TW200808434A - Polymeric separation membrane and method for manufacturing the same - Google Patents

Abstract

The invention provides a polymer separation membrane that is excellent in separating characteristics, a permeating ability, a chemical strength (particularly chemical resistance) and a physical strength, and also excellent in a stain resistance, and a producing method therefor. The fluorinated resin-type polymer separation membrane includes a layer having a three-dimensional network structure, and a layer having a spherical structure, wherein the layer of three-dimensional network structure is formed by a fluorinated resin-type polymer composition containing a hydrophilic polymer, and the hydrophilic polymer is a substantially water-insoluble hydrophilic polymer containing at least one of a cellulose ester, an aliphatic vinyl ester, vinylpyrrolidone, ethylene oxide and propylene oxide as a polymerization component. The polymer separation membrane is applicable as a filtration membrane for water treatment, a battery separator, a charged membrane, a fuel cell membrane or a blood cleaning filtration membrane.

Description

200808434 IX. Description of invention: i. / ;;s ' [Invention: Technical field to which it belongs] The present invention relates to a polymer separation membrane, a suspension, a Cang, an old eight J for use as a drinking water system 2:: Water treatment field such as wastewater treatment; pharmaceutical manufacturing field; field of charged film; field of fuel cell; membrane of membrane 4 for blood purification. [Prior Art] In the past, the 'polymer separation membrane' has been used as a substrate in various fields such as drinking water production, water purification treatment, waste water treatment, and the like. In the field of water treatment, such as drinking water manufacturing, water treatment: wastewater treatment, filtration using separation membranes, starting and substituting the previous sand filtration or agglutination steps to remove the Yongzhong’s miscellaneous shells and In the field, a separation membrane is used for the purpose of separating and removing the yeast or concentrated liquid which is used in the fermentation, and the yeast or concentrated liquid is used. As such, a polymer separation membrane is used in various fields. For example, in the field of water treatment such as water purification treatment or wastewater treatment, (4) the amount of water to be treated is relatively large, so that it is required to further improve the water permeability during filtration. If the water permeability is excellent, the membrane area of the separation membrane used in the ruthenium treatment can be reduced, and the filtration treatment device becomes small. Therefore, the equipment cost can be saved, and it is also advantageous from the viewpoint of the membrane replacement cost or the installation area. In addition, 'in the water treatment field towel, for the material ^ Xiao poison or to prevent biological contamination of the membrane surface 'and add disinfectant such as sodium hypochlorite in the water in the membrane module' or by acid, test, chlorine and surfactant The cleaning flag itself is required, so the separation membrane is required to be chemically chemical. N3556.doc 200808434 Further, in the field of tap water manufacturing, it has been apparent since the 2Q9 century, and it is impossible to treat pathogenic microorganisms that are resistant to chlorine, such as cryptospores from livestock manure, etc., in the treatment of tap water. All removed 'and mixed into the handling of the Taixi Xuan # ^ ^ . J accident, so in order to prevent such accidents, the requirement = the membrane has sufficient separation characteristics 'to remove the target substance in the raw water does not enter here $ 7] In C, it has a high physical strength that does not cause breakage or breakage of the separation membrane even after continuous enthalpy treatment. Therefore, the separation membrane is required to have excellent separation characteristics, chemical strength (especially chemical resistance), physical strength, and permeability. Therefore, a separation membrane made of a polyvinylidene fluoride-based resin having both chemical strength (especially chemical resistance) and physical strength has been used in many fields. However, the polyvinylidene-based resin which constitutes the separation film of the polyethylene-based polyethylene resin is originally hydrophobic, and thus has a disadvantage that the surface of the film is easily contaminated by hydrophobic interaction. In particular, in the case of the drug production step, when it is used for separation or purification of a physiologically active substance such as a protein, the physiologically active substance is adsorbed on the surface of the film to be modified, so that the following problems are easily caused: the recovery rate is lowered, and the film is caused to be in the film. The pores are clogged and the transition speed is drastically reduced. ^ In order to improve these problems, the company has considered hydrophilization of a polyvinylidene fluoride-based resin separation membrane to improve its stain resistance, and has proposed several techniques for hydrophilization. For example, a technique for hydrophilizing a hydrophobic resin film by introducing a polyethyleneimine copolymer by a chemical reaction has been proposed in Japanese Patent Laid-Open Publication No. SHO 577-1741. However, since the introduced hydrophilic polymer has a charged group, it is produced by a solution containing a substance f having a charge, particularly as a humic substance in the amphoteric 113556.doc 200808434, or a protein of the reverse electrolysis I or in the surface water. The opposite effect. /, Spear] A method of hydrophilization of polyvinyl phthalate or cellulose acetate vinegar mixed with a polyvinylidene fluoride resin. θ

In the Japanese Patent Publication No. Sho 61-257203, a technique of producing a knife-off film by mixing a resin composition of a vinylidene ester and a polyvinylidene fluoride-based resin is proposed. However, polyvinyl acetate is mixed until When the separation membrane which exhibits hydrophilicity and privacy is chemically cleaned by acid, test, chlorine or the like, there is a problem that the physical strength is easily lowered. Further, if the chemical strength is increased, the separation membrane is changed. When it is thick, there is a problem that it is difficult to obtain the water permeability necessary for practical use in the case of the water permeability reduction. Therefore, as a method of improving the hydrophilicity without increasing the content of the polyvinyl acetate, Japanese Patent No. 32 In the publication No. 95, it is proposed to saponify polyvinyl acetate in a separation membrane made of a mixed resin of polyvinyl acetate and polyvinylidene fluoride resin under alkaline conditions to form a poly(copolyhydrin). The separation membrane comprising a mixed resin of polyvinyl alcohol and a polyvinylidene fluoride-based resin produced by such a method exhibits excellent hydrophilicity and exhibits excellent stain resistance to proteins and the like. When the separation membrane is chemically cleaned by an acid, an alkali, chlorine or the like, the polyvinyl alcohol is likely to be invaded by chemicals, resulting in a decrease in performance. Further, since the polyvinyl alcohol is highly hydrophilic, it has a water-soluble property. Sexually, if it is used in filtration in water systems, it will dissolve slowly. Therefore, in applications where it is not desirable to infiltrate water, especially in the use of drinking water or water purification, 'use a separation membrane containing polyvinyl alcohol. In addition, since the solubility of the polyethylene glycol is increased with the increase of the water temperature, it is not suitable for the treatment of high-temperature water such as boiler cooling water recovery. Under the special conditions, the polyethylene dioxide resin is also treated, and there is a possibility that the coloring or physical strength is lowered, and it is easy to damage the excellent properties of the polyvinylidene fluoride resin. In Japanese Laid-Open Patent Publication No. Hei No. 2-78425, the technique of manufacturing/dissolving a mixed resin of m-dimensional (four) (four) polyethylene-based resin is disclosed. In the case where a separation membrane which is necessary for exhibiting hydrophilicity = cellulose acetate s is mixed, if physical acid or chemical chlorine is used for chemical cleaning, physical strength may be lowered. In order to increase the physical strength and make the separation membrane thicker, the water permeability is required for the water permeability necessary for practical use. · Difficulty 4 ▲ Therefore, in Japanese Patent Laid-Open No. 4_3! 〇223, it is disclosed that: cellulose The hydrophilicity of acetic acid vinegar is reduced by the method of increasing the physical strength with respect to the mixing ratio of the polyethylene dioxide system. Then, the cellulose acetate vinegar is mixed with the polyvinylidene fluoride resin in the publication. In the case of Dream 2 (4), the cellulose acetate brewing soap in the separation membrane is made into a cellulose having higher hydrophilicity. In this way, the cellulose containing cellulose and the polyvinylidene chloride resin are obtained. The separation membrane of the mixture is excellent in hydrophilicity and exhibits excellent stain resistance to proteins, etc. However, due to the surface Ψ ^ A Μ , it is found that the two hydrophilic celluloses are uniformly distributed in 2 In the film, "but if by Of the acid, inspection, physical chemical drugs such as chlorine wash months' immersion in the presence of chemicals in the entire separation membrane, may cause decrease of physical strength. Further, if the specialization is carried out under the conditions of the test, the presence of the fluoroethylene fine resin is also treated, resulting in a possibility of coloring or physical strength reduction. Further, in the case of International Publication No. 03/1 06545, there is disclosed a separation membrane which can smooth the surface of the film and ingeniously control the pores of the surface. The separation membrane is a composite membrane in which a surface layer portion having a separation function is coated on an inner layer portion having excellent physical strength, and the inner layer portion and the surface layer portion are each composed only of a polyvinylidene fluoride-based resin. Therefore, even if chemical cleaning is performed The advantage of physical strength is not reduced. However, since it is composed only of a hydrophobic polyvinylidene fluoride-based resin, there is a problem in that it is easy to adsorb humus in surface water and the like, and the filtration resistance is increased, so that it is difficult to perform stable operation for a long period of time. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A polymer separation membrane which can improve the above problems of the prior art, and which is excellent in separation characteristics, water permeability, chemical strength (especially chemical resistance), physical strength, and excellent in stain resistance. SUMMARY OF THE INVENTION In order to achieve the above object, a polymer separation membrane of the present invention is characterized in that it is a fluororesin polymer having a three-dimensional network structure layer and a spherical structure layer n3556.doc 200808434 'The three-dimensional network structure layer contains a fluororesin containing a hydrophilic polymer and a mouthpiece', and the hydrophilic polymer comprising at least one of a cellulose ester, a fat (B), a B-material (4), and an epoxy b-epoxypropane as a polymerization component. And it is essentially water insoluble. The second f' is preferably a fluororesin-based polymer constituting the three-dimensional network structure layer, and is broadly: ::2% of the hydrophilic polymer with respect to the amount of the gas-based polymer. The above ratio of less than 2% by weight, containing a hydrophilic high score: wide, preferably a fluororesin-based polymer constituting a three-dimensional network structure layer: a hydrophilic polymer 'system' containing cellulose Ester and/or fatty acid vinegar as a polymeric component, and it is soluble in the real f, and further preferably: 糸 糸 self-contained cellulose acetate series, cellulose acetate vinegar vinegar, cellulose acetate vinegar vinegar, and Ethyl acetate vinegar is a polymerization component and is at least one selected from the group consisting of water-insoluble hydrophilic polymers. In: Preferably, the spherical structure layer does not substantially contain a hydrophilic polymer, and ::: a resin-based polymer. It is preferred that the surface layer of the polymer separation membrane of the present invention is a three-dimensional network structure layer. It is preferred that the average diameter of the solid component present in the spherical structure layer is 〇1 _ or more and 5 _ or less. It is preferable that the average pore diameter of the pores of the surface of the three-dimensional network structure layer is 1 nm or more! Below μπι. When the separation membrane is in the form of a hollow fiber, it is preferred that the penetration property of the pure water of 5 () coffee and 25 C is 〇 2 〇 or more and the breaking strength is 6 or more, and the elongation at break is above or above. . As the polymer separation membrane, it is particularly suitable as a membrane for a membrane module. A preferred method for producing the polymer separation membrane of the present invention is 113556.doc 200808434. The method of coating a surface of a spherical structure layer comprising a fluororesin polymer includes coating a cellulose ester. a fluororesin-based polymer liquid having at least one of a fatty acid vinyl ester, a vinyl pyrrole ketone, an ethylene oxide, and a propylene oxide as a polymerization component and a water-insoluble hydrophilic polymer. It is solidified in the bath, whereby a three-dimensional network structure layer is formed on the surface of the spherical structure layer. Here, it is preferred that the spherical structure layer containing the fluororesin-based polymer substantially does not contain a hydrophilic polymer. Further, another preferred method for producing the polymer separation membrane of the present invention is characterized in that it comprises a cellulose ester, a fatty acid vinyl ester, a vinyl pyrrolidone, an ethylene oxide, and an epoxy resin. A fluororesin-based polymer solution of at least one of the hydrophilic polymers which are at least one selected from the group consisting of a water-insoluble hydrophilic polymer and a fluororesin which is substantially free of hydrophilic ruthenium molecules The molecular solution is simultaneously ejected from the nozzle and solidified in the coagulation bath, thereby forming a three-dimensional network structure layer containing the fluororesin-based polymer containing the hydrophilic polymer, and a spherical structure containing the fluororesin Layered film. In the above-mentioned production methods, it is preferred that the fluororesin-based south molecular solution containing the hydrophilic polymer is 2% by weight based on the amount of the fluororesin-based polymer contained in the solution. The above ratio of less than 2% by weight contains a hydrophilic polymer. Further, it is preferable that the hydrophilic polymer mainly contains a cellulose ester and/or a fatty acid ethylene as a polymerization component, and is substantially a water-insoluble hydrophilic polymer, and particularly preferably a cellulose-containing cellulose. Acetate, cellulose acetate propionate, cellulose acetate butyrate, and vinyl acetate as polymeric components, and substantially water-insoluble 113556.doc -12- 200808434 steep hydrophilicity selected in the molecule ^ Kind. Further, it is preferred that the coagulation bath which is in contact with the coated or sprayed resin liquid-containing polymer solution containing a hydrophilic hexahydrate or a hexa-factory four-knife is a non-solvent containing a relatively high polarity. [Effect of the Invention] The polymer separation membrane of the present invention comprises a composite separation membrane of a spherical structure layer and a three-dimensional network structure layer, and since the hydrophilic polymer of the material is contained in the -dimensional network structure layer, the substance is The spherical structure layer containing no hydrophilic polymer can sufficiently exhibit chemical resistance and can prevent physical strength from being low. That is, since the spherical structural layer bears the physical strength of the entire film, even if chemical cleaning is performed, the physical strength of the entire film is not lowered, and breakage or film breakage can be prevented. On the other hand, by the hydrophilic polymer in the three-dimensional network structure layer, adsorption of a pollutant represented by humic substances in surface water can be suppressed. Further, due to the presence of a spherical structural layer that bears physical strength, the three-dimensional network structure layer can be made thinner than the prior art, and the water permeability can be further improved. Therefore, the polymer separation membrane of the present invention is excellent in separation property, water permeability, chemical strength (especially chemical resistance) and physical strength, and can be improved in stain resistance without impairing such excellent (4). Stain resistance. Then, by using the separation membrane for water treatment, the filtration life can be prolonged and the cost of desalinated water can be reduced. [Embodiment] The fluororesin-based polymer separation membrane of the present invention is characterized in that it has a three-dimensional network structure layer and a spherical structure layer. The three-dimensional network structure layer contains a specific hydrophilicity such as cellulose. The polymer fluororesin is a two-part 113556.doc 200808434 sub-composition. Fig. 1 is an electron micrograph showing a cross section of a separation membrane in which a three-dimensional network structure layer and a spherical structure layer are laminated (1, an electron micrograph of the surface of the network structure layer (6_2 =;: part of a three-dimensional network structure) The layer and the lower part are spherical structure layers. As shown in Fig. 2, the surface portion (upper side portion) is shown in Fig. 2, in which the resin is solid-distributed, -, quasi-shoulder, . a junction that is quasi-ground and unfolded into a mesh: (4) this is a two-dimensional network structure. In the three-dimensional network structure, the scattered # is formed by the solid resin forming the mesh, and is formed in detail in FIG. Black indicates ., '(Work gap). The pores are distributed in a spherical structure layer with a nearly spherical shape (including a spherical shape) (rib mouth:: 'Direct or separate strip-shaped solid-shaped sub-links The structure is formed (referred to as a spherical structure). Furthermore, the spherical structure layer of the mouth microscope is photographed by a 3000-fold cross-section of the polymer-separated electrosurgical knife, and the spherical shape can be observed. The layer of the structure. $仃拍“ The layered structure of the spherical layer and the three-dimensional network membrane At the time of scanning, the use of scanning electrons to smear the layers of the layered structure of the 払 払 以 以 以 以 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 The remaining layer is a three-dimensional network structure layer. The layer structure of the polymer separation membrane of the present invention is not particularly limited as long as both the spherical layer i layer and the two-dimensional layer== layer exist. The good thing is that (4) there is a Yongjiji layer and a three-dimensional network structure layer, and the layer of 曰 重 聂 夕 夕 夕 夕 夕 夕 夕 、 、 、 、 、 、 、 、 、 、 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 When the layers are firmly connected to the h-shape at the interface, the layers on the interface will be opposite each other and there is a film inside. 113556.doc -14- 200808434

,,. The structure is easy to be dense, and the permeability is reduced. On the contrary, in the case where the layers on the interface are not intercalated, although the permeability is not lowered, the peeling strength of the interface is low. As such, the peel strength at the interface of the layers has an opposite tendency to the penetration 11, so it is desirable to achieve a level that is simultaneously satisfied. From this point of view, it is preferred that the number of laminated interfaces of the spherical structural layer and the three-dimensional network structure layer, that is, the number of laminated layers is small, and particularly preferably includes one layer of spherical structural layer and one layer of three-dimensional network structural layer. A total of 2 floors. Further, the layer other than the spherical structure layer and the - quasi-network structure layer may contain, for example, a carrier layer such as a porous substrate as another layer. The material constituting the porous substrate may be an organic material, an inorganic material or the like, and is not particularly limited. From the viewpoint of easy weight reduction, organic fibers are preferred. Further, as the porous substrate, a woven or non-woven three-dimensional network including organic fibers such as fibrin fibers, cellulose acetate fibers, polyester fibers, polypropylene fibers, cut-off fibers, and polyethylene fibers is preferable. The arrangement of the structural layer and the spherical structural layer (the upper and lower layers in the case of the flat membrane, and the inner and outer layers in the case of the hollow fiber membrane) can be changed depending on the filtration method. In the separation crucible of the present invention, the three-dimensional network structure layer functions as a separation function, and the spherical structure layer bears the physical strength. Therefore, it is preferable to arrange the three-dimensional network structure on the raw water side when the separation membrane is used. It is particularly preferable to arrange the three-dimensional network red layer on the outermost layer of the raw water side in order to suppress the decrease in permeability due to the adsorption of the raw water: U dye. Three-dimensional network structure layer and spherical junction: each thickness of the layer 'T to meet the separation characteristics, water permeability, chemical strength, which is chemical resistance), physical strength and stain resistance requirements 113556.doc -15 - 200808434 The way to make appropriate adjustments. If the three-dimensional network structure layer is too thin, there is a tendency that the separation property or the physical strength is lowered; if it is thick, the water permeability is low. If the spherical structure layer is thin, the physical strength tends to decrease, and when the right side is thick, the water permeability tends to decrease. This is not the case for the balance of the above properties or the operating cost of the membrane filtration. The thickness of the three-dimensional network structure layer is preferably 8 〇 or less, and more preferably 20 μηι or more and 6 〇 μπι or less. Particularly preferably, it is 3 〇 Φ μΠΊ or more and 50 μη ΐ or less. Further, the thickness of the spherical structure layer is preferably 500 μη or less on 1 〇〇 μηι 乂, and further preferably 2 〇〇 m or more and 3 〇〇妗 m or less. Further, the thickness ratio of the three-dimensional network structure layer to the spherical structure layer is greater than the above-mentioned σ 1±month or film; the operating cost of the time is also relatively heavy, and if the proportion of the three-dimensional network structure layer becomes large, Physical strength is reduced. Therefore, the ratio of the average thickness (Α) of the three-dimensional network structure layer to the average thickness (Β) of the spherical structure layer (Α/Β) is preferably 〇〇3 or more and 25 or less, and further preferably 〇惠 is above 0.15. In the molecular separation membrane of the present invention, the matrix polymer of the three-dimensional network structure layer and the spherical structure layer is an I resin-based polymer, and the three-dimensional network structure layer contains a specific hydrophilic polymer. The hydrophilic polymer contained in the three-dimensional network structure layer is selected from at least one selected from the group consisting of cellulose oxime, saponin & C ethylene, vinyl pyrrolidone, ethylene oxide, and epoxy propylene. A hydrophilic polymer which is a polymer component and is substantially water-insoluble. Further, the murine resin-based polymer is a vinylidene fluoride homopolymer and/or a vinylidene fluoride copolymer. It may also contain a plurality of kinds of difluoroacetic acid copolymers I13556.doc 200808434. Further, in the case where a small amount of the characteristics of the separation membrane of the present invention is not impaired, other polymers may be used in combination. As the partial ethylene-diethyl ether copolymer, for example, it can be selected from the group consisting of vinyl fluoride, tetrafluoroethylene <RTIgt; hexafluoropropene, and trichloroethylene to a copolymer of vinylidene gas. Further, the weight average molecular weight of the polymer of the resin can be appropriately selected according to the strength and water permeability of the desired polymer separation membrane. When the weight average molecular weight is increased, there is a decrease in the water content of f. If the weight average molecular weight is small, there is a tendency that the strength is low. Therefore, the weight average molecular weight is preferably 50,000 or more and 10,000 or less. In the case of a polymer used in a water treatment application requiring chemical cleaning, in the case of a film, the weight average molecular weight of the fluororesin-based polymer is more than 100,000 to 700,000 or less, and more preferably 150,000 or more. Below 10,000. * Again: the hydrophilic polymer added to the three-dimensional network structure layer can be fiber-optic, and X' can also be selected from the group consisting of fatty acid vinyl ester, vinyl pyrrolidine: ethane and propylene oxide. At least one kind of hydrophilic polymer which is polymerized into a knives and is water-insoluble in the permeation; and, red, can be self-contained, fragrant vinyl vinegar, vinyl bismuth, epoxy epoxide and epoxy Propane can be selected from the hydrophilic molecular unit of the species to modify the cellulose vinegar: the cellulose vinegar; and further, in the case of not causing greater damage to the hydrophilic properties of the cellulose vinegar, The hydrophilic molecular unit is not. a modified cellulose ester modified with a cellulose ester. The hydrophilic polymers are as follows: in the main chain and/or side: the upper part contains the selected from the fiber (four), the monthly fatty acid ethyl vinegar, the yoghurt (four) hospital eight... At least one of the derived hydrophilic knives is early as a molecular unit that exhibits hydrophilicity. N3556.doc 200808434 Cellulose vinegar's degree of hydrolysis of its repeated singles, can be easily... § 曰 base, by adjusting it, etc., it is easy for Japanese people to achieve good 舆 fluororesin polymer, 6r, And the polymer separates the surface of the film from the good hydrophilicity, so it can be used well. Examples of the fiber sounds include cellulose acetate, cellulose acetate propionate, and cellulose salt acid butyrate. Further, in the cellulose ester, a cellulose I-modified product having a hydrophilic molecular unit such as fatty acid ethylene may be introduced by grafting t 5荨. Further, in the case of a hydrophilic polymer having a hydrophilic molecular unit derived from vinyl ketone, ethylene bromide or propylene bromide, it is highly hydrophilic in order to be water-insoluble in the permeation. Molecules also contain other molecular units than the above: X 〖 生: 子单兀. Examples of the monomer constituting the other molecule unit are, for example, an alkene such as ethylene or propylene, an alkyne such as acetylene, an ethylene halide, a vinylidene halide, methyl methacrylate or methyl acrylate. In particular, ethylene, methyl methacrylate, and methyl acrylate are preferred because they are available in lower molecular weight and are easily introduced into the main chain and/or side chains. As such a method of introduction, a well-known polymerization technique such as radical polymerization, anionic polymerization, or cation polymerization can be used. Since the hydrophilic polymer is added to the fluororesin-based polymer for forming the three-dimensional network structure layer, it is preferably mixed with the fluororesin polymer under appropriate conditions. In particular, when the hydrophilic polymer and the fluororesin-based polymer are mixed and dissolved in a good solvent of the fluororesin-based polymer, the processing is easy, and therefore it is particularly preferable. When the content of the hydrophilic molecular unit in the hydrophilic polymer is increased, the hydrophilicity of the obtained two-molecule separation membrane is increased, and the permeability or the stain resistance is improved, so that it is not damaged. In the above, it is preferred that the content of the mixture is broad, and the mixture of molecules is m: the aqueous molecular unit is in the hydrophilic high-concentration and the molecular separation film is also required to be mixed with the gas-based polymer. The sex fly is more than %, better and different, and it is better to have more than 60% of the 50 moles. Among them, 'the yield of hydrophilic molecules, strict gp is vinylpyrrolidine I, epoxy B.. The rate of over-horse' shows water solubility'. Therefore, it is better that the rate is not too high, for example Up to 50 m / 〇. That is, the ancient eight, eight, and eight knives of the present invention are used in the filtration of water in the membrane. Therefore, the three-dimensional network J is required. The hydrophilic polymer in the layer must be water-insoluble. Hydrophilic, ^I wish that the water-returning molecule itself is water-insoluble, or that it is properly treated to make it into water. In the case where the main chain and/or the side chain have a hydrophilic polymer of ethylene base, epoxy bake, or epoxy propylene, it is preferable to copolymerize with other monomers to be water-insoluble. method. For example, 'Ethylene base. A graft copolymer (PMMA_g_pvp) of a random copolymer of piroxicam with methacrylic acid (PMMA CO PVP), 4 vinyl t-grafted onto poly(methyl methacrylate), The copolymerized molar ratio is appropriately set to make it a water-insoluble hydrophilic polymer. On the other hand, in the case of a cellulose ester or a hydrophilic polymer containing a hydrophilic molecular unit derived from a fatty acid vinyl ester, it is generally not water-soluble even if the content of the hydrophilic molecular unit becomes high. Therefore, the content rate can be adjusted within a large range. Examples of the hydrophilic polymer containing a molecular unit derived from a fatty acid vinyl ester include a homopolymer of a fatty acid vinyl ester, a copolymer of a fatty acid vinyl ester with other monomers of 113556.doc -19-200808434, and a graft of a fatty acid B (tetra). a copolymer polymerized on other polymers. As a homopolymer of the fatty acid ethyl acetate, the price of the polyvinyl acetate vinegar is lower and w is added, so it is preferable. As a fatty acid ethylene vinegar disk, it is preferable that the copolymer of the monomer: ethylene-vinyl acetate 0 copolymer is low in price and easy to process. If the cellulose is partially hydrolyzed, the hydrophilicity is higher than that of the vinegar. When the ratio of the base group is increased, the miscibility with the hydrophobic resin is reduced. However, the hydrophilicity of the obtained polymer separation membrane is increased, and the permeability or the stain resistance is improved. From the viewpoint of the improvement of the performance of the separation membrane, it is preferable that the cellulose vinegar or the fatty acid in the three-dimensional network structure layer is in a range in which the compatibility with the fluororesin polymer can be maintained. - a method of partial hydrolysis. In the case of hydrolysis by this method, in order to prevent the hydrolysis from being caused by the (four) ringing, the preferred dibutyl quinone is such that the two-dimensional network structure layer is located at the outermost portion of the separation membrane (the surface side in contact with the liquid phase to be treated) The outermost) and minimize the thickness of the layer. Further, in particular, in the polymer separation membrane having the three-dimensional network structure layer and the spherical layer layer of the present invention, the three-dimensional network structure contains hydrophilic interphase molecules, mainly from cellulose esters. And/or fatty acid ethylene s is a hydrophilic polymer. The reason is that if the hydrophilic paleomolecule mainly contains cellulose brewing and/or fatty acid ethylene brewing, it can be adjusted in a wide range in the range in which the compatibility with the gas: lipid sulphonium molecule is not impaired. The degree of hydrolysis 'is easy to impart hydrophilicity to the obtained polymer separation membrane. The so-called macromolecule containing cellulose vinegar and/or fatty acid yigui duck can be expressed as follows: in the case of cellulose vinegar or fatty acid B 113556.doc -20- 200808434 vinegar, the content rate is 70 mo More than or equal to the ear; and in the case where both the vitamin C and the fatty acid B (four) are included, the ratio of the content of the cellulose ester to the combination of the fatty acid vinyl ester and the mystery is 70. The rate is better than 80%. In the range of the effect of the present invention, it is possible to contain other components such as other organic substances, inorganic substances, polymers, and the like in the high force, (4) three-dimensional network structure layer and the spherical structure layer of the present invention. The southern molecular slitting Zhao _ m of the present invention only contains a special 冋 knife in the three-dimensional network structure layer, so in order to improve the peeling resistance of the interface, the interface between the spherical structural layer and the three-dimensional network structure layer is preferred. Two structures. In the case where the spherical structure layer and the three-dimensional network structure layer are both formed of a fluororesin-based polymer, the hydrophobic separation interaction between the high scores of the latex resin is difficult to produce. Peeling of the interface between the spherical structural layer and the three-dimensional network structure layer. When the hydrophilic polymer different from the gas-based polymer is present only in one layer on one side, the effect of preventing the interface peeling due to the hydrophobic interaction between the resin-based polymers is large. By reducing the 'and the coexistence of the hydrophilic polymer, not only the hydrophobic interaction is reduced' but also the repulsion between the hydrophilicity and the hydrophobicity is caused, so that the peeling of the interface is more likely to occur. Therefore, it is preferable to reduce the interface peeling. It is to reduce the hydrophilicity I in the vicinity of the interface. For example, 'by making the hydrophilicity in the three-dimensional network structure layer high: the content of the sub-particles is controlled as small as possible, and the hydrophilicity in the vicinity of the interface can be reduced. From the viewpoint of preventing the peeling of the interface, a preferred 113556.doc 200808434 is a ratio of the amount of the hydrophilic polymer (a) to the amount of the fluororesin-based polymer (b) in the three-dimensional network structure layer (a) /b) is 2% by weight or more and less than 2% by weight, more preferably 5% by weight or more and 15% by weight or less. Further, the amount of the hydrophilic polymer relative to the amount of the fluororesin-based polymer (weight The concentration of the hydrophilic polymer (al% by weight) and the concentration of the fluororesin polymer (bl% by weight) in the polymer solution for forming the three-dimensional network structure layer, (al/bl) xl00 Calculated by the formula.

, ', ',,, ‘mouth 曰,, q, cleaver j jade. It is only customary to ask the ratio of the knife (a/b) to meet the requirements of separation properties, water permeability, chemical strength (chemical resistance), physical strength, and stain resistance. The method of suppressing the peeling of the interface is arbitrarily adjusted to achieve optimization. Here, when the content of the hydrophilic polymer is too small, it is difficult to impart durability. On the other hand, when the content of the hydrophilic polymer is too large, not only the t strength or the physical strength is lowered, but also the interfacial peeling is likely to occur, and since the high density is the film densification, the water permeability is lowered. ::, the following method is also better '31, the amount of hydrophilic polymer in Sancheng is from the high-eight θ T-shaped inclined structure, thereby reducing the boundary 2:: surface: the interface slowly decreases to form such a tilted structure, Good ^ Amount of water-based molecules. Use as a non-solvent as a non-solvent to form a crucible such as 'use a more polar solidified liquid, so that the "side...forms hydrophilicity 2, and contacts the surface side of the film. By such as: The molecular structure of the menstrual system is highly hydrophilic, and the polarity is still on the side of the fluorine tree. Therefore, the hydrophilicity is formed in the polymer separation membrane. 3556.doc The slow reduction of the knot-22-200808434 The hydrophilicity of the high-resolution hand near the interface is +, and the doorknife is relatively reduced. The non-solvent of the higher polarity is selected from the non-solubilizing choices of the following types, especially the polarity of the water. Τ- 4. V. is relatively low and the price is low. Therefore, if the average diameter of the nearly spherical solid in the spherical structure layer of the separation membrane is j, the void ratio becomes high and the water permeability increases, but Physical strength reduction = - aspect 'If the average diameter becomes smaller, the void ratio decreases, and the physical sound is strong, but the water permeability is lowered by 1 'the average diameter is better: =_ below 'better' is 05, Above 4μ1η. The average diameter of the nearly spherical solid part of the spherical knot can be obtained by For example, use a scanning electron microscope to shoot a polymer separation film at 1 〇 _ and measure any arbitrarily: 2°: the diameter of the near-spherical solid fraction above, and calculate the average == Using the shirt image processing device #, find the diameter of the circle (equivalent circle) with the near spherical solid shape. Use the 44 effect® straight (four) for the near spherical solid shape to the two-dimensional network structure. When the layer is used as a separation and separation membrane, B# — ώ j is the surface on which the surface layer is broken. Then: the top layer of the layer is microscopically observed, and the pores can be observed. Because of the three-dimensional worship, therefore, μ Fu continued to control the optimum separation value of the separation of the fine pores on the surface of the ruthenium structure layer, and the surface is controlled according to, for example, in order to make the Λ different according to the substance to be separated, It is better that the resistance of the plant and the higher water permeability coexist. The average pore size is above 1 nm ϊ μπι, and the better is below. 疋 5 nm or more, in water treatment, the average pore diameter is I13556. .doc -23- 200808434 Please range 5~〇·5_, more It is good that (4) the average pore diameter of the surface of the seven 陴 is within this range, it is difficult to cause pollution due to water (4) = = pore: plug, and it is difficult to cause a decrease in water permeability, so that it is possible to use a molecular separation membrane for a longer period of time. In addition, when the η membrane is clogged with pores, the contaminant on the surface of the membrane is removed by so-called backwashing or air washing: the substance to be dyed varies depending on the water source, for example, In the / in the flow or in the lake, etc., the inorganic substances or colloids derived from the earth or the mud at the end of the biological material, and the humus derived from the plants are mentioned. The so-called backwashing is performed by the operation of passing the permeated water or the like in the opposite direction to the normal passing. The air is cleaned and washed by the transport 1 for the hollow fiber. The clearing of the membrane causes the hollow fiber membrane to shake, and shakes off the cleaning operation of the pollutants accumulated on the surface of the membrane. The average pore diameter of the pores on the surface of the three-dimensional network structure layer can be any one or more. It is preferable that the diameter of the hole is measured, and the diameter of the hole is measured, and when the calculation is performed, the number of holes can be counted as a circle. The circle of the area (equal, etc., the diameter of the hole is the diameter of the pore. 0), and the diameter of the equivalent circle is used as the polymer of the present invention. / When filling a Lr hollow fiber membrane with a hollow fiber braided or flat braided separation membrane, it has the advantage of being able to efficiently take advantage of it, so it is in the middle of the module and increases the effective membrane area per unit volume. The hollow fiber membrane is in the upper part of the present invention. 'Preferably satisfy the requirements of the practical 113556.doc -24 - 200808434 permeability, impurity blocking property and the strength and elongation properties. For example, as the permeability of 5 kPa, the pure water permeation performance at 25 ° C is preferably 〇·2〇m / m 2 · hr or more and 1 〇 m 3 / m or less, more preferably 〇 3 〇 • Above 7 m3/m2.hr. When the pure water permeation performance of the polymer separation membrane is less than 〇·2〇 m3/m2*hr, the water permeability is too low, which is not suitable for practical use. And 'opposite to the case where the penetration performance of pure water exceeds 1 〇 m3/m\hr

The pore size of the molecular separation membrane is too large, and the impurity barrier property is lowered, so that it is not preferable. The resistivity of particles having a diameter of 0·843 μm (specifically, μπι polystyrene milk particles) indicates that the average particle size of the impurity barrier property is 0.843. More preferably, the impurity resistance is such that the blocking ratio of the particles of the diameter 843·843 μη is 9〇% or more preferably 95% or more. When the blocking ratio is less than 9%, the performance is too low and it is not suitable for practical use. on. The elongation at break is preferably more than 50%, more preferably 7% by weight: the rupture strength is less than 6 MPa, or the elongation at break is less than 50%, the operability of the treatment of the southern molecular separation membrane It is not good because it is broken, broken, broken, and broken. On the other hand, if the breaking strength or elongation at break becomes larger, the water permeability is lowered, so the breaking strength or elongation at break of the south is separated, and the properties are good; 5, tablets, Lu Rshi + & By the above-mentioned balance of the _ permeability or operating cost of the material of the material, it is determined by the conditions of the pure water permeability, impurities and elongation at break. Wear, k, and strong fracture 2 A polymer separation membrane with sufficient strength and water permeability for use in water treatment, belt II3556.doc * 25 - 200808434 for batteries and blood purification membranes. The pure water permeation performance of the membrane and the barrier ratio of the particles of diameter 〇 843 are determined by manufacturing a small membrane module having a length of 200 mm containing four hollow fiber membranes and performing a filtration test. In the case of a film, the measurement is carried out by cutting a film into a circular shape having a diameter of 43 mm and setting it in a cylindrical shape.

The filter holder (agitated mtrah〇lder UHp_43K manufactured by Advantech Co., Ltd.) was subjected to a filtration test by a filter device formed thereby, and was measured by the small membrane module or the filtration device at a temperature of 25t: Under the condition of a differential pressure of 16 kPa, 'the flow of the permeated water is determined by the membrane transition of the external filtration by one pressure for 1 minute. The amount of permeated water (m3) is converted into a value per unit time (hr) and a unit effective membrane area (m2), and further multiplied by (10) (6) to convert the permeate water amount (m3/m2.hr) at a pressure of 50 kPa. As pure: the value of the permeability performance. Moreover, by using the small-sized membrane module or the over-packing i, the polystyrene latex particles having an average particle diameter of ca μηι are dispersed under the conditions of temperature, filtration, and differential pressure of 16 kPa. The water as the raw water 'H) is filtered by the membrane under external pressure, and the ultraviolet (4) number of fine wavelengths (10) is used to obtain (4) the strong production of the milk shaft in the water (4)' and the latex particles in the water. Concentration (B). The barrier performance was obtained by (ι·Α/Β)χΐ〇^. Further, the pure water permeation performance of the separation membrane can be obtained by converting the value obtained by pumping or pumping 113556.doc •26· 200808434. The water temperature of the ancestral mussels can be changed as appropriate by the viscosity of the liquid (raw water) of the object.祀 According to the rupture strength and fracture extension of the disused separation membrane, for example, the 敎 method is not a special machine, # is measured by μ φ ^ method, and the tensile test is used, 隹-&amp ; h, the length of the mouth is 50 mm, the mouth is subjected to the tensile test method, and the rate changes the strength and elongation of the A, j, and the broken clothes.

:... five times or more of the tensile test, "the average of the breaking strength and the average of the elongation at break, the strength and the elongation at break. The fracture of the separation membrane ▲ 2 has a three-dimensional network structure layer and a spherical structure layer. The I resin-based hazelnut separation membrane can be produced by various methods. For example, a three-dimensional fluororesin-based polymer solution containing a specific hydrophilic south molecule can be formed on a fluororesin layer containing a spherical structure. a method of reticular layer; or two or more (four) (four) polymer solutions (one of which is a resin-based polymer solution containing a specific hydrophilic polymer) simultaneously ejected from a nozzle to form a three-dimensional network structure layer and a ball First, a method of forming a three-dimensional network structure layer containing a fluororesin polymer solution containing a specific hydrophilic polymer on a fluororesin layer containing a spherical structure will be described. In the case of the method, first, a fluororesin-based film (layer) containing a spherical structure is produced. The fluororesin-based polymer is 20 wt%/0 or more and 6 〇 weight 0/〇 or less. The higher concentration of the left and right is dissolved in the poor solvent or good solvent of the polymer at a relatively high temperature, thereby preparing a polymer solution, which is ejected from the nozzle to form a hollow fiber membrane or a flat membrane. And cooling and solidifying in a bath of cooling Π 3556.doc -27- 200808434, thereby separating the phases to form a spherical structure. Here, 'so-called bad> granules' means low temperature below 60 C It is impossible to dissolve 5% by weight or more of the above-mentioned molecules, and is above 60 ° C and below the melting point of the polymer (for example, the point where the polymer is composed of the vinylidene fluoride homopolymer alone is 17 8 C In the temperature range of the left and right), a solvent of the above polymer of 5 wt% or more is dissolved. In contrast, a solvent which dissolves 5 wt% or more of the polymer in a low temperature region of 6 Å or less is defined as a good solvent. The solvent is defined as a non-solvent which does not dissolve or swell the polymer at a high temperature of the melting point of the polymer or the boiling point of the solvent, and is a non-solvent for the fluororesin-based polymer. Cyclohexanone, Fulcone, γ·butyrolactone, methyl isoamyl ketone, dimethyl phthalate, propylene glycol, propylene carbonate, dipropanol, triacetin, etc. Alcohol series, organic carbonates, etc., and the like, even if it is a mixed solvent of a non-solvent and a poor solvent, if it satisfies the definition of a conscience, it is also treated as a poor solvent. Listed Ν-methyl ~ 比略院_, dimethyl ya, dimethyl ethyl: amine, dimethylformamide, methyl ethyl ketone, acetone, tetrahydrocarbazone, and S (4) The base_, the dip, and the mixed solvent of the same. Further, 'as a non-solvent, water, hexane:, alkane: present, toluene, methanol, ethanol, carbon tetrachloride, o-dichlorobenzene, trimethyl : alkene: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol pentyl alcohol, hexanediol, low molecular weight ¥ r - Sa Meng Guan a, poly 4 aliphatic hydrocarbon , 杳面面 hydrocarbon, aliphatic polyol, 芳吞 - 仙~l #彳香私多读, chlorinated hydrocarbon, or Α other organic liquid and its mixed Soluble solvent. In the above production method, it is preferred that the fluororesin-based polymer is at 80 to 170 ° C at a higher concentration of about 20% by weight or more and about 6% by weight or less. At a higher temperature on the left and right, the polymer solution is prepared by dissolving in a poor solvent or a good bath of the polymer. When the concentration of the polymer solution is higher, a polymer separation membrane having higher strength and elongation can be obtained. When the concentration is too high, the porosity of the polymer separation membrane becomes small, and the permeability is lowered. Further, from the viewpoint of easy processing of the molecular solution or film forming property, it is preferred that the solution viscosity is within an appropriate range. Therefore, it is more preferable that the concentration of the polymer solution is 30% by weight or more and 5 Å by weight. /. The following range. In order to cool and solidify the polymer solution into a specific shape such as a hollow fiber membrane or a flat membrane, it is preferred to spray the polymer solution from the nozzle into the cooling bath. In this case, as the cooling liquid used in the cooling bath, it is preferred to use a liquid having a poor solvent or a good solvent at a temperature of 5 to 50 ° C and a concentration of 60 to 100% by weight. In the cooling liquid, in addition to the solvent, the non-solvent may be contained in a range that does not hinder the formation of the spherical structure. Further, when a liquid which is a non-solvent as a main component in the cooling liquid is used, the phase separation due to the non-solvent infiltration is more difficult to obtain the spherical structure than the phase separation caused by the cooling solidification. Further, a solution prepared by dissolving a fluororesin-based polymer in a poor solvent or a good solvent of a cough polymer at a higher temperature by a higher rolling degree is quenched and solidified. In the case of manufacturing a polymer separation membrane, the conditions are different, and the structure of the separation membrane is not a spherical structure, but the dense network structure is a spheroidal structure, and the polymer is appropriately controlled. The combination of the concentration and temperature of the solution, the composition of the solvent used, the composition of the cooling liquid, and the temperature II 3556.doc -29- 200808434.

In the case where the shape of the molecular separation membrane is made into a hollow fiber membrane, the prepared south molecular solution can be ejected from the outer tube of the cannula nozzle, and the hollow portion forming fluid is self-sleeve. The inner tube of the tubular nozzle was sprayed out and cooled and solidified in a cooling bath to form a hollow fiber membrane. In this case, a gas or a liquid can be usually used as the fluid for forming the hollow portion. In the present invention, it is preferred to use a liquid having a poor solvent or a good solvent in a concentration of 60 to 100% by weight, similar to the cooling liquid. Further, the fluid for forming the hollow portion can be red-cooled and then supplied. However, the hollow fiber membrane can be sufficiently solidified only by the cooling ability of the cooling bath, and the fluid for forming the hollow portion can be supplied without being cooled. Further, when the shape of the polymer separation membrane is made into a flat membrane, the prepared polymer solution is ejected from the slit nozzle and solidified in a cooling bath to form a flat membrane. The fluororesin-based film (layer) having a spherical structure obtained as described above is formed (laminated) into a three-dimensional network structure containing an i resin-based high molecular solution containing a specific hydrophilic polymer. The laminating method is not particularly limited to the following, and is a fluorine-containing ruthenium molecular solution containing a specific hydrophilic polymer, which is a fluorine-based film on a film (layer). After that, it is immersed in a coagulation bath, thereby laminating a layer having a three-dimensional structure. This is used to form a fluororesin-based polymer solution containing a specific hydrophilic workmanship, and it is a specific hydrophilic polymer or a gas-polymer polymer. For the solvent, it is preferably 113556.doc -30- 200808434. A good solvent for a fluororesin-based polymer is used as the solvent. As a good solvent for the fluororesin-based polymer, the above-mentioned good solvent can be used. In general, the polymer concentration in the fluororesin-based polymer solution containing a hydrophilic polymer is preferably from 5 to 3 % by weight, more preferably from 10 to 25% by weight. If it is less than 5% by weight, the physical strength of the three-dimensional network structure layer tends to be lowered, and if it exceeds the external weight %, the water permeability tends to decrease.

Further, the fluororesin-based polymer solution containing the hydrophilic polymer has an optimum dissolution temperature depending on the type/concentration of the fluororesin polymer or the hydrophilic polymer, the type of the solvent, and the type/concentration of the following additives. It is different. In order to prepare a stable solution in the polymer solution with good reproducibility, it is preferred that the surface is heated at a temperature below the boiling point of the solvent for several hours to prepare a transparent solution. Further, it is also important to apply a polymer resin-based polymer = temperature at the time of liquid separation to produce a polymer having excellent characteristics. For example, in order to stably produce a polymer separation membrane, it is preferred to control the temperature in such a manner that the stability of the resin-based polymer solution is controlled, and the penetration of the broad agent is prevented. Also, if the fluororesin is high when applied: '...the temperature is too rainy', then the surface part of the spherical structural layer is dissolved, and the sputum molecule is formed on the three-dimensional network structure layer to form a dense layer, resulting in a secret ~v The interface of the Fu layer is easy to reverse, if... The permeability of the separation membrane obtained is reduced. Phase two = \: When the liquid temperature is too low, the "deuteration" of the solution forms a decrease with more defects during the coating process. Therefore, the temperature of the solution at the time of coating must be adjusted according to the performance of the separation membrane or the target. It is an optimum temperature. In the case of a hollow fiber-like polymer separation membrane of k, as a surface of a fluororesin-based hollow fiber membrane (layer) containing a spherical structure of ί 13556.doc 200808434, the coating contains: a hydrophilic The method of polymer-reducing a polymer solution of a polymer is preferably a method of immersing a hollow fiber membrane in a polymer solution or dropping a polymer solution onto a surface of a hollow fiber membrane. Hollow

The method of applying a gas resin 糸 分子 molecular solution containing a specific hydrophilic polymer to the inner surface side of the cut film is preferably a method of injecting the polymer solution into the hollow fiber membrane. At this time, 'as a method of controlling the amount of coating of the polymer solution: 'The following method may be used: a method of controlling the coating of the polymer solution for coating itself; or after immersing the polymer separation membrane in the polymer solution; After the polymer solution is applied to the polymer separation membrane, a part of the attached polymer solution is removed or the air knife is blown off to adjust the coating amount. Further, it is preferred that the condensed towel which is impregnated after coating contains a non-solvent of a resin-based molecule. As the non-solvent, the non-solvent as described above can be preferably used. By contacting the coated resin solution with a non-solvent, the non-solvent induces phase separation to form a three-dimensional network structure layer. After coating the resin-based polymer solution containing a specific hydrophilic polymer and then immersing it in the case of the present invention, it is preferable to use a non-solvent having a relatively small polarity, for example, water, as the coagulation bath. U is used to control the average pore diameter of the pores on the surface of the three-dimensional network structure layer to be within the dry circumference of the Moon King (for example, l nm or more! _ or less), and the hydrophilicity contained in the fluorofusate-based polymer solution is high. The type or concentration of molecules is different, for example, the following method can be employed. In the fluororesin-based polymer solution containing a hydrophilic polymer, 113556.doc -32-200808434 is added to control the pore size additive' when the three-dimensional network structure is formed, or after the two-dimensional network structure is formed, the valley is precipitated. Additives to control the average pore size of the pores on the surface. Examples of the pore size controlling additive include the following organic compounds or inorganic compounds. As the organic compound, a solvent which is dissolved in a gas-resin polymer solution and a non-solvent which causes non-solvent-induced phase separation can be preferably used. For example, a polyethylene-based sputum, a polyethylene Water-soluble polyglycans such as diol, polyethyleneimine, polyacrylic acid, and glucoside, surfactants, glycerin, and saccharides. The inorganic compound is preferably a solvent which is dissolved in a fluororesin-based polymer solution and a non-solvent which causes a non-bath-induced phase separation, and examples thereof include calcium chloride, magnesium chloride, and lithium chloride. Barium sulfate, additives 'by adjusting the coagulation bath, ',. The type, concentration, and temperature of the non-solvent of the addition 4 are not used, and the phase separation speed is controlled, and the phase separation speed is fast, and the surface is uniform. Usually, if it is slower, the average lit of the surface becomes smaller. If the phase separation speed is > non-solvent is added to the valley liquid, the phase separation speed is controlled. The knives and the following are used as the fluororesin system for the production of the present invention. The fluorocarbon wax of the layer and the spherical structure layer has a two-phase structure, and the two or more trees are separated from the knife by the knife, that is, the fluororesin of the molecule. Sorghum: two or more - the species contains a specific hydrophilic high three-dimensional network structure layer and a spherical shape: the nozzle is sprayed out 'at the same time as the manufacturing method, for example, 4 to be explained. The fluororesin-based polymer solution, ruthenium, and ν are a solution of a fluororesin-based polymer U3556.doc ' 33 - 200808434 for forming a three-dimensional network structure and a spherical structure, and are discharged from a nozzle in a layered state.匕 Containing non-solvent, but solidified in cold, to produce a two-layer separation membrane. According to the ★ female method, a three-dimensional network structure layer and a spherical structure layer can be simultaneously formed,

The steps are simple. I Here, the above-mentioned specific hydrophilic polymer is mixed with a fluororesin-based polymer solution for forming a three-dimensional network structure, and after the discharge, a part of the molecular bath is separated from the cold material by a non-solvent-phase separation to form a three-dimensional shape. Web-like surname. In other words, the fluororesin-based polymer is dissolved in a solvent, and the solution containing the aqueous polymer is brought into contact with the coagulation bath to produce a solvent: phase separation to form a three-dimensional network structure. In view of the characteristics of the obtained polymer separation membrane, it is preferable that the amount of the hydrophilic polymer contained in the sub-fourth is the fluorine resin of the three-dimensional network structure, and the gas resin-based high knife is used. The weight of 2 is more than 1% and less than 2% by weight. Further, the fluororesin-based polymer solution for forming a spherical structure can be formed by cooling and solidifying in a cooling bath after being congratulated to form a spherical structure. For example, a fluororesin-based polymer is dissolved at a relatively high temperature (80 to 17 (about rc) at a relatively high concentration of about 20% by weight to 6% by weight or less, and is dissolved in a fluororesin-based polymer. The fluororesin-based polymer, the hydrophilic polymer, the coagulation bath, the poor solvent, and the good solvent used herein may be used as the above-mentioned ones in the form of a poor solvent or a good solvent. In the case of a resin-based polymer solution and a spherical material, when the fluororesin-based polymer solution is simultaneously sprayed, the spray is not particularly limited, for example, in the form of a flat membrane-like polymer separation. It is better to use a double-slit nozzle in which two slits are juxtaposed. 113556.doc -34· 200808434 In the case of a fiber-like polymer separation membrane in the middle of the Hummer, it is better to use a three-tube type spinning The three-dimensional network structure is formed by spraying a fluororesin-based molecular solution from the outer tube of the three-tube spinning nozzle, and the fluororesin-based polymer solution for forming a spherical structure is discharged from the intermediate nozzle, and the hollow portion is hollow. Forming the body from the inner tube And cooling and solidifying in a cooling bath to form a medium-fiber membrane. The manufacturing method of the hollow fiber membrane has a fluid volume for forming a hollow portion, and is less than a cooling solidified liquid when a flat membrane is produced. In addition, it is particularly preferable that the fluororesin-based polymer solution for three-dimensional network structure is ejected from the outer tube and the fluororesin-based polymer solution for spherical structure formation is ejected from the intermediate tube. A three-dimensional network structure layer is disposed on the outer side, and the spherical structure layer is provided with a fluorine fiber: film. Conversely, by forming a three-dimensional network structure, a fluorine-containing February==sub-solution is ejected from the intermediate tube, and the spherical structure is formed. The molecular solution is ejected from the outer tube to form a three-dimensional network, and the spherical structure layer is disposed on the outer middle layer of the film. The polymer of the present invention is separated from the σ#-, and is provided with a raw liquid inlet or The management of the set of ice outlets 4 is infiltrated. For example, in the case where the membrane is used to dry the right 4 + and the "door force" diaphragm is a hollow fiber membrane, the following types are not used. : will plural In the middle of the loss device, and by the poly" or epoxy bundle / stored in the cylindrical end of the two ends or - end to form the assembly structure, knowing the hollow fiber membrane ^ ^ ^ boat recovered through the hollow fiber membrane The type of permeate of the aldehyde surface; or the membrane-like recovery of μ瞑 is fixed through the hollow fiber membrane to the ends of the μμ, and the type of permeate of the surface is removed. In the case of a flat film, the following group 113556.doc -35 ^ 200808434 is exemplified: the flat film is folded into an envelope shape around the liquid collecting tube and wound into a spiral shape, and is housed in a cylindrical container for recycling. The module structure of the permeate passing through the membrane surface; or the flat membrane is disposed on both sides of the liquid collection plate, and the periphery of the flat membrane is water-tightly fixed to the plate, and the neostructure of the permeate passing through the surface of the membrane is recovered. And the membrane modules may be provided with a pressure device at least on the side of the raw liquid or a suction device on the side of the permeate to allow the permeate fluid (especially water) to permeate the surface of the membrane for use as demineralized water or A device for fluid bypass. The device can be used as a suction device by using '7 U using the pressure generated by the water level difference, and a pump or a siphon can be used. : Separation of the membrane separation device from ❹, if it is used for water treatment, it can be used in water treatment, tap water treatment, wastewater treatment, and manufacturing, etc., as water, lake, water, seawater, sewage, and wastewater. A polymer separation membrane for water and a subterranean disk can be used as a separator for a battery in which the positive electrode is oxidized inside the battery. In this case, it is expected that the battery performance can be improved by the ion: high: The durability of the battery is improved due to the high breaking strength. And the polymer separation membrane manufactured by the production method of the present invention, ... the electric base (ion exchange group) is made into a film with a two-effect of the film, or the electrification thinning due to the high breaking strength is improved. And so on. In the case where the polymer separation membrane of the present invention is impregnated with the ion exchange resin, the scorpion exchange membrane is used in a fuel cell, especially when the use of the fuel as a fuel is used. Since the separation is suppressed, it is expected that the swelling caused by the fuel cell performance, the fuel power generated by the high breaking strength, and the like. The improvement of the durability of the electric forbearing is to separate the polymer of the present invention, and it is expected that the film for decontamination of blood waste can be used as a film, and the film of the liquid for purification of the liquid can be removed from the T-day. Increased durability, etc. And the present invention is exemplified below. The present invention is set forth in the examples. The present invention is not limited to the numerical value or film properties of the membrane structure of the separation membrane, and the following method is carried out.曰 曰 以 [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 高分子 高分子 高分子 高分子 高分子 高分子 高分子,, ϊ ϊ 丄疋 丁 丁 丁 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据The average diameter of the pores on the surface of the structural layer] Using the scanning electron microscope described above, the surface portion of the high molecular separation = 6 is photographed by 〇, 〇〇〇 times, according to the photograph, the 敎 three-dimensional network structure table: any 30 The diameter of the pore diameter of the pores, and the average is calculated to obtain the average [average thickness or spherical thickness of the three-dimensional network structure layer of the separation membrane] 卞I13556.doc -37- 200808434 using the above sweep;} junction 4 φ 7 畑The eight-tailed microscope was used to measure the cross-section of the Gaobazi separation membrane at 100 times and 1000 times, and the thickness of each layer was calculated according to the photo below. _ There are two, ♦ mesh structure layers, and the inner layer is provided with a layer of spherical layer The average thickness of the structure of the structure of the large m structure. f. One, the quasi-net is 1000 times the micro-clock day is the π piece, starting from any point η of the outer surface, in relation to the external shavings ;", occupying the first observation of the distance of the spherical knot (10) layer into the thick layer of the 'network structure layer. The distance is a three-dimensional number, thereby calculating the average thickness of the three-dimensional network structure layer In the same way, the average value can also be calculated in the sphere, due to the +-thickness of the octa-amine # layer in the following examples, which is thicker than the spherical structure layer of the microscope. The surface of the inner layer to the opposite side = the method is to collect the photographs from the outer layer of the polymer separation film in a piece of photograph, and measure several photos. Because: S is inside, so use _ times In the cross section of the film of the following example, the distance from the ruthenium molecule is determined as the distance from the surface of the inner layer on the thick side of the polymer separation film, and the average is calculated to determine the polymer. The operation is carried out at 30 places, and the average of the separation from the polymer Thick carcass, average thickness. Following the average thickness, the thick sound of the spherical structure layer, the first, quasi-mesh structure layer [pure water permeability of the separation membrane] is obtained. X is used for the hollow separation of the polymer separation membrane. In the case of the case, a small membrane module having a length of 200 mm of a hollow fiber membrane of 113556.doc -38-200808434 was produced. Further, when the polymer separation membrane was a flat membrane, a circle having a diameter of 43 mm was cut out. The shape is set on the cylindrical over-tank as a filtering device. The pure water filtered by the reverse osmosis membrane is used as the raw water at a temperature of 25. The differential pressure is 16 kpa, and the lower 3' is driven for 1G minutes. The outer pressure (4) of the membrane (4) is used to determine the permeate water (m) ° secondly, the permeate water f (m3) is converted into the unit time (four) and the unit effective membrane area -), and then multiplied by _6) By this, converted into

The enthalpy is a permeate water value (m3/mMir) of 5 GkPa as a pure water permeation performance. [Layer particle blocking property of separation membrane]: In the same manner as described above, the small membrane module in the case where the polymer separation membrane is a hollow fiber membrane, and the filtration device in the case of a flat membrane membrane have an average particle size The water with the diameter of 〇 843 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The concentration of the latex particles in the raw water (4) and the concentration of the latex particles in the permeated water (b) were determined by measuring the ultraviolet absorption coefficient of the second curved 40 nm. The blocking performance (%) is obtained by (l-A/B)xl〇〇. Further, in the measurement of the ultraviolet absorption coefficient at a wavelength of 24 feet, a spectrophotometer ((4) manufactured by Hitachi Hitachi, Ltd.) was used. [Fracture strength and elongation at break of the separation membrane] Using a tensile tester (TENSIL〇N, RTM_1〇〇) (Toyo Β & ι_η (manufactured by T〇y〇 (4) Co., Ltd.), at 50 mm/min Tensile speed 'A tensile test was performed on a sample having a measured length of 5 mm, and the strength and elongation of the broken coat 1 were determined. The sample was changed 'five times to obtain the breaking strength of 113556.doc -39-200808434 The average value of the average elongation at break and the elongation at break. In the case of a flat membrane, the width of the sample is set to 5 mm. ... [Evaluation of Air Washing Durability of Separation Membrane] To evaluate the physical durability of the separation membrane The air washing durability test was carried out as follows: 1500 hollow fiber membranes were bundled and inserted into a cylindrical transparent container having a diameter of 1 〇cm and a length of 1 〇〇cm to produce a membrane module. Fill the membrane module with drinking water, continuously supply air from the lower part of the vessel at 1 〇〇L/min, and air-wash the membrane surface. Continue to wash the air for 122 days, check: ! No break within 22 days. , the 122 days, equivalent to the actual operation: It is used for every 3G minutes! The frequency of the operation of the minute air washing operation is 10 years of air washing. [Assessing the filtration operability of the separation membrane] The air washing durability evaluation towel is not broken. The hollow fiber membrane was subjected to the following operational evaluation. The hollow fiber membrane module was manufactured to have a diameter of 3 cm, a length of π cm, and an effective membrane area of 0.3 m2. Using the hollow fiber membrane module, the lagoon water was used as raw water. The constant flow rate and external pressure are all filtered. The filtration operation is performed by pressurizing the raw water with a pressure pump on the raw water side. The filtration line speed is 3 m/d. Every 120 minutes, it is carried out by a 5 ppm sodium hypochlorite aqueous solution. Backwashing for 30 seconds, followed by 〗 〖minute cleaning with air air to clean the membrane surface. The filtration operation was continuously performed from October 5, 2004 to nA5 days. The measurement filtration operation was started. Filtration to pressure (A) after physical cleaning, and the filtration differential pressure at the end of the filtration operation. I13556.doc •40- 200808434 Filtration, the lower the filtration differential pressure (A) at the beginning of #, the more Low energy In addition, by the formula of (Β-Α)χ(1/Α)χ100, the degree of increase in filtration differential pressure (%) is calculated. The lower the degree of increase in the differential pressure of filtration is, the more stable the operation can be performed, that is, This means that the operability is excellent. Therefore, it means that the lower the filtration differential pressure (A) and the filtration differential pressure rise at the start of the filtration operation, the more stable the operation can be with low energy. The filtration time (120 minutes) was evaluated for operability in a short period of time, and was set to be longer than the filtration time (3 〇 minutes) assumed in the actual operation. <Example 1 > The weight average molecular weight was The 41.70 million vinylidene fluoride homopolymer and the succinimide S 曰 were dissolved at a temperature of i 70 at a ratio of 38% by weight and 62% by weight, respectively. The butyrolactone was used as a hollow portion to form a liquid which was ejected from the nozzle with the polymer solution at a temperature of 2 Torr. The crucible was cured in a cooling bath containing an 80% by weight aqueous solution of 丫-butyrolactone to prepare a hollow fiber membrane containing a spherical structure. Next, 'difluoroethylene ethylene homopolymer having a weight average molecular weight of 284,000 was 14% by weight, and cellulose acetate (tricellulose acetate, 〇^435_758 manufactured by Eas (10) Chemical Co., Ltd.) was 1% by weight, n. -Methyl-2·pyrrolidone is 77% by weight, polyoxyethylene sorbitol liver oil, fatty acid vinegar (manufactured by Sanyo Chemical Industry Co., Ltd.), trade name: 〇〇η^ τ· 2〇C, below Referred to as T_20C), it is 5% by weight, and water is 3 weights 〇/. The ratio was mixed and dissolved at a temperature of 95 t to prepare a polymer solution. The ruthenium film stock solution is uniformly applied to the surface of the hollow fiber membrane containing the spherical structure, and immediately solidified in a water bath, and is formed on the spherical structure layer to form II3556.doc -41 - 200808434 two-dimensional Hollow fiber membrane of the network structure layer. The hollow fiber membrane is obtained, the ice, the external service is 〖340 μηι, the inner diameter is 78〇μηι, and the average of the spherical structure is 3·〇μηι, and the average pore diameter of the three-dimensional network structure layer is 0.04. clothes

Mm two-dimensional network structure layer average 34 μπι, spherical structure layer " sentence occupancy is 246 μιη, pure water permeability performance ',, · · mm · latex particle blocking performance is 99%, 8.2MPa, elongation at break The rate is 88%. Again

Fig. 1 shows an electron micrograph (1000 magnifications) of the cross section of the iridium film and the ruthenium film obtained. Further, Fig. 9 shows that the surface of the hollow fiber membrane (the surface of the three-dimensional network structure layer) is taken as an electron micrograph (60,000 times) which is obtained from α-kg. Only the air wash" strip durability Ping Shi Moss Note The result of the estimate is that the head is not observed at all after 122 days. The result of the operation is 1±# estimation. The result is that the filtration differential pressure is 30 kPa at the beginning of the filtration operation. The filtration differential pressure is 34 kPa at the end of the transition operation, and the filtration differential pressure at the beginning of the 遽 operation is lower. Further, it can be seen that the filtration differential pressure rise is as low as 13 · 3 %, and the operation can be stably performed. Therefore, the hollow fiber membrane obtained is excellent in workability and excellent in workability, so that it can be stably operated for a long period of time. Furthermore, the results of the 5 evaluations are summarized and shown in Table 1. <Example 2> First, an empty fiber membrane including a spherical structure was produced in the same manner as in Example i.氤Ethylene homopolymer secondly, with a weight average molecular weight of 284,000, 113,556.doc -42 - 200808434, 14% by weight, cellulose, and 曰酉夂酉g propionate (manufactured by Eastman Chemical Co., Ltd., CAP482-〇) .5, a 】 壬 3 1 heavy summer %, N-methyl-2 · pyrrolidone is 77% by weight, T- 2 0 C is 5 heavy 〇 / /. 里 / G, water is 3% by weight, Dissolve the mixture at a temperature of 95 ° C, and prepare a solution of the South Molecular Solution.

It is uniformly applied to the surface of the jade fiber membrane containing the ball makeup gentleman M, ', and the mouth structure, and is immediately solidified in a water bath, and is formed on the clock to form a three-dimensional network structure on the spherical structure layer. A hollow fiber membrane of the layer. The hollow fiber membrane of the name is also called the outer diameter of i34Q, the inner diameter is μ, and the average diameter of the crucible is 2·4 array. The average pore diameter of the surface of the three-dimensional network structure layer is (Κ05 _, three-dimensional The average thickness of the network structure layer (4) μπι, the level of the spherical structure layer is 洚3 2 and the degree of uniformity is 251 μηι, the permeability of pure water is 1,0 m /m 'hr 'The blocking performance is 99%, fracture The strength is 8·5 MPa, and the elongation at break is 87%. The evaluation of the durability of the knees of the two-gas wash is suitable for the Azure A 1 m > 1 king < the result is not observed after 122 days. Broken head. Implementation of operational evaluation, the result is: the differential pressure is 28 kPa at the beginning of the operation, the transitional differential pressure is Lica at the end of the operation, and the transition of the transition operation is low. It is understood that the filtration differential pressure rise is as low as 7.1%, and the operation can be carried out stably. Therefore, it is understood that the obtained hollow fiber membrane is excellent in physical durability and excellent in workability, so that it can be stably carried out for a long period of time. Operation. Furthermore, the evaluation results are summarized and shown in the table. <Example 3> First, the same method as in the "Example" was carried out to prepare a hollow fiber membrane of 113556.doc -43-200808434 containing a spherical structure. Secondly, a polyvinylidene fluoride having a weight average of 8% and a molecular weight of 28,400,000 was used. The homopolymer was 14% by weight, cellulose acetate butyrate (manufactured by Eastman Chemical Co., Ltd., CAB5 51-〇.2M!% by weight, N-methyl ketone, each ketone was 77 liters/〇T 20C 5 weight ° / ❻, water is 3% by weight ratio, at a temperature of 95 ° C, 4 such a solution is dissolved to prepare a polymer solution. The film forming solution is uniformly distributed in the 匕 s spherical structure The surface of the hollow fiber membrane is immediately prepared in a water bath to prepare a hollow fiber membrane formed by a three-dimensional network structure layer on the spherical structure layer. The second fiber membrane is obtained in the jin, and the outer diameter is pm. The diameter is 7 (10) ', the average diameter of the spherical structure is 2·8 μιη, and the surface of the three-dimensional network structure layer: the flat sentence hole t is 〇·〇6 μηι 'The average thickness of the three-dimensional network structure layer is 29 μηι, spherical The structural layer of the witch 3 2 has a thousand-thickness of 250 μm, pure water permeability of 1·1 m /m · hr, and the blocking performance is 99. %, the breaking strength is 8.3 Mpa, and the elongation at break is 82%. The endurance evaluation of air washing is carried out, and the result is that no breakage is observed after 122 days. The performance of Bega operation is evaluated as follows: At the beginning of the operation, the filtration differential pressure is 28 kPa. At the end of the filtration operation, the filtration differential pressure is 3i kpa, and the enthalpy difference at the beginning of the filtration operation is low. It can be seen that the filtration difference is as low as 10.7%, and the operation can be stably performed. Therefore, it is understood that the obtained hollow fiber membrane is excellent in physical durability and excellent in workability, so that it can be stably operated for a long period of time. Furthermore, the results of the evaluation are summarized and expressed in the table. 113556.doc -44- 200808434 <Example 4> First, a hollow fiber membrane including a spherical structure was produced in the same manner as in Example 1.

Next, a polyvinyl acetate having a weight average I average molecular i of 284,000 and a vinylidene fluoride homopolymer of 14% by weight and a polymerization degree of 500 (a concentration of 75% ethanol solution, Nacalai Tesque Co., Ltd.) Manufactured as: 125% by weight, N•mercapto-2-pyrrolidone is 76.75 wt%, butyl-2〇 (: 5 weight 0/〇, water 3% by weight, at 95 ° C temperature) The solution of the ruthenium molecule is prepared by mixing and dissolving, and the film forming solution is uniformly applied to the surface of the hollow fiber membrane containing the spherical structure, and immediately solidified in a water bath to form a spherical or sigma layer. Hollow fiber membrane of the reticular structure layer. The hollow fiber membrane obtained has an outer diameter of 1340 μm, an inner diameter of 780 μπι, an average diameter of the spherical structure of 30 μm, and an average pore diameter of the surface of the three-dimensional network structure layer. 0·04 μηι, the average thickness of the three-dimensional network structure layer is 28 μηι, the average thickness of the spherical structure layer is 252 μηι, the permeability of pure water is 〇·6 mW·hr, the barrier property is 99%, and the breaking strength is 88. Mpa, elongation at break is 85%. Air wash durability The results of the evaluation showed that no breaks were observed after 122 days. The operational evaluation was carried out, and the results showed that the filtration differential pressure was 33 kPa at the beginning of the filtration operation, and the filtration and the differential dust were η kpa at the end of the operation. The filtration differential pressure at the beginning of the filtration operation is low. Further, it can be seen that the filtration differential pressure rise is as low as 12.1%, and the operation can be performed stably. Therefore, it is understood that the physical durability of the obtained hollow fiber membrane is excellent 113556.doc - 45- 200808434 ^=Excellent workability, (4) It can be operated stably for a long time. The results of η flattening are summarized and shown in Table 1. <Example 5> W Example 1 The same method was used to produce a spherical shape. Structure

Hollow fiber membrane. Fu I

The vinylidene fluoride homopolymer having a weight average molecular weight of 284,000 is m, ethylene-vinyl acetate vinegar copolymer (containing 68. 5 to 715 mol% of vinyl acetate, manufactured by Dacheng Chemical Co., Ltd. , ρ 堕 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量The polymer solution was prepared by mixing the solution of the mixture, and the film solution was applied to the surface of the hollow fiber membrane of the spherical structure of the bag, and immediately solidified in a water bath to form a spherical structure layer. The hollow fiber membrane obtained from the hollow fiber membrane of the three-dimensional network structure layer has an outer diameter of 1340 μπι, an inner diameter of 78 〇b, an agricultural shape, and an average diameter of 冓5·4 (four), a three-dimensional network structure layer. The average pore diameter of the surface is 〇.〇3 μηι, and the average thickness of the three-dimensional network structure layer is %. (IV) The average thickness of the silk/structure layer is 251, and the permeability of pure water is 〇·5 m3/m2.hr. It is 99%, the breaking strength is 8.7, and the elongation at break is 85%. As a result, no breakage was observed after 122 days. The κ target operation was evaluated by the , target, and the result was: filtration differential pressure at the beginning of the filtration operation: ,, a filtering at the end of the filtration operation, and the differential pressure was 41 kPa. Filtration operation 113556.doc -46- 200808434 The filtration rate at the beginning is low. Moreover, it can be seen that the differential pressure rise is as low as 17.1%, and the operation can be performed stably. Therefore, it is known that the obtained hollow fiber is different. Further, since the operability is also excellent, the operation can be stably performed for a long period of time. Further, the results of the evaluation are summarized and shown in the table. &lt;Example 6 &gt; First, the same method as in Example! A hollow fiber membrane comprising a spherical structure. Secondly, a vinylidene fluoride homopolymer having a weight average molecular weight of 284,000 is a weight percent, a vinylpyrrolidone having a weight average molecular weight of 420,000, and a methyl acrylate containing no Copolymer (copolymer molar ratio: Μ, hereinafter referred to as PMMA-co-PVp, ^) tongue 0/ χτ rvu is 1% by weight, N_methyl-2_pyrrolidone is 77% by weight, T-20C 5% by weight and 3% by weight of water, at 95% [The mixture is dissolved at the temperature to prepare a polymer solution. The film forming solution is uniformly applied to the surface of the hollow fiber membrane containing the spherical structure, and immediately solidified in a water bath'. The hollow fiber membrane is formed with a three-dimensional network structure layer. The obtained hollow fiber membrane has an outer diameter of 134 〇 _, an inner diameter of (10) μ spherical shape, and an average direct control of the mouth 2 is 2·5 array, three-dimensional The average pore diameter of the surface of the network structure layer is 〇.〇3 μηι, the average thickness of the three-dimensional network structure layer is Β spherical, and the average thickness of the mouth layer is 246 哗, and the permeability of pure water is 〇.4n^/ m, hr, the resistance performance is burning, the breaking strength is 8.3 MPa, and the elongation at break is 88%. The air washing durability evaluation was carried out, and the result was that no break was observed after 122 days. 113556.doc -47- 200808434 was observed. Λ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ It can be seen that the differential pressure rise = 21.1%, and the operation can be performed stably. Therefore, it is understood that the obtained hollow fiber membrane has excellent physical durability and excellent operability, so that it can be stably operated for a long period of time. again

The results of the evaluation are summarized and shown in Table 1. <Example 7> First, a hollow fiber membrane containing a sphere was produced in the same manner as in the embodiment. Secluded &lt; except that T-20C is not added, and (i) base ~ than smoldering ketone is changed to 82 liters. Other than the other examples! A polymer solution was prepared in the same manner, and a hollow fiber membrane in which a three-dimensional network structure layer was formed on the spherical structure layer was produced in the same manner as in Example! / The obtained hollow fiber membrane has an outer diameter of m"m, an inner diameter of 78 yoke, an average diameter of the spherical structure of 25 μηη, and a thousand-to-average pore diameter of the surface of the three (four)-shaped structural layer (4) 2 μΠ1, three-dimensional network The average thickness of the structural layer is 25, the average thickness of the structural layer is 255 _, the pure water permeability is = 'blocking performance is '%, the breaking strength is Wa, the breaking: the long rate is 85%, and the water permeability is lower than the implementation. Example ι film. Only % air washing durability evaluation, Shi observed the broken sputum. - After 122 days, the operation was not implemented at all. The result is: (4) The 开始 遂 113556.doc -48 , 200808434 is 48 kPa 'filtering operation at the end of the filtration differential pressure is 6 〇 kpa, low penetration 'Therefore, the filtration differential pressure at the beginning of the filtration operation is slightly higher than the example of the vehicle and the middle 'can be seen that the filtration differential pressure rises as low as 25 〇 Therefore, it is understood that the hollow fiber membrane obtained has a slightly higher filtration differential pressure at the start of the filtration operation, but is excellent in physical durability and excellent in workability, and can be stabilized for a long period of time. Operation at the ground. Again, the results of the assessment The results are shown in Table 2. 〈Example 8&gt; First, a hollow fiber membrane containing a spherical structure was produced in the same manner as in Example 1. Further, Next, it was prepared in the same manner as in Example 1. The polymer and the sputum were separated, and a hollow fiber membrane having a three-dimensional network structure layer formed on the spherical structure core was produced in the same manner as in Example 1. The coated vehicle was a multi-molecular solution to make The three-dimensional network structure layer is thicker than the hollow fiber membrane obtained in the embodiment ,^, the outer diameter of the 1400 1400 1400 array, the inner diameter is 780 μΐϋ 'the average diameter of the spherical structure is 夕亚仏, one, the mouth is 2· 5 The average pore size of the surface of the three-dimensional network structure layer is 0,02 μηι, and the average thickness of the three-dimensional network layer is 60.

Pm, the average thickness of the spherical structure is Α ft9 3/ 2 u 1 and the degree is 25〇 (four), the permeability of pure water is 〇_2 m /m · hr, and the barrier performance is 9 &amp; 8.3 MPa, the elongation at break was 87%, which was the three-dimensional net skin name, and the average thickness of the ° layer was thicker than that of the film of Example 1. Throughout the air washing durability evaluation, 1 surname ^, ν, σ fruit was 122 days and no broken ends were observed at all. 113556.doc •49- 200808434 Implementation of operational evaluation, /, the result is · filtration, nuclear filter at the beginning of the differential pressure is 5 5 kP a 'over '^ p, / after the end of the filter, the differential pressure is 67 kPa The average house earning degree of the three-dimensional network structure layer is relatively thick, so the filter difference at the beginning of the filtering operation is slightly higher than that of the first embodiment. Α &quot; In the case, it can be seen that the filtration differential pressure rise is as low as 218%, and the operation can be performed stably. Therefore, it is possible to know the shame; ^ / 曰 , , and the hollow fiber membrane of the hall, although the transition pressure at the beginning of the filtration operation is slightly higher, the physical durability is excellent, and the operability is excellent.

Therefore, it is possible to operate stably for a long time. Furthermore, the results of the evaluation are summarized and shown in Table 2. &lt;Example 9&gt; A hollow fiber membrane comprising a spherical structure was produced in the same manner as in Example 1. Further, by using a conventional method, polyethylene glycol methyl ether methacrylate (Ahidch's t-made average molecular weight of 475) and ? The isopropyl acrylate was subjected to random copolymerization to prepare a random copolymer having a copolymerized molar ratio of 55:45 and a weight average molecular weight of 45,000 (hereinafter, abbreviated as pMMA = PEGMA). Specifically, 12% by weight of polyethylene glycol formamidine methacrylate and 18% by weight of decyl decyl acrylate, 699% by weight of ethyl acetate as a solvent, and 0.1% by weight of The polymerization initiator 2,2,·azobisisobutyronitrile was polymerized at a polymerization temperature of 60 t: and a polymerization time of 4 hours. Secondly, the vinylidene fluoride homopolymer having a weight average molecular weight of 284,000 is i 4 wt%, PMMA-c〇-PEGM^% by weight, and the group methyl-2-pyrrole is 77 wt%, T- The ratio of 20C to 5% by weight and water to 3% by weight, 113556.doc -50-200808434, the mixture was dissolved at a temperature of 95C to prepare a polymer solution. The film forming solution was applied uniformly to the surface of the reticular film containing the spherical structure, and immediately solidified in a water bath. A hollow fiber membrane having a three-dimensional network structure layer formed on the spherical structure layer was produced. The obtained hollow fiber membrane has an outer diameter of 14 〇〇, an inner diameter of _μ, and an average diameter of 2·5 _, and the average pore diameter of the surface of the three-dimensional network structure layer is 〇·〇. The average thickness of the 5 μ 2D, μ-quasi-structure layer is 31 μπι 'the average of the spherical structure layer is 3 2 Ί ^ sub-degree 252 , the pure water permeability is hr, the resistance δ performance is 99%, fracture The strength is 8.4 Mpa, and the elongation at break is 87%. 空气 The air-washing durability is applied, and the results are as follows: 122 days later, no broken ends were observed at all. Operational evaluation, basin gentleman · ',,,,. The result is · filtration differential pressure at the beginning of the filtration operation ^ 30 wide: filtration, end of operation (four) differential pressure (four) heart, filter operation after the beginning of the operation In addition, it is known that the filtration differential pressure is rhythm and can be stably operated. ' Therefore, it can be seen that the hollow fiber membranes of the hemispheres and the chambers have different physical durability, and the operability is excellent, so that it can be used for a long time. The operation is carried out steadily. In addition, the results of the evaluation are recorded as M-N, which is shown in Table 2. &lt;Implementation Example 10&gt; First, a hollow fiber membrane containing a spherical structure was produced in the same manner as in Example 又. Further, a polypropylene glycol methyl ether methacrylate was obtained by a conventional method (manufactured by Aldrich Co., Ltd., Helmet) Random average copolymerization of methyl methacrylate 113556.doc 200808434 was carried out to prepare a random copolymer having a copolymerized molar ratio of 55:45 and a weight average molecular weight of 38,000 (hereinafter referred to as pMMA). -C0_

PpGA). Specifically, 14% by weight of polypropylene glycol methyl ether methacrylate, 16% by weight of methyl propyl methacrylate, and 69.9% by weight of the condensed product are exemplified, and 〇·1 The % of 2,^,_azobisisobutyronitrile as a polymerization initiator was reset and polymerized at a polymerization temperature of 6 (TC, polymerization time of 5 hours).

Next, the vinylidene fluoride homopolymer having a weight average molecular weight of 284,000 was 14% by weight, ΡΜΜΑ·ε〇_ρρ (3ΑΛ 1% by weight, and n-methyl·2·pyrrolidone was 77% by weight, T-20C is a ratio of 5% by weight and water of 3% by weight, and is 95. The mixture is dissolved at a temperature of 〇 to prepare a polymer solution. The film forming solution is uniformly applied to a hollow containing a spherical structure. The surface of the fiber membrane is immediately solidified in a water bath. A hollow fiber membrane is formed on the spherical structure layer to form a three-dimensional network structure layer. The obtained hollow fiber membrane has an outer diameter of 14 〇〇 and an inner diameter of The average diameter of the 78〇, 衣, and .D structures is 2.5 μιη 'the surface of the three-dimensional network structure layer w = U彳二 is 〇·〇6 μηι, and the average thickness of the two-dimensional network structure layer is μ I' ^ The average thickness of the structural layer is 251 (four), and the permeation performance of pure water is as shown in column 6 as the 'resistance performance is tearing. The elongation at break of strong Mpa is 88%. The breakage of the durability of the shell fine * empty strip is observed. The result is that after 122 days, the filtration pressure difference is 3 8 kP a at the beginning of the complete unfiltering operation, filtration, operation For the implementation of the operational evaluation, the result is: 3 3 kPa, the filtration difference at the end of the filtration operation 113556.doc -52 - 200808434 It can be seen that the filtration differential pressure rise is as low as the filtration pressure at the beginning is lower 1 5 · 1 Since the hollow fiber membrane obtained is excellent in physical durability and excellent in workability, it can be stably operated for a long period of time. Further, the results of the evaluation are summarized and expressed in the table. 2. In Example 11 &gt; A film comprising a spherical structure was produced in the same manner as in Example! Next, a dimerized ethylene glycol homopolymer having a weight average molecular weight of 284,000 was used as a double i %, cellulose acetate vinegar (same as the user in the examples) is 75% by weight of 重N/methyl-2-pyrrolidone, 5% by weight of T_2〇c, and 3% by weight of water' The polymer solution is prepared by dissolving the mixture at a temperature of 9th generation, and the film forming solution is applied to the surface of the hollow fiber membrane containing the spherical structure, and is immediately solidified in a water bath to produce; 2, formed on the structure Hollow fiber membrane of the network structure layer. The obtained hollow fiber membrane has an outer diameter of 134 〇, an inner diameter of _, and an average diameter of a spherical structure of 2.5 (four), and an average pore diameter of the surface of the three-dimensional network structure layer. The average thickness of the three-dimensional network structure layer is 0.02 μπι′ Μ·the average thickness of the spherical structure layer is 244 _, the permeability of pure water is 99%, the breaking strength is 81%, and the elongation at break is 75%. The air washing durability evaluation was carried out. The result was that the broken head was observed. 』Wang Wanghe implemented the operational evaluation' The result is: filtration, the beginning of the operation, the difference is H3556.doc -53- 200808434 is 52 kPa ' At the end of the filtration operation, the filtration differential pressure was 67, and the water permeability was low, and the filtration differential pressure at the start of the filtration operation was slightly higher than that of Example 1. Among them, the filtration and the differential pressure rise are as low as 28.8%, and the operation can be stably performed. Therefore, it is understood that the obtained hollow fiber membrane ′ has a slightly higher filtration differential pressure at the start of the filtration operation, but is excellent in physical durability. Excellent operability,

Therefore, it is possible to operate stably for a long time. Furthermore, the results of the evaluation are summarized and shown in Table 2. &lt;Comparative Example 1 &gt; θ is 25 wt% of a vinylidene fluoride homopolymer having a weight average molecular weight of 284,000, and cellulose acetate (same as the user in the Example) is 2.5 畺/〇N The ratio of methyl-2-° to η ketone was 64.5 wt%, T-20C was 5% by weight, and water was 3% by weight, at 95. The mixture was dissolved and dissolved at a temperature of ’ to prepare a polymer solution. 2 g% by weight of methyl-2 broth (4) was used as a hollow portion to form a liquid, which was ejected from the nozzle with the polymer solution, and solidified in a water bath at a temperature of 4 (TC), and was produced only by a three-dimensional network. The hollow fiber membrane is composed of the structure. The obtained hollow fiber membrane has an outer diameter of 1340 μπι and an inner diameter of 78〇μηι, the average pore diameter of the surface of the two-dimensional network structure layer is 〇, and the average thickness of the three-dimensional network structure layer is 28G μπι. The pure water permeation performance is 98% for 〇4 mWhr', the breaking strength is 2 2 Μρ&, and the elongation at break is 28%. Since the obtained hollow fiber membrane does not have a spherical structural layer, the breaking strength is The film with a low elongation at break. The air washing durability evaluation was carried out. The result was that the head was observed 113 days later, and the number of broken ends was observed after 20 days. When the breakage was observed in the evaluation of the washing durability, it was judged that it was difficult to carry out the long-term operation, and the operability evaluation was not performed. Further, the evaluation results were summarized and shown in Table 3. <Comparative Example 2> Production of the ball shape First, a hollow fiber membrane was produced in the same manner as in Example 1.

Secondly, the weight average molecular weight is 284,000 m ethylene dimer: 15% by weight, N methyl-2·pyrrolidone is 77% by weight, T-20C is 5% by weight, and water is 3% by weight. The mixture was dissolved at a temperature of 95 ° C to prepare a polymer solution. This film-forming stock solution was uniformly applied to the surface of the hollow fiber membrane containing the spherical structure, and immediately (4) was formed on the spherical structure layer to form a hollow fiber membrane having a three-dimensional network structure layer formed thereon. The average pore diameter is 0.05 μηι, the average thickness of the three-dimensional network structure layer is 3〇', the average thickness of the f-like structural layer is 25〇μηι, the pure water permeability is 10 m3/m, hr, the barrier property is 98%, and the fracture The strength is 9 2 Mpa and the elongation at break is 80%. The obtained hollow fiber membrane has an outer diameter of 134 〇 _, an inner diameter of an 烬 spherical structure, and an average diameter of 2. 〇μηι, the surface of the three-dimensional network structure layer is subjected to air washing durability evaluation, and the result is 122 days. No broken ends were observed at all. The operability evaluation was carried out, and the result was that the filtration differential pressure at the start of the filtration operation was 27 kPa, and the filtration differential pressure at the end of the filtration operation was 7 〇 kpa, and the filtration differential pressure at the start of the filtration operation was low. However, it can be seen that the filtration differential pressure rise is as high as H3556.doc -55 - 200808434 160% 'unable to operate stably. This shows that the obtained hollow fiber membrane is excellent in physical durability and has a poor operation, so that it cannot be stably operated for a long period of time. Furthermore, the results of the sweat evaluation are summarized and shown in Table 3. &lt;Comparative Example 3&gt; First, a hollow fiber membrane including a spherical structure was produced in the same manner as in Example 1. φ, its _ person, 14 wt% of a vinylidene fluoride homopolymer having a weight average molecular weight of 284,000, and polymethyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd., Dianal BR-85) is 1 The weight 〇/0, N-methylpyrrolidone is 77 s s %, butyl 〇 〇 (: 5% by weight, water is 3 重量 %), the mixture is dissolved at a temperature of 95 C, and is prepared. The polymer solution is uniformly applied to the surface of the hollow fiber membrane including the spherical structure, and is immediately solidified by water cooling, and a hollow fiber membrane having a three-dimensional network structure layer formed on the spherical structure layer is prepared. Φ The hollow fiber membrane obtained has an outer diameter of 1340 μηι and an inner diameter of 780.

The average diameter of the Pm 'spherical structure is 厶5, the average pore size of the surface of the three-dimensional network structure layer is 0·04 μηι, and the average thickness of the three-dimensional network structure layer is 23'. The average thickness of the spherical structure layer is 257, pure The water permeability is 〇·8 m3/m2·!!!· 'The barrier performance is 99%, the breaking strength is 8.7 MPa, and the elongation at break is 84%. The air washing durability evaluation was carried out, and the result was that the broken head was not observed at all after 122 days. m operability evaluation, the result is: the filtration differential pressure 113556.doc * 56 - 200808434 is 36 kPa at the beginning of the filtration operation, and the 遽 difference is (9) at the end of the filtration operation, and the filtration differential pressure at the beginning of the operation is compared low. However, it can be seen that the filtration differential pressure rise is as high as 66.7%, and the operation cannot be performed stably. Therefore, it is known that the total secret of the bamboo is the best. operating. Furthermore, the results of the evaluation are summarized and shown in Table 3. &lt;Comparative Example 4&gt;

In the same manner as in Example 1, a hollow fiber and a ruthenium film having a spherical structure were produced, and the _U was made to have an average thickness of 28 G _ to slightly increase the outer shape. In the hollow fiber membrane, evaluation was carried out in the case where a three-dimensional network structure layer was not formed on the spherical structure layer. The obtained hollow fiber membrane has an outer diameter of 1340 μ-spherical structure of 25 / "780 7 7 straight 2 2 5 5 μιη, and the average thickness of the spherical structural layer is 280 μ ΐΏ, pure water permeability It is 2〇, the barrier property is 97/〇' breaking strength is 8.3 Mpa, and the elongation at break is μ%. The air washing durability evaluation is carried out, and the result is that the broken head is completely observed after 122 days. The result is that the filtration pressure is 15 kPa at the beginning of the filtration operation, and the filtration differential pressure is 148 hearts at the end of the filtration operation. The filtration is performed at the beginning of the operation, and the dust is low. The filtration differential pressure rise was as high as 887%, and the operation could not be performed stably. Therefore, it was found that the hollow fiber membrane obtained was excellent in physical durability, but the workability was poor, so that it was impossible to operate stably for a long time. The results of the assessment are summarized and presented in Table 3. Π 3556.doc -57- 200808434

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Claims (1)

200808434 X. Patent application scope: 1 · A southern molecular separation membrane characterized in that it is a fluororesin-based polymer separation membrane containing a three-dimensional network structure layer and a spherical structure layer, and the three-dimensional network structure layer contains hydrophilicity The polymer fluororesin-based polymer composition' includes a cellulose ester, a fatty acid vinyl ester, vinyl pyrrolidone, ethylene oxide, and propylene oxide as a polymerization component, and is substantially water. Insoluble. 2. In the fluororesin-based polymer composition constituting the three-dimensional network structure layer, the amount of the hydrophilic polymer is 2 in the fluororesin-based polymer. More than % by weight and less than 2% by weight. 3. The molecular separation membrane of the present invention, wherein the hydrophilic polymer contains cellulose _ and/or fatty acid _ as a polymer in the resin-based polymer composition constituting the three-dimensional network structure layer. A hydrophilic polymer which is a component and is substantially water-insoluble. 4. The polymer separation membrane of the present invention, wherein the hydrophilic polymer is contained in the fluororesin-based polymer composition constituting the three-dimensional network structure layer, and comprises cellulose acetate _ and cellulose vinegar (tetra) propionic acid. The cellulose acetate is at least one selected from the group consisting of acid hydrazine and vinyl acetate vinegar as a polymerization component and substantially water-insoluble hydrophilic polymer. 5. The polymer separation membrane of claim 1 wherein: the spherical structure layer does not substantially "see a water-based polymer" but contains a fluororesin-based polymer. 1: The two-molecule separation membrane of claim 1 The outermost layer has a three-dimensional network structure layer. 113556.doc 200808434 7. The polymer separation membrane of claim 1, wherein the average diameter of the nearly spherical solid portion present in the spherical structure layer is 〇1 μηη or more and 5 μιη 8. The two-molecule separation membrane of claim 1, wherein the average pore diameter of the pores on the surface of the three-dimensional network structure layer is 1 nm or more and 1 or less. 9. The polymer separation membrane according to the claim , Hollow-fiber separation membrane, and the permeability of pure water at 50 kPa and 25T: is below 〇2〇m3/m2.hr and below 1〇m3/m2.hr, the breaking strength is above 6 Mpa, and the elongation at break It is 50% or more. 10. A membrane module which uses the polymer separation membrane of claim 1 as a filter or a membrane. 11. A method for producing a molecular separation membrane, characterized in that it is attached to Surface coating of a spherical structural layer containing a chaotic resin polymer A fluororesin-based high-knife solution containing at least one of a cellulose ester, a fatty acid vinyl ester, a vinyl pyrrolidone, an ethylene oxide, and a propylene oxide as a hydrophilic polymer which is polymerized into a knife and is water-insoluble in quality. And solidifying in a coagulation bath, thereby forming a three-dimensional network structure layer on the surface of the spherical structure layer. 12. A method for producing a polymer separation membrane according to claim π, which comprises a fluororesin polymer The spherical structure layer substantially does not contain a hydrophilic polymer. A method for producing a knife-removing membrane characterized by containing a cellulose ester, a fatty acid vinyl ester, a vinyl pyrrolidone, and an ethylene oxide. And at least one of the at least one selected from the group consisting of propylene oxide and the insoluble hydrophilic polymer having high hydrophilicity: 113556.doc 200808434 The fluororesin polymer solution and substantially no hydrophilic polymer The fluororesin-based polymer solution is simultaneously ejected from the nozzle and solidified in the coagulation bath, thereby forming a gas containing the hydrophilic polymer. A three-dimensional network structure layer of a polymer and a laminated film comprising a spherical structure layer of a fluororesin polymer. The method for producing a polymer separation membrane according to claim 11 or 13, wherein the method comprises a method for producing a polymer separation membrane In the fluororesin-based polymer solution of the molecule, the amount of the hydrophilic polymer is ≥ 2% by weight or more and less than 20% by weight based on the amount of the fluororesin-based polymer contained in the solution. In the fluororesin-based polymer solution containing a hydrophilic polymer, the hydrophilic polymer mainly contains a cellulose ester and/or a fatty acid vinyl ester as a polymerization component, and It is essentially water insoluble. 16. The method for producing a polymer separation membrane according to claim 11 or 13, wherein in the fluororesin-based polymer solution containing a hydrophilic polymer, the hydrophilic high φ molecular system mainly comprises cellulose acetate and cellulose. Acetate propionate, cellulose acetate butyrate, and vinyl acetate are at least one selected from the group consisting of a polymerized knife and a hydrophilic polymer which is water-insoluble on the babe. The method for producing a polymer separation membrane according to claim 1 or 13, wherein the coagulation bath which is in phase contact with the coated or discharged hydrophilic polymer-containing fluororesin-based polymer contains a high polarity Non-solvent. 113556. doc 200808434 VII. Designated representative map: (1) The representative representative of the case is: (2). (2) A brief description of the symbol of the representative figure: (No description of the symbol of the component) 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 113556.doc