JPS625823A - Method and device for manufacturing thin film - Google Patents

Abstract

PURPOSE:To permit to manufacture the thin film having large area continuously by a method wherein first liquid is supplied onto second liquid by an interfacial tension in a method wherein a thin layer is formed on the surface of the second liquid by extending the first liquid and the thin film is formed by removing solvent from the thin layer. CONSTITUTION:The first liquid 3 of organic solvent solution having the principal constituent of film forming material exists in the lower part of a tank 1 and the second liquid 4 is poured onto the first liquid 3. The first liquid 3 is deployed on the second liquid 4 along the interface between the second liquid 4 and the upper space of the tank 1. The first liquid 3 is spread on the second liquid 4 in a thin thickness and organic solvent, constituting the first liquid 3, is vaporized into the upper space thereby forming the thin film 5. The thin film 5 is contacted with and adhered to a supporting body 9, sent out of a supplying roll 6 along a control roll 7, to reel it around an upper reeling roll 8. When the thin film 5 is taken up continuously, the first liquid is supplied continuously from a supplying section 2 into the upper space of the tank, therefore, the thin film may be manufactured continuously.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for manufacturing a thin film, and more specifically, to a novel method for manufacturing a thin film using a water surface spreading method.

[Prior Art] As a method for manufacturing a thin film, a so-called water surface spreading method is known, in which a solution of a polymer in a non-aqueous solvent is spread on a water surface to form a thin film layer of the solution, and then the solvent is removed. It is being

This method utilizes the spreading of the solution based on the interfacial phenomenon that occurs when small droplets of the solution are dropped onto the water surface. It has been quite difficult to use it industrially because of the non-uniformity of the film due to the difficulty of rolling and the difficulty of obtaining a thin film over a large area.

In recent years, various methods have been proposed in which a polymer solution is supplied not as droplets but in a linear form onto the water surface in order to produce large-area thin films.

For example, ■ a method in which a pair of partition rods is installed above the water surface, and a polymer solution is dripped into the area divided by the partition rods, and the distance between the partition rods is increased (Japanese Patent Publication No. 5.8-33
Q, 86), ■Use a solvent with a higher density than water, pass the solution through a movable surface such as a rotating roll in a solution reservoir installed below the water surface with a V to avoid adhesion to the roll surface, and then lower the solution to the water surface. A method in which the solution is forcibly spread on the water surface by pulling it up (U.S. Patent No. 3,767,737); A method of controlling the liquid level position (Unexamined Japanese Patent Publication No. 5
8-92526), ■ A method of supplying a polymer solution to the water surface along a plate-shaped body with one end immersed in water (Japanese Patent Application Laid-Open No. 1983-22724), ■ A method of supplying a polymer solution to the water surface by crossing a partition plate and contacting a supporting liquid. (Japanese Unexamined Patent Publication No. 156508).

However, in method (2), the thin film is continuously
However, method (2) has the disadvantage that the solution adhering to the movable roll surface does not necessarily completely transfer onto the water surface, which impairs the uniformity of the thin film.

Generally speaking, when manufacturing thin films continuously using methods ①, ②, and ②, the balance between the speed at which the formed thin film is removed from the water surface and the speed at which the polymer solution is injected must be controlled extremely precisely. It has the disadvantage that it has to be done.

[Problem to be Solved by the Invention 1] The present invention aims to solve the problem by injecting a film-forming material solution onto a developing solvent or by controlling the width of the thin film to be produced in the continuous production of thin films having a large area. We investigated a method in which the film-forming material solution is applied linearly across the direction and in an amount corresponding to the film-forming speed - silently and easily supplied onto the developing solvent. A concept completely different from the concept of dropping a solution onto a developing solvent, that is, it is expressed in terms of capillarity and wettability.
By introducing the concept of supplying the film-forming material solution to the developing solvent surface by utilizing the interfacial tension between the film-forming material solution and the supply section, the amount of the film-forming material solution can be adjusted according to the film forming speed. was spontaneously supplied onto the developing solvent, making it easy to continuously fabricate a thin film with a large area.

[Means for Solving the Problems] The present invention has the configuration as described in the claims section.

In the present invention, the film-forming material generally includes any polymer (including polymer mixtures, graft polymers, block polymers, and copolymers) that can form a substantially non-porous film by solvent casting. ). Both natural products and synthetic products can be used as such polymers, and any of anomalous polymers, inorganic polymers, and organic-inorganic copolymers can be used. Generally, various materials can be used depending on the purpose of the thin film. Examples of these polymers include polyolefins, vinyl polymers, poly(meth)acrylic acid esters, general purpose polymers such as polyamides, polyesters, and polyethers, ABS, polyphenylene oxide, polycarbonate, polysulfone, and polyether. Engineering plastics such as sulfone, methylpentene polymer, polyethylene terephthalate 1--isophthalate 1-copolymer, fluorine-containing polymers such as polyvinylidene fluoride, synthetic polymers such as polyorganosiloxanes, billulose derivatives, polyamino acids, etc. Examples include, but are not limited to, natural polymers. More specifically, polymers for exhibiting liquid and body separation performance, particularly cellulose diacetate and trivinegar, which can be used for salt removal and valuable material recovery by reverse osmosis. Cellulose derivatives such as t-lulose, aromatic polyamide, polyamide hydrazide, polyamic acid, polyimidazopyrrolone, polysulfonamide, polybenzimidazole, polybenzimidacylon, polyarylene oxide, polyvinyl methyl ether, polyacryloni-1-lyl, polyhydroxyethyl Methacrylate, polyvinylidene carbonate, etc. can be used.

Separation of water and alcohol -■, Yes means polymers used for liquid separation, such as polyurea, polyether amide, polyether urea, polyamide, polyester, polyether, polyvinyl halide, cellulose derivatives, chitin, chitin Polymers such as -1nan, silicon-containing polymers such as polysiloxane, substituted acetylene polymers such as poly(1-trimethylsilyl-1-propyne), etc. can be used. Examples of gas separation polymers include vinyl polymers such as known poly(4-methyl-1-pentene), polybutadiene, polystyrene, polyacrylic acid alkyl ester, polymethacrylic acid alkyl ester, polyvinyl pivalate, cellulose derivatives such as ethyl cellulose, Inorganic polymers such as polycarbonate, polyphenylene oxide and its derivatives, polysulfone, fluorine-containing polymers, substituted acetylene polymers such as polytert-butylacetylene, polyorganosiloxane and its derivatives, and polyphosphazene can also be used.

Sarani film-forming material L/T: Langmu i
Amphiphilic substances capable of forming a monomolecular film by the r-Blodgett method, such as carbonic acids having long-chain alkyl groups, and biological lipids such as alcohol and cholesterol, can also be used.

In the present invention, the organic solvent of the first liquid has a positive expansion coefficient given by the following formula, and expansion coefficient S=
γ1, -γ,. −γ.

(γv,: surface tension of water, γ1..: interfacial tension between solvent and water, γ0: surface tension of solution) In addition, it uniformly dissolves the film-forming material, and furthermore, it is easy to remove the solvent from the thin film when spreading on the water surface. A solvent with suitable volatility is used.

Examples of such solvents include aliphatic hydrocarbons such as n-hexane, cyclohexene, n-hebutane, and cyclohexene, and derivatives thereof; aromatic hydrocarbons such as benzene; and derivatives thereof; ~ Lichloroethane (boiling point 47°6°C1 specific gravity 1.57.25
surface tension at °C 17°86 yn/cm), carbon tetrachloride (boiling point 76.7 °C1 specific gravity 1.59.25 °C surface tension 26.9 dyn/cm), chloroborum (boiling point 6
1~62°C1 Specific gravity 1.48.Surface tension at 25°C2
5,5 dyn/cm), methylene chloride (boiling point 39.
75°C1 specific gravity 1.33.Surface tension at 25°C28.
0dVn/cm), 1,1.1-h-lichloroethane (
Examples include halogenated organic solvents having a boiling point of 74.1°C and a specific gravity of 1.34>. Furthermore, when the film-forming material is difficult to dissolve in these solvents, the first liquid can also be prepared by dissolving the film-forming material in a solvent and then diluting it with the above-mentioned solvent.

In addition, a variety of solvents can be used as the solvent for the first liquid, such as mixtures of the solvents listed above or with other solvents, depending on the solubility of the film-forming material used, operating conditions, etc. It is preferable that the solvent be appropriately selected.Furthermore, there is no problem in that components other than the solvent may be present to the extent that the effects of the present invention are not diminished.

For example, in order to increase the expansion coefficient S of the first liquid and quickly spread it on the second liquid, alcohols, carboxylic acids, peroxides, aldehydes, carbons, amines,
A compound having a hydrophilic group such as amide, an oil-soluble surfactant, an oligomer 1 polymer having a hydrophilic group, etc. may be added.

In the present invention, the ratio of the film-forming material to the organic solvent in the first liquid is determined experimentally as appropriate, taking into consideration the film-forming concentration of the film-forming material used, film thickness, solubility, operating conditions, etc. Although desirable, it is generally 10% by weight or less, more preferably about 0.01% to 5% by weight.

In addition, in the present invention, the second liquid does not mix with the first liquid, forms a clear interface with the first liquid, and dissolves the film-forming material or immerses the formed thin film. A solvent with a high surface tension is used. Although any solvent having such properties may be used, polar solvents are preferred. Such polar solvents include water (specific gravity 1, surface tension cuff 2.8 d at 0.25°C);
yn/cm) is particularly preferred. Although the present invention can be carried out using such a solvent alone, it is also possible to use an aqueous solution of an inorganic salt to reduce the solubility of the film-forming material or increase the surface tension, thereby facilitating the formation of a thinner film.

In the present invention, supply using interfacial tension refers to a supply process that occurs due to the interfacial tension between the first liquid and the surface of the supply material, as seen in wetting of the first liquid to the supply material or capillary action. The first liquid is supplied to the surface of the second liquid by utilizing the directional behavior of the first liquid. In order to produce such directional behavior of the first liquid, the supply part must be made of a material that is selectively wettable by the first liquid rather than the second liquid, or must have a structure that causes capillary action. It is preferable to have. In the present invention, a material that is selectively wettable by the first liquid rather than the second liquid refers to the material plane that is measured by dropping droplets of the first liquid and the second liquid on the smooth surface of the material and each liquid. The material is determined by the value of the contact angle with the droplet, and the value of the contact angle formed by the droplet of the first liquid is smaller than the value of the contact angle formed by the droplet of the second liquid. .

The contact angle between the first and second liquids and the material can be easily measured using a contact angle meter. If the material does not contain a substance to be changed, the contact angle between each solvent of the first liquid and the second liquid and the material may be more easily compared.

In addition, materials with a large difference between the contact angle formed by the second liquid and the contact angle formed by the first liquid have a high affinity with the first liquid, and can be used to quickly form the first liquid, which is the object of the present invention. This means that stable supply can be achieved more effectively. In the present invention, as described above, an organic solvent with a surface tension of 30 dyn/cm or less is preferably used as the solvent for the first liquid, and water (surface tension cuff 2,8 dyn/cm) is preferably used as the second liquid. , a material that is more selectively wettable by the first liquid than by the second liquid has a critical surface tension of 3.
A material having a thickness of 0.06 yn/cm or less is preferable. Specific examples of such materials include polytetrafluoroethylene,
Fluorine-containing polymers such as polytrifluoroethylene, Te1-rafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinylidene fluoride, polyethylene,
Polyolefins such as polypropylene and silicone polymers such as polyorkanosilkylene are preferred. In particular, fluorine-containing polymers that are not easily immersed in the first and second liquids are preferably used.

In the present invention, supplying the first liquid onto the second liquid by using a supply portion made of a material that is selectively wettable with the first liquid rather than the second liquid has the following surface chemical effects. It takes advantage of the phenomenon. In general, assuming that the solid surface α is covered by the liquid phase B, the liquid T that does not mix with this is α/
When dropped onto the β interface, if the interfacial free energy of the α/γ interface is lower than the interfacial free energy of the α/β interface,
The droplet γ displaces the liquid β and spreads on the solid surface α.

In the present invention, by using a material with higher affinity for the first liquid than for the second liquid as the material for the solid surface, the free energy obtained by displacing the first liquid or the second liquid on the solid surface is This is used as the driving force for supplying the liquid.

In the present invention, a specific method of supplying the first liquid onto the second liquid using the wetting of the first liquid according to the above principle is as follows.
Although not particularly limited, for example, the first liquid is poured into a bat-shaped container whose inner wall is made of a material that has a higher affinity for the first liquid than the second liquid, and the second liquid is poured from above. There is a way to enter. At this time, the first liquid in the lower layer rises by pushing the second liquid away from the inner wall of the material of the container, and the first liquid immediately starts spreading onto the second liquid.

In this case, the entire inner wall of the bulk container serves as the supply section in the present invention. Further, in order to give directionality to the spreading of the first liquid, it is also preferable to use a material that is more selectively wettable than the second liquid only on a part of the inner wall.

In the present invention, structures that produce a capillary phenomenon and close the V include those having a capillary such as a capillary, those having a slit formed by two plate-like bodies, a plate-like body having grooves on the surface, etc., as well as woven and knitted fabrics, Nonwoven fabrics, polymeric foams with communicating pores, microporous ceramics, microporous metals, and the like can be mentioned. For structures such as capillaries that have pores or slit openings only in specific parts of the structure, it is important to strictly control the position of the surface of the second liquid to match the opening. This is necessary for prompt and stable supply.

On the other hand, structures such as non-woven fabrics or plate-shaped bodies with grooves on the surface can provide continuous openings on both the first and second liquid surfaces through the interface between the second liquid and the atmosphere. Since the surface of the second liquid can always be in contact with the opening, the precise position of the surface of the second liquid can be controlled. -〇-ru is unnecessary, and the desired thin film can be manufactured more easily.

A specific example of the present invention using a supply section having a structure that causes capillary action will be described with reference to the drawings.

FIG. 1 is a cross-sectional view illustrating a typical method suitable for implementing the present invention. However, the present invention is not limited to FIG.

In the bathtub 1, a first liquid 3 of an organic solvent solution containing a film-forming material as a main component is present below, and a second liquid 4 is poured onto it. Next, a supply section 2 for the first liquid is provided at the end of the second liquid and in the vicinity of the vessel wall of the bathtub. The supply section 2 has one opening in the first liquid and the other opening above the second liquid level, and is designed to raise the level of a portion of the first liquid. Any structure may be used as long as it causes a capillary phenomenon that pushes the first liquid up to the vicinity of the upper space.

Then, the first liquid is spread on the second liquid along the interface between the second liquid and the upper space. The first liquid spreads thinly on the second liquid,
The organic solvent constituting the first liquid evaporates into the upper space, and the thin film 5
is formed. This thin film 5 is brought into contact with and adheres to a support 9 that is fed out from a supply roll 6 along a control roll 7, and is wound onto an upper winding roll 8. For winding, a release paper may be laminated between the thin films, and endless bells 1 to 3 may be used as the support 9. The thickness of the thin film can also be appropriately controlled by roughly controlling the winding speed of the support 9.

When the thin film 5 is continuously taken up as described above, the first liquid is continuously supplied from the supply section 2 to the upper space, so that the thin film is continuously produced.

In FIG. 1, it goes without saying that the first liquid may be continuously supplied from the outside. Further, the first liquid and the second liquid do not necessarily need to be placed in one bathtub, but may be placed separately in two or more bathtubs.

Generally speaking, in order to stably supply the first liquid, it is more preferable to combine a material that is selectively wettable with the first liquid rather than the second liquid with a structure that causes capillary action. For this purpose, for example, Teflon plates with arbitrary shapes and arbitrary number of grooves, commercially available fluoropolymer nonwoven fabrics and woven and knitted fabrics (trade name, manufactured by Daikin Industries, Ltd., Polyflon Paper, Gunze Co., Ltd.) can be used. PFA nonwoven fabric, etc.) can be cited as the supply unit. If such a supply part is used, the second liquid will not enter the pores or slits in the supply part from the opening, even if the second liquid is present not only on the surface of the second liquid but also in the second liquid. Therefore, the first liquid flows unhindered through the pores or slits, resulting in a rapid supply of the first liquid. A porous channel body made of a material that is selectively wettable by the first liquid rather than the second liquid.
By simply separating the first liquid and the second liquid, which are bound to meet each other, only the first liquid selectively permeates through the porous channel body and reaches the second liquid side, and the first liquid Spread quickly on the second liquid surface.

That is, when the porous structure separates the first liquid and the second liquid from side to side, the porous structure selectively absorbs the first liquid and retains the first liquid in its inner pores. become. When the surface of the second liquid comes into contact with the porous structure in such a state, the first liquid is pulled by the surface tension of the second liquid and spreads on the surface of the second liquid.

Such a supply method will be explained using FIG. 2.

Although FIG. 2 is a cross-sectional view showing a typical example of a method suitable for implementing the present invention, the present invention is not limited to FIG.

In a bathtub 10, a first liquid 11, which is an organic solvent solution containing a film-forming material as the main component of the solute, and a second liquid 12, which is a developing solvent, are separated by a porous supply part 13 near the surface of the second liquid. It has been put in place. Such a porous supply section 13 allows the first liquid to permeate through it more easily than the second liquid, so by placing it in a position as shown in FIG. 2, only the first liquid is held therein. The first liquid held inside the supply section 13 is spread on the second liquid surface by the surface tension of the second liquid on the second liquid side surface of the supply section.

The organic solvent constituting the first liquid from the spread first liquid evaporates into the upper space, and a thin film 14 is formed.

This thin film 14 is supplied. From roll 15 to control roll 16
The film contacts and adheres to the support body 18 that is sent out along the winding roll 17 at the top. In addition, when winding, release paper may be laminated between the thin films, and support 1B
may use Endless Bell 1~. Rough support 1
By controlling the winding speed in step 8, the thickness of the thin film can be appropriately controlled.

As described above, when the thin film 14 is continuously taken up, the first liquid is continuously supplied from the supply section 13 onto the second liquid, so that the film is continuously manufactured.

In FIG. 2, it goes without saying that the first liquid may be continuously supplied from the outside.

In addition, the supply FJA (D control) of the first liquid can be appropriately controlled depending on the porosity, thickness, pore diameter, etc. of the porous supply part.Furthermore, the control can be performed by making the first liquid storage part a closed system and pressurizing it. You may do so.

In the present invention, the shape of the supply section that utilizes interfacial tension is not particularly limited. In order to produce a thin film with a larger area, when forming a wide film, widening the contact area between the supply section and the surface of the second liquid makes it possible to continuously supply the first liquid over a wide width. Since the first liquid is uniformly supplied to each part of the section, no new drawbacks or problems arise due to the widening of the width.

Furthermore, in the present invention, it is preferable that the thin layer of the first liquid formed on the second liquid be desolvated (evaporation of the solvent) by adjusting the surrounding atmospheric temperature or the like. For example, as a solvent for the first liquid, 1-lifluoro-1-lichloroethane (boiling point 4
7.6°C), and when using methylene chloride (boiling point 39.8°C), the thin layer of first liquid formed can be desolvated by rubbing the ambient temperature from 25 to 35°C. This occurs naturally and quickly, and a thin film of the film-forming material is directly formed on the second liquid. Further, when using a high boiling point solvent, temperature control by infrared ray irradiation or the like is preferable in order to form a uniform thin film on the surface of the second liquid without disturbing it. In addition, gentle ventilation may be performed, or the upper space may be maintained at a reduced pressure.

Further, in the present invention, any gas may be used in the upper space, and air, nitrogen gas, water vapor, carbon dioxide gas, etc. can be used depending on the purpose of film formation. Among them, it is most rational to do it when it is popular in terms of safety and economy.

The thickness of the thin film depends on the concentration of the film-forming material in the first liquid, the film forming speed in the case of continuous film formation, and the difference between the boiling point of the solvent in the first liquid and the atmospheric temperature for desolvation. It is possible to control this by, for example, It is also possible to control the thickness of a so-called ultra-thin film to a thick film as appropriate.

Generally speaking, it is also possible to form these thin films using a first liquid containing a film-forming material and its crosslinking agent as a solute, and then carry out a crosslinking reaction of the thin film while avoiding contact with a crosslinking catalyst solution. Ru.

Furthermore, any conventional method can be used to pick up the formed thin film. For example, a method is used in which the second liquid is wound onto a rotating roll that is in contact with the surface of the second liquid, or a method in which the second liquid is scooped onto a support using a rotating roll.
The method is not particularly limited to these methods.

In the present invention, various supports can be used as necessary. For example, a thin metal membrane is used in the production of Contin 1, and a porous raw support is often used in the production of selectively permeable membranes for liquid separation and gas separation. Examples of porous supports include microfilters such as polypropylene porous membranes (product name: Duraguard), Teflon porous membranes (product names: NiGore-Tex, Fluoropore), polysulfone porous membranes, and cellulose acetate porous membranes. However, it is not particularly limited to these.

The thin film manufacturing apparatus of the present invention is not particularly limited as long as it is an apparatus that embodies the above-described thin film manufacturing method, but it is preferable to use interfacial tension to transfer the second liquid to the second liquid. A means for supplying the liquid onto the liquid surface, a first liquid storage tank part, a second liquid storage tank part that can keep the second liquid surface stable, and a means for continuously taking off the thin film formed on the second liquid surface. It is possible to use the equipment that has it. The means for supplying the first liquid onto the second liquid surface using interfacial tension means a supply section made of a material that is selectively more wettable with the first liquid than the second liquid, or a means using capillary action. It is necessary to include at least a supply section having a groove path for generating the flow. Further, the first liquid storage tank portion and the second liquid storage tower portion may have a preferable shape and configuration determined depending on the means for supplying the first liquid, but each storage tank portion may be provided separately, or as shown in FIG. It is also possible to form a first liquid storage tank part and a second liquid storage part by putting the first liquid in the lower layer of one bag-shaped container and the second liquid in the upper layer. Although there are no particular limitations on the means for continuously taking off the thin film formed on the second liquid surface,
Generally, a device is used in which a rotating roller-m in contact with the second liquid surface and a support are brought into continuous contact with the thin film.

In the thin film manufacturing apparatus of the present invention, in addition to the above-mentioned supply means, storage tank section, and withdrawal means, necessary equipment may be attached depending on various conditions such as film forming conditions and the area of the film to be formed. Good too. For example, a part of the heater to promote solvent removal, a temperature control device to keep the liquid temperature of the first and second liquids constant, a water surface cleaning device, and a metering pump to supply the first liquid to the supply section. By using such equipment, it becomes possible to configure optimal film forming conditions, and such ancillary equipment is effective for producing more homogeneous thin films.

Hereinafter, the present invention will be specifically explained with reference to Examples.

Reference Examples In order to investigate the compatibility between various solvents used in the following examples and Teflon, a contact angle meter CA-D manufactured by Kyowa Interface Science Co., Ltd. was used.
When the contact angle of various solvents on a Teflon plate was measured using a mold, the results shown in Table 1 were obtained.

Table 1 Example 1 Polymer solution-1 ~ (manufactured by GE, trade name "Lexan" 1)
A mixed solution of 21-111> (2@% chloroform) was prepared. This solution 1001111 was placed at room temperature of about 25°C in a size of 20 cm (length) x 17 cm (width) x 2.5 cm.
(depth) and add distilled water to almost cover the surface of the polymer solution.A thin layer of polymer solution is formed on the entire surface of the distilled water, and the solvent is gradually removed. A thin film of the polymer was formed.

This thin film was continuously collected from above the water surface and its thickness was measured using a dial gauge and found to be 3.2μ.

Example 2 Three vinegar cellulose (Gosumi ~ Mankodatsu 9 Shasha) 0
．． A 5% suspended methylene chloride solution was prepared at room temperature at 25°C. From this, a thin film was formed in the same manner as in Example 1, and taken up on a polysulfone porous support crotch at a speed of 0.5 m/min to form a laminated composite film. The thickness of the obtained thin film was 1200 (measured by Ellipsome 1 to 1).

When we measured the salt rejection rate by reverse osmosis using the laminated composite membrane prepared in this way, we found that it was 0.1 at 25°C.
5% Na CQ 7J (by passing the solution under pressure at 30'9/cm, Rej 65.2%, FI
The membrane performance was UX=0.17 mB/m2·day.

Example 3 0.17 heavy prize poly(4-methyl-1-pentene) (
(manufactured by Mitsui Petrochemical Co., Ltd.) was dissolved in a mixed solvent of 33.16 parts by weight of cyclohexene and 66.67 parts by weight of trichloro-1-trifluoroethane to prepare a solution. 100 ml of this solution was heated to 20 CIt at room temperature of about 25°C.
It was placed in a Teflon-coated pad 1~1 (length) x 17 cm (width) x 2.5 cm (depth), and 500 ml of distilled water was added thereon. This container has 5cm (height) x 14
A board with nine parallel grooves of 0.5 mm (width) X C) and 5 mm (depth) at 1.5 cm intervals in the height direction on a Teflon plate of cm (width) Xo and 3 cm (thickness). It was placed vertically along the widthwise wall of the container. At this time, the poly(4-methyl-1-pentene) solution phase provided on the Teflon plate communicates with the air through the aqueous phase and the surface of the aqueous phase. -1-pentene) solution was carried to the surface of the aqueous phase and immediately spread over the entire surface of the aqueous phase, forming a thin layer of polymer solution, which was gradually desolvated to form a thin film of the polymer. This thin film was brought into contact with a rotating roll wrapped with a polysulfone porous support film having a crosslinked polydimethylsiloxane layer on the surface.
The thin film was wound onto the support membrane at a speed of m/min. At this time, the polymer solution continuously spread on the surface of the aqueous phase through the grooves provided in the Teflon plate, and a thin film was continuously formed on the water surface whenever the Teflon plate was wound up.

The thickness of the poly(4-methyl-1-pentene) layer thus formed was measured using an Ellipsome 1-Lee test and was found to be 920 mm.

Example 4 A solution was prepared by dissolving 0.5 parts by weight of polysulfone (Udel, manufactured by Union Kahai 1) in 99.5 parts by weight of chloroform. Using this solution, a polysulfone thin film was formed on the water surface in the same manner as in Example 3. This thin film was recovered from the water surface and its thickness was measured using a tile gauge and found to be 0.8 μm.

Example 5 0.17 parts by weight of poly(4-methyl-1-pentene) (
manufactured by Mitsui Petrochemicals, Inc., in a mixed solvent of 33.16 parts by weight of cyclohexene and 66.67 parts by weight of 1-lichloro-1-lifluoroethane was prepared. 100 ml of this solution was heated to 20 cm at room temperature of about 25°C.
(Length) x 17cm (Width) x 2.5cm (Depth) Teflon-coated bag] and add 50ml of distilled water on top.
Added 0ml. 5cm (height > x 14cm) in this container
(Width) Teflon nonwoven fabric (Polyflon Filter PF-2 manufactured by Toyo Roshi) was vertically erected along the widthwise wall of the container. At this time, only the poly(4-methyl-1-pentene) solution in the lower layer penetrates into the Teflon nonwoven fabric and rises, immediately spreading from the part of the nonwoven fabric in contact with the surface of the water layer to the surface of the water layer, and then removing the solvent. A thin film of the polymer was formed.This thin film was continuously collected in the same manner as in Example 3 onto a polysulfone porous support membrane having a crosslinked polydimethylsiloxane layer on its surface.

The thickness of the poly(4-methyl-1-pentene) layer thus formed was measured using an ellipsometry and was found to be 760.

Example 6 As shown in Fig. 2, a second liquid seed storage part of 50cm (width) x 7Qcm (length) x 10cm (depth)
(width) x 3 cm (length > 3 cm (depth) at the boundary of the liquid tank with the first liquid storage tank part (in the depth direction)
Provide an opening of x49cm (width direction), and insert Daikin Polyflon Paper PA-101 (thickness 1.0mm) there.
＞ was fixed by stacking two sheets. In addition, 0.33 ffli parts of poly(4-methyl-1pentene) (Mitsui Petrochemical Co., Ltd.)
) with 33.17 parts by weight of cyclohexane and 66.50 parts by weight of
A solution was prepared by dissolving the heavy prize in a mixed solution of 1-lichlorotrifluoroethane. 200 ml of this solution was put into the first liquid storage tank, and distilled water was added to the second liquid storage tank so that the surface of the polymer solution and the water surface were in contact with the surface of the Polyflon paper as shown in FIG.

At this time, only the Botsummer solution penetrates into the Polyflon paper, and the polymer solution comes out on the water surface from the opposite surface of the Polyflon paper and is spread on the water surface. A thin film of methyl-1-pentene) was formed. This thin film was brought into contact with a rotating roll wrapped around a polysulfone porous support membrane having a crosslinked polydimethylsilokinane layer on its surface, and the thin film was wound onto the support membrane at a speed of 0.5 m/min. At this time, the polymer solution is continuously spread on the surface of the water phase from the polyflon paper,
A thin film was formed continuously.

[Effects of the Invention] According to the present invention, compared to the production of thin films by the conventional water surface spreading method, which requires precise control in continuous processing and is difficult to widen, it has the following advantages. Become.

(2) Since the film-forming material solution is spontaneously supplied onto the second liquid surface, the film-forming material solution is continuously supplied as the formed thin film is collected. This eliminates the need for a precise injection device.

(2) Since the film-forming material solution 1 spreads from the entire area where the supply part and the second liquid surface are in contact, the uniformity of the film can be maintained even if the width is wide. In addition, widening can be easily achieved by simply increasing the width of the supply section.

■ The film-forming material solution is produced in such a way that the supply part and the second liquid surface contact each other.
Since the second liquid can be supplied from any part of the supply section, precise control of the liquid level position of the second liquid is not necessary.

Therefore, by using an extremely simplified apparatus, it is possible to easily and continuously manufacture a wide thin film, which has been difficult with conventional methods, and it is possible to significantly reduce manufacturing costs.

[Brief explanation of the drawing]

1 and 2 show one embodiment of the present invention. 2, ] ] 3: 2nd - 2nd supply department 3.11: First liquid 4.12: Second liquid 5,]4: Thin film

Claims (8)

[Claims] (1) A first liquid consisting of an organic solvent solution containing a film-forming material as the main component of the solute is supplied onto a second liquid that is substantially immiscible with the first liquid, and the second liquid is spread by spreading the first liquid. In the method of forming a thin layer of the first liquid on the surface of the liquid and removing the solvent from the thin layer to form a thin film of the film-forming material, the first liquid is supplied onto the surface of the second liquid by interfacial tension. A method for producing a thin film, characterized by: (2) The first liquid is supplied onto the second liquid surface by a supply section that utilizes interfacial tension.
) The method for producing the thin film described in item 2. (3) The supply of the first liquid onto the second liquid surface is made of a material that has selective wettability for the first liquid over the second liquid, or has a structure that causes capillary action. 2. A method for producing a thin film according to claim 2, wherein: (4) The method for producing a thin film according to claim (2), wherein the supply portion is made of a material having a critical surface tension of 30 dyn/cm or less. (5) Claims characterized in that the supply part has continuous pores or slits with one opening opening into the first liquid and the other opening opening onto the surface of the second liquid. The method for producing a thin film according to item (2). (6) A supply section that includes a first liquid tank and a second liquid tank, and supplies the first liquid onto the second liquid surface using interfacial tension between the first liquid tank and the second liquid tank. What is claimed is: 1. A thin film manufacturing apparatus comprising: a second liquid surface; and means for continuously taking off a thin film formed on a second liquid surface. (7) The supply section that supplies the first liquid onto the second liquid surface using interfacial tension is made of a material having a critical surface tension of 30 dyn/cm or less (
6) The thin film manufacturing apparatus described in item 6). (8) The supply unit that supplies the first liquid onto the second liquid surface using interfacial tension can have one opening opened into the first liquid and the other opening opened onto the surface of the second liquid. Claim No. 6 is characterized in that it is a structure having continuous pores or pores.
) The thin film manufacturing apparatus described in item 2.