JPH0657519A - Finely porous polymer and its production - Google Patents

Abstract

PURPOSE:To provide a production process of excellent productivity for a micro- cellular polymer having a uniform pore distribution and a sharp and narrow micro-cellular diameter distribution. CONSTITUTION:A combination of a thermoplastic polymer and a solvent where the polymer is solubilized at elevated temperature to form a stable fused solution and solidified to form a stable gel, when the solution is cooled down during the forming process, is rapidly formed and fed at a specific ratio into a screw- kneading extruder having a kneading function to form a uniform molten constitution. Then, the constitution product is injected into a mold connected to the extruder to give a molded product of a prescribed shape. Then, the solvent is removed from the molded product to give the objective micro-cellular polymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polymer separation membrane used in a reverse osmosis method, an ultrafiltration method and a microporous membrane separation method, and a separation device and a filtration device using these polymer separation membranes. It is about. Recent developments in chemical engineering technology
Even for the filtration and separation operation, it is a great advancement from the conventional concept of simply "filtering out", and it requires advanced functions. Water obtained by desalination from seawater or ground brine by combining reverse osmosis and ion exchange Manufacturing, production of ultrapure water supplied to precision industry, concentration of uranium from seawater, concentration of fruit juice in food industry combining reverse osmosis and ultrafiltration, recovery of protein and sugar from wastewater ( For example, recovery and fractionation of cheese whey and soybean whey) recovery and removal of inorganic salts from wastewater of the plating industry, etc. by filtration collection of paint particles in water-soluble electrodeposition coating using ultrafiltration, rolling and machining. There is an extremely high demand for the development and improvement of functions of high-performance separation / filtration materials, separation / filtration devices and separation / filtration systems used for the separation and recovery of oil from oil-water emulsion, purification of pool water, etc. Industrial super Demand for development of high-performance filter media such as clean air supply filters and high-performance battery separator filter media, development of high-performance filter media such as automobile gasoline filters and oil filters, and rationalization of its production system and product production process There is also a great demand for the development of filter media that can be reformed, and the supply of separation media and filter media that can meet the above demands is extremely strong from the perspective of the development of related industries, and the contribution effect is great. The present invention also relates to an air-permeable covering material such as an air-permeable garment that utilizes the air permeability (moisture permeability) of the fine porous polymer membrane, a synthetic leather, and a method for producing the same.
In addition to leather products such as shoes, there are many products in the clothing field that require a function that allows air to pass through but does not allow water to pass, such as coats, jumpers, and rain gappa. As industrial materials, there are many materials such as house wrapping materials, which are required to have the function of allowing air to pass through but not water, and supply such highly functional products and manufacture them with high productivity. Development of methods is desired. The present invention is
As described above, the present invention is an invention that responds to the demands in the fields of various filter media and air-permeable coated products and contributes to the development of industry related thereto.

[0002]

2. Description of the Related Art A fine porous polymer separation membrane used in a reverse osmosis method, an ultrafiltration method and a fine porous membrane separation method has a chemical structure, a crystal structure, a crystallinity, a fine structure and a fine porous material of a membrane constituent substance. The function is determined by the size and distribution of pores, the density and distribution of pores, the type of pores, etc., so the optimum filter medium is selected and the optimum manufacturing is performed to obtain a higher performance filter medium. As a result of efforts to develop a filter medium in which the pore size distribution is uniform, the pore size distribution is smaller, and the pore sizes are evenly distributed, by selecting the method and conditions, the following methods have been developed and manufactured. It was That is, by mixing insoluble fine particles with the film-forming polymer and forming a film, the fine particles are extracted with a non-solvent of the film-forming polymer and a solvent of the fine particles, or by solubilizing the fine particles using a chemical reaction. A method of removing and making it microporous, for example, as a classical example, mixing fine starch particles with viscose dope to form a film, and solubilizing and removing the starch particles present in the film with the aid of an enzyme to make them microporous. There is a method of doing. By emulsion-polymerizing a hydrophobic monomer in an aqueous solution of a water-soluble polymer and extracting fine particles of the hydrophobic polymer from the polymer film, the hydrophobic polymer is graft-polymerized or block-copolymerized with the hydrophilic polymer. A method for obtaining a fine porous polymer, a method for obtaining a fine porous polymer by irradiating polyester or polycarbonate with radiation, and then performing alkali etching, a polymer having a high crystallization rate such as polypropylene, and a highly crystalline polymer, A method of forming a film or yarn under high crystallization conditions, and then stretching this to generate microvoids to obtain a finely porous polymer, mixing a foaming substance with a thermoplastic polymer substance, and performing melt extrusion. A method for obtaining a finely porous polymer by performing film formation or yarn making and foaming, and the polymer substance is expanded with a good solvent for the polymer substance. Dissolve in a mixed solution of a wetting agent or a non-solvent to form a stable sol, form a film, then evaporate a part of the good solvent from this sol to cause gelation, evaporate and remove the good solvent, or immerse in a non-solvent There is a method for producing a fine porous polymer based on the so-called coacervation method by further promoting gelation and extracting and removing a good solvent. The method is one of the most widely used manufacturing methods at present. It is a combination of polymer-solvent system, film formation-
Many concrete methods have been developed and implemented by elaborating on the conditions of gelation-porosification, and one example is dissolving cellulose triacetate in a mixed solvent of magnesium perchlorate, water, and acetone. After cooling and adjusting, this dope was cast on a cooled glass plate to form a film, allowed to evaporate acetone for a few minutes, and then immersed in cold water to extract and remove residual acetone and magnesium perchlorate before use. There is a method of producing a membrane for reverse osmosis by heat-treating with hot water for several minutes. Further, also in the production of a coating having moisture permeability or a synthetic leather, a method of applying a composition similar to the above to a substrate to dissolve and remove fine particles to make fine pores, and polyurethane containing a foaming agent similar to A method of applying the composition to a substrate and making it finely porous has been used and manufactured.

[0003]

However, among the methods that have been conventionally performed, the above-mentioned methods (1) to (3) require a fine filter which is required for the reverse osmosis method and the ultrafiltration method. There is a problem that it is difficult to manufacture perforated microporous bodies having a narrow pore size distribution with pores having a narrow pore size distribution and evenly distributed in the filter medium. Each of the above-mentioned methods has a large number of steps, and it is essential to set the conditions of each step extremely strictly, and it is possible to perform production under high quality control with high productivity and reproducibility. It was a difficult manufacturing method, and it was difficult to say that it was an industrial manufacturing method with high productivity. Further, as is apparent from the above-mentioned production method, there are common problems in the production methods of the moisture permeable fine porous coating material and the synthetic leather.

The inventor has previously proposed a method for solving the above problems and producing a fine porous body having fine pores having a narrow pore size distribution and being uniformly dispersed and distributed in a filter medium, and perforated. Japanese Patent Publication No. 41-19910 discloses a method "a thermoplastic polymer-solvent-based or plasticizer-based heating solution or sol which forms a uniform and stable sol when heated and is cooled in the molding process to form a stable gel. A method for producing a fine porous polymer molded article, which is characterized in that it is formed into a film or plate, gelled by air cooling in the forming process, and a solvent or a plasticizer is extracted from the gel. Invented and disclosed. This method is a very excellent method as long as it has a narrow pore size distribution of stable fine pores and has a fine pores evenly distributed and distributed in the filter medium to produce a fine porous body. There is no need for complicated and strict condition setting and strict condition control as in the conventional method, the number of steps is reduced, and the combination of the thermoplastic polymer-solvent system and the thermoplastic polymer / solvent ratio are used to form fine pores. It was an epoch-making method that was able to determine the basic performance of the microporous body such as the pore size and porosity of the product. However, the production method had the following fatal defects and the productivity was poor, and the quality was stable on an industrial scale. Was not suitable for the production of the above products and was difficult to put into practical use. That is, it is extremely difficult to dissolve a thermoplastic polymer in a solvent system or a plasticizer that forms a uniform and stable sol when heated and is cooled in the molding process to form a stable gel. It is necessary to prepare, store and use a large amount of solution because it is difficult to obtain and it takes a long time to dissolve and it takes a long time to dissolve. It is unavoidable to undergo thermal history over time, during which oxidative deterioration of the thermoplastic polymer, depolymerization, interaction between the thermoplastic polymer and solvent, such as deterioration of quality due to ester exchange reaction or ester-amide exchange reaction, etc. It is unavoidable, and since these progress with time and change in quality over time, not only the physical properties of the product deteriorate due to decomposition and deterioration, but also the quality of the product changes significantly over time, making it impossible to manufacture products of constant quality. There was a fatal defect. Furthermore, in the case of a polymer having a degree of polymerization sufficient to obtain a fine porous polymer having excellent mechanical properties, the dissolution becomes more difficult and the viscosity of the obtained solution is extremely high. Defoaming work is indispensable, and deterioration of the polymer further progresses during this difficult work, resulting in defects in the product due to incomplete defoaming, and products requiring a high degree of complete defoaming (eg hollow fiber, film, etc.) Was impossible and was out of symmetry. Further, in the method disclosed in Japanese Patent Publication No. 41-19910, since no consideration was given to a molding process for forming a fine porous structure, no consideration was given as a process suitable for forming the molding process. The limitation is that the method of obtaining a sheet-like material by the coating method can be assumed at most, and it is difficult to develop the application such as the production of the separation / filtration device element such as the hollow fiber separation membrane or the fine porous molded body. For the above-mentioned particular reasons, the method disclosed in JP-B-41-19910 discloses an extremely excellent basic technique (principle) for producing a fine porous polymer having uniformly distributed fine pores. It was not established as a method for the stable industrial production of a product of a certain quality, and it was essential to implement the basic measures described in Section 2 to establish it as an actual production process.

The present invention solves these conventional problems, and under the easy production method and conditions, the high productivity and highly quality controlled reverse osmosis method, ultrafiltration method, and microporous membrane separation. Fine pores used in the method have a narrow pore size distribution,
Disclosed are a method for producing a microporous polymer separation membrane which is formed into a predetermined shape by being evenly distributed and distributed in a filter medium and formed into a perforated shape, a separation device using these polymer separation membranes, and a method for producing a filtration device. In addition, the present invention provides a highly productive moisture-permeable microporous coating material and a method for producing synthetic leather.

[Means to solve the problem]

The present invention was previously invented and published in Japanese Patent Publication No. 41-199.
Based on the basic principle disclosed in Japanese Patent Publication No. 10, the invention is a reformed invention in which the above-mentioned problems or items to be eliminated and solved in order to be established as an actual production process are fundamentally eliminated.
Thermoplastic polymer-solvent system of a thermoplastic polymer and a compound (hereinafter referred to as a solvent) which forms a uniform and stable molten solution or sol at high temperature and solidifies when cooled in the molding process to form a stable gel As a measure to dissolve the mixture rapidly and continuously in a prescribed mixing ratio and uniformly without deterioration / deterioration, a manufacturing process was invented to realize the basic principle by using a kneading screw extruding mechanism, and further invented. We have invented a manufacturing system that also includes the process of molding products in a shape, and have high productivity and stable quality with fine pore diameters that have a narrow pore diameter distribution and are evenly distributed in the filter medium to form fine pores. They have invented a process for producing a porous body.

That is, the basic constitution of the present invention, as described in the claims, is compatible with the thermoplastic polymer at a high temperature to form a uniform and stable molten solution or sol, which solidifies when cooled in the molding process. It is a combination of a thermoplastic polymer-solvent system with a solvent that forms a stable solid body (gel) having a predetermined shape, and the composition of the thermoplastic polymer / solvent in the combination of the thermoplastic polymer-solvent system. The ratio is from 75 to 20 parts of the thermoplastic polymer / 25 to 80 parts of the solvent, and a uniform blending ratio (sol) of the thermoplastic polymer-solvent system combination is rapidly and continuously maintained at a constant compounding ratio. As a method for constantly forming while maintaining the above, a screw kneading and extruding mechanism having a kneading function is used, that is, a. First, the thermoplastic polymer is continuously and quantitatively supplied to a heated screw kneading extruder (or screw type injection molding machine) having a kneading function to melt, and b. Then, the solvent is continuously and quantitatively supplied from a supply hole provided in a measuring portion (metering zone) of the screw kneading extruder (or screw type injection molding machine) or is also connected to the screw extruder. Continuously and quantitatively supplying from the solvent supply hole of the kneading screw extruder to knead and knead both to uniformly mix and dissolve, and subsequently, a molding die connected to the screw kneading extruder (For example, a hollow fiber spinning spinneret or T-die or an inflation method film extrusion spinneret) is extruded to form a hollow fiber or a film / sheet, or kneaded and dissolved in a molding die connected to the screw type injection molding machine. Alternatively, the melt is injected to be cooled and solidified (gelled) to produce a molded product, or alternatively, the screw kneading extruder is connected to the plunger part of the injection molding machine to form a molding metal. It is injected into a mold, cooled and solidified to produce a molded product of a predetermined shape, and the solvent contained in the molded product obtained is extracted as a non-solvent of the polymer and a solvent of the solvent to obtain fine porosity. It is a method for producing a fine porous polymer having a hollow fiber shape, a film / sheet shape, or a predetermined shape, which is obtained by qualifying.
The outline of the configuration of the present invention has been shown above, and the embodiments of the respective components constituting the present invention will be specifically and specifically described below.

As described above, in the present invention, the polymer is made to be finely porous by being compatible with the thermoplastic polymer at a high temperature to form a uniform and stable molten solution or sol and solidifying at a low temperature to form a gel. The thermoplastic polymer / solvent system combination with the solvent to be mixed is heated and mixed by using a kneading screw extrusion mechanism to form a uniform molten fluid, and this molten fluid is extruded through a molding die to a temperature below its melting point. After cooling, solidification molding into a molded product of a predetermined shape is carried out to obtain a molded product of a predetermined shape in which the solvent is uniformly incorporated in the thermoplastic polymer, and the solvent contained therein is extracted and removed to obtain fine particles. A method for obtaining a porous substance, the pore size and the amount of fine pores can be adjusted by the type and amount of the solvent used for forming fine pores after extraction and removal of the solvent, and based on the principle of the present invention. Extremely narrow Because a very uniform perforation distribution and size distribution is guaranteed, it is than is possible to provide a very excellent microporous body which can not be obtained in a conventional manner. The solvent in the thermoplastic polymer-solvent system of the present invention is compatible with the thermoplastic polymer only when heated and forms a uniform melt when mixed and heated, showing a melting point drop and being uniform. A compound that forms a stable thermoplastic polymer-solvent mixed system, and forms a stable and uniform solid phase (gel) of the thermoplastic polymer-solvent mixed system at a temperature below its melting point. It is not a solvent that dissolves the plastic polymer, but a compound that is not soluble at low temperatures and is soluble only at high temperatures, and is described here as a solvent for convenience. There are many suitable combinations of thermoplastic polymer-solvent systems that satisfy the requirements for carrying out the present invention, as exemplified below.
When selecting a solvent, in addition to the basic requirements required for the above-mentioned solvent, the solvent must be stable, have a high boiling point, be less toxic, not flammable, not highly reactive, and be removed by extraction. It is necessary to select the one that satisfies the conditions such as the ease of operation. Further, according to the method of the present invention, unlike the conventional method, the molded product of the thermoplastic polymer-solvent-based melt melt has a desired shape by the change of the state, that is, simply by solidification by cooling. Since it is faithfully molded and does not undergo any volume shrinkage, morphological change due to solvent evaporation or extraction, or morphological change due to flow, it is possible to apply a high fidelity fine porous polymer molded product to a normal molding process. It has the characteristic that it can be easily manufactured.

Representative examples of practically meaningful thermoplastic polymer-solvent system combinations satisfying the requirements of the present invention are shown below. Examples of polyamide-solvent system combinations include general-purpose nylons such as nylon 6, nylon 12, nylon 66, and nylon 610, and copolyamides having these nylons as a matrix (for example, nylon 6/66 copolymer and nylon 66).
/ 610 copolymer etc.), lactams such as ε-caprolactam, capryllactam, laurinlactam, benzil alcohol, and ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (for example, PEG200, 400, 600, 1).
000, ... 4,000, 20,000) Propylene glycol, polypropylene glycol (for example,
Solvents such as glycols such as PPG400 and 700) and ethers thereof and the like are mentioned as the compound (referred to as a solvent) satisfying the requirements of the invention. Examples of the polyester-solvent system combination include polyethylene terephthalate, polybutylene terephthalate, and copolyesters having these polyesters as a matrix.
(Eg, polyethylene terephthalate / isophthalate, polyethylene terephthalate / adipate, etc.) to ε-caprolactam, benzil alcohol, and ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (eg, PEG200, 400, 600, 1,000,
……… 4000, …… 20000) Propylene glycol, polypropylene glycol (eg PPG4
00, 700 etc.), solvents such as glycols and ethers thereof, and lactones such as ε-caprolactone, caprylolactone, enanthlactone, etc. are mentioned as compounds (referred to as solvents) satisfying the requirements of the invention. Examples of the ethylene-vinyl alcohol copolymer-solvent system combination include ethylene glycol, diethylene glycol, triethylene glycol, and ethylene / vinyl alcohol copolymerization ratios of 20/80 to 45/65. Solvents such as benzil alcohol, propylene glycol and the like are mentioned as the compound (referred to as a solvent) satisfying the requirements of the invention. In addition to this, representative examples of thermoplastic polymer-solvent system combinations for many general-purpose polymers to which the present invention is applicable for producing microporous polymers are shown in Table 1. It was shown to.

[0012]

[Table 1]

The thermoplastic polymer-solvent system homogeneously melted solution of the present invention is prepared and used at a high temperature, so that it undergoes oxidative deterioration and thermal decomposition, and due to the interaction between the polymer and the solvent, for example, depolymerization, There is a possibility that the quality will be remarkably deteriorated by undergoing an ester exchange reaction, an ester-amide exchange reaction, or the like, or by being hydrolyzed and deteriorated when the solvent contains water. Examples of deterioration reactions to be particularly noted other than common deterioration reactions such as thermal decomposition and oxidative deterioration that occur in the molten solution of the thermoplastic polymer-solvent system of the present invention are shown below. For example, in the case of a combination of polyester and ethylene glycol, nylon 6 and ω-caprolactam, a reverse reaction based on the polymerization equilibrium, that is, a decrease in the degree of polymerization due to a depolymerization reaction occurs, and polyamides (nylon 6, nylon 66, nylon) 610, ..., etc.) and ethylene glycol, diethylene glycol, ..., or between polyurethanes and ethylene glycol, diethylene glycol, ...
Between combinations of polyesters (polyethylene terephthalate, polybutylene terephthalate, etc.) and ω-
Between the combinations of caprolactam, etc., the main chain is cleaved by the transesterification (ester amide exchange reaction), and the molecular weight of the polymer is reduced, and between the combinations of polyesters (polyethylene terephthalate, polybutylene terephthalate ... ……) and polyethylene glycols. , Between the elastic polyester and polyethylene glycol, etc., the molecular weight decreases due to the transesterification reaction, between the polyester (polyethylene terephthalate, polybutylene terephthalate, etc.) and the lactone, and between the elastic polyester and the lactone. When the solvent contains water, the polyesters, elastic polyesters, and polyamides are hydrolyzed to reduce the polymerization degree. Be such, many interactions are present to cause the allowed property decrease progression degradation of the polymer. Therefore, for this measure, it is essential to prepare the melt solution promptly and use the prepared melt solution with the retention time as short as possible. It is essential to carefully select manufacturing conditions that will not cause That is, in such a method that a pellet is simply put in a solvent and heated and stirred to prepare a molten solution, it takes a long time to prepare and the deterioration of the polymer is unavoidable. Therefore, it is not possible to produce a product of stable quality because of the progress of the deterioration of the, the solvent is supplied into the molten polymer using the kneading screw extrusion mechanism of the present invention to knead under high temperature and high pressure to rapidly melt the solution. The manufacturing process of adjusting and immediately molding into a predetermined shape solves the conventional problems for the first time.
The manufacturing principle disclosed in Japanese Patent Publication No. 19910 can be put into practical use.

An outline of a manufacturing process for carrying out the present invention will be described with reference to a flow sheet in a schematic representation of a typical embodiment. A flow sheet of an exemplary embodiment is shown in Figure 1. As shown in. That is, in the left column of the flow sheet, the thermoplastic polymer was supplied to a screw extruder having a kneading function, melted and supplied at a constant extrusion speed (amount) to a screw extruder for kneading connected thereto, and this kneading was performed. A uniform and stable melt (sol) is formed with the thermoplastic polymer at a constant supply rate (amount) from the separately formed supply holes of the screw extruder for heating, and solidifies when cooled and forms a gel. The method of supplying a solvent and kneading to form a uniform and stable molten constituent (sol) rapidly and continuously steadily at a constant mixing ratio is shown. The flow sheet left column shows the thermoplastic polymer. The solvent is constantly supplied at a constant speed (quantity) through a hole formed in a metering portion (metering zone) of a screw extruder having a kneading function of melting and constantly supplying a constant amount of the screw extruder. Kneading In the left column of the flowsheet, the thermoplastic polymer-solvent is shown in the left column of the flow sheet. As a method for rapidly and continuously forming a stable molten constituent (sol) that maintains a constant compounding ratio of the combination of systems,
An example of using a twin-screw kneader instead of the single-screw extruder for kneading used in the above embodiment is shown. The above example shows an example of a typical embodiment, in which a screw kneading extruder having a kneading function is continuously and constantly fed with a constant blending ratio of a thermoplastic polymer-solvent system combination. Any method based on the technical idea disclosed in the present invention that a stable molten constituent (sol) is rapidly and continuously formed constantly belongs to the category of the present invention, and is not limited to the above-mentioned embodiment examples. Of course, it is not something that is done. Then, in the right column of the flow sheet, any of the melted component supply device (screw extrusion mechanism having the kneading function) shown in or is used as a hollow fiber, a film,
Extruded laminating, or connected to either a molding device (a to d) having a predetermined shape, and consisting of a stable melted composition that maintains a constant compounding ratio of the combination of the thermoplastic polymer-solvent system and cooled to a predetermined shape. Hollow fiber containing a solidified molded solvent,
An embodiment of a production system for extruding (injecting) a film, an extrusion laminated product, or a molded product having a predetermined shape is illustrated. Although not shown in the figure, in the production process of the present invention, the polymer obtained by solidifying and molding the solvent thus obtained into a predetermined shape is a solvent which dissolves the solvent but is a non-solvent of the polymer. By immersing it in the cleaning layer of
A fine porous polymer can be produced by exposing to a saturated vapor of a solvent and extracting and removing the solvent.

2 to 5 show in more detail a concrete example of a typical embodiment of the mixing-dissolution mechanism of the thermoplastic polymer-solvent system according to the present invention. Figure 2. Through FIG. In the above description, a molding device following the admixture-dissolution mechanism is connected, but these molding devices can be connected to any admixture-dissolution mechanism according to the purpose, and are not unique to the illustrated combination. Absent. Figure 2. FIG. 3 illustrates an example of a specific manufacturing apparatus for manufacturing a product in which a fine porous body is laminated by extrusion laminating using a mixing-dissolving mechanism in a flow sheet. As shown in the figure, the mixing-dissolving mechanism in this manufacturing apparatus is such that a thermoplastic polymer is quantitatively supplied to a screw extruder used for manufacturing a synthetic fiber or film in a predetermined amount, melted and extruded, and then connected to the screw extruder. Is supplied to the kneading screw extruder, and the solvent preheated to a predetermined temperature is quantitatively supplied from the other supply hole of the kneading screw extruder using a high-pressure metering pump such as a plunger pump to a constant temperature. The kneading-dissolving apparatus for continuously kneading at a predetermined mixing ratio under high pressure to rapidly form a uniform molten solution, quantitatively supplying it to a T-die through a gear pump, and extruding it is illustrated. In this apparatus, the screw extruder for the first thermoplastic polymer does not show a metering pump, but the solvent to be mixed is supplied to the kneading extruder through the metering pump and exits from the kneading extruder. Since a metering pump is installed in this, it is possible to constantly maintain the ratio of the thermoplastic polymer / solvent at a predetermined ratio. The kneading extruder comprises a measuring section and a kneading section, and the kneading zone of the screw is preferably used as a dullage type, kneader type, pin type or the like in order to give a kneading effect. Also, if a solvent supply hole to the kneading screw extruder is provided below the supply hole of the thermoplastic polymer melt and supplied, the solvent is supplied to the viscous polymer melt that is being forwarded and mixed. Since it is melted, there is no risk of backflow to the bearing portion of the kneading extruder, and there is no need to specially provide a shaft sealing device. Therefore, such a design is desirable. Further, it is desirable to provide a check valve in the solvent supply line to prevent the molten polymer from flowing back. Figure 3. Figure 4. FIG. 4 is a drawing showing specific production equipment for producing a microporous polymer by using a mixing-dissolving mechanism in a flow sheet. In this apparatus, without using a separate screw kneading machine for kneading, only a screw extruder having a kneading function of melting and extruding a thermoplastic polymer is used at once, and the thermoplastic polymer-solvent system mixing-
A method for melting is shown, and as shown in the figure, a thermoplastic polymer is supplied from a hopper of a screw extruder, and quantitatively, a solid transport section (solid convex zone) of the extruder →
It is pressed into the compression section (compression zone) → melting and melting section (melting zone) → metering section (metering zone) to melt and extrude, while at the same time the solvent supply hole provided in the metering section of this screw extruder brings it to a predetermined temperature. Quantitatively press the warmed solvent using a high-pressure metering pump such as a plunger pump, merge with the thermoplastic polymer, and knead,
Further, the kneading is completed in the kneading section, and a homogeneously mixed and melted solution of thermoplastic polymer / solvent having a constant mixing ratio is quantitatively and constantly prepared via a gear pump installed at the exit of the screw extruder, and then connected. It shows a state in which a fine porous polymer is produced by extruding and supplying it to a hollow fiber and a molding device for producing a film. Also in this apparatus, if the solvent supply holes are provided in the second or third ridges of the metering zone of the screw extruder, the solvent is compressed and melted in the compression section / melting / melting section of the screw extruder, and is melted and transferred. Since it is supplied into the viscous polymer melt stream, stable mixing and kneading can be performed without the risk of backflow in the direction of the solid transport section of the screw extruder. The installation of the check valve in the solvent supply line is significant for preventing the backflow of the molten polymer into the solvent supply line. Further, it is also convenient to make the screw groove depth of the solvent merging portion slightly deeper as necessary to facilitate solvent press-fitting. Further, the screw shape of the kneading zone is preferably a dullage type, a kneader type, a pin type or the like in order to improve the kneading effect. By adopting such a thermoplastic polymer-solvent system mixing-dissolution mechanism, the solvent is mixed quantitatively and constantly into the molten polymer while maintaining a predetermined mixing ratio, and kneading is performed with a strong shearing force under high pressure. Therefore, even if the polymer-solvent combination, which has a high degree of polymerization and a high viscosity and is difficult to dissolve by a simple stirring operation under normal pressure, it is possible to rapidly melt and dissolve the polymer without causing deterioration of the polymer (or at a minimum level). It is possible to create a homogeneous molten solution. Thus, a film, sheet, or tube-shaped filter and separation membrane made of a fine porous polymer, a fine porous polymer is laminated on a reinforcing substrate, or a reinforcing substrate is a fine porous polymer. Filters and separation membranes, synthetic leathers, and breathable sheets that are embedded and reinforced in the united body have extremely high productivity and have desired fine pores with a uniform pore size distribution and a narrow pore size distribution. It can be manufactured.

A typical specific example of injection molding a fine porous molded body by applying the manufacturing process of the present invention is shown below. An example of this is shown in FIG. Figure 4. A manufacturing process in which the tip of the kneading extruder is connected to the injection molding plunger part using the kneading / extruding mechanism shown in Fig. 1, which is a manufacturing system corresponding to a so-called screw pre-plastic injection molding system, and is a flow sheet Fig. 1. d. It is shown in. Also, as shown in FIG. An example of a manufacturing system using a screw-in-line type injection molding apparatus (screw type injection molding apparatus) is shown in FIG. Figure 5. In the manufacturing system shown in Fig. 1, a solvent supply hole is provided in a screw measuring portion of a screw-in-line injection molding machine driven by a servo motor, and a solvent preheated to a predetermined temperature can be quantitatively supplied using a plunger pump. It is a normal injection molding system, not a special one except that it corresponds to the manufacturing system of. Even in this manufacturing system, the injection molding machine has a kneading / extruding mechanism using a kneading screw, and FIG. Figure 4. Since there is basically no difference from the thermoplastic polymer / solvent dissolution / kneading / extrusion mechanism shown in (4), there is no fundamental difference in the device design / mechanism for solvent supply and kneading / dissolution. However, the point to be noted is Fig. 3. Figure 4. Instead of continuous extrusion as in the example of Fig. 1, it consists of an intermittent process with a cycle of a series of processes of plasticizing, kneading, measuring, preloading, injecting, and holding pressure of the material accompanied by forward and backward movement of the screw and stop of driving. Therefore, the control mechanism configuration of the manufacturing equipment incorporates not only the original injection molding control but also the solvent supply mechanism, which ensures a constant thermoplastic polymer / solvent ratio and a uniform kneading state. It is necessary to program to control the system as much as possible,
From this point of view, it is more preferable to apply the servo motor driven injection molding machine. According to such a method, as shown in FIG. A filter element as exemplified in (a) can be manufactured by injection molding with high productivity, and by further mounting it in a casing to form an (b) in-out type filter, an engine oil filter for automobiles. We provided a production system that supplies a lot of filters such as a gasoline filter and a gasoline filter with low man-hours and high production efficiency. Also in the case of batteries, if a partition that is made of a fine porous polymer is manufactured by injection molding, and if it is devised in a production system that installs it together with the electrodes in the casing, a production system with low man-hours and high production efficiency can be obtained. Can be provided.

The molding apparatus for manufacturing a molded product having a predetermined shape and the equipment related to the molding process do not require any special specifications, and the known equipment conventionally used can be used as it is for the thermoplastic polymer of the present invention. -Can be used by connecting to a solvent kneading and mixing mechanism. That is, in the production of the film / sheet-like product, the production line of the film / sheet having the T die or the inflation method film extrusion die which has been conventionally used can be applied as it is, and the film / sheet-like product to be produced can be applied. Immediately as it is, or after it is once wound up, it is supplied to a solvent extraction device and the contained solvent is extracted and removed to produce a microporous film / sheet, which can be extruded and laminated to form a film / sheet-like material on a reinforcement. Laminated product or reinforcing material in film
Similarly, a microporous sheet embedded in a sheet-like material can be manufactured by applying it to an existing extrusion laminate manufacturing process. Further, in the production of hollow fibers, a well-known spinneret for producing hollow fibers (for example, a C-type nozzle shown in British Patent No. 843179 or the like, and Japanese Patent Publication No. Showa 39-166).
A gas-introducing capillary tube shown in Japanese Patent No. 886, etc. is attached and spun in a usual manner with a spinning nozzle or the like), or it is spun at a high spinning speed at a spinning speed of several thousand meters / minute and finely stretched. -Oriented crystallization can be performed at the same time and wound up, and the solvent contained in the spun yarn can be extracted and removed in the next extraction step to produce a fine porous hollow fiber. Also in the production of injection-molded products, the same molding die and molding device as those used in the production of ordinary injection-molded products are connected to the kneading / melting / extruding mechanism to obtain a molded product, and the solvent included in the extraction step is added. By extracting and removing, it is possible to manufacture a fine porous molded article having a shape faithful to the molding die. In the method of the present invention, a molded product that is kneaded and kneaded by the kneading and dissolution mechanism and is supplied as a molten melt of a uniform thermoplastic polymer-solvent to a molding device (step) to be cooled and solidified is no longer flowable. Since it does not undergo any morphological change due to evaporation or removal of the solvent, the reproducibility of the imparted shape is extremely high and the desired fine porous molded article can be manufactured accurately and easily.

The solvent extraction device does not need any special one, and the solvent contained in the molded body may be removed by using the extraction device conventionally used. The simplest universal example is the application of a countercurrent continuous extraction tank. However, in the production of the microfiltration separation membrane, it is necessary to avoid contamination by fine dust during the washing process, so Fig. 7. It is more preferable to adopt the method of exposing the substance to be extracted to the saturated vapor of the solvent as shown in (3) above for extraction.

The method for producing a separation membrane / filtration material product comprising the fine porous polymer according to the present invention will be described below with reference to specific examples.

Example 1 FIG. The polyethylene terephthalate (intrinsic viscosity: 0.650 measured at 30 ° C. dissolved in a mixed solvent of phenol / tetrachloroethane = 3/2, which is dissolved in a mixed solvent of a screw extruder having a kneading function shown in FIG. Polyethylene glycol (PEG1000) heated to 160 ° C from the solvent supply hole provided in the metering section of the machine was press-in using a plunger pump and kneaded in the kneading zone to gradually lower the melt temperature to 230 ° C and set the pre-filter section. Through a through gear pump, a uniform mixed melt having a weight mixing ratio of polyethylene terephthalate / PEG1000 of 65/35 was constantly provided, and 50 holes of C-shaped slit-shaped orifice (orifice outer diameter 1.6 mm) with a hollow ratio of 65% were provided. It is sent to a spinning head with a nozzle that has been drilled, and the spinning temperature is 210 ° C. Discharge rate 10 g / min in extrusion per, 5,000 m / min. At high take-up speed, high-speed spinning is performed and the bobbin is once wound. This hollow fiber was passed through a methanol vapor reflux extraction column (FIG. 7) to extract and remove the contained PEG1000 to obtain a hollow fiber made of fine porous polyethylene terephthalate. In order to measure the fine pore diameter and the pore diameter distribution state of this hollow polyethylene terephthalate fiber, the measurement was carried out by a so-called mercury penetration method using a [CARLO ERBA mercury intrusion porosimetry device: porosimeter]. ．
Pore size distribution in the range of 1 to 0.4μ and pore volume ratio is 4
It turned out to be 5%. In addition, as a result of microscopic observation, it was confirmed that this fiber was a hollow fiber having a cavity penetrating in the center of the fiber along the fiber axis, and it was confirmed that the micropores were open through the peripheral wall forming the hollow fiber. . The breaking strength of the obtained microporous hollow polyethylene terephthalate yarn was 2.5 g / d, the breaking elongation was 20%, and the boiling water shrinkage ratio was 3%.

Second Embodiment FIG. Nylon 6 from the hopper of the screw extruder having the kneading function of the film manufacturing apparatus shown in 3
(Relative viscosity: 2.40) was supplied, and ε-caprolactam that had been melted by heating at 120 ° C. through a solvent supply hole provided in the measuring section of the screw extruder was pressed into the kneading zone using a plunger pump. Knead and gradually raise the melt temperature to 23
The mixture ratio of nylon 6 / ε-caprolactam is 70 through the gear pump.
/ 30, 60/40, 50/50% by weight of a uniform melt is constantly extruded through a T-die to obtain a film having a thickness of 30μ,
Figure 7. The ε-caprolactam contained in the methanol vapor reflux extraction column as shown in (3) was extracted and removed and dried to obtain a fine porous polymer film. The fine pore size and the pore size distribution state of the obtained fine porous nylon 6 film were measured by the mercury porosimetry method, and when the mixing ratio was 70/30: circle equivalent pore size: 0.03 to 0.3μ The average circle-converted pore diameter is 0.1μ, and the pore volume ratio is 30%. When the mixing ratio is 60/40: The circle-converted pore diameter is distributed from 0.1 to 0.6μ, and the average circle-converted pore diameter is 0.4μ. Is 40% When the mixing ratio is 50/50: Pore diameter converted to circle: 0.4 to 1.0μ distributed, mean pore diameter converted to circle 0.7μ Pore volume ratio is 50%, and the main physical properties of the microporous membrane are When the mixing ratio is 70/30: breaking strength; 18 kg / mm,
Breaking elongation: 40%, boiling water shrinkage rate: 1.5% Mixing ratio 60/40: Breaking strength; 14 Kg / mm,
Breaking elongation: 40%, boiling water shrinkage rate: 1.5% When mixing ratio is 50/50: Breaking strength; 10 Kg / mm,
Breaking elongation: 30%, boiling water shrinkage: 1.5%.

Third Embodiment FIG. The beige colored elastic polyester resin (Toyobo Perprene R) is supplied to the screw extruder from the hopper of the extrusion laminating device shown in Fig. 1 and extruded to the kneading screw extruder connected to it, and further for the kneading. Using a plunger pump from the other solvent supply hole provided in the screw extruder
Polyethylene glycol (PEG60) preheated to 50 ° C
0) is supplied, both are mixed and kneaded, and a uniform melt of elastic polyester / PEG600 is mixed at a mixing ratio of 50/50 wt% through a gear pump and extruded from a T-die to form a sea-island composite of polyethylene terephthalate-polystyrene. Non-woven web made of fibers is entangled with a needle punch machine, non-woven web made of fine fibers obtained by extracting and removing polystyrene is temporarily adhered with Povar, impregnated with polyurethane resin, and a wet coagulation method is applied. On the manufactured artificial leather base cloth (Basis weight: 550 g / m 2) is extruded and laminated to a thickness of 60 μ, and passed through a countercurrent continuous extraction tank to extract and remove PEG600 contained in warm water at 60 ° C. Then, a predetermined surface layer pattern was applied to produce an artificial leather having a fine porous air-permeable silver surface. Typical properties of the artificial leather thus obtained are as follows: Tensile strength: 35 (vertical) x 25 (horizontal) (K
g / in. ) Elongation: 50 (vertical) x 65 (horizontal)% Skin layer peel strength (T-peel test peel strength): 5.0
(Kg / in.) Gurley stiffness: 3,000 (mg) Moisture vapor transmission rate: 1,250 (g / m 2/24 hr.) And leather having excellent moisture permeability was provided.

Fourth Embodiment FIG. 7. Polyethylene terephthalate (dissolved in a mixed solvent of phenol / tetrachloroethane = 3/2 and measured at 30 ° C. in the polymer supply hopper of the screw type injection molding device shown in FIG.
Of polyethylene glycol (PEG1000) heated to 160 ° C. from a solvent supply hole provided in the measuring section of the screw type injection molding device.
Press-fit using a plunger pump, and the polyethylene terephthalate / PEG1000 weight mixing ratio is 45/5.
6. The uniform mixed melt of No. 5 was constantly kneaded in the kneading zone, the temperature was set so as to obtain a uniform melt of 230 ° C., and the mixture was injected into the mold. A filter element having the shape shown in FIG. That is, the number of filter element tubes: 4
5 filter element tube tube diameter: 10mm
φ Filter element tube tube length: 100 mm Outermost filter element tube arrangement outer circumference (R 3):
Inner circumference of 100 mmφ filter element flange (R 4): 105 m
mφ Filter element flange outer circumference (R 5): 120 m
mφ Filter element tube thickness: 0.5 mm Filter effective area: 1,450 cm 2 Also, the circle equivalent pore size distribution measured by mercury porosimetry of this filter element: distributed in 0.6 to 1.4 μ, and the average circle equivalent pore size: 1.0μ Porosity volume ratio: 55%, and by mounting this on the casing, Fig. 6.
It is possible to supply a filter having a large filtration area as shown in (b), excellent filtration performance, uniform filtration performance, and excellent oil resistance and heat resistance with extremely low man-hours. (If necessary, it is possible to increase the number of filter element tubes with this size and obtain a filter element with a filter effective area of 2,000 cm 2.)

Example 5

Example 4 Polyethylene terephthalate-PE as a raw material for producing a microporous polymer for a filter element in Example 4
Only the combination of G1000 is ethylene-vinyl alcohol copolymer (Solarite M manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).
The filter element was manufactured by substituting the combination of R) -diethylene glycol. The filter performance such as the filter size and the filter element fine pore size and fine pore size distribution is the same as that of "Example 4", but since this filter has extremely excellent chemical resistance and solvent resistance of the constituent materials, it is particularly strong alkaline solution. It was most suitable as a filter for strong acid solutions.

[0020]

INDUSTRIAL APPLICABILITY As described above, the present invention "forms a molten solution or sol that is compatible with a thermoplastic polymer at a high temperature and solidifies and solidifies when cooled in a molding process to form a stable gel. , The mixing ratio of the thermoplastic polymer-solvent type thermoplastic polymer and the solvent is [thermoplastic polymer 75 to 20].
Parts] / [solvent 25 to 80 parts] so that a uniform melt composition of the blended composition can be rapidly obtained by constantly supplying to a screw kneading extruder or screw type injection molding machine having a kneading function and melt kneading. And then extruded through a hollow fiber spinning die or a film-forming die connected to the screw kneading extruder, hollowed or molded into a film / sheet, cooled and solidified, or connected to a screw-type injection molding machine. A method for producing a "fine porous polymer, characterized in that the solvent contained in these molded articles is produced by extracting with a solvent of the polymer and a solvent of the solvent after solidification by injection molding in a mold. Since it is a fine porous polymer separation membrane / filter and a film / sheet, it has the following characteristics and effects.

The fine pore distribution in the fine porous body is extremely uniform, and the fine pore size distribution is narrow and sharp. The micropore size depends on the composition of the thermoplastic polymer-solvent combination.
It can be easily adjusted arbitrarily by selecting the blending ratio. Further, since fine pores are formed based on such a fine pore forming mechanism, it is possible to continuously and arbitrarily manufacture from a separation membrane having a reverse osmosis separation membrane as a symmetry to a porous body having a precision filter and the like as a symmetry. By the screw kneading extrusion (injection) mechanism, in order to consistently and rapidly form a uniform molten constituent of a given blending composition of a given thermoplastic polymer-solvent system, the interaction between the thermoplastic polymer and the solvent Degradation reactions such as depolymerization reaction, transesterification reaction, ester amide exchange reaction, oxidative deterioration, and hydrolysis of the resulting polymer can be suppressed to a minimum, and quality does not fluctuate due to differences in the progress of deterioration reaction. It is possible to constantly obtain a microporous polymer having excellent physical properties of Thermoplastic polymer under high temperature and high pressure due to strong kneading mechanism
In order to form a uniform molten composition of the solvent system, a thermoplastic polymer-solvent combination that is difficult to dissolve by the operation of adding the polymer to the solvent and stirring and a high polymerization degree required to secure the physical properties of the product. Dissolution of the coalesced product can be carried out quickly and easily, and the desired desired thermoplastic polymer-solvent combination can be easily selected without any trouble. Further, since a strong kneading mechanism forms a uniform molten composition of the thermoplastic polymer-solvent system under high temperature and high pressure, defoaming does not occur because bubbles are not involved in the thermoplastic polymer-solvent system molten composition. It is not annoying to operate, and there is no need to worry about defects in the product quality due to the foam contained. A desired hollow fiber / film / sheet because it is composed of a manufacturing process in which a die for manufacturing a desired molded body or a molding die is connected to a kneading / dissolving mechanism that constitutes a predetermined thermoplastic polymer-solvent system molten composition. The microporous polymer and the microporous molded product having a desired shape can be continuously produced with high productivity. In addition to providing quality and outstanding productivity that cannot be obtained by conventional methods, it has made it possible to reform the production system for microporous separation membranes and filters.

[Brief description of drawings]

1 is a flow sheet of an exemplary embodiment of the present invention. This figure illustrates that the process of the present invention is composed of a combination of left and right rows of flow sheets. Flow sheet left column: Thermoplastic polymer-solvent kneading dissolution mechanism example: Kneading dissolution mechanism by screw extruder for thermoplastic polymer + screw extruder for thermoplastic polymer-solvent kneading (see FIG. 2 for details): Example of mechanism in which kneading is performed using a single screw kneading extruder An example of a method in which a thermoplastic polymer is supplied from a hopper, and a solvent is press-fitted from a metering unit (see FIGS. 3 and 4 for details): 2 Example of kneading method using axial kneading extruder Flow sheet right column: Example of molding device connected to kneading and extruding mechanism a: Hollow fiber spinning device assumption diagram b: Film forming device assumption diagram c: Extrusion laminating equipment assumption diagram d: Injection molding facility assumption diagram

[Fig. 2] Screw extruder for thermoplastic polymer + thermoplastic polymer-screw extruder for solvent kneading Extruding machine for fine porous polymer extrusion using kneading dissolution mechanism Figure Example: For thermoplastic polymer extrusion Screw extruder: Thermoplastic polymer-solvent kneading screw extruder: Thermoplastic polymer hopper: Solvent tank: Solvent supply pump: Thermoplastic polymer-solvent kneading melt discharge gear pump: T-die: Film Discharge: Reinforcement cloth A: Screw extruder solid transport section (solid-convection zone) B: Screw extruder compression melting section (compression-
Melting zone) C: Screw extruder weighing section (metering zone) D: Pre-filter E: Spinning head F: Laminating device G: Reinforcing cloth feeding device

[Fig. 3] Device for kneading and extruding fine porous hollow fibers by using a single screw kneading extruder Ex. Example: Hopper for thermoplastic polymer: Tank for solvent: Screw type kneading extruder: Solvent supply pump: Heat Gear pump for discharging plastic polymer-solvent kneaded melt: Hollow fiber spinning nozzle: Circular quench device: Discharge yarn: Take-off device A: Screw extruder solid transport section (solid convection zone) B: Screw extruder compression dissolution section ( Compression-
Melting zone) C: Screw extruder weighing section (Metalling zone) D: Prefilter E: Spinning head section

[Fig. 4] Device for kneading and extruding a fine porous film by using a single screw kneading extruder Ex .: Hopper for thermoplastic polymer: Tank for solvent: Screw type kneading extruder: Pump for solvent supply: Thermoplastic Gear pump for polymer-solvent kneading melt discharge: T-die: Film discharge: Cleaning device (cleaning tank) A: Screw extruder solid transportation part (solid convection zone) B: Screw extruder compression dissolution part (compression-
Melting zone) C: Screw extruder weighing section (Metalling zone) D: Prefilter E: Spinning head section

[Fig. 5] Apparatus for producing a microporous molded product using a screw in-line injection molding machine Example: Hopper for thermoplastic polymer: Tank for solvent: Screw-type kneading extruder: Pump for solvent supply: Mold: Check valve A: Screw extruder solid transport section (solid-convection zone) B: Screw extruder compression melting section (compression-
Melting zone) C: Screw extruder weighing unit (metering zone) D: Servo motor E: Mold clamping drive unit

FIG. 6 (a) Microporous filter element (X-
X'cross section) (b) Filter (state diagram with the above element assembled in the casing)

FIG. 7: Extraction device using solvent vapor for producing solvent by extracting solvent from thermoplastic polymer-solvent kneading discharge body Illustration Example: Thermoplastic polymer-solvent kneading discharge body: Microporous body: For extraction Solvent: Extraction tower ,: Cooler

[Table 1]

[Table 1]

Claims (7)

[Claims] 1. A thermoplastic polymer-solvent system which is compatible with a thermoplastic polymer at high temperatures to form a uniform and stable molten solution or sol which solidifies when cooled in the molding process to form a stable gel. So that the mixing ratio of the thermoplastic polymer and the solvent is [thermoplastic polymer 75 to 20 parts] / [solvent 25 to 80 parts], the screw is constantly fed to the screw kneading and extruding mechanism having a kneading function and melted. Kneading is carried out to rapidly form a uniform molten composition consisting of 75 to 20 parts of a thermoplastic polymer and 25 to 80 parts of a solvent, and the mixture is injected into a molding die connected to the screw kneading and extruding mechanism or hollow fiber. After being extruded through a spinning spinneret for spinning or a T-die for film formation or an extrusion film extrusion spinner, molded into a predetermined shape and cooled and solidified, the solvent contained in the molded product is a non-solvent for the polymer and Method for producing it microporous molded and hollow fiber or film sheet-like microporous polymers characterized be prepared by extraction with a solvent of the solvent 2. A thermoplastic polymer which is compatible with a thermoplastic polymer at a high temperature, forms a uniform and stable molten solution or sol, and solidifies when cooled in the molding process to form a stable gel.
Thermoplastic polymers 75 to 2 in solvent system combinations
In order to form a uniform molten composition consisting of 0 parts and 25 to 80 parts of solvent, the thermoplastic polymer is continuously and quantitatively supplied to a heated screw kneading extruder having a kneading function and melted. , The solvent is continuously and quantitatively supplied from a supply hole provided in a metering portion of the screw kneading extruder, or alternatively, the solvent is supplied separately from the kneading screw extruder connected to the screw extruder. Continuously and quantitatively through the supply holes of the two to knead them and uniformly dissolve them to form a molten solution with a predetermined mixing ratio constantly, and spinneret for hollow fiber spinning or T-die for film formation or insulation. After being extruded through a film extrusion die, molded into a hollow fiber or a film / sheet and cooled and solidified, the solvent contained in the molded product is extracted with a non-solvent of the polymer and a solvent of the solvent. Method for producing a hollow fiber or film sheet-like microporous polymers characterized in that it granulation 3. A homogeneous and stable molten solution or sol, which is formed by the method described in claim 1 and which is compatible with the thermoplastic polymer at high temperature and solidifies when cooled in the molding process. Thermoplastic polymer with solvent that forms stable gel-
A homogeneous and stable molten mixture consisting of a combination of solvent systems
Extruded from a die and laminated on a reinforcement made of a woven or knitted fabric or a non-woven fabric, or embedding the reinforcement in a melt extruded from a T-die to solidify by cooling. And then the solvent contained in the film / sheet-shaped molded product is extracted by a non-solvent of the polymer and a solvent of the solvent to produce a reinforced microporous film / sheet. Method of manufacturing objects 4. A thermoplastic polymer-solvent system which is compatible with a thermoplastic polymer at a high temperature, forms a uniform and stable molten solution or sol, and solidifies when cooled in the molding process to form a stable gel. Heated thermoplastic screw injection molding having the function of kneading the thermoplastic polymer in order to form a uniform molten composition of 75 to 20 parts of the thermoplastic polymer and 25 to 80 parts of the solvent. It is continuously and quantitatively supplied to the machine to melt, and the solvent is continuously and quantitatively supplied from a supply hole provided in a measuring portion of the screw type injection molding machine to uniformly mix and dissolve both of them, and a predetermined amount is obtained. Injection molding in the mold, which causes the molten solution of the mixing ratio to be constantly formed,
Alternatively, the kneading and dissolving mechanism described in "claim 1" is connected to an injection molding plunger part, and a molten solution having a predetermined mixing ratio in which both are uniformly kneaded and melted is supplied, and injection molding is performed in a mold by the injection molding mechanism. After cooling and solidifying, the solvent contained in the injection-molded product is extracted by a non-solvent of the polymer and a solvent of the solvent to produce a fine porous molded product. 5. A fine porous separation membrane and a filter medium produced according to the method of "claim 1" to "claim 4". 6. A separation device or a filtration device produced by using the fine porous polymer according to claim 5. 7. A permeable coating material and a synthetic leather product manufactured using a sheet manufactured according to the method of "claim 1" to "claim 3".