely used. In fact, such a composite membrane can be made as thin as about 1 .mu.m or less than 1-i since the strength of the membrane can be depended on the support.

A common composite membrane is polypropylene, for example.

A thin film of a polymer material such as polyethylene or polyacrylonitrile and having a function of 90 on a porous support in the form of a film, a tube, a hollow fiber, etc.; I can give it to you.

Among these types of membranes, those in which the porous support is in the form of thin hollow fibers (usually called "hollow fiber composite membranes") are
It is extremely superior in terms of high film density.

To manufacture a hollow fiber composite membrane, that is, to coat a thin film of a tetrad material on a porous hollow fiber, plasma polymerization, vacuum deposition, etc. are sometimes used, but solutions are not required. The coating method is a common method because it requires simple equipment and has high productivity. In the solution coating method, a coating solution is usually prepared by dissolving a thin polymeric film in an appropriate organic solvent, and after immersing a porous hollow fiber in this coating solution, a predetermined production process is carried out. It consists of drying.

[Problem that the invention seeks to solve]

Melt 1f! When manufacturing hollow fiber composite membranes by coating method,
Several issues arise that must be resolved.

For example, poly(4-methylpentene-1) (TPX) has oxygen enrichment properties in porous hollow fibers made of polypropylene.
When obtaining a hollow fiber composite membrane by coating a thin film of
2 to 49 of the TPX polymer was added with cyclohexane solution (
coating? 77rW) To VC8! While the hollow fibers are immersed and passed through the bath solution, the polymer bath solution penetrates into the porous walls of the hollow fibers and, in some cases, even into the P9 part, and during the subsequent drying process, the cyclohexane in this solution is removed. Due to the evaporation of the polymer, crater-cane micro-defects occur in the thin polymer film that is forming on the outer periphery of the hollow fiber. These micro defects are caused by the extremely high affinity between the polypropylene hollow fiber as the support and the cyclohexane as the main ingredient, making it easy for the coating solution to break through. -It is thought that this occurred. Roughly, support and coating m
When the affinity of the liquid with the Z agent is high, the shape M”G is formed on the support.
The arbitrary coating method increases the thickness of the polymer thin film applied too much, making it impossible to obtain satisfactory separation performance.
Non-uniformity in the thickness of the polymer 74 film often occurs, therefore, in this technical field, what solutions have been widely used in the past? It is now desired to provide a V method with an improved hollow fiber composite membrane that can replace the Pζ method. According to the invention, there is a method for producing a hollow fiber peritoneal membrane comprising a porous hollow fiber support and a thin film of a polymeric material having a separation function coated on the outer periphery of the support, which includes the following steps. : guiding the hollow fibers into a D-forming atmosphere of liquid C of the polymeric material; and atomizing atmosphere I! Drying the thin film of the polymer Muraishi formed on the outer periphery of the thread by passing through B2, and drying it by the method of using the hollow fiber membrane using as a tube machine. Can be done.

Porous medium fibers which can be used as a support in the rush of the present invention can be made of common polymeric materials such as polypropylene, polyenalene, polyacrylonitrile, polyvinylidene fluoride, etc. Such op'l': yarn is preferably 1.45200/1
80-500/450. The dimensions of cryr+ (outer diameter/inner diameter) are approximately 30 to 809 square holes! Such hollow fibers having an average pore size of about 0.1 to 0.3 μm are prepared by extruding the melt of the starting polymeric material through the orifice according to the conventional method. Spun 9 medium yarns using
This can advantageously be shaped by further stretching.

Examples of polymeric thin film forming materials that can be used in the present invention include poly(4-methylpentene-1), cellulose acetate, cellulose diacetate, cellulose triacetate, polydimethylsiloxane, poly(2-methylpentene-1), and cellulose triacetate.
, 6-dimethylphenylene oxide], polyvinyl alcohol, etc. For example, benzene is a thin film-forming material such as benzene.

Toluene, acetone, hexane, cyclohexane.

The described 9 compound compound 2 can be generated from solutions obtained from various agents such as tricrene, methanol, ethanol, methylene chloride, etc. or their lachrymal mixtures.

It has been found that in order to generate such atomization, a dilute solution of the film-forming material described above, generally about 1 to 3 degrees F9, can be used.

Ultrasonic vibrators, air guns, etc. can be used as means for generating the atomized atmosphere.The atomized droplets of the thin film-forming material that create the atomized atmosphere are preferably about 3 μm or less, q″f preferably has a diameter of about 2 μm and is distributed in a highly dense manner.
Although it depends on the forming means, about 10~
101 means that the droplets are distributed. The smaller the droplet diameter (/J) is, the more advantageous it is.

According to the present invention, in order to form a membrane-forming membrane, the porous hollow fiber described above is completely extracted with the solution using the solution. Give the dog enough time to protect it.

The elapsed time for one cycle of the atomization calculation cycle of the hollow fiber is determined by the guiding speed of the hollow fiber (generally about cL15~0.6 m/m
in) Although it varies depending on the VC, it is preferably about 30 seconds to 2 minutes. The hollow fibers are taken out from the surrounding fibers, and the hollow fibers to be converted into sigma are naturally dried in a room or at about 20 to 60 degrees Celsius for about 30 seconds to 2 minutes. Heat and dry.

Approximately 200 to 500 p.
A porous hollow fiber support having an outer diameter of 1.0 m and a maximum of 1.0 m on the outer circumference of this support. Evenly coated with a film thickness of 1m.
A hollow fiber composite membrane consisting of ijJ'fi and yoshimo material having properties as a membrane? You can get crabs. ,;1
In general, the film thickness of the tt slope is 4-(1) higher and τ to ensure a real separability.
II? ? It is advantageous to be I.

Next, a preferred example of the present invention will be described with reference to the attached No. 1'21'r.

Porous 7 = Pull out the hollow fiber 2 from the hollow fiber roll 1,
Guide the No. 2 coated glass 1 coating tube 4 through the guide 3. Inside the coating tube 4 (C is a thin, film-shaped RYT polymer material diagonal 9 liquid). ]9
are distributed according to the degree of thunder. Kagaru Atmosphere 9
In the case 7 shown in the figure, the Tsukasa Sonic Fuku J-Eiko 5 is used. f, that is, the “°9ization R” shown in the figure is t
65? , a bell jar type glass vessel 6 having an iH2 vibrator 5 at the bottom, and capable of introducing an empty atmosphere 9 from a polymer material bath liquid 8 contained in the lamp 1 into the coating tube 4. ing. In order to send the atomized atmosphere to the coating tube 4, the glass container 6 is filled with 0ill!
Air charging pad G7 is attached to & [arrow is 9'7. Flow], Hollow fiber 2, inside the atomizing atmosphere 9, J9'r foot I holed up and passed through and turned into a ventral membrane fl, just in case, winding roll 11: τ winding It will be done. Hollow fiber composite membrane 1
0 is a warm [τ
dried naturally.

After completion of peritoneum formation, hollow fibers with a cross section as shown in FIG. 2 are obtained. It is understood that this C gold film consists of a porous hollow fiber support 12 and a thin polymer film 13 covering the outer periphery of this support. An enlarged view of the 20th line segment ■-■! From FIG. 3 showing the +5 surface, the polymer 74 membrane 13 penetrates and bonds only to the surface portion of the porous γF support body 20 (however,
This union! It will be understood that the product is very strong and does not cause peeling of the film during use.

[Implementation Guide] Next, the following facts ησ1jζ・ζX will be applied to the present invention.
=;'I'll explain in 4 ways.

Example 1: Outer diameter/inner diameter = 2'30/240μm; 4 holes 224
A polypropylene porous hollow fiber with an average pore diameter of 0.08□I1m [E-shishi Ion ■ Armor] and a tree Rtz next.

In addition, the volume of the glass vessel is 500 me and the length of the glass coated tube is 30 crn.
Both 1M openings with a pore diameter of 2-2mm were prepared.For this 71st conversion, acetic acid η = 409 and minute 1 = 40.ODD cellulose acetate (Daicel ■
)], force an acetone solution to 1.65MH
By the vibration of the ultrasonic transducer of z, g(
The diameter of the droplet is approximately 1.8 μm), and then add this 100 μm to the glass coated tube. F
The polypropylene pores are then fed into the coating tube, which is filled with an atomized atmosphere of cellulose acetate. Rtb g-thread 2
．． - person, so 0 jurisdiction x, , -2 i Wj Q, 6
FFI /mnon, triple second 17i+; m
Removed from the tube and removed from the piping hole.F: After drying with a Miyuki, a cellulose acetate film with a thickness of 0.3 μm was uniformly formed on the outer periphery of the polypropylene hollow fiber. I noticed that something had happened. Check out the surface condition of this hollow fiber composite membrane using a tau electron microscope (SEM)! However, a thick and defective membrane, TF1, was observed. The fourth rgA is a SEM' showing the surface condition of the polypropylene hollow fibers of this cellulose acetate membrane:
It is 4X (6000 times).

In this example, the moisture permeable membrane of the hollow fiber composite membrane is 2.0×
10 2・Positive//-19+@-〇C, sub-H2, and can be advantageously used as a moisture-permeable membrane 75: Possible.

Example 2 (ratio N!1 example): 1,000? as described in Example 1 above. ! : Money repeated. However, in the case of this example, since the polypropylene hollow fibers are guided through a triple base 9 of cellulose acetate sprayed with an acetone solution, the polypropylene hollow fibers are guided through the triple base 9 of cellulose acetate. The thread was dipped and a so-called solution coating method was performed. After soaking for about 2 to 3 seconds, pull it up with a hollow fiber and cut into pieces.

It was thoroughly dried in the subsequent drying tower. When we observed the surface appearance of the unusual eP empty fiber composite membrane using a SEM, we found that it had immersed deeply into the pores of each porous medium fiber support. This is caused by the acetone along the coating 1 being released as it dries, resulting in minute film defects. Admitted. -5 is a SEM photograph (6 Or 30 times) showing the surface condition n of the polypropylene hollow fibers of this cellulose acetate membrane.

When the above method was repeated by further reducing r of cellulose acetate, the same 9 small film defects as above were observed.
He became an author. , Opposite (with the above method f6-1-? using one shuttle of acetone to remove cellulose acetate)
However, although the .--T defect (--t) or 9 could be eliminated, a noticeable increase of 1 μm or more occurred, and the properties as a separation film deteriorated.

Decoy 13: Moisture permeability test Each of the medium 9-thread composite membranes prepared in Examples 1 and 2 above was comparatively evaluated in terms of moisture permeability.

In order to be subjected to this test, the hollow fiber composite membrane of Example 1 and the q fiber composite membrane of Example 20 (triple-3% solution?! 2 soaked and 27 strips of t7 crushed in solution for 5 hours and 9 hours) were prepared. ] In Fig. 6, numeral 14 is a pressure-resistant container;
At both ends of the stiffness there are openings 15 for charging moisture-containing air, openings 16 for discharging dehumidified air, and in the center of this, moisture-containing gas (
Also, an opening 17 is arranged for humidifying and air exhaust. The pressure container 14 is preferably made of resin such as acrylic resin, and has an umbrella-shaped bottom, and its size is generally about 2 mm.
0 to 40 ePR (Content contract Q, 2 to 2 tK compatible).This size 1"i, the size and number of threads that accommodate the ICs in the container, the desired separation performance, etc. can vary. Probably.

The VC in the pressure vessel 14 accommodates a large number of dispersed hollow fiber composite membranes 1C.
are bundled to form a medium 9-thread composite membrane bundle 18, and this bundle has a size of approximately 30>l.
Trim the τ and attach the W on both ends with Evokin Bunzoku adhesive.
'￥l1 is tightly sealed and then filled into the container (c) using the sealing member 19.As a result of such sealing, the inside of the pressure-resistant container 14 is divided into three zones, namely, the end portion 5 ;101
5ji-band 20, including 16 end openings 21.
And it is divided into a zone 22 including the central opening 17, and
There is no mutual movement of bands 20.21 and 22.

At V in FIG. 6, hollow fiber composite tear module 230 opening 1
As shown by the arrow in 5, when [τ and t embankment f-% enter, water vapor is separated in each of the hollow fiber composite membranes 10.
Nitrogen (see arrow B) and humid air are exhausted from the opening 17 (see arrow C). To explain the water vapor branch in more detail, the moisture vapor flowing inside the hollow fiber composite membrane 10 is pumped into the hollow fiber by the action of a vacuum pump (not shown) to provide a pressure difference on both sides of the membrane 10. The air is separated into air containing a large amount of water vapor (moist air) that can pass through the perforated molecular thin film coated on the yarn support and dehumidified air (dry air).

Humid air I; y, (temperature q = 25°C and relative 0° EI (to = 80)) was introduced into the opening 15 of the obtained *t'P ramie film mold metal membrane at various flow rates. However, in an example in which air with different humidity is taken out from the opening 16, the power output is 250W.
Use the same pump once again to reduce the pressure on the outside of the hollow fiber. Comparative evaluation of humidity performance was performed by measuring the humidity of the air coming out through the hollow fibers, and the results shown in FIG. 1 were obtained. From the graph shown, it can be seen that the present invention example
) and conventional example TIT (5 layers: immersed in 1.9 tons of ci).

Example 4: This example describes the use of a hollow fiber composite membrane prepared according to the present invention as a gaseous membrane.

The procedure described in Example 1 was repeated. However, in the case of this example, a 3 wt % cyclohexane n solution of TPX polymer was used in place of the 3 wt % acetone solution of cellulose acetate. As in the case of Side 1, a hollow fiber composite membrane with a smooth and defect-free membrane surface was obtained.

Subsequently, 24 hollow fiber composite membrane modules as shown in Figure 6 were made using the obtained hollow fiber composite membrane (the above side!1).
I want to be illuminated.] This hollow fiber composite membrane module/V Shiraguchi 15i'C boiled air (temperature = 25℃ and 1 vs. humidity R
H=40%) flow; it/min.

At the time of introduction, 409 g of diaryne was added; the enriched air was removed from the opening 17u). D Xl 0-' CCl32-
qec, cmHf. From this result, the present invention: τ
: Hollow fiber composite membrane; It is also found to be useful as a 4-layer composite membrane for 2 parts and 1 part.

I15: Repeat the method described in side 4 for 1 hour. 3?-9/benzene core 1.=6;tq.

In this example, medium q thread siri! As a result of introducing the dry 9 air, oxygen-enriched air with an oxygen concentration of 38γ comes out from the opening 17.
j 0.7 X 10 CC/nt ・5CC0av
+H9, from this result 4, same as above side 4, tP by invention Cτ? The usefulness of the 7-thread syndesmosis membrane as a gold film that attracts the i body parts can be seen.

[Efficacy of invention: rL]

According to the great invention, there are no disadvantages such as the formation of small defects, poor separation performance, and uneven film thickness, which were unavoidable in the conventional G liquid coating method, which has been widely used in the past. So, you can command Naguichi/'l Nen Hollow Thread Complex with one simple method. Great invention VCZi, 4zu, Sarajτ, about 1μ? Since it is possible to improve the performance of F1 or less, it is possible to improve the performance of Zl, which forms a membrane of F1 or less. It has many uses such as! , will be,

[Brief explanation of the drawing]

11th! S! 111-1:, Book 7P: A diagram showing one ingenious example of the method -1, illustrating 12 sections, Figure 12 is an enlarged sectional view of a gold membrane hollow spine according to the present invention, 13 The figure is an enlarged cross-sectional view of the note m-re-nizo-t of Figure 2, and the surface shape of the force-condyle-width-width-empty control according to the present invention. Fig. 1 shows the surface shape of a hollow paddle made by the prior art; Using yarn composite membrane? A favorable example of a hollow fiber composite membrane module developed by III is shown below.1. 'p: Approximately 1,000, and Figure 7 is a graph showing the results for the transparent bar condition i. In the figure, 1 is a roll of porous yarn, 2 is a hollow fiber, 3 guides, 4 coated tubes, 5 are ultrasonic rollers, 6 are
Keperger type glass container, 7 x 9 air charging tube, 8: Kouben-7 material q gate, 9: snowy atmosphere drum, 1011 hollow fiber i, and 11: winding roll. 81 Mouth 2 Diagram 63 Diagram 40 Vessel 351

Claims (1)

[Scope of Claims] 1. A method for producing a hollow fiber composite membrane comprising a porous hollow fiber support and a thin film of a polymeric material having a separation function coated on the outer periphery of the support, comprising: the following steps: guiding the hollow fiber into an atomizing atmosphere of a solution of the polymeric material, and forming a thin film of the polymeric material on the outer periphery of the hollow fiber by passing through the atomizing atmosphere; A method for producing a hollow fiber composite membrane, comprising: drying. 2. The atomizing atmosphere is one in which mist droplets with a diameter of 3 μm or less are generated at a high density from the dilute solution of the polymeric material.
A manufacturing method according to claim 1. 3. The manufacturing method according to claim 2, wherein the atomizing atmosphere is generated using an ultrasonic vibrator. 4. Generating the atomizing atmosphere using an air gun;
A manufacturing method according to claim 2. 5. The manufacturing method according to any one of claims 1 to 4, wherein the hollow fiber passes through the atomization atmosphere for 30 seconds to 2 minutes. 6. The drying process is carried out at a temperature of 20 to 60°C for 30 seconds to 2
Claims 1 to 5 are carried out over a period of minutes.
The manufacturing method according to any one of Items.