JPH0120966B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to an apparatus for continuously producing ultrathin membranes having selective permselectivity for mixed fluids, particularly mixed gases. In recent years, separation technology using membranes has made remarkable progress in various fields. However, separating gas mixtures using membranes is a relatively recent technology. The technical difficulties in separating a particular gas from a gas mixture, as well as the development of materials capable of permeating that particular gas with sufficient selectivity and sufficient permeation rate, are practical problems. The goal is to establish a technology for producing extremely thin films of uniform thickness and a wide area made of different materials. In other words, the amount of gas that permeates through a homogeneous membrane is generally calculated by the following formula: Here, X is the gas permeation rate (cc(STP)/
sec), P is the gas permeability coefficient (cc(STP)・cm/
^cm2 ·cmHg·sec), _P1 - _P2 is the difference in gas partial pressure on both sides of the membrane (cmHg), A is the membrane area ( ^cm2 ), and l is the membrane thickness (cm). Since it is defined by the formula expressed by the following formula, it is clear that once the material of the membrane and the gas to be permeated are specified, the amount of permeation of that gas depends on the membrane thickness and membrane area. It is desirable to make the film thickness as thin as possible and to make the film area as large as possible. Conventionally, in an attempt to manufacture a membrane with a thin membrane thickness and a large membrane area, a solution of a methylpentene polymer and an organopolysiloxane-polycarbonate copolymer in a solvent was dropped onto the surface of water. A batch method for producing ultrathin films that spontaneously expands on the surface is known (see US Pat. No. 4,192,842). As disclosed in the specification, this method makes it possible to spontaneously expand the solution on the surface of water by using an organopolysiloxane-polycarbonate copolymer. The specification of USP 4,192,842 also includes a method using a solution of methylpentene polymer alone in a solvent, but according to the research of the present inventors, this solution, that is, a method using a solution of methylpentene polymer alone in a solvent, Methods using non-containing solutions have not succeeded in producing ultrathin films with uniform thickness and large film area. Therefore, the above
Although the method using a solvent solution of methylpentene polymer alone disclosed in USP 4,192,842 is an attempt to produce an ultra-thin film, such a method cannot achieve a uniform film thickness that is suitable for practical use. It is at least not easy to produce ultrathin films with large film areas. The parent application whose divisional application is USP4192842
Perhaps for this reason, USP 4,192,824 claims only an extremely thin film made of a blend of methylpentene polymer and organopolysiloxane-polycarbonate. In addition, USP 4155793 discloses that two reservoirs provided in opposite directions on the surface of the aqueous medium,
each by supplying a solvent solution of the polymer and allowing each solvent solution to spread on the surface of the aqueous medium, continuously supplying a web penetrating into the aqueous medium at a position intermediate the two reservoirs, thereby Then, the web holds two thin films formed by expanding from the solvent solution onto the water surface, and a composite film is continuously produced in which two thin polymer films are stacked and held on the web. A method and apparatus are disclosed. This method involves forming two thin films in succession on a stationary aqueous medium, and simultaneously depositing two thin films on a stationary aqueous medium.
It is unique in that it is held on one sheet-like porous support and continuously collected from the surface. However, according to this method, since the polymer solution is supplied in a dropwise manner, the liquid surface is disturbed and the thickness is uneven.
Wrinkles are likely to occur, and it is difficult to stably and continuously produce a uniform ultra-thin film over a wide area. Therefore, an object of the present invention is to provide an apparatus for continuously producing an extremely thin membrane from a polymer, which has a uniform thickness and exhibits a gas separation coefficient that is almost the same as the gas separation coefficient inherent to the polymer. be. More specifically, the object of the present invention is to continuously and stably supply a polymer solution to the liquid surface of a liquid support consisting essentially of water, and to allow the solution to spontaneously expand on the liquid surface. The object of the present invention is to provide an apparatus for forming an ultra-thin film of a polymer and continuously and stably taking out the ultra-thin film from the liquid surface while being accompanied by a sheet-like porous support. The objects and advantages of the invention will become apparent from the description below. The present inventors have developed a method for continuously and stably supplying the polymer solution in order to continuously and stably produce an extremely thin film having a uniform thickness and exhibiting the inherent separation coefficient of the polymer, and Focusing on a method for stably expanding the polymer solution onto the liquid surface of a liquid support consisting essentially of water, intensive research was conducted using polymer solution physics, surface chemistry, and other physicochemical analysis methods. As a result, we have arrived at the present invention. That is, the present invention continuously supplies a polymer solution to the liquid surface of a liquid support consisting essentially of water from a polymer solution supplying means so that the solution does not leave the liquid surface. , the solution is allowed to spontaneously expand on the liquid surface to form an ultra-thin film of the polymer, and the ultra-thin film thus formed is taken out from the liquid surface while being accompanied by a sheet-like porous support. An apparatus for continuous production of coalesced membranes, wherein a guide plate is installed so as to be partially inserted into the liquid support of the apparatus, and the guide plate is centered on the side where the supply means is located. The present invention relates to an apparatus for continuously manufacturing an ultra-thin polymer film, which is characterized by being curved. The present invention will be explained in further detail with reference to the accompanying drawings FIGS. 1 and 2. As shown in FIG. 1 (partial schematic plan view) and FIG. 2 (partial schematic cross-sectional view), the apparatus for continuously producing ultrathin polymer films according to the present invention mainly has the following structure. (1) Polymer solution supply system Polymer solution supply means 1 set so as not to leave the liquid surface of the liquid support; metering pump 19 for supplying polymer solution; polymer solution temperature control section 20; Control devices 16, 17. (2) Ultra-thin polymer film forming section guide plate 2; liquid support 2 consisting essentially of water
1; supply parts 3, 4 for the liquid support; a weir 7 for overflowing the liquid support and its drainage part 8;
A tank 9 for the liquid support. (3) Ultra-thin polymer membrane winding system Sheet-like porous support unwinding section 13; guide rollers 5, 14 for the porous support; preliminary winding roller 6 for the ultra-thin membrane at the start of membrane production. As a detailed explanation of the present invention, first, the guide plate 2 will be explained. The guide plate 2 protrudes above the surface 11 of the liquid support and prevents the polymer solution supplied from the supply port 1 to the liquid surface 11 from spreading in the direction opposite to the direction in which the ultra-thin film is taken up. At the same time, it helps the polymer solution to spread in a direction perpendicular to the direction in which the ultra-thin film is pulled. The guide plate 2 is preferably curved so that its center is on the side where the supply port 1 is located, and in particular, the guide plate 2 has an average radius of about 10 cm to about 1 cm.
It is better to be m. If the guide plate is not curved and is a single flat plate, wrinkles are likely to occur in the extremely thin film, making stable continuous production impossible. That is, if the length of the flat plate is longer than the spontaneous expansion width of the polymer solution, both ends of the ultra-thin film produced will be wavy, resulting in uneven film thickness. It becomes easily damaged. Further, when the length of the flat plate is shorter than the spontaneous expansion width of the polymer solution, the polymer solution spontaneously expands at both ends of the guide plate in the opposite direction to the direction in which the ultra-thin film is taken, Since some of it intermittently adheres to the normal ultra-thin film, it is not possible to obtain a uniform ultra-thin film. Furthermore, attempts were made to manufacture ultra-thin films by bending the flat plate at the center and placing the polymer solution supply means at the center of the inside, changing the bending angle in various ways.
As with the case where a single flat plate was used as a guide plate, the membrane production was extremely unstable. Compared to the case where a flat plate is used as a guide plate,
In an ultra-thin film manufacturing apparatus using a curved guide plate, the desired ultra-thin film can be uniformly and continuously obtained. In particular, the average radius of the curved guide plate is approximately 0.1 to 1 m.
It is preferable that it is within the range of . More specifically, the degree of curvature of the guide plate, that is, the average radius, depends on the type of polymer in the polymer solution, the variety of solvents, the concentration of the polymer, the temperature of the solution, the ambient temperature, and the degree of curvature of the guide plate. The optimum value is determined while considering conditions such as the temperature of the support. Next, the positional relationship between the guide plate and the polymer solution supply means will be explained. That is, the supply means 1 for the polymer solution is located on the center line of the arc of the guide plate 2, and the shortest distance r between the supply means 1 and the guide plate 2 is
and the average radius R of the guide plate (r/R) is
The ratio (r/R) is preferably in the range of 0.005 to 0.5, particularly preferably in the range of 0.005 to 0.1. The smaller the ratio (r/R) is, the more stably and uniform an ultra-thin film can be obtained. That is, it is preferable for the solution supply means 1 to be located close to the guide plate 2; on the other hand, if it is too far away, the polymer solution will spontaneously expand in the opposite direction to the direction in which the ultra-thin film is taken up, and a portion of it will be interrupted. A phenomenon in which the thin film is easily torn off and adheres to the normal ultra-thin film is likely to occur, making stable continuous production difficult. More specifically, the allowable range of the shortest distance r between the polymer solution supply means and the guide plate changes depending on the average radius R of the curved guide plate, and when the average radius R is large, the allowable range of the shortest distance r changes. It becomes wider. That is, the average radius R of the curved guide plate,
The shortest distance r between the guide plate and the polymer solution supply means
The ratio (r/R) shall be in the range of 0.005 to 0.5, preferably in the range of 0.005 to 0.1. Next, the length of the chord of the arc of the curved guide plate will be explained. The length of the chord of the arc of the guide plate is determined by the width of the target ultra-thin film, the type of polymer, the type of solvent for the polymer solution, the concentration of the polymer, the temperature of the solution, and the amount of liquid that is essentially water. The optimum value is determined depending on various conditions such as the temperature of the support and the ambient temperature. The relative relationship between the chord length of the arc of the guide plate and the width of the ultra-thin film will be described in more detail. The length of the chord of the arc is
If the width is too large compared to the width of the ultra-thin film, both ends of the ultra-thin film will become wavy and the film will be easily damaged or cracked, making stable continuous production difficult. Also, if the length of the arc is too small compared to the width of the ultra-thin film,
The polymer solution also spontaneously expands in the opposite direction to the direction in which the ultrathin film is taken up, and the film is likely to be damaged or redeposited, making stable continuous production difficult. Thus, the length of the chord of the curved arc of the guide plate is in the range of 10 cm to 4 m. Further, the thickness, width, fixing method, etc. of the guide plate are not particularly limited, and any guide plate may be used as long as it satisfies the above-mentioned functions. Next, a device for forming a gentle flow of liquid support in the direction in which the formed ultra-thin film 15 is accompanied by the sheet-like porous support 12 will be explained using FIGS. 1 and 2. . In the present invention, when carrying out the continuous production of ultra-thin films, by flowing the liquid support 21 consisting essentially of water, the polymer solution expands spontaneously while riding the flow of the liquid support. In order to
The continuous change of conditions from the polymer solution to the production of the solid membrane proceeds very smoothly, thus forming a solid membrane with a more uniform thickness and desired gas separation coefficient. Furthermore, by fluidizing the liquid support, the temperature distribution of the liquid support and the concentration distribution of the polymer solvent in the liquid support can be made more uniform. However, the temperature of the entire liquid support is controlled to be constant by a temperature control device (not shown). Therefore, as shown in FIG. 2, a supply pipe 3 and a supply port 4 for continuously supplying the liquid support, and an overflow weir 7 and a discharge port 8 for discharging the liquid support are provided. By flowing the liquid support 21 slowly in the direction in which the ultrathin film is taken, stable continuous production is possible. The position of the supply pipe for the liquid support is preferably behind the guide plate, but it is also possible to place it on the same side as the guide plate.
The number of supply ports may be any number as long as a uniform flow is obtained, and the direction of the supply ports may be in any direction as long as a uniform flow is obtained. Furthermore, part or all of the liquid support can be recycled and reused. Furthermore, as a means for forming a gentle flow of the liquid support, not only an external supply method using the above-mentioned supply pipe or the like, but also an internal circulation method within a tank can be applied. Next, the materials of the tank walls and the like in the region where the ultra-thin film is formed until it is attached to the sheet-like porous support will be explained. In the process of forming an ultra-thin film, if the walls on both sides of the liquid support tank are made of a material to which the ultra-thin film easily adheres, wrinkles, cracks, etc. are likely to occur in the film, making safe continuous production difficult. Therefore, the side wall of the supply port side of the guide plate 2 and the solid film forming zone of the water tank 9, that is, the zone from the guide plate 2 to the porous support guide roller 5, is made of a material to which a solid film does not adhere or is made of such a material. Preferably, it is made of surface-treated material.
For example, fluororesins such as polytetrafluoroethylene and copolytetrafluoroethylene-hexafluoropropylene are used as materials that do not adhere to solid films, and silicone oils such as dimethylpolysiloxane are used as surface treatment agents with similar effects. used. Next, a detailed explanation of the present invention other than the above explanation will be given. The polymer used in the present invention is an addition polymer obtained from at least one of a hydrocarbon monomer having an ethylenically unsaturated bond and a hydrocarbon monomer having a conjugated unsaturated bond. Such a hydrocarbon polymer has 2 to 2 carbon atoms.
In particular, 4 to 10 aliphatic or alicyclic compounds can be mentioned as preferred. for example,
Hydrocarbon monomers having ethylenically unsaturated bonds, such as ethylene, propylene, butene, isobutene, pentene, methylpentene, hexene, methylhexene, heptene, cyclohexylpentene, styrene, α-methylstyrene, or mixtures thereof; Preferred compounds include hydrocarbon monomers having conjugated unsaturated bonds such as butadiene, isoprene, cyclooctadiene, or mixtures thereof. Methods for preparing addition polymers from such monomers are themselves well known to those skilled in the art. Such addition polymers used in the process of the invention may be homopolymers or copolymers of the monomers described above, and the copolymers may be random, graft or block copolymers. good. Preferably a homopolymer is used. Examples of such homopolymers include, for example, polyethylene,
polypropylene, polybutene, polyisobutene,
Examples include polyheptene, polymethylpentene, polyhexene, polymethylhexene, polycyclohexylpentene, polystyrene, polyα-methylstyrene, poly1,4-butadiene, poly1,2-butadiene, polyisoprene, polycyclooctadiene, and the like. In addition, examples of silane compounds include vinyl or allyl compounds with alkylsilane attached to the side chain, or polysiloxane compounds.
Examples include poly(4-methylpentene-1-allyltrimethylsilane) copolymer, poly(4-methylheptene-1-allyltrimethylsilane) copolymer, and polybutadiene-polysiloxane copolymer. These addition polymers can be used alone or in combination of two or more. Particularly preferred are polybutene, polypentene, polymethylpentene, polyhexene, polymethylhexene, polybutanediene and polyisoprene, with polymethylbentene being especially preferred. These particularly preferred polymers have, among other things, relatively high gas permeability, do not soften at room temperature, and have pressure resistance. The solvent for dissolving the polymer used in the present invention is preferably one that dissolves the polymer and is sparingly soluble or insoluble in water. Which solvent is suitable depends primarily on the type of polymer. In addition to the organic liquid medium, the solvent has the following distribution coefficient k k = 0.5 to 35 (preferably 1.0 to 25), where k is the ratio of the temperature of the other organic compound in the organic liquid medium to the concentration in water. be. may contain other organic compounds having
In addition, the solvent has the following formula c ₁ - (a ₁ + b ₁ )≧25, where c ₁ is the surface tension of water (dyne/cm), and a ₁ is the polymer solution in which the addition polymer is dissolved in this solvent. The surface tension (dyne/cm) and b ₁ are the interfacial tensions (dyne/cm) between the polymer solution and water. The one that satisfies the following is used. Preferred solvents include, for example, cyclohexene, cyclohexane,
Cyclopentene, n-hexane, n-heptane,
Aliphatic, alicyclic, or aromatic hydrocarbons that are liquid at room temperature such as benzene and toluene; for example, chlorinated hydrocarbons such as trichloroethylene, 1,2,3-trichloropropane, methylene chloride, tetrachloroethylene, and chloroform. can be mentioned. The above solvents may be used alone or as a mixed solvent of two or more. Such a water-immiscible organic liquid medium has a distribution coefficient k of 0.5 to 35, preferably 1.0 to 35, as described above.
May contain 25 other organic compounds. Such other organic compounds can include, for example, alicyclic or aromatic alcohols, ketones, amines, aldehydes, carboxylic acids, peroxides, and mixtures thereof. For example, cyclohexenol, cyclohexanol, phenol, cyclohexenone, cyclohexylamine,
Aniline, furfural benzoic acid, cyclohexenyl peroxide, or a mixture thereof is particularly preferably used. These other organic compounds are contained in an amount of about 0.1 to about 15% by weight, preferably about 0.5 to about 10% by weight, based on the solvent used in the present invention. The concentration of the polymer dissolved in these solvents is influenced by the solubility of the polymer in the solvent, viscosity, desired film thickness, etc., but is usually 0.1 to 20% by weight, preferably 0.5 to 10% by weight. be. If the concentration is higher than this range, not only will the viscosity of the solution become too high, but it will also be difficult to obtain a thin film. On the other hand, if the concentration is lower than the above range, the film thickness will be too thin to maintain strength, and it will be difficult to continuously take it up on a porous support. The temperature of the polymer solution depends on the type and combination of the polymer and solvent used, but is generally within the range of the lowest temperature that dissolves the polymer and the boiling point of the solvent. For example, when cyclohexene is used as a solvent, the temperature of the solution is preferably in the range of 20 to 80°C. Next, a method for manufacturing an ultra-thin film using the manufacturing apparatus according to the present invention will be explained. Supplying the polymer solution onto the liquid support is provided in contact with the liquid surface or in the vicinity thereof.
This is carried out from the polymer solution supply means. Preferably, the feeding takes place in the direction of gravity. When the supply is performed from a supply means provided near the liquid surface, the supply means may be located above the liquid surface or may be located below the liquid surface. The supply means can be a supply port or, when located above the liquid level, a thin wire. When it is a thin linear object, the polymer solution is supplied through the linear object. If the supply means is a supply port, the shape is such that the polymer solution supplied onto the liquid surface expands spontaneously and at a rate that produces a solid film of uniform thickness. Any supply may be used as long as it can supply continuously or intermittently. Since the polymer solution is usually supplied as a dilute solution of the addition polymer, the supply port should preferably have a not too large area. A supply opening of any shape, such as a narrow slit, a thin line, a circular shape with a small area, or other polygonal shapes, is usually used.
As the narrow slit, one having an opening width of about 0.001 mm to about 1 mm is preferably used.
As the supply port having a circular or other polygonal shape with a small area, one having an opening area of about 0.01 mm ² to about 3 mm ² , preferably 0.05 mm ² to about 1 mm ² is preferably used. As the supply means, a circular or polygonal shape (for example, triangular, pentagonal, etc.) having a small area is preferably used. Such feeding means can be the tip of a thin hollow tube, which tip can also be sharp. The polymer solution supplied to the liquid support rapidly and spontaneously expands on the liquid surface, and simultaneously with or following the expansion, the solvent is gradually released and the polymer solution solidifies. It is believed that the temperature of the polymer solution supplied onto the liquid support quickly approaches the temperature of the liquid support. Therefore, the temperature of the liquid support influences the surface tension of the polymer solution and the liquid support as well as the interfacial tension between them, while at the same time the rate of spontaneous expansion of the polymer solution on the liquid support. Or it greatly affects the degree of expansion. That is, if the temperature of the liquid support is too high, the volatilization of the solvent from the polymer solution will be too large, making it difficult to obtain the desired expansion rate and degree of expansion, whereas if the temperature of the liquid support is too low, On the other hand, since the solvent volatilizes too slowly, the rate at which it solidifies becomes slow. According to the method of the invention, generally about 0°C to 80°C, preferably about 1°C to about 50°C, more preferably about 3°C.
A temperature of ˜about 30° C. is employed as the temperature of the liquid support. The feeding rate of the polymer solution varies depending on the type of feeding means, the volatility of the solvent, etc., but when feeding from a preferably used circular or polygonal feeding port with a small opening area, it is, for example, about 0.1 to about 20 c. .c./min,
The rate is preferably about 0.3 to about 10 c.c./min. The extremely thin film formed on the liquid support is removed from the liquid surface of the support while being continuously accompanied by a porous sheet. The porous sheet usually moves at a constant speed, and moves along the liquid support so as to come out onto the liquid surface again. The porous sheet-like material can move so as to separate the ultra-thin film from the liquid surface when it runs along or when it emerges from the liquid surface. It is preferable that the rate is approximately equal to the rate of formation of the ultra-thin film at the liquid surface. In other words, the speed should be set so that a large tension is not applied to the ultra-thin membrane when the ultra-thin membrane is separated from the liquid surface, and the ultra-thin membrane does not sag. However, when starting production, before attaching the ultra-thin membrane to the porous sheet material, the ultra-thin membrane is rolled up in advance using a pre-winding roller (6 in attached Figure 2) to ensure a stable and constant flow of the ultra-thin membrane. Preferably, it is formed on a liquid support. The polymer membrane proposed by the present invention is extremely thin, has uniform thickness and excellent gas separation ability. In particular, the ultra-thin film supported by a porous sheet and manufactured by the continuous method of the present invention not only has the above-mentioned properties but also has a wide area, so it is actually possible to use two or more types of films. It can be used to produce a mixture of gases, such as air, enriched with certain gases, such as oxygen gas. The porous sheet-like material is used in the present invention to compensate for the lack of self-supporting properties of the ultra-thin membrane due to its thinness, and has virtually no effect on the gas separation ability of the ultra-thin membrane of the present invention. do not have. Examples of such porous sheet materials include Japanese paper, nonwoven fabric, synthetic paper, paper, cloth, wire mesh, membrane,
Many small pores such as ultrafiltration membrane porous film,
Any sheet-like material that is smooth and self-supporting can be used. In particular, polyethylene porous films (e.g.
Sekisui Chemical Co., Ltd. (trade name: Cellpore), polypropylene porous film (for example, Celanese (trade name))
Celgard), cellulose ultrafiltration membranes (e.g.
Polycarbonate porous film (product name: Nucleipore, manufactured by Nomura Microscience Co., Ltd.), polysulfone ultrafiltration membrane (product name: Toyo Shisha Co., Ltd.)
Toy-Ultrafilter) is preferably used, and polypropylene porous film is particularly preferred because it has good adhesion to the ultra-thin film of the present invention. The ultra-thin membrane according to the present invention can be supported on the porous sheet-like material in one or more layers. In particular, two ultrathin membranes stacked together and supported on a porous sheet material (in this case, the thickness of the plurality of polymer membranes is preferably about 50 to about 5000 Å) are suitable for gas separation. It exhibits excellent gas separation ability when used in applications, and in many cases exhibits a gas separation coefficient that is almost equivalent to the original gas separation coefficient of the addition polymer that forms the ultra-thin membrane. The porous sheet material supporting the ultrathin membrane according to the present invention can be used for gas separation in the same state as produced as described above, or can be used for gas separation before being used for such a purpose. under conditions of temperature and time that will not melt the ultra-thin film (for example, in the case of atmospheric heating, for example,
℃ to 300℃, preferably 80℃ to 200℃, for example 3
It is possible to further improve the adhesion between the ultra-thin film and the porous sheet material by heat treatment (from 5 seconds to 20 hours, preferably from 5 seconds to 20 hours), and then use it. As described above, the ultra-thin membrane according to the present invention is used to obtain a gas enriched with a specific gas from a mixture of two or more gases. For example, production of oxygen-enriched air from the atmosphere, production of _H2- enriched gas from a gas mixture containing _H2 and CO, removal of _H2O from a gas mixture containing _H2O , _SO2 and/or Alternatively, it is used for removing SO ₂ and/or NOx from a mixed gas containing nitrogen oxide gas (NOx), producing He-enriched gas from a mixed gas containing He, etc. It is particularly preferably used for producing oxygen-enriched air (eg, oxygen content of about 30 to about 45%) from the atmosphere. Hereinafter, the present invention will be explained in more detail with reference to Examples. The membrane performance of the ultrathin polymer membrane in the examples is expressed as the ratio of the oxygen permeability coefficient to the nitrogen permeability coefficient (hereinafter referred to as selectivity), and these permeability coefficients were measured using a gas permeability measuring device (Rika). Measured by Seiki Co., Ltd. (3BR-SSS). Examples 1 to 5, Comparative Examples 1 to 5 Poly 4-methylpentene-1 (manufactured by Mitsui Fuyu Chemical Co., Ltd.) was added to a solvent in which 4.75 parts of cyclohexenyl hydroperoxide was dissolved in 90.25 parts by weight of cyclohexene.
A solvent was prepared in which 5.0 parts by weight of TPXDX-810) was dissolved. From this polymer solution, the ultrathin polymer membrane of the present invention was continuously produced using the apparatus shown in FIGS. 1 and 2 by changing the shape and position of the guide plate. The polymer solution was maintained at 30° C. in a container 20 and was continuously supplied to the water surface 11 from the supply port 1 in contact with the water surface at a rate of 61 c.c./hr. Water 15 in the water tank 9 was maintained at 5° C., was supplied from the water supply pipe 3, overflowed the water tank 7, and was discharged from the water outlet 8. At the beginning of continuous production of the ultra-thin polymer film, the ultra-thin polymer film is wound up by the pre-winding roller 6 for about 3 minutes until it is confirmed that the ultra-thin polymer film is stably manufactured. Ivy. Next, a polypropylene porous membrane 12 having a thickness of 25 μm and a width of 30 cm is fed into the water from an unwinding roller 13 at a speed of 2.5 m/min via a guide roller 5, and the extremely thin polymer membrane is entrained therein. , and was taken over via the drive roller 14. In the example, on the guide plate 2 and the side wall of the water tank 9, where the ultra-thin polymer film comes into contact, Toshiba's release silicone Mold Ace Thread TSM- was applied, respectively.
6821 was applied. The results thus obtained are shown in Tables 1 and 2.

【table】

[Table] Comparative Example 6 A polymer membrane was obtained using the same method as in Example 1, but the guide plate 2 and the water tank 9 were made of stainless steel as they were, and the polymer membrane was attached to the polypropylene porous membrane 12. I pulled it up. The results obtained are shown in Table 3.

【table】 [Brief explanation of drawings]

The attached drawings schematically show an apparatus for continuously producing ultrathin polymer membranes of the present invention. That is, FIG. 1 shows a partial schematic plan view of the manufacturing apparatus, and FIG. 2 is a schematic cross-sectional view of the apparatus shown in FIG. Other parts necessary for operation are shown. To explain in more detail with reference to FIGS. 1 and 2, the ultra-thin film continuous device of the present invention has the following structure. (1) Polymer solution supply system Polymer solution supply means 1 set so as not to leave the liquid surface of the liquid support; metering pump 19 for supplying polymer solution; polymer solution temperature control section 20; Control devices 16, 17. (2) Ultra-thin polymer film forming section guide plate 2; liquid support 2 consisting essentially of water
1; Supply parts 3, 4 for the liquid support; Weir 7 for overflow of the liquid support and its drainage part 8; Tank 9 for the liquid support. (3) Ultra-thin polymer membrane winding system Sheet-like porous support unwinding section 13; guide rollers 5, 14 for the porous support; preliminary winding roller 6 for the ultra-thin membrane at the start of membrane production.

Claims (1)

[Scope of Claims] 1. Continuously supplying a polymer solution to the liquid surface of a liquid support consisting essentially of water from a polymer solution supplying means so that the solution does not leave the liquid surface. Then, the solution is allowed to spontaneously expand on the liquid surface to form an ultra-thin film of the polymer, and the ultra-thin film thus formed is taken out from the liquid surface while being accompanied by a sheet-like porous support. An apparatus for the continuous production of polymer membranes, wherein a guide plate is installed to be partially inserted into the liquid support of the apparatus, the guide plate being centered on the side where the supply means is located. A continuous manufacturing device for ultra-thin polymer membranes characterized by their curved shape. 2. The average radius R of the guide plate is in the range of 0.1 to 1 m, and the ratio (r/R) of the average radius R to the shortest distance r between the guide plate and the supply means is in the range of 0.005 to 0.5. An apparatus for continuously producing an ultrathin polymer film according to item 1. 3 The length of the chord of the curved arc of the guide plate is 10 cm or more
4. An apparatus for continuously producing an ultra-thin polymer film according to item 1 or item 2, which has a thickness of 4 m. 4. The ultra-thin polymer membrane according to items 1 to 3, comprising means for forming a gentle flow of the liquid support in the direction in which the formed ultra-thin film is accompanied by the sheet-like porous support. continuous manufacturing equipment. 5. In the area where the ultra-thin film is formed and the area until the formed ultra-thin film is attached to the sheet-like porous support, at least the surface portion in contact with the ultra-thin film is made of the polymer adhesion prevention material. An apparatus for continuously producing ultrathin polymer films according to items 1 to 4. 6. Items 1 to 6, wherein the polymer is an addition polymer obtained from at least one of a hydrocarbon monomer having an ethylenically unsaturated bond and a hydrocarbon monomer having a conjugated unsaturated bond. Continuous manufacturing equipment according to any of paragraph 5. 7. The continuous production apparatus according to any one of items 1 to 6, wherein the polymer solution is obtained by dissolving a polymer in a solvent mainly consisting of a substantially water-immiscible organic liquid medium. 8 The polymer solution is an addition polymer obtained from at least one of a hydrocarbon monomer having an ethylenically unsaturated bond and a hydrocarbon monomer having a conjugated unsaturated bond. In addition, the addition polymer is dissolved in a solvent mainly consisting of a substantially water-immiscible organic liquid medium capable of dissolving the addition polymer, and the solvent has, in addition to the organic liquid medium, the following distribution coefficient k k = 0.5 to 35. , k is the ratio of the concentration of this other organic compound in the organic liquid medium to the concentration in water. may contain other organic compounds having
In addition, the solvent has the following formula c ₁ − (a ₁ + b ₁ )≧25 where c ₁ is the surface tension of water (dyne/cm), and a ₁ is the surface of the solvent solution in which the addition polymer is dissolved in this solvent. Tension (dyne/cm) and b ₁ are the interfacial tensions (dyne/cm) between the solvent solution and water. The continuous manufacturing apparatus according to any one of items 1 to 7, which satisfies the following. 9 The solvent has the following formula c ₁ −(a ₁ +b ₁ )≧35, where the definitions of a ₁ , b ₁ and c ₁ are the same as above. 9. The continuous manufacturing apparatus according to item 8, which satisfies the following. 10 The other organic compound has a distribution coefficient k of 1.0 to 25
9. The continuous manufacturing apparatus according to claim 8, having: