JP2017164698A - Adsorbent with enhanced ratio of polymer brush and method for removing useful or harmful material using the adsorbent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fibrous adsorbent capable of exhibiting stable performance even in a high speed treatment for overcoming a situation that a separation conventional function fibers using a radiation graft polymerization, especially an ion exchange fiber or a chelate fiber cannot exhibit stable adsorption performance when absorbing ion existing at trace quantity or large sized molecule at high speed and satisfying requirements for enhancement of adsorption performance in a carrying type adsorption material, a manufacturing method and an application method thereof.SOLUTION: A fibrous adsorbent with enhanced ratio of a polymer brush is manufactured by emulsion graft polymerization or gas phase graft polymerization. Adsorption performance is enhanced by enhancing ratio of the polymer brush.SELECTED DRAWING: Figure 1

Description

  The radiation graft polymerization method has been used in various fields, and its usefulness has been demonstrated. Since ion exchange groups and chelate groups can be introduced into polymer materials such as existing membranes and fibers, utilization methods are taking advantage of physical properties such as the shape of the polymer materials. Among polymer products, fiber is the most frequently used material for radiation graft polymerization because of its high adsorption rate and good moldability. When a fiber is selected as the base material for radiation graft polymerization, a method of use has been proposed that takes advantage of such features as a high adsorption rate due to a large surface area, easy molding, and low water resistance. The present invention relates to a separation functional material using a radiation graft polymerization method, and particularly to a separation functional fiber material.

  In the present invention, the radiation graft polymerization method, which is a method of introducing a graft chain having an ion exchange group and / or a chelate group, irradiates a substrate with ionizing radiation such as gamma rays or electron beams, and the substrate surface or group. This is a method of growing a graft chain from a substrate by polymerizing a polymerizable monomer (hereinafter referred to as “monomer”) using radicals generated in the material. A characteristic of the radiation graft polymerization method is that radicals can be easily generated not only on the surface of the substrate but also inside the substrate by irradiation with radiation. Therefore, since the monomer can be polymerized not only on the surface of the base material but also inside the base material, the number of graft chains introduced into the base material increases, and thus the number of functional groups introduced into the base material also increases.

  Graft means “grafting” and represents a state where one end of the graft chain is fixed to the base material and the other end is a free end that is not fixed. Since the graft chains have such morphological characteristics, small ions to large molecules can easily enter between the graft chains. This is a feature that is greatly different from that of an ion exchange resin having a crosslinked structure. In particular, when a fixed charge such as an ion exchange group or a chelate group is present in the graft chain, the fixed charges repel each other electrostatically, so that the graft chain elongates and the graft chains repel each other. For this reason, a wide space is formed between the graft chains. Some graft chains in the vicinity of the substrate surface remain in the substrate (referred to as polymer roots), but there are those that exit from the substrate surface, which are referred to as polymer brushes.

  The radiation graft polymerization method can freely use an existing organic polymer material as a base material, but the fiber base material has a feature that the adsorption rate is high because of its large surface area. Furthermore, it has extremely excellent features such as easy molding and low water resistance, and is a material suitable as a separation functional material.

  Hereinafter, the manufacturing process will be described by taking a fiber as an example and taking a fibrous adsorbent by a radiation graft polymerization method, particularly a fibrous adsorbent having an ion exchange group as an example. First, the substrate fiber for radiation graft polymerization is selected from commercially available fibers, and then irradiated with radiation. In this step, irradiation with radiation is performed while cooling the fiber in an inert gas atmosphere such as nitrogen. Next, there is a graft polymerization step in which a monomer having an ion exchange group is graft-polymerized, or a monomer that can be converted into these functional groups is graft-polymerized in a liquid phase. Here, if the monomer itself has no functional group and can be introduced by a secondary reaction after graft polymerization, a functional reaction for introducing a functional group is performed by further performing a chemical reaction for introducing the functional group. Is added.

  As the usable fiber, it is preferable that the radical generation efficiency is high and the radiation degradation and the environmental degradation are small, and it can be selected from commercially available fibers. These are generally hydrophobic for durability. Existing general-purpose polymers such as polyolefin represented by polyethylene, nylon and polyester are also hydrophobic to some extent, and can be suitably used as the fiber material of the present invention.

  As radiation used industrially in the radiation irradiation process, there are gamma rays and electron beams. Since the energy of these radiations is usually several hundred keV or more, radicals are uniformly generated even inside the fibers.

  Graft polymerization is performed by bringing a monomer having a double bond into contact with the irradiated fiber base material. Usually, pre-irradiation liquid phase grafting in which polymerization is performed while the irradiated base fiber is immersed in the monomer solution is generally performed.

  Here, many of the monomers having an ion exchange group are water-soluble. Even if these monomers are graft-polymerized to a hydrophobic general-purpose polymer fiber, no graft polymerization is performed at all or only a very low graft ratio is obtained. In particular, a monomer having a strongly acidic cation exchange group or a strongly basic anion exchange group that is important for ion exchange has a very high hydrophilicity, so that it is difficult to perform graft polymerization with the monomer alone. The graft ratio is a value defined by the weight increase rate before and after graft polymerization.

  In such a case, usually a graft polymerization of a mixed monomer of a hydrophilic monomer and an auxiliary monomer is performed. For example, it is difficult to graft-polymerize vinylbenzyltrimethylammonium chloride (VBTAC) having a quaternary ammonium group alone, but it is a nonionic hydrophilic monomer and can be graft-polymerized alone. It has been proposed to perform graft polymerization using a mixed monomer in combination with (Patent Document 1). In this case, although graft polymerization is possible, since the auxiliary monomer is also graft polymerized at the same time, there has been a problem that the target quaternary ammonium group introduction amount becomes small. For example, in the case of co-graft polymerization using a mixed monomer of VBTAC and HEMA, a graft ratio of 40 to 50% can be easily obtained. A value of 50% for the graft ratio is calculated as a large value of 1.5 mmol / g if VBTAC alone is used, and is easily used for ion exchange treatment. However, in practice, the ion exchange capacity reaches only about 0.5 meq / g due to the presence of auxiliary monomers. As a result, it can be applied only to a technical field that can be used even if the ion exchange capacity is small.

  When a monomer that does not have an ion exchange group per se as a monomer after radiation irradiation but can be converted to an ion exchange group is graft-polymerized, the monomer generally has a hydrophobic property, and the hydrophobic base fiber is On the other hand, graft polymerization is easy, and a high graft ratio of 100% or more can be easily obtained. Therefore, a high ion exchange capacity can be obtained by the subsequent functional group introduction reaction. A typical example of such a monomer is glycidyl methacrylate (GMA). Assuming that graft polymerization of GMA is performed and a graft ratio of 100% is obtained and then a sulfonic acid group having a high introduction ratio is introduced, a large ion exchange capacity of 2.5 meq / g is obtained in calculation (Patent Document 2). ).

  In this way, in the radiation graft polymerization method, the energy of the gamma rays and electron beams used is high, so radicals can be generated even inside the fiber substrate. Unlike other surface modification methods, functional groups can be incorporated into the substrate. Although it does not have a functional group by itself, it has a feature that a large functional group concentration can be obtained by introducing a functional group in a secondary reaction.

  Removal of ions in water using ion-exchange fibers produced by radiation graft polymerization is achieved by trapping the adsorbed ions on the fiber surface and diffusing and moving the trapped ions into the fiber. The trapping of the adsorbed ions by the fiber is dominated by the electrostatic attractive force between the charged layer and the adsorbed metal ion formed from the peripheral edge of the fiber toward the liquid. The larger the layer, the more the adsorbed ion is captured. Is advantageous. The trapped ions diffuse into the fiber along the graft chains having ion exchange groups. The larger the ion exchange capacity, the faster the trapped ions diffuse into the fiber and the ion adsorption rate is maintained. In addition, since the charged layer does not affect the water flow resistance, the pressure loss is kept small.

  Therefore, in order to make full use of the features of the fibrous adsorbent by the radiation graft polymerization method, by increasing the thickness of the charged layer formed on the peripheral edge of the fiber, ions in the water can be adsorbed quickly, and the adsorbed ions A large ion exchange capacity is required to diffuse and move the particles into the fiber.

  A large ion exchange capacity can be obtained by increasing the graft ratio. At a large graft ratio, the graft chain partially grows outside the fiber, but most grows inside the fiber. Although the fiber diameter increases and the voids also increase, the proportion of the charged layer that is important for trapping ions does not increase significantly, and the ions that pass through the voids between the fibers and leak into the treatment liquid are not greatly reduced.

  The ion exchange resin is usually used in a packed column. Therefore, the problem is clarified by examining the case where the ion exchange fiber is cut and packed in a column and subjected to the same ion exchange treatment as that of the ion exchange resin.

  When the column is filled with an ion exchanger, the packing rate is completely different between the ion exchange resin and the ion exchange fiber. The ion-exchange fiber is at most a filling rate of 30% and the voids occupy 60% or more. Since the packing rate of ion exchange resins exceeds 60%, assuming that the ion exchange capacities per weight of both are almost the same, the ion exchange capacities per column unit volume of the ion exchange fibers are less than 1/2 of the resin. Become. Since the fiber has a large porosity, the water flow resistance is very small and the surface area is large, so there is a tendency to increase the flow rate several times that of the ion exchange resin. However, when the liquid flow treatment is performed at high speed, the treated water quality is not stable. This tendency is recognized.

  When ion exchange fibers are used in a column system, it is difficult to exceed ion exchange resins in terms of ion exchange capacity. For this reason, in many cases, not the same usage method, but a usage method that takes advantage of its features has been studied. For example, the idea of winding a fiber around a perforated core and molding it into a wind filter, and taking advantage of the particle removal performance of the filter and the ion exchange function of the fiber itself is a typical example of such use. . However, the flow rate of the wind filter is SV2000 or more with respect to the fiber, and the ion exchange rate is too fast, and it is hardly expected to remove ions.

  Under such circumstances, it is preferable that the ion exchange capacity of the fiber itself is as large as possible. In the graft polymerization, a hydrophobic monomer is used to obtain a large graft ratio, and then a chemical reaction for introducing a functional group is performed. The process is adopted. And about the removal performance, the optimal condition was calculated | required and carried out by performing the laboratory experiment which considered application conditions, for example, the height of a packed bed, a liquid flow rate (SV), etc. As a result, it is currently only used to remove very small amounts of ions in ultrapure water production.

  In recent years, fibrous adsorbents that carry organic or inorganic compounds have been proposed taking advantage of the size of the surface area and the ease of molding. As a typical example, a decontamination material was developed to remove radioactive materials released into the environment in the event of the accident at the Fukushima Daiichi nuclear power plant. The main radioactive substances released into the environment are radioactive cesium, radioactive strontium, and radioactive iodine. In order to remove these, a fibrous adsorbent supporting an inorganic compound using a radiation graft polymerization method has been proposed.

  Radioactive cesium belongs to an alkali metal, and it is necessary to selectively remove radioactive cesium from a large amount of sodium ions present in the environment, which is difficult to remove with conventional adsorbents having ion exchange groups or chelate groups. It is. In addition, radioactive strontium is a divalent metal, but like cesium, it must be selectively removed from calcium ions and magnesium ions present in large amounts in the environment, and adsorbents using conventional functional groups Then removal is difficult. Therefore, an adsorbent in which an inorganic compound having high selectivity for each radioactive substance is supported on another carrier has been proposed.

  The present inventors have proposed an adsorbent in which an ion exchange group is introduced into a fiber and further an inorganic compound is supported by a radiation graft polymerization method. For example, for radioactive cesium, a material in which an insoluble metal ferrocyanide is supported between graft chains has been proposed (Patent Document 3). Moreover, what carried | supported sodium titanate is proposed with respect to radioactive strontium (patent document 4). For radioactive iodine, those carrying silver chloride have been proposed (Patent Document 5), both of which are fibrous, and are characterized by a high adsorption rate and a good molding process. ing.

  However, the performance of these supported adsorbing materials is not limited as long as the number of supported materials is increased, and even if the supporting rate is increased, the performance may not be improved. In particular, the chemical form of the radioactive material is not simply as ions, but is more often in the form of fine particles or colloidal particles, and the decontamination effect cannot be improved unless both the forms of ions and solids are removed.

  The same applies to the removal of radioactive strontium and radioactive iodine, and it is rare that these radioactive substances exist only in ionic form. As in the case of radioactive cesium, there are many radioactive substances that are present in a colloidal state, in an aerosol or in fine particles. Therefore, in order to effectively remove the radioactive material, the ionic and non-ionic forms of the radioactive material must be removed simultaneously. There are few decontamination materials having both functions, and this is one of the reasons why the contaminated water treatment does not proceed appropriately.

  Rare metals such as rare earth elements are not calculated in Japan, but are calculated in biased regions such as China and Africa. Therefore, advanced separation techniques have been developed to recover these metals. Solvent extraction is an important elemental technology, but environmental problems such as the use of large amounts of organic chemicals have been pointed out.

  As a means for solving the problem, a solid phase extraction method has been proposed. In the solid-phase extraction method, a liquid containing a rare metal is passed through an adsorbing material carrying an extraction reagent to adsorb the metal, and it is regenerated by passing an acid or an alkali to concentrate and recover the rare metal. In addition, it consists of a cycle that moves to the adsorption process. Since a separation / recovery process using a solid adsorbent can be constructed, it is characterized by the fact that it is possible to eliminate the complexity of operation and that there is little environmental pollution such as organic solvents.

  As part of this technique, a solid-phase extraction material in which a graft chain is introduced into a polymer substrate by radiation graft polymerization and an extraction reagent is supported has been proposed (Patent Document 6). Here, after introducing an octadecylamino group or dodecylamino group which is a hydrophobic group for supporting an extraction reagent on the graft chain, an extraction reagent such as bis (2,4,4-trimethylpentyl) phosphinic acid or It is said that a novel solid phase extraction material can be produced by carrying an extraction reagent such as octylmethylammonium chloride.

  The metal adsorption performance by the solid-phase extraction material carrying the extraction reagent greatly depends on the amount of the extraction reagent carried on the fiber surface. At present, since the carrying amount is not large, the adsorption capacity is small, and frequent regeneration operations are required, resulting in high costs. Therefore, studies have been made to increase the amount of extraction reagent supported.

  In precision industries such as semiconductor factories, it is necessary to clean not only water but also air. An air purification filter that removes chemical contaminants in a clean space such as a clean room has been proposed (Patent Document 7). Here, a non-woven fabric that is an aggregate of fibers is used as a base material, and after irradiation with radiation and GMA is graft-polymerized, a sulfonic acid group is introduced to obtain a strongly acidic cation-exchange non-woven fabric. This material discloses a technique for removing chemical contaminants, such as ammonia, present in the air. In the material in which the anion exchange group is introduced, removal of acidic gas such as organic acid and hydrogen chloride can be removed. The air purification filter is often processed at a high flow rate exceeding SV50000, and is required to have a performance capable of bringing about 1 ppm of ammonia to a ppb level with a contact time of 1 second or less.

In order for the air cleaning filter to always exhibit stable removal performance, the nonwoven fabric sheet is laminated to increase the adsorption capacity, the pleat fold number is increased to prevent pressure loss, and the nonwoven fabric surface passing speed is increased. It is applied to the actual machine while designing the safety side, such as lowering.
However, there are high cost problems such as an increase in the number of filters and an increase in the capacity of the blower. Therefore, it is expected that a nonwoven material having a small pressure loss and a large removal rate will be maintained while maintaining the adsorption capacity.

  Safety awareness of air environment such as health hazards due to PM2.5, hay fever and avian influenza virus is increasing. Functionalized masks have been developed as preventive measures to prevent the spread of contamination. Many of the masks currently on the market respond by incorporating a non-woven fabric having a high blocking effect and a small pore diameter into the mask.

  Since these fine particles are removed by a filtering action, in order to increase the removal efficiency, there is a big problem that the pore diameter must be reduced and breathing becomes difficult. Although the invention has been devised to increase the filtration area and decrease the flow rate by folding the nonwoven fabric in pleats, increasing the number of pleats increases the cost and impairs the mounting feeling, making it impractical.

  In order to solve such a problem, a pollen adsorbent in which a graft side chain having an anion exchange group is introduced into a fiber by a radiation graft polymerization method has been proposed (Patent Document 8). Here, it is shown that a positive charge derived from an anion exchange group can be retained in a fiber, and microorganisms such as pollen and MRSA can be removed, and furthermore, a bad odor such as ammonia can be removed by a fiber into which a cation exchange group is introduced. Inactivating viruses is also disclosed.

  A mask using this functionalized fiber has high performance but is very expensive, so it has not been widely used despite being a general-purpose product. Therefore, there is a high demand for the development of a material with high particle removal performance that does not make you feel stuffy. And materials that do not cost as much as possible are expected.

  Moreover, the technique which utilizes the fiber material by a radiation graft polymerization method for the adsorption / desorption of the water | moisture content in the air is proposed (patent document 9). A desiccant air conditioner is a type of air conditioner that rotates a desiccant rotor that can absorb and desorb moisture, absorbs moisture by absorbing part of the rotor, and sends dehumidified air by sending heated air to the other part. Performance such as rotation speed and heating conditions changes greatly. As the desiccant material has a higher moisture absorption / desorption rate, the size of the rotor can be reduced and the rotation speed can be increased. In addition to inorganic materials, organic materials with functional groups such as ion exchange groups, chelate groups, and nonionic hydrophilic groups have been proposed as materials to be used. There are great expectations for improved performance, such as ease of use and waste disposal.

  When the radiation graft polymerization method is applied to a polymer substrate, radicals are generated not only on the surface of the substrate but also on the inside, and graft chains grow inside and outside the substrate. A technique for adsorbing protein adsorption to a polymer brush, which is a graft chain grown outside a substrate, has been proposed.

  A technique is disclosed in which GMA is graft-polymerized by radiation graft polymerization using a porous hollow fiber membrane as a base material and then reacted with diethylamine to adsorb bovine serum albumin (BSA) (Non-patent Document 1). Here, since BSA has a size of about 5 nanometers and cannot enter the material, it is adsorbed exclusively on the polymer brush. BSA is adsorbed in multiple layers on the graft chain, and the length of the polymer brush can be estimated from the number of layers.

  Various technologies have been developed using this technology. For example, materials that adsorb proteins such as bovine serum albumin by introducing neutral hydroxyl groups and hydrophobic groups into the surface of the pores of polyolefin-based porous substrate membranes using a radiation graft polymerization method have been proposed. (Patent Document 10). Furthermore, an adsorbent material that can separate egg white proteins by introducing neutral hydroxyl groups and diethylamino groups after graft polymerization of GMA onto the porous membrane by a radiation graft polymerization method has been proposed (Patent Document 11). In addition, after graft polymerization of GMA to the porous sheet by radiation graft polymerization, iminodiacetic acid groups are introduced, and then converted to nickel ion type, so that proteins such as cysteine, histidine or tryptophan having affinity for the metal ions can be obtained. A technique for adsorbing is disclosed (Patent Document 12).

  Thus, there is a prior study on the production technique of the protein adsorbent by the radiation graft polymerization method. However, there are many precedent examples in which graft chains are introduced into a specific polymer substrate, the types of functional groups introduced into the graft chains are changed, and the interaction with proteins is researched and developed. There was no research aimed at improving the amount of protein adsorption by increasing the length. By increasing the ratio of the polymer brushes, it seems that not only proteins but also large specific substances in the biochemical field such as enzymes, viruses, genes, antigens and antibodies can be adsorbed and separated efficiently.

  As explained above, functional fibers such as ion-exchange fibers and chelate fibers manufactured by radiation graft polymerization have the advantage of high adsorption speed and low pressure loss, and are molded into a filter shape to allow liquid to pass at high speed. Processing has been done. In addition, it has become possible to use it in various environments, such as by processing it into a mall and braiding it in a large amount of accumulated water. In air purification, it has come to be applied to precision industrial chemical filters and mask materials. In the case of a conventional ion exchange resin, it can be said that a significant expansion of the usage mode has been achieved in view of the fact that it can be used only in the column system.

  The function introduced into the polymer substrate by the radiation graft polymerization method is that ion exchange groups and chelate groups, and inorganic compounds and extraction reagents are supported between the graft chains. And removal of solids by electrostatic adsorption. In addition, it has become possible to adsorb proteins and viruses with a polymer brush and remove redox substances with a catalyst support material.

  However, the radiation graft polymerization method emphasizes the point that the polymer base material can be freely selected and the molding process is easy, and another important feature of the radiation graft polymerization is that one end is fixed to the base material. However, there have been few attempts to actively utilize the unique polymer structure in which the other end is a free end. In particular, since a polymer chain has a graft chain extending outside the substrate, a material having a large brush length or number has great potential as a separation functional material.

JP-A-6-49236 JP 2002-20959 A JP 2013-011599 A JP 2013-212484 A Japanese Patent Laid-Open No. 2006-024183 JP 2005-331510 A Japanese Patent Publication No. 6-20554 Japanese Patent No. 504467 Japanese Patent No. 4176932 JP-A-5-209071 Japanese Patent Laid-Open No. 11-12300 JP 2009-101289 A

“High-throughput processing of proteins using a porous and tenuous anion-exchange membrane” Satoshi Tsuneda, Journal of Chromatography A2 (68)

  It is a problem to improve the function of the fibrous adsorbent shown below by increasing the ratio of the polymer brush which is a graft chain extended outside the fiber by the radiation graft polymerization method. It is a first object of the present invention to propose an adsorbent having an adsorption performance capable of improving the adsorption performance of ion exchange fibers and chelate fibers and removing ions and particles at high speed, and a method for producing and using the same. In supported adsorbent materials using ion-exchange fibers, chelate fibers, and hydrophobic groups, the support can be firmly fixed and the amount supported can be increased, while maintaining the functions of ion-exchange groups and chelate groups. It is a second problem to provide a composite fibrous adsorbent having a function of developing the function and a method of using the same. Furthermore, in air purification, it is a third object of the present invention to propose an adsorbent that can efficiently remove ionic gas and suspended particulate matter simultaneously, and a method for producing and using the same. A fourth problem is to provide a fibrous adsorbent having an increased ratio of graft chains, that is, polymer brushes, capable of adsorbing large molecules such as proteins and viruses.

  The present invention provides a fibrous adsorbent having the following characteristics, a production method and a method for using the same, and intends to solve the above-described problems.

  (1) Separation functional fiber in which a functional functional group is introduced into the graft chain, wherein the ratio of the polymer brush is based on the amount of bovine serum albumin adsorbed than the ratio of the polymer brush of the adsorbent obtained by the liquid phase graft polymerization method An adsorbent in which the ratio of the polymer brush is increased so that the adsorption capacity is 5 mg / g-fiber or more and 500 mg / g-fiber or less.

(2) The adsorbent having an increased ratio of the polymer brush according to (1), wherein the functional functional group is selected from at least one of an ion exchange group, a chelate group, a nonionic hydrophilic group, and a hydrophobic group.

(3) The shape of the separation functional fiber is selected from at least one of a fiber, a single fiber, a twisted yarn that is an aggregate of fibers, a woven fabric, a nonwoven fabric, a cut fiber, a hollow fiber, and a processed product thereof (1) ) To (2) are adsorbents having an increased ratio of the polymer brush.

(4) The ratio of the polymer brush according to (1) to (3) is increased, wherein the graft chain is provided by a method selected from a pre-irradiation gas phase graft polymerization method and a pre-irradiation emulsion graft polymerization method. Adsorbent.

(5) The pre-irradiation emulsion graft polymerization method uses an oil-in-water emulsion solution containing a non-hydrophilic monomer, a surfactant and water, and the graft ratio is 20 to 200% (1) to (4) Adsorbent with increased ratio of the described polymer brush.

(6) The adsorbent having an increased ratio of the polymer brush according to any one of (1) to (5), wherein the non-hydrophilic monomer used in the emulsion graft polymerization method is glycidyl methacrylate.

(7) The adsorbent with an increased ratio of the polymer brush according to (1) to (6), wherein a support is supported between the polymer brushes of the adsorbent with the increased ratio of the polymer brush.

(8) The support is a ferrocyanate metal salt insolubilized product, hydrous titanium oxide, metal titanate, at least one of silver and a silver compound, at least one of a platinum group element and a platinum group element compound, a transition metal element And an adsorbent with an increased ratio of the polymer brush according to any one of (1) to (7), which contains an extraction reagent and an enzyme.

(9) A method for treating a fluid, wherein the adsorbent having an increased ratio of the polymer brush according to (1) to (8) is contacted with a fluid containing a useful substance or a harmful substance.

(10) The useful material or harmful substance according to (9) is removed by simultaneously removing ions and colloidal particles in the liquid by the adsorbent with the increased ratio of the polymer brush according to (1) to (8). A method of treating a fluid in contact with a fluid to be treated.

(11) The substance removed from the liquid by the adsorbent in which the ratio of the polymer brush described in (1) to (8) is increased is a metal ion, halide ion, ionic and / or colloidal radioactive material. Useful substances or harmful substances according to (10) selected from cesium, ionic and / or colloidal radioactive strontium, ionic and / or colloidal radioactive iodine, colored substances including humic substances, viruses and microorganisms A method for treating a fluid, which is brought into contact with a fluid containing a substance.

(12) The useful substance or harmful substance according to (9), wherein malodorous substances and suspended particulate matter in the air are simultaneously removed by the adsorbent having an increased ratio of the polymer brush according to (1) to (8). A method for treating a fluid, which is brought into contact with a fluid containing a substance.

(13) The substance removed from the air by the adsorbent with the increased ratio of the polymer brush described in (1) to (8) above is selected from basic gas, acid gas, virus, pollen, and aerosol. (12) is a method for treating a fluid that is brought into contact with a fluid containing a useful substance or a harmful substance.

(14) The substance adsorbed or purified by the adsorbent with the increased ratio of the polymer brush described in (1) to (8) above is selected from proteins, enzymes, viruses, antigens, antibodies, and biochemical related substances. (9) is a method for treating a fluid that is brought into contact with a fluid containing a useful substance or a harmful substance.

(15) The useful substance or harmful substance according to (9), wherein the substance to be treated is an oxidizing / reducing substance by the adsorbent having an increased ratio of the polymer brush according to (1) to (8). A method for treating a fluid in contact with a contained fluid.

  As a result of intensive studies, the inventors have found that the higher the ratio of the polymer brush that is a graft chain extending from the substrate surface toward the outside of the substrate, the higher the proportion of the graft chain distributed from the substrate surface to the inside. The present inventors have found that the adsorption rate of the substance to be adsorbed is increased and arrived at the present invention. In particular, it has been found that fine particles such as colloidal particles can be removed simultaneously with harmful or useful metal ions, and that the material of the present invention can effectively adsorb large biochemical related substances such as proteins. Furthermore, it has been found that by increasing the ratio of the polymer brush, the support of the support-type adsorption material can be firmly fixed, and the adsorption function by the support and the adsorption function of the colloidal particles can be expressed more effectively. . Furthermore, it has been found that the effect of this polymer brush is effective not only for liquid treatment but also for air purification. As a result of the present invention, it was also found that there are many portions that are not graft-polymerized in the vicinity of the center of the substrate, the decrease in physical strength is small, and the mechanical properties of the adsorbent are improved.

  FIG. 1 shows the appearance of the surface layer part of the fiber cross section in order of the fiber base material, the usual liquid phase graft polymerization, and the fiber material in which the ratio of the polymer brush of the present invention is increased in order from the left. In the fiber base material, fibers are composed of the amorphous part 1 and the crystalline part 2 of the polymer. Since this is a state before graft polymerization, there is no equivalent to the polymer brush 4. As shown in the center figure, the graft fiber obtained by a normal liquid phase graft polymerization method has few polymer brushes 4 and most of the graft chains 3 are formed inside the fiber. This part is called polymer roots. The adsorbent in which the ratio of the polymer brush 4 of the present invention is increased has fewer graft chains at the center of the fiber than the one obtained by a normal liquid phase graft polymerization method, and many exist on the outside of the fiber. This comparison diagram is an image diagram when compared with the same radiation dose and the same graft ratio, and is created so that it can be easily understood visually.

  Increasing the ratio of the polymer brush can be achieved by increasing the number and length of graft chains extending to the outside of the base fiber. Since it is extremely difficult to separate the polymer brush from the base material, it is impossible to quantify the number and length of the polymer brush. It is known that large molecules of do not penetrate into the inside of the fiber and are adsorbed in multiple layers on the graft chain (Non-patent Document 1). By measuring the adsorption capacity of BSA, the number and length of polymer brushes can be estimated indirectly, which is sufficient for practical use.

  The effects obtained by the fibrous adsorbent with an increased polymer brush ratio are as follows. The thickness of the charged layer is increased to improve colloidal particle removal efficiency as well as ion removal. Also, in air purification, the removal efficiency of ionic gas and aerosol is increased. In addition, the support rate of the support in the support-type adsorbent material is improved and it is firmly fixed. Realization of further multi-layering of large biochemical substances such as protein adsorbed on the brush. This will be described in more detail below.

  The inventors have obtained a measure of the ratio of the polymer brush by conducting a BSA flow test using an experimental apparatus using the syringe type column 6 and the syringe pump 5 shown in FIG. A breakthrough curve as shown in FIG. 3 is created by passing a BSA solution of a predetermined concentration through the syringe filled with the adsorbent 7 at about SV10 and measuring the BSA concentration of the treatment liquid 8. From the breakthrough curve, the product of the stock solution BSA concentration up to the point at which 10% of the stock solution BSA leaks out and the fluid passage volume (representing how many times the filling volume was passed through) is taken as the dynamic adsorption capacity. Yes. This is a portion indicated by a shadow in FIG. Compared to an adsorbent obtained by a normal liquid phase graft polymerization method, a material having a dynamic adsorption capacity of 5 times or more is referred to as an adsorbent with an increased polymer brush ratio. Here, the manufacturing conditions for comparison need to be the same substrate, the same radiation source, the irradiation amount, the functional group type, and the graft ratio.

  The dynamic adsorption capacity of the fibrous adsorbent obtained by the pre-irradiation liquid phase graft polymerization method is 5 mg / g-fiber or less, and the removal rate of a trace amount of metal ions and the BSA adsorption capacity become unstable. Therefore, the dynamic adsorption capacity of BSA is preferably 5 mg / g-fiber or more. When the dynamic adsorption capacity exceeds 500 mg / g-fiber, the ion adsorption capacity increases, but the BSA adsorption capacity does not increase much. The dynamic adsorption capacity varies depending on the type and chemical structure of the base material, and the ratio of the polymer brush is increased for fibers having a large hydrophobicity such as polyethylene. Further, as problems other than the adsorption capacity, there are problems in the production process and use such as deterioration of physical strength of fibers, abrasion due to graft chain rubbing, and increase in the amount of washing water. preferable. Therefore, the dynamic adsorption capacity of BSA is in the range of 5 to 500 mg / g-fiber, preferably 10 to 400 mg / g-fiber, more preferably 15 to 350 mg / g-fiber. A fibrous adsorbent having a BSA dynamic adsorption capacity in the range of 5 to 500 mg / g-fiber is referred to as an adsorbent with an increased polymer brush ratio.

  Also, an adsorbent with an increased ratio of polymer brush cannot obtain a sufficiently large adsorptive separation performance if the brush is contracted. In order to swell the polymer brush, when an ionic dissociation group such as an ion exchange group or a chelate group or a nonionic hydrophilic group is introduced into the graft chain, the graft chain swells due to charge repulsion or coordination of water molecules. Since cation exchange groups such as sulfonic acid groups and carboxyl groups are negatively charged, and anion exchange groups such as quaternary ammonium groups and tertiary amino groups are positively charged, the charge repulsion of the graft chain occurs and the polymer brush extends. To do.

  Since nonionic hydrophilic groups such as amide groups and hydroxyl groups also coordinate water molecules around the functional group, the graft chain swells. In addition, since iminodiacetic acid group, ethylenediamine group, amidoxime group and the like, which are typical chelate groups, have a hydrophilic group or an ionic dissociation group, the graft chain is swollen and the polymer brush is elongated. Since the carboxyl group forms a hydrogen bond with the adjacent hydroxyl group, it is necessary to adjust the salt type depending on the use conditions such as conversion to a sodium salt type. Similarly, in the case of a weakly basic anion exchange group having a tertiary amine, it is necessary to pay attention to acid treatment before use. It is important that a functional group that swells the graft chain is introduced into the graft chain.

  The hydrophobic group is used as a scaffold for supporting an extraction reagent or the like. For example, linear alkylamines such as dodecylamine and octadecylamine have an amino group at the terminal and react with the epoxy group of GMA. The amino group is closer to the graft chain, and the straight chain alkyl is extended to the outer side away from the graft chain, so that the extraction reagent bis 2-ethylhexyl hydrogen phosphate (HDEHP) is easily supported. Since an organic solvent such as isopropyl alcohol is used in the extraction reagent loading step, a large amount of extraction reagent can be loaded when the ratio of the polymer brush having a hydrophobic group is high.

  Although various existing polymer moldings can be used as the polymer material to which the radiation graft polymerization method can be applied, there are many types of products that can be used for the fiber, and the fibrous graft adsorbent is applied by applying the radiation graft polymerization method. After being manufactured, it is a suitable material because it can be easily molded according to the application location. In particular, since the packing density is small in addition to the high adsorption rate, the characteristics such as low pressure loss despite the high flow rate can be utilized even when used in a column. By the proposal of the adsorbent with the increased ratio of the polymer brush of the present invention, more stable treatment can be performed even at a high flow rate.

  FIG. 4 shows a method for producing an adsorbent in the radiation graft polymerization method. Performing radiation irradiation on the substrate in advance before graft polymerization is called pre-irradiation. In the case of producing a separation functional material by a radiation graft polymerization method, generally, pre-irradiation liquid phase graft polymerization in which a graft polymerization reaction is performed while an irradiated base material is immersed in a monomer solution is employed. The material obtained by this method has a small ratio of polymer brushes compared to the adsorbent material of the present invention because the monomer penetrates into the base material and the amount of homopolymers is small. It has sufficient performance for adsorption. FIG. 4 shows a step of performing a functional group introduction reaction after the graft polymerization. However, when a monomer having a functional group in advance is grafted alone, the functional group introduction step is unnecessary. To achieve the object of the present invention, the flow of FIG. 4 using a water-insoluble monomer to which the emulsion graft polymerization method can be applied is preferable.

  In the material in which the ratio of the polymer brush of the present invention is increased, it is preferable that the rate of penetration of the monomer into the substrate is small during the radiation graft polymerization, and the graft polymerization occurs near the substrate surface. As a radiation graft polymerization method in which such graft polymerization occurs, there is an emulsion graft polymerization method in which a monomer solution is prepared as an emulsion solution. The emulsion graft polymerization method is a known graft polymerization method, and a large graft ratio can be obtained even if the monomer concentration and the radiation irradiation dose are small. Therefore, the emulsion graft polymerization method is attracting attention from the viewpoint of cost reduction and environmental load reduction.

  When pre-irradiation emulsion graft polymerization is performed using an oil-in-water emulsion monomer solution with a non-hydrophilic monomer, micelles break down on the substrate surface at the initial stage of polymerization, and the monomer adsorbs on the substrate surface. Polymerization occurs. Since the monomer supply rate into the substrate is small, the rate at which the monomer penetrates into the substrate is small. As the polymerization proceeds, the surface of the substrate is covered with graft chains, and it is considered that the micelle breakage and the monomer supply rate increase. Therefore, when the time-dependent change of the graft rate is examined, there is an induction period in which the graft polymerization rate is low at the initial stage of polymerization, and after this period, the graft polymerization rate increases, and the graft rate becomes an equilibrium value in the latter half of the graft polymerization. Draw a so-called S-shaped curve. The length of the induction period, the point at which the graft polymerization rate suddenly increases, the polymerization rate, the point at which the equilibrium value is reached, and the value are the substrate type, radiation dose, monomer type and concentration, and surfactant type. It varies depending on the amount, graft polymerization temperature, liquid / base material ratio, etc., and needs to be confirmed in advance by preliminary experiments.

  The graft ratio obtained by the emulsion graft polymerization method does not have to be large, but has an appropriate range. When the graft ratio is 20% or less, the length of the polymer brush is not sufficient, the removal rate and the dynamic adsorption capacity become unstable, and the adsorption performance cannot be exhibited. On the other hand, if it is 200% or more, crosslinking, homopolymer generation, and graft polymerization progress to the inside of the fiber, and the ratio of the polymer brush does not increase. Further, when graft polymerization into the fiber proceeds, strength deterioration occurs. Therefore, the preferable graft ratio is 20% to 200%, more preferably 20% to 150%, and the most preferable range is 30 to 130%. Usually, an emulsion solution is prepared with a composition of a monomer concentration of several percent, a surfactant concentration of 1% or less, and water of 90% or more.

  In addition to the emulsion graft polymerization method, there is a gas phase graft polymerization method as a graft polymerization method for increasing the ratio of the polymer brush. The gas phase graft polymerization method using monomer vapor is advantageous in extending the polymer brush because the polymerization starts by the adsorption of the monomer to the substrate surface. The gas phase graft polymerization method can only be applied to volatile monomers. Since the vapor pressure varies depending on the type of monomer, the polymerization conditions are preferably determined by preliminary experiments. In order to obtain a uniform graft, at least either the substrate or the monomer vapor must be moving.

  There is also an impregnation graft polymerization method positioned between the liquid phase graft polymerization method and the gas phase graft polymerization method. This method is a graft polymerization method in which a monomer amount is calculated in advance so that a predetermined graft ratio is obtained, and a necessary amount of monomer is immersed in an organic polymer molded body in advance. If the substrate is fibrous, it is easy to hold the monomer solution, and emulsion graft polymerization can also be applied to this method.

  A polymer brush having an ion exchange group extends along the outer periphery of the fiber to form a charged layer. The charged layer is a region where charges are formed outside the polymer brush. When ion exchange fibers with an increased ratio of polymer brush are used to adsorb ions in the liquid, the ions in the water are attracted and captured by the charged layer 10 as shown in FIG. For example, when the fibrous adsorbent 9 having a sulfonic acid group which is a typical cation exchange group is used to adsorb and remove a trace amount of metal ions 11 from pure water, the effect of the charged layer is remarkable. This is effective when, for example, several ppm of metal ions are brought to the ppb level. When the coexisting salt concentration reaches a high salt concentration of several thousand mg / L or more, the osmotic pressure increases, so water molecules between the graft chains decrease, the polymer brush contracts, and the distance covered by the charge also decreases. As a result, the thickness of the charged layer is reduced. Therefore, the low salt concentration can exhibit the effect of the polymer brush. In the case of using a fiber with a high ratio of polymer brush in a distribution system, there is an effect of increasing the surface area without substantially increasing the water flow resistance of the fiber, which is practically important.

  Similarly, in the case of a polymer brush having an anion exchange group, the anion is attracted and trapped because the polymer brush layer forms a positively charged layer. Here, it is important that the polymer brush can ion-exchange adsorb anions, but it is particularly important that the negatively charged colloidal particles and aerosol can be electrostatically adsorbed.

  Colloidal particles and fine solids in a liquid are often negatively charged. These can usually be removed with a porous membrane having fine pores. However, the removal with the porous film has a problem that frequent cleaning operation is required because clogging occurs immediately. Further, although it can be removed by coagulation sedimentation treatment, the coagulation sedimentation treatment requires chemical injection equipment, a stirring tank, a sedimentation tank and sludge treatment, and the treatment system becomes large.

  Colloidal particles and fine solids are usually negatively charged in the environment and can be removed with ion exchange fibers having a positively charged polymer brush. Since the anion exchange group is positively charged, it is suitable for removing the negative colloidal particles by electrostatic adsorption, and can be removed without increasing the water flow resistance. In particular, a polymer brush having a quaternary ammonium group is capable of capturing colloidal particles that are fine enough to pass through a microfiltration membrane. The size of colloidal particles is defined as 5 to 100 nm, which is much larger than the size of ions. Therefore, in removing the colloidal particles, the polymer chain extending outside the fiber is used instead of the graft chain inside the fiber. Again, it is preferable that the charged layer capturing the colloidal particles is large. Therefore, the fibrous adsorbent having an increased ratio of the polymer brush is effective for removing minute solids such as colloidal particles.

  The pure water production process is composed of a plurality of water treatment apparatuses. Generally, raw water with a salt concentration of several hundred mg / L is coarsely desalted with an ion exchange resin tower or reverse osmosis membrane device until the salt concentration reaches several mg / L, and the remaining ions are mixed-bed type ion exchange. Desalination is performed by a resin tower or an electric desalination apparatus until the salt concentration reaches the order of μg / L. Further, when high purity ultrapure water is required, the treatment is performed by an ultrapure water treatment apparatus including a membrane treatment apparatus, an oxygen removal apparatus, a TOC removal apparatus, and the like.

  To remove humic colloids such as humic acid that cause membrane surface contamination of the reverse osmosis membrane device and irreversible contamination of the anion exchange resin by installing ion exchange fibers with increased polymer brush ratio upstream of the pure water production equipment It becomes possible, and the soundness of a pure water manufacturing apparatus can be improved.

  By installing ion exchange fibers with an increased ratio of polymer brush inside or downstream of the pure water production apparatus, it becomes possible to further remove a small amount of ions as shown in FIG. Can do. Moreover, when the ultrapure water treatment apparatus is further installed in the back | latter stage of a pure water apparatus, the load to an ultrapure water treatment apparatus can be reduced. The ion exchange fiber may be installed at a place where the cut fiber is filled in an existing ion exchange resin tower, or another adsorption tower may be installed. When installing separately, what was processed into the cartridge filter was stored in the housing, or a cylinder type container filled with cut fibers was connected by piping, so that it could be installed easily.

  A conventional filtration filter such as a wind filter or a pleat filter shown in FIG. 6 is housed in a housing and used as a pre-filter for a general water treatment apparatus for filtering relatively coarse particles. In the case of a filter having a filter length of 25 cm, the filtration filter is used in a flow rate range of about 10 L / min (600 L / h) or more. Since the amount of fiber used is around 300 ml, it becomes SV2000, and the flow rate of the ion exchange resin is twice as large as that of general SV10-30. By using fibers with increased polymer brush ratio for this filter, in addition to the removal function of relatively large particles originally possessed by the wind filter, it becomes possible to remove even finer colloidal particles and ions, The performance is significantly improved.

  Thus, since the contaminants can be removed without contributing to the capacity increase of the entire apparatus in terms of ion exchange capacity, it is possible to exert an extremely great effect on maintaining the soundness of the apparatus. It is also effective for removing a very small amount of impurity ions in ultrapure water, which is required in the precision industry, or for removing harmful substances remaining in wastewater or released into the environment.

  In the accident at Fukushima Daiichi Nuclear Power Station, radioactive materials were released into the environment. Typical radioactive substances are radioactive iodine, radioactive cesium, and radioactive strontium, but most of the radioactive substances are not ionic, but often adhere to colloidal or fine particles. For example, it is clear that the chemical form of radioactive cesium is 10% or less in ionic form and the remaining 90% or more is colloidal or attached to fine particles. Colloidal cesium is often negatively charged. There are many non-ionic radioactive strontiums and radioactive iodines, though not as much as radioactive cesium.

  What is important in the removal of radioactive substances is that ions can be removed with a supported inorganic compound crystal in a supported adsorption material, and colloidal radioactive substances can be removed with a positively charged polymer brush. Hereinafter, the radioactive substance removing material will be described in more detail.

  Regarding the radioactive cesium removal material, the present inventors have already proposed a fibrous adsorbent. According to Patent Document 3, first, a support is made by introducing an anion exchange group into a base fiber by a radiation graft polymerization method. Next, it is brought into contact with an aqueous potassium ferrocyanide solution to adsorb ferrocyanide ions by ion exchange. Thereafter, insoluble inorganic crystals of cobalt ferrocyanide and nickel ferrocyanide are deposited and supported on the periphery of the fiber by contacting with an aqueous solution of cobalt chloride or nickel chloride. The produced cobalt ferrocyanide precipitate is weakly charged at a few mV, and is thus electrostatically adsorbed to a positively charged graft chain of +20 to 40 mV. By increasing the ratio of the polymer brush, the supported precipitate can be firmly held. At the same time, the polymer brush extending out of the fiber can remove more negative colloidal particles.

  Inorganic crystals such as cobalt ferrocyanide and nickel ferrocyanide can selectively adsorb cesium ions from the contaminated water having a high salt concentration, such as seawater, because cesium ions are selectively taken into the crystal. Then, colloidal radioactive cesium is removed by the polymer brush. Radiocesium ions and colloidal cesium can be removed simultaneously.

  Zeolite and radioactive cesium adsorbents carrying ferric ferrocyanide on zeolite have been proposed. However, these are intended to remove only ionic radioactive cesium. It can be said that radioactive cesium could be completely removed only by removing the colloidal substance. According to the present invention, radioactive cesium can be completely removed.

  The chemical form of radioactive strontium is said to be colloidal or particulate, although not as much as the proportion of radioactive cesium. In the radioactive strontium adsorbing material, first, titanic acid is ion-exchanged and adsorbed on a graft chain into which an anion exchange group has been introduced, and then sodium titanate crystals are supported between the graft chains through an alkali treatment such as sodium hydroxide. Patent Document 4). According to the fibrous adsorbent with an increased ratio of the polymer brush of the present invention, not only can the amount of the titanate metal salt insolubilized material supported be increased and the adsorption capacity of strontium ions can be increased, but as in the case of radioactive cesium, At the same time, colloidal particles containing can be adsorbed.

  Radioactive iodine has a very complex chemical form and is often released into the atmosphere. For radioactive iodine in water, a technique is disclosed in which a silver chloride compound is supported on the periphery of a fiber basically using a graft chain having an anion exchange group (Patent Document 5).

  The production method of the radioactive iodine adsorbing material is the same as the production method of the radioactive cesium adsorbing material. First, after anion-exchange groups are introduced into the base fiber by a radiation graft polymerization method, the carrier is used to adsorb chloride ions. The silver chloride is supported on the fiber by contacting with an aqueous silver nitrate solution. Iodide ions react with silver chloride on the fiber to form silver iodide, which is deposited and removed. Colloidal iodine is removed with a polymer brush.

  Radioactive iodine is released into the air and taken into the human body by breathing, causing serious damage to the thyroid gland. Therefore, when severe accidents occur, it is important to reduce exposure by quickly removing radioactive iodine in the air and not inhaling it. The chemical form of radioactive iodine in the air is said to be mainly iodine (I2), hypoiodous acid (HIO), methyl iodide (CH3I), and aerosol.

  Iodine, hypoiodous acid, and aerosol are removed by ion exchange and electrostatic adsorption by a fiber having an anion exchange group introduced into the graft chain. Therefore, according to the fibrous adsorbent in which the ratio of the polymer brush is increased, the removal performance can be further improved. Methyl iodide can be removed with an adsorbent material in which triethylenediamine (TEDA) is introduced into the graft chain. By increasing the ratio of the polymer brush, the effect of removing ionic and aerosol-like radioactive iodine can be enhanced. Depending on the charged state of the aerosol, a strongly acidic cation exchange fiber can be used in combination.

  All of the three types of radioactive substance removing materials described above are adsorbents produced by producing anion exchange fibers by a radiation graft polymerization method and then carrying an inorganic compound with high selectivity, and can be said to be supported adsorbent materials. In each of the supported adsorbing materials, an anion exchange group is introduced into the grafted fiber by the radiation graft polymerization method, and an inorganic compound is precipitated inside the fiber using an ion exchange reaction and a precipitation reaction. Many of these inorganic compounds are crystals having a negative charge, and are adsorbed at multiple points with a graft chain having an anion exchange group. It does not mean that the inorganic compound is supported simply by soaking, and is highly resistant to environmental changes such as friction, pH, and salt concentration, and no omission is observed.

  In the fibrous adsorbent in which the ratio of the polymer brush of the present invention is increased, the use of a polymer brush having an anion exchange group can contribute to the stabilization of the supported material while maintaining the colloid removal performance. In addition, the support is unevenly distributed at the peripheral edge of the fiber, which is advantageous for removing ionic radioactive substances.

  Radioactive materials such as radioactive cesium diffused into and out of nuclear power plants due to accidents, so pollution was caused by decontamination of rivers, forests, fields, ports, lakes, wells, gutters, buildings, or decontaminated water. It extends to various places such as tanks that store water. In addition, unlike during the steady operation of nuclear power plants, radioactive materials are present in the form of ions, colloids or fine particles. In such pollution sites, it is difficult to apply existing decontamination techniques. If there is a large amount of contaminated water in the tank or tank and there is an installation space, the handling of the contaminated water can be managed, so a raw water tank, a coagulation sedimentation device, and an adsorption tower can be installed. . The cartridge filter described above (FIG. 6) can also be used.

  At other contaminated sites, the fibrous adsorbent twisted yarn 13 shown in FIG. 7 is molded around the core 14 in the form of a molding (braid), etc. Radioactive cesium can be used to adsorb and remove both ionic and colloidal forms by simply mooring. It can also be laid by matting or netting in the soil of the intermediate storage. After adsorption, the radioactive material can be concentrated and separated simply by collecting the material. Further volume reduction is possible by burning. Thus, the fibrous adsorbent produced using the radiation graft polymerization method can be used after being processed according to various environments. Moreover, what is necessary is just to wind up a fiber structure in order to collect | recover used fibers.

  As for typical transition metals such as iron and manganese, a metal or a metal oxide can be supported through an oxidation or reduction treatment after adsorbing a transition metal ion to a graft chain having an ion exchange group. For example, a technique in which an ion exchange group is introduced into a fiber using a radiation graft polymerization method to carry a manganese oxide is disclosed (WO02 / 005960). This manganese oxide supporting material has a catalytic action to reduce ozone in the air to oxygen. If the fibrous adsorbent with the increased ratio of the polymer brush according to the present invention is used, the loading amount can be increased, the reduction reaction can be effectively functioned, and the physical strength is hardly deteriorated. The same applies to transition metals such as iron and cobalt.

  Platinum group metal elements are also well known as catalytic metals. After graft polymerization of a monomer such as GMA onto the fiber by a radiation graft polymerization method to obtain a graft chain having an anion exchange group, palladium chloride is adsorbed on the graft chain, and then a reducing agent such as hydrazine is contacted with palladium. A technique for supporting a metal on a fiber has been proposed. This catalyst metal-supporting fiber is used as a catalyst for removing hydrogen peroxide in water. By using an adsorbent in which the ratio of the polymer brush is increased as a catalyst carrier, the performance can be improved by increasing the amount of catalyst metal supported. Moreover, there is little physical degradation.

  Some supported adsorbing materials carry organic compounds in addition to those carrying inorganic compounds. The inventors have proposed an adsorbent in which an extraction reagent is supported on a graft chain, particularly a polymer brush (Patent Document 6). In the production of this adsorbent, a fibrous adsorbent with an increased ratio of polymer brush is effective as a carrier for increasing the amount of extraction reagent supported.

  The extraction reagent-carrying adsorbent material is obtained by grafting GMA by graft polymerization to a polymer substrate by radiation graft polymerization, and then introducing a hydrophobic group such as octadecylamino group or dodecylamino group, alkyl group, alkylthiol group, The hydrophobic group carries an extraction reagent such as bis (2,4,4-trimethylpentyl) phosphinic acid or trioctylmethylammonium chloride to produce a solid phase extraction material. Unlike the conventional fibrous adsorbing materials, an alkylamine having an amino group in the epoxy group of the graft chain is introduced to support the extraction reagent. In order to increase the adsorption capacity, it is necessary to increase the amount of the extraction reagent carried. By introducing linear alkylamine into the graft chain with an increased polymer brush ratio, the hydrophobic polymer brush and linear alkylamine swell in the subsequent extraction reagent loading step in an organic solvent, increasing the loading amount. And the adsorption capacity can be increased.

  Polymer brushes can adsorb proteins in multiple layers (Non-patent Document 1). More proteins can be adsorbed in multiple layers by the adsorbent with a higher polymer brush ratio. The inventors found and announced for the first time that bovine serum albumin (BSA) can be adsorbed in a multilayer manner to a polymer brush having a tertiary amino group by applying a radiation graft polymerization method to a hollow fiber (Non-patent Document 1). FIG. 8 shows a state in which BSA is adsorbed in multiple layers along the polymer brush. As can be seen from this figure, by increasing the number and length of the polymer brushes, more biochemical substances represented by BSA can be adsorbed.

  Biochemical-related substances whose adsorbed substance size is larger than ions and up to about colloidal particles can be adsorbed in multiple layers in the same way as proteins. Examples of biochemical substances include enzymes, viruses, genes, antigens, and antibodies. Infectious viruses such as Norovirus and Influenza virus are negatively charged and can be removed by increasing the proportion of polymer brushes with anion exchange groups. It can also be used as a carrier for immobilized enzyme for adsorbing an enzyme. In the application to biochemical-related substances, it can be applied to adsorption separation of target substances or adsorption removal of impurities.

  As a functional group for protein adsorption, an example is disclosed in which GMA is graft polymerized on a porous membrane using a radiation graft polymerization method, and then a sulfonic acid group is introduced to adsorb lysozyme (Japanese Patent Laid-Open No. 11-266862). ). Further, after GMA is graft-polymerized to the porous sheet by a radiation graft polymerization method, an iminodiacetic acid group, which is a typical chelate group, is introduced into a metal ion type. A technique for removing cysteine or tryptophan having affinity for this functional group has been disclosed (Patent Document 12). The adsorbent having an increased ratio of the polymer brush of the present invention can also be used to remove these proteins. Since the ratio of the polymer brush to the graft chain for introducing these functional groups is increased according to the present invention, the adsorption capacity is increased.

  Microorganisms include Gram negative bacteria (eg, E. coli) and Gram positive bacteria (eg, Staphylococcus aureus). Since the surface has a negative charge, it is adsorbed at multiple points with a polymer brush having a positive charge. Therefore, microorganisms can be better adsorbed with a material having a higher polymer brush ratio.

  Microorganisms such as Escherichia coli and Cryptosporidium are also efficiently removed by multipoint adsorption with a polymer brush having an anion exchange group. By converting the anion exchange group to the iodide ion type, it is possible to further suppress the growth of microorganisms and the like, and the antibacterial property increases. Therefore, the safety of drinking water can be ensured in an emergency where chlorination is difficult. Further, it can be used as a microbial carrier for biofilm treatment in a water treatment process employing a biological treatment apparatus.

  It has been described that ions in water are attracted and trapped by the charged polymer brush layer 10 as shown in FIG. This phenomenon is the same for ionic gas in the air. For example, basic gases such as ammonia and trimethylamine, which are typical malodorous substances, can be removed with a polymer brush having a strongly acidic cation exchange group (H type). An acidic gas such as isovaleric acid can be removed with a polymer brush having a strongly basic anion exchange group (regenerative type).

  Even in the air, water molecules according to the humidity in the environment are coordinated around the ion exchange group, and the polymer brush is extended. For example, in the case of a sulfonic acid group which is a strongly acidic cation exchange group, a fiber having a neutral salt decomposition capacity of 2 meq / g is affected by humidity but is usually regenerated (H type) and has a water content of around 20%. Contains moisture. This amount of water is calculated as about 10 water molecules coordinated around the sulfonic acid group. Moreover, since there is also a charge repulsion between adjacent graft chains, the polymer brush extends, and a layer corresponding to the charged layer in the water treatment is formed. The basic gas is attracted to the charged layer and captured by a neutralization reaction with the polymer brush. Therefore, the adsorption performance can be further improved in the fibrous adsorbent with an increased ratio of the polymer brush.

  In the case of acid gas, it is removed by a fiber into which a quaternary ammonium group which is a strongly basic anion exchange group is introduced, as in the case of basic gas. When a quaternary ammonium group is converted to a regenerative type (OH type) with an alkali, a water content of nearly 20%, which is the same as that of a sulfonic acid group, is usually obtained. Since the polymer brush having a positive charge extends toward the outside of the fiber while being repelled, the acid gas can be removed. Also, negatively charged aerosols can be removed at the same time.

  Although serious air pollution due to PM2.5 has become a problem, the suspended particulate matter present in the atmosphere is also charged, the ratio of the polymer brush of the present invention is increased, and charges due to ion exchange groups and the like are increased. It can be removed by the fibrous adsorbent. Influenza and noroviruses are also negatively charged and can be adsorbed with polymer brushes with anion exchange groups. Pollen is larger in size than viruses, but by increasing the ratio of the polymer brush, it can be easily adsorbed at multiple points to improve performance.

  Mask materials and wiping paper that can absorb viruses and reduce the virus infectivity can be proposed. The mask is always exposed to exhalation and has high humidity, but it is preferable for the swelling of the polymer brush and the expression of the ion exchange function as compared with those charged by physical means. By applying antibacterial ions to infectious viruses, etc., adsorption and sterilization (or inactivation) can be achieved, and the spread of contamination can be prevented. For example, a fibrous adsorbent adsorbed with iodide ions or triiodide ions is reliably inactivated or sterilized after adsorbing viruses and microorganisms, and does not expand contamination. Antibacterial fibrous adsorbents can be attached to the end of the faucet in emergency and areas where infrastructure is not available, helping to ensure the safety of drinking water.

  Nonionic hydrophilic groups include amide groups and hydroxyl groups. Since the polymer brush having these functional groups also coordinates water to the functional group, the present invention can improve the function of the polymer brush, for example, the function of trapping hydrophilic substances such as water and the exclusion of hydrophobic substances. it can.

  By immersing the GMA-grafted fiber in about 1% dilute sulfuric acid and heating at 70 ° C., the epoxy group of GMA is ring-opened to form a diol having two hydroxyl groups. Since the hydroxyl group is a nonionic hydrophilic group, it can be used for moisture adsorption / desorption.

  Nonionic hydrophilic groups are also used for eliminating hydrophobic substances and moisture-absorbing materials. By using a fiber material having a nonionic hydrophilic group and an increased ratio of the polymer brush as a diaper material, moisture can be quickly absorbed and uncomfortable feeling can be eliminated. Moreover, by using this fiber material as a desiccant material for an air conditioner, moisture in the air can be quickly absorbed and desorbed, and can be utilized for the efficiency design of the desiccant rotor. The ion exchange group has a strong hydrophilicity and can be used for moisture absorption and desorption, and at the same time, can be deodorized.

  When a graft chain having an ion exchange group, a chelate group or a nonionic hydrophilic group is introduced into the fiber, the tensile strength and the elongation are reduced. Since the fiber obtained by a normal liquid phase graft polymerization process proceeds to the center of the fiber, the physical strength is lowered when a function such as an ion exchange group is introduced. The adsorbent having an increased ratio of the polymer brush of the present invention has a relatively low density of graft chains inside the base material, and can suppress a decrease in physical strength of the base fiber. It is possible to create a functional fiber that maintains the strength inside the fiber and is provided with an adsorption function by a polymer brush at the periphery of the fiber.

  According to the present invention, in the separation functional fiber to which the radiation graft polymerization method is applied, it is possible to further improve the functions already provided and to add new functions. Fiber removal is achieved by ion exchange treatment at high flow rates and simultaneous removal of colloidal substances, simultaneous removal of gas and aerosol at high flow rates, improved performance of supported adsorbent materials, and improved adsorption capacity for large molecules such as proteins. Various applications that make full use of the features of the

  In addition, when functional groups are introduced even inside the base material, there are problems such as weakness and difficulty in maintaining the shape of the molded product. However, increasing the ratio of the polymer brush results in a graft polymerization. It was possible to concentrate on the peripheral edge of the material fiber, the physical strength increased, and the molding process had an excellent effect.

Image diagram showing the state of the polymer brush on the fiber cross-section surface layer Syringe type column test equipment for BSA adsorption test BSA breakthrough curve Fabrication route of ion exchange fiber by radiation graft polymerization Illustration of ion adsorption Wind filter Mall-shaped adsorbent BSA multilayer adsorbed on graft chain Bobbins with twisted fibers twisted around a core Diagram showing the relationship between graft rate and BSA dynamic adsorption capacity Test device for evaluation of deodorization and tobacco smoke removal performance

  As shown in the flow sheet of FIG. 4, the production method of the adsorbent material by the radiation graft polymerization method comprises three stages of radiation irradiation, graft polymerization, and functional group introduction into the graft product. When ionizing radiation is irradiated to the organic polymer molded body, radicals are generated on the surface and inside of the organic polymer molded body. When a monomer having an ion exchange group or a chelate group or a monomer that can be converted to the functional group is brought into contact therewith, the monomer is polymerized from the generated radical as a base point to form a graft chain. FIG. 4 shows an example in which it does not have an ion exchange group or a chelate group by itself, but is converted into an ion exchange group or a chelate group by a secondary reaction.

  A commercially available product can be freely selected as the organic polymer molded body serving as the substrate. For example, fibers, nonwoven fabrics, woven fabrics, twisted yarns, membranes, porous membranes, powders, and the like can be freely selected according to applications. Among these, since the fiber has a large surface area, a large adsorption rate can be expected when used as an adsorbing material. Further, since the fiber can be easily formed into a sheet shape such as a nonwoven fabric or a woven fabric in addition to the twisted yarn that is a fiber assembly, it is suitable for the use of the present invention. For example, a twisted yarn that is an aggregate of fibers can be processed into a molding (braid). In addition, woven fabric and non-woven fabric can be easily filtered, and the filter function and the adsorption function can be combined. Further, even when the cut fiber is packed in a column and used in a flow system, the water flow rate can be increased because of low pressure loss.

  Examples of the fiber material useful as the substrate of the present invention include synthetic fibers, cellulosic fibers such as cotton, animal fibers, mineral fibers, regenerated fibers, or mixed fibers thereof. Synthetic fibers include polyester, polyamide, acrylic, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polyurethane, polyvinyl alcohol, fluorine, and the like. Cellulosic fibers include natural cellulose fibers such as cotton and hemp, viscose rayon, copper ammonia rayon, regenerated cellulose fibers such as polynosic, purified cellulose fibers such as tencel, and semi-synthetic fibers such as acetate and diacetate. It is. Animal fibers include animal hair fibers such as wool, silk and the like. The recycled fiber includes chitin / chitosan fiber, collagen fiber and the like. Among these, hydrophobic synthetic polymers such as polyethylene, polyester, and polyamide, which are easy to graft polymerize an oil-in-water emulsion solution with a hydrophobic monomer, are particularly preferable.

  Organic polymer moldings, especially ionizing radiations that irradiate fibers, include α rays, β rays, gamma rays, electron beams, neutron rays, etc., but from the surface of organic polymer moldings that are base materials to deep parts. It is industrially preferable to use gamma rays and electron beams having the ability to transmit. Radiation irradiation conditions are not particularly limited, but in order to obtain sufficient grafting efficiency in the next step, it is preferably 5 to 200 kGy, particularly 30 to 100 kGy in a deoxygenated state. At this time, the oxygen concentration may be a concentration at which graft polymerization can be achieved at a required polymerization rate, and is preferably 1% or less, more preferably 100 ppm or less.

  Conventionally, as a radiation graft polymerization method generally performed, there is a pre-irradiation liquid phase graft polymerization method in which an irradiated substrate is immersed in a monomer solution and polymerization is performed as it is. In this method, since the monomer is sufficiently supplied, the graft polymerization proceeds rapidly to the inside of the base material due to dissolution and permeation of the monomer into the amorphous part.

  In order to increase the ratio of the polymer brush, it is necessary to reduce the penetration rate of the monomer into the fiber at the time of contact between the fiber and the monomer solution. As such a radiation graft polymerization method, an emulsion graft polymerization method is used. And gas phase graft polymerization.

  The emulsion graft polymerization method is a polymerization method in which an emulsion solution is prepared with a mixed solution composed of a monomer, water and a surfactant, and then brought into contact with the fiber. The graft polymerization rate is relatively high, and the penetration rate of the monomer into the fiber is high. Since it is small, the ratio of the polymer brush can be increased. In particular, for hydrophobic fibers such as polyethylene, polyester, and polyamide, oil-in-water droplets using a hydrophobic monomer, such as a monomer having a double bond such as glycidyl methacrylate, styrene, or chloromethylstyrene, a surfactant, and water. It can be suitably obtained by graft polymerization using a mold emulsion solution. These have a relatively high vapor pressure and are liable to vapor phase graft polymerization. In addition to the monomers listed above, acrylonitrile, acrolein, vinylpyridine, glycidyl acrylate, and the like can be suitably used.

  Monomers that do not have ion exchange groups or chelate groups are often hydrophobic and are suitable for preparing oil-in-water emulsion solutions. As the surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant and the like can be appropriately selected and used. Moreover, you may use in combination of multiple types among these. The anionic surfactant is not particularly limited, and examples thereof include alkylbenzene-based, alcohol-based, olefin-based, phosphoric acid-based, and amide-based surfactants, and examples thereof include sodium dodecyl sulfate. The cationic surfactant is not particularly limited, and examples thereof include octadecylamine acetate and trimethylammonium chloride.

  In order for the adsorbent having an increased ratio of the polymer brush of the present invention to function, an ion exchange group, a chelate group, or a nonionic hydrophilic group is introduced into the hydrophobic graft chain, and hydration can be performed in an aqueous solution. It is necessary to swell by applying repulsion to the graft chain by charge repulsion. In the case of a hydrophobic group, it is necessary to swell in an organic solvent. Although a general chemical reaction can be used for the functional group introduction reaction, it can be determined empirically by a preliminary experiment or the like from the viewpoint of swelling the graft chain.

  Among the monomers listed above, GMA is an optimal monomer because it has a double bond necessary for polymerization and an epoxy group for introducing a functional group. For example, a sulfonic acid group can be introduced by heating the GMA graft product in a mixed solution of sodium sulfite, water and isopropyl alcohol. Moreover, a quaternary ammonium group can be introduce | transduced by heating a GMA graft | grafting thing to about 80 degreeC in triethylenediamine aqueous solution. These strongly acidic cation exchangers introduced with sulfonic acid groups and strongly basic anion exchangers introduced with quaternary ammonium groups dissociate over a wide pH range, so that the graft chains swell and the polymer brush functions effectively. Can do.

  An iminodiacetic acid group, which is a typical chelate group, can be easily introduced into the GMA graft product. In this case, if the carboxyl group is a sodium salt type or a potassium salt type, the chelate group is dissociated and a repulsive force acts on the graft chain. However, when the acid treatment is performed to regenerate the H type, the hydrogen bond works and the graft chain shrinks. In addition, when dimethylamine is reacted with the GMA grafted product and an amino group of a weakly basic anion exchange group is introduced, by adsorbing an acid such as hydrochloric acid or sulfuric acid, a sufficient repulsive force acts on the graft chain. become. The post-treatment of these functional groups can be appropriately selected depending on the substance to be treated and the treatment method.

  Styrene monomers such as styrene and chloromethylstyrene are also suitable monomers. For the styrene graft product, a sulfonic acid group can be introduced by dipping in a chlorosulfonic acid / dichloromethane solution. Further, after chloromethylation, a quaternary ammonium group can be introduced by reacting trimethylamine or the like using a chloromethyl group. Further, chloromethylstyrene, which is a monomer already having a chloromethyl group, can also be suitably used. A quaternary ammonium group can be introduced into the chloromethylstyrene graft product in an aqueous trimethylamine solution.

  Functional groups necessary for swelling the polymer brush include sulfonic acid groups, carboxyl groups, phosphoric acid groups, quaternary ammonium groups, and primary to tertiary amino groups as ion exchange groups. Representative chelate groups include amino acid groups, aminophosphate groups, iminodiacetic acid groups, amidoxime groups, and hydroxamic acid groups. Nonionic hydrophilic groups include amide groups and hydroxyl groups, and those selected from these may be used alone or in combination. Further, for example, a hydrophobic group such as a linear alkylamine introduced product swells a polymer brush in an organic solvent, and is effective in supporting an extraction reagent.

  In the case of a water-soluble monomer, it is difficult to prepare an oil-in-water emulsion solution, but if an emulsion solution can be prepared, it is considered possible to apply the same emulsion graft polymerization method as in the case of a hydrophobic monomer. Water-soluble monomers can form water-in-oil emulsions in contrast to non-water-soluble monomers, but they are the most suitable monomers for introducing the hydrophilic or hydrophobic properties of the selected substrate fiber itself and the necessary functional groups. The graft polymerization conditions can be determined by preliminary experiments in consideration of the type of the above.

  In order to directly measure the length of a polymer brush, it is necessary to isolate the brush from the base fiber, but it is very difficult. However, the length information of the polymer brush can be indirectly obtained by measuring the amount of bovine serum albumin (BSA) adsorbed on the polymer brush. In the present invention, the ratio of the polymer brush is evaluated based on the dynamic adsorption capacity of BSA.

  The ratio of the polymer brush can be evaluated by conducting a BSA flow test using an experimental apparatus using the syringe type column 6 and the syringe pump 5 shown in FIG. A BSA solution with a predetermined concentration adjusted to 1 g / L of BSA and Tris-hydrochloric acid buffer 20 mM (pH 8.0) was passed through the syringe filled with the adsorbent 7 at about SV10 to 60, and the treatment liquid 8 was continuously supplied. Collect. The BSA concentration in the collected processing solution is measured by measuring the absorbance at a wavelength of 280 nm, and a breakthrough curve is created. From the breakthrough curve, the product of the stock solution BSA concentration up to the point at which 10% of the stock solution BSA leaks out and the fluid passage volume (representing how many times the filling volume was passed through) is taken as the dynamic adsorption capacity. Yes. An example is shown in FIG. Here, the manufacturing conditions for comparison need to be the same substrate, the same radiation source, the irradiation amount, the functional group type, and the graft ratio.

  As the fiber base to be used, various shapes such as twisted yarn, non-woven fabric, woven fabric, and cotton lump shape can be used. The optimum shape can be selected in consideration of the usage method suitable for the application location. The twisted yarn is a single fiber twisted from several tens to several hundreds. The twisted yarn 17 is generally handled as a bobbin wound around the perforated core 12 as shown in FIG. Radiation graft polymerization is also carried out in the form of a bobbin, and thereafter, from irradiation to graft polymerization and secondary reactions are carried out in the form of a bobbin. Functional group-introduced fibers with an increased polymer brush ratio are also produced in a bobbin shape.

  Bobbin-shaped twisted yarn is used and processed using a dedicated molding device. The twisted yarn can be cut and processed into cut fiber, wind filter or braid. In the case of a sheet like non-woven fabric or woven fabric, it is possible to react while being wound like a bobbin, but the roll-to-roll reacts by moving the sheet wound around the roll from roll to roll. A scheme is also possible and either can be used. Nonwoven fabrics and woven fabrics are in sheet form and can be processed into pleated filters that are pleated and wound around a perforated core. It can also be processed into a laminated filter in which a sheet is wound around a perforated core.

  Further, it can be molded into a molding fiber structure as shown in FIG. The molding-like structure is a kind of braid having a structure in which twisted yarns 13 that are fibrous adsorbents are radially projected outside the core 14. Depending on the usage situation, the entire length of the molding can be cut into a predetermined length and used. When a mall is used, harmful substances in liquid or gas can be removed by hanging the mall. The radioactive cesium released from the Fukushima Daiichi nuclear power plant exists in various forms, but many are said to be in a colloidal state or attached to fine particles, such as stagnant water, soil, buildings, harbors, rivers, It exists in various environments such as drainage channels and gutters. A mall-like fiber structure is optimal because it can capture radioactive cesium and suppress diffusion by simply laying it in a pond or ditch. It can be processed into a sheet such as a non-woven sheet or woven cloth and used as wiping paper. In addition, mats and nets can be placed on the floor and road to prevent the spread of contamination. Those that diffuse into the air, such as radioactive iodine, can be used like curtains and goodwill, and can be used in shelters and waiting areas. Of course, it can also be used for masks. It can be used according to the situation on the spot. The used molding can be easily disposed of by winding it up by an appropriate means, and the amount of waste generated is small.

  The cut fiber can be used in a packed tower system in the same manner as a normal ion exchange resin. Since the ion-exchange resin has a large filling rate of about 60% and a high pressure loss, the liquid passing treatment or the aeration treatment is usually performed at a flow rate of about SV5 to 50. Since cut fibers have a filling rate as small as 30%, pressure loss is small and high-speed processing of SV100 or higher is possible. The cut fibers can be used in a fluidized bed as well as a fixed bed. Furthermore, it is also possible to use in a slurry system in which cut fibers are put into stagnant water or running water, adsorbed by pump circulation for a predetermined time, and then filtered and separated with a mesh or wire mesh having a predetermined opening.

  As described above, the fibrous adsorbent using the radiation graft polymerization method can be used in various ways depending on the use environment. The function of the fibrous adsorbent with an increased polymer brush ratio can be greatly improved.

  Hereinafter, although an Example demonstrates concretely, the aspect of this invention is not restricted to a following example.

[Example 1]
BSA adsorption test (production of fibrous adsorbent A1 by emulsion graft polymerization method)
A nylon fiber having a diameter of about 45 μm was irradiated with 40 kGy of gamma rays. Next, it is immersed in an emulsion monomer solution of glycidyl methacrylate (GMA) / surfactant TWEEN 20 / water (= volume ratio 5 / 0.5 / 94.5) previously deoxygenated by nitrogen bubbling and reacted at 45 ° C. for 6 hours. did. After completion of the reaction, the fiber was immersed in a dimethylformamide solution and methanol and washed. A weight increase rate (graft rate) of 116% was obtained by measuring the weight after drying. Next, the GMA graft fiber was immersed in a 50% diethylamine (DEA) / 50% water solution and heated at 40 ° C. for 6 hours to introduce DEA groups. The fiber was washed with methanol, and then the dry weight was measured. From the weight increase rate, a DEA-introduced fiber of 1.5 mmol / g was obtained.

(BSA adsorption test)
0.3 g of fibrous adsorbent A1 was sampled and cut to a length of about 1 cm, and then filled into the syringe of FIG. 2 so that the layer height was 10 mm. Next, as a pretreatment, a 20 mM Tris-HCl buffer solution (pH 8.0) was passed through SV30 for 1 hour. Thereafter, a BSA stock solution prepared with a 20 mM Tris-HCl buffer solution (pH 8.0) so as to be 1 g / L of BSA was passed through SV10, and a treatment solution was collected. The BSA concentration in the treatment liquid was measured by measuring the absorbance at 280 nm, and a breakthrough curve was created. The dynamic adsorption capacity of BSA of 20 g-BSA / L-filled volume (66 mg / g-fiber) from the product of the flow-through volume up to the point when 10% of the stock BSA concentration leaks from the breakthrough curve. Got.

[Comparative Example 1]
(Production of fibrous adsorbent B1 by liquid phase graft polymerization)
In the method for producing the fibrous adsorbent A1 of Example 1, liquid phase graft polymerization was performed at 45 ° C. for 5 hours while the irradiated nylon fibers were immersed in a 10% GMA / methanol solution. The GMA graft fiber after the reaction was washed and dried in the same manner, and a graft rate of 124% almost the same as in Example 1 was obtained. Next, DEA groups were similarly introduced to obtain 1.6 mmol / g DEA-introduced fiber.

(BSA adsorption test)
When the same BSA adsorption test was performed using the fibrous adsorbent B1, BSA leaked from the beginning of the liquid flow, and the dynamic adsorption capacity was 1.5 g-BSA / L-filled volume (5 mg / g-fiber ) And a small value.

  According to Example 1 and Comparative Example 1, the BSA adsorption amount of the fibrous adsorbent A1 obtained by the emulsion graft polymerization method is about twice or more compared with the liquid phase graft polymerization method even at the same graft ratio and the same ion exchange capacity. It was found that the ratio of the polymer brush was 10 times or more.

[Example 2]
Relationship between Graft Rate and Dynamic Adsorption Capacity of BSA Using the same emulsion graft polymerization method as the production method of fibrous adsorbent A1, changing only the graft polymerization time, 10 samples with different graft rates from 10% to 250% Then, a DEA group was introduced in the same manner as in Example 1. This fiber was subjected to a BSA flow test and the dynamic adsorption capacity up to 10% leakage of the BSA stock solution concentration was measured.

  The relationship between the graft ratio and the BSA dynamic adsorption capacity is as shown in FIG. 10. When the graft ratio was 20% or less, the BSA dynamic adsorption capacity was small and the ratio of the polymer brush was not high. Above 150%, the adsorption capacity of bovine serum albumin was large up to 200%, but physical strength deterioration was observed. In the emulsion graft polymerization method, 20 g / L-fiber (60 mg / g-fiber) or more was shown on a bovine serum albumin adsorbed basis in comparison with the liquid phase graft polymerization method when the graft ratio was in the range of 20 to 200%. Therefore, the graft ratio obtained by the emulsion graft polymerization method is preferably 20% to 200%. More preferably, it is 20% to 150%, and most preferably 30% to 130%.

[Example 3]
Sodium ion removal test (production of fibrous adsorbent A2 by emulsion graft polymerization method)
The GMA graft fiber of Example 1 was immersed in a solution of 10% sodium sulfite, 13% isopropyl alcohol and 77% water, and a sulfonation reaction was performed at 80 ° C. for 16 hours. The obtained sulfonated fiber was dipped in 1N hydrochloric acid for 1 hour to regenerate to H type and thoroughly washed with pure water. Then, it was immersed in 1N sodium chloride aqueous solution for 1 hour, and the fiber was removed. The fiber was washed with pure water, and the washing liquid was also added to the immersion liquid. The total amount of this solution was neutralized with 0.1 N hydrochloric acid to measure the ion exchange capacity. As a result, a strongly acidic cation exchange fiber having a neutral salt decomposition capacity of 2.3 meq / g was obtained.

(Ion exchange test)
5 g of the strongly acidic cation exchange fiber of the fibrous adsorbent A2 was cut to a fiber length of 0.5 to 1 cm and regenerated into an H shape. This fiber was packed in an acrylic column having an inner diameter of 15 mm so that the layer height was 10 cm. The column was washed with 5 L of ultrapure water (specific resistance: 18 MΩ · cm or more) manufactured by Millipore. Sodium chloride was dissolved in this ultrapure water to prepare raw water for ion exchange test with a Na concentration of 1 mg / L. This raw water was passed through the column at a flow rate of 10 L / h (SV400), and the Na concentration at the outlet was measured using ICP-AES and found to be 0.048 mg / L.

[Comparative Example 2]
(Production of fibrous adsorbent B2 by liquid phase graft polymerization)
The GMA liquid phase graft polymer of Comparative Example 1 was sulfonated according to Example 3 and the ion exchange capacity was measured. As a result, a strongly acidic cation exchange fiber having a neutral salt decomposition capacity of 2.2 meq / g was obtained. It was.

(Ion exchange test)
Using this fiber, the same ion exchange test as in Example 3 was performed. The Na concentration at the column outlet was 0.12 mg / L, which was slightly higher than that of the example.

  From Example 3 and Comparative Example 2, both the strongly acidic cation exchange fiber obtained by the emulsion graft polymerization method and the strongly acidic cation exchange fiber obtained by the liquid phase graft polymerization method have almost the same neutral salt decomposition capacity. In the ion exchange test, the treated water quality of the fibrous adsorbent 3 obtained by emulsion graft polymerization is better. In the high-speed liquid passing test such as SV400 or higher, the higher the ratio of the polymer brush, the higher the ion exchange performance. I also found it good. The removal performance with respect to sodium ions was higher than that obtained by the usual liquid phase graft polymerization method, and the effect of increasing the ratio of the polymer brush was recognized.

[Example 4]
Colloidal particle removal test from soil (production of fibrous adsorbent A3 by emulsion graft polymerization)
The GMA graft-polymerized fiber of Example 1 was immersed in a solution of 10% by weight of triethylenediamine (TEDA), 20% of isopropyl alcohol and 70% of water and heated at 70 ° C. for 6 hours to introduce triethylenediamine. . 1.6 mmol / g of TEDA was introduced from the weight change before and after the introduction of TEDA. Further, after being immersed in a 5% aqueous sodium hydroxide solution for 30 minutes, it was thoroughly washed with pure water and the ion exchange capacity was measured. As a result, a strong basicity having a neutral salt decomposition capacity of 1.5 meq / g was obtained. It was an anion exchange fiber.

(Removal of chromaticity components derived from soil)
50 g of soil in front of the Chiba University Faculty of Engineering was collected, put into a drum can containing 200 L of tap water, and stirred for 1 hour. After standing for 24 hours, the supernatant was filtered through a filter manufactured by Millipore having a pore size of 0.45 μm, and the passed liquid was used as raw water for evaluation. When the turbidity and chromaticity of the raw water were measured by the water test method, the turbidity was 2 ° and the chromaticity was 30 °. The fibrous adsorbent A3 was cut to 5 mm to 10 mm, and 1.5 g was packed in a column having a diameter of 15 mm. The layer height was 30 mm. Raw water for evaluation was passed through this column at a flow rate of 2.7 ml / min, and the chromaticity of the treatment liquid was measured. As a result, the turbidity was 2 degrees or less and the chromaticity was 3 degrees from the initial stage of passing the liquid to 3 L. The chromaticity started to increase when it exceeded 3 L and reached 5 degrees. The turbidity was kept below 2 degrees.

[Comparative Example 3]
(Production of fibrous adsorbent B3 by liquid phase graft polymerization)
Using the GMA graft fiber of the fibrous adsorbent 11 used in Comparative Example 1, TEDA was introduced under the same conditions as in Example 4. The TEDA introduction amount calculated from the change in weight was 1.5 mmol / g, and the neutral salt decomposition capacity was 1.4 meq / g.

(Removal of chromaticity components derived from soil)
When the chromaticity removal test was conducted under the same conditions as in Example 4 using the fibrous adsorbent B3, the turbidity was 2 degrees or less and the chromaticity was 3 degrees at the beginning of the liquid passage. The chromaticity exceeded 5 degrees at the time of 1.3 L. Turbidity was maintained at 2 degrees or less.

  The colored components derived from the soil that passed through the 0.45 μ filter are mainly colloidal particles composed of humic substances and fine clay minerals. It was confirmed that the fibrous adsorbent A3 having a long polymer brush can remove the pigment component well and has a high effect of removing colloidal particles as compared with the fibrous adsorbent B3 produced from ordinary liquid phase graft polymerization.

[Example 5]
Cesium removal test (production of fibrous adsorbent A4 by emulsion graft polymerization)
The fibrous adsorbent A3 of Example 4 was immersed in a 5% aqueous potassium ferrocyanide solution at room temperature for 1 hour to adsorb ferrocyanide ions. Next, it was immersed in a 1% aqueous solution of cobalt chloride for 1 hour, and insoluble cobalt ferrocyanide was deposited and supported on the fibrous adsorbent A3. After drying, the weight was measured, and the weight difference from when the original fibrous adsorbent A3 was collected was divided by the weight after loading to obtain a loading rate of 10.3%.

(Cesium removal test)
Cesium chloride was dissolved in artificial seawater to prepare raw water for a radioactive cesium adsorption experiment with a cesium concentration of 9.3 mg / L. 5 g of fiber was added to 500 ml of raw water for evaluation, and the cesium concentration in the liquid was measured by ICP-MS. The cesium concentration in the liquid was 1.1 mg / L, 0.3 mg / L and 0.1 mg / L or less after 5 minutes, 10 minutes and 15 minutes, respectively.

[Comparative Example 4]
(Production of fibrous adsorbent B4 by liquid phase graft polymerization)
The same procedure for carrying cobalt ferrocyanide as in Example 5 was performed on the fibrous adsorbent B3 of the comparative example. The amount of cobalt ferrocyanide supported was 7.3%.

(Radiocesium removal test)
When an experiment of cesium was performed in the same manner as in Example 5, the cesium concentration in the liquid was 2.0 mg / L, 1.1 mg / L, and 0.5 mg / L after 5 minutes, 10 minutes, and 15 minutes, respectively. Indicated.

  Cobalt ferrocyanide crystals with high selectivity to radioactive cesium were supported on strongly basic anion exchange fibers. The fiber supported on the longer side of the polymer brush had a higher loading rate compared to 10.3% on the shorter side, which was 7.3%, and the removal rate of cesium from seawater was higher.

[Example 6]
(Simultaneous removal test of ionic and colloidal cesium)
Cesium was added to a filtrate of 2 mg / L to the filtrate obtained by filtering the soil in front of the engineering building of Chiba University in Example 4 with a filter made by Millipore having a pore diameter of 0.45 μm. This solution was passed through the fibrous adsorbent A3 at SV30, and the cesium concentration in the treatment liquid in the initial stage of passing without causing chromaticity leakage was measured. The cesium concentration was 0.6 mg / L. Since the fibrous adsorbent A3 has a positively charged polymer brush, colloidal cesium can be removed. As a result, it was found that 70% of cesium added at 2 mg / L was colloidal and 30% was ionic. A column packed with the same fibrous adsorbent A4 (radioactive cesium removal fiber) as in Example 5 was passed under the same conditions, and the cesium concentration in the treatment liquid was measured. At the beginning of the liquid flow, the cesium concentration in the treatment liquid was 0.1 mg / L or less, and gradually increased to 0.3 mg / L at 2.1 L where chromaticity began to leak.

[Comparative Example 5]
A test similar to Example 6 was performed using the fibrous adsorbent B4. Initially, the concentration of cesium was 0.1 mg / L, but at 1.0 L, the concentration began to rise to 0.3 mg / L, and the color began to leak.

  When Example 6 and Comparative Example 5 were compared, it was found that the increase in cesium concentration coincided with the leakage of chromaticity. At this time, since the adsorption capacity of ionic cesium has not been reached from Example 5 and Comparative Example 4, it can be confirmed that both ionic and colloidal cesium are removed until the chromaticity starts to leak. It was. Therefore, it was found that the higher the polymer brush ratio, the higher the removal rate of both cesium ions and cesium colloids. In addition, it was found that the colloid removal rate was smaller when the larger amount of cobalt ferrocyanide was loaded than when it was not loaded, and the colloid removal performance was affected by the loading rate.

[Example 7]
Iodide ion removal test (production of fibrous adsorbent A5 by emulsion graft polymerization)
The TEDA introduction fiber of the fibrous adsorbent A3 was immersed in a 5% sodium chloride solution for 30 minutes to convert the quaternary ammonium group at the TEDA introduction site into a chloride ion type. Next, 3% of silver nitrate was brought into contact to obtain a silver chloride-supporting fibrous adsorbent having a support rate of 20%.

[Comparative Example 6]
(Production of fibrous adsorbent B5 by liquid phase graft polymerization)
The TEDA-introduced fiber used in Comparative Example 3 was treated in the same manner as in Example 7 to produce a silver chloride-carrying fiber. The silver chloride loading was 12%.

  The iodide ions in the liquid by the silver chloride-supporting fibrous adsorbent are removed by replacing the chloride ions of silver chloride with iodine ions. Therefore, it was found that the fibrous adsorbent having a high ratio of the polymer brush having a large silver chloride loading amount is superior in removing iodine ions.

[Example 8]
Extraction reagent support material (production of fibrous adsorbent A6 by emulsion graft polymerization)
The GMA graft fiber of Example 1 was immersed in dodecylamine 40 v / v% / isopropyl alcohol (IPA) 90 v / v%, reacted at 70 ° C. for 8 hours, washed with acetone, and weight change after drying. To 1.7 mmol / g of dodecylamine-introduced fiber. Dodecylamine is an amine having a linear alkyl group having 12 carbon atoms. Since the epoxy group of GMA reacts with the amine, the structure after the reaction is a structure in which the side chain having 12 carbon atoms extends like a branch at a ratio of one ethylene unit of the graft chain. Extraction reagent bis 2-ethylhexyl hydrogen phosphate (abbreviation HDEHP) was immersed in a solution of HDEHP10 / IPA90 at a volume ratio of 2 hours at 40 ° C. After washing with water, the dry weight was measured and the amount supported was 34%.

(Neodymium adsorption test)
Neodymium chloride was dissolved in 0.01M hydrochloric acid to prepare a neodymium adsorption evaluation stock solution having a neodymium concentration of 103 mg / L. A fibrous adsorbent 0.5 g was cut to a fiber length of 0.5 to 1 cm and packed into an acrylic column having an inner diameter of 10 mm so that the layer height was 20 mm. The neodymium adsorption evaluation stock solution was passed through this column with SV20, and the neodymium concentration in the treatment liquid was measured. When the dynamic adsorption capacity was determined from the flow rate until the neodymium concentration reached 10 mg / L, which was 10% of the stock solution, it was 67 mg / g.

[Comparative Example 7]
(Production of fibrous adsorbent B6 by liquid phase graft polymerization)
The same dodecylamine as in Example 8 was introduced into the GMA-grafted fiber of Comparative Example 1 to obtain 1.5 mmol / g of dodecylamine-introduced fiber. Furthermore, when HDEHP was supported under the same conditions, the amount of HDEHP supported was 9.6%.

(Neodymium adsorption test)
An adsorption test similar to the neodymium adsorption test of Example 8 was performed. The neodymium adsorption capacity was 18.5 mg / g, which was about 1/3 smaller than that of the example.

  The adsorption capacity of the extraction reagent-carrying material depends on the amount of extraction reagent carried. The graft chain and hydrophobic group after introduction of dodecylamine was a swelling system under the extraction reagent loading condition with HDEHP 10% / IPA solution, and the loading amount could be increased. Neodymium adsorbs one neodymium ion to three molecules of the extracted extraction reagent. Therefore, it was clear that the fibrous adsorbent with a higher ratio of the polymer brush is more advantageous because it has a larger amount of extraction reagent.

[Example 9]
Removal of Hydrogen Peroxide with Palladium-Supported Fiber The fibrous adsorbent A1 described in Example 1 was immersed in a 2% aqueous solution of palladium chloride (PdCl4 ²⁻ ) at room temperature for 1 hour to adsorb palladium chloride complex ions. After performing batch washing three times with a 0.2% hydrochloric acid solution, it was immersed in a 10% aqueous solution of hydrazine for 1 hour. After performing pure water washing 5 times,
The amount of palladium immobilized measured from the dry weight was 70 mg / g.

(Hydrogen peroxide removal test)
The fibrous adsorbent A7 was cut to 0.5 to 1 cm, and 2 g was packed in the column of Example 2. The layer height was 30 mm. Hydrogen peroxide 100 μg / L was passed through the column at different flow rates, and the hydrogen peroxide concentration in the treatment liquid was measured by the phenol phthaline method. The removal rate of hydrogen peroxide was 100% until SV4500.

[Comparative Example 8]
(Production of fibrous adsorbent B7 by liquid phase graft polymerization)
Palladium was immobilized on the fibrous adsorbent 11 described in Comparative Example 1 in the same manner as in Example 9. The amount of palladium immobilized was 58 mg / g.

(Hydrogen peroxide removal test)
The fibrous adsorbent B7 was cut to 0.5 to 1 cm, and a hydrogen peroxide removal test was performed in the same manner as in Example 9. The removal rate of hydrogen peroxide was 100% until SV3000, but the removal rate gradually decreased after SV3000.

  Palladium, a metal element representing a white metal catalyst, was immobilized on a fibrous adsorbent. It was found that by increasing the ratio of the polymer brush, the amount of palladium immobilized was increased and the reduction performance of hydrogen peroxide was improved. The improvement in the function of the oxidation / reduction catalyst can be said for other catalytic metals other than palladium.

[Example 10]
Removal of Ammonia in Gas Using Strong Acid Cation Exchange Fiber An ammonia removal test in the gas phase was conducted using the fibrous adsorbent A2. 1 g of this strongly acidic cation exchange fiber was inserted into a 10 L tedra bag and sealed with a policyler. Next, 10 L of air was introduced into the bag using a pump, and ammonia was further injected from the gas sampling port with a syringe so that the concentration in the bag was 100 ppm. Immediately after the start of injection, the ammonia concentration in the bag was measured with a gas detector tube, and it decreased to 1 ppm or less in 30 minutes.

[Comparative Example 9]
Using the fibrous adsorbent B2, the same ammonia removal test in the gas phase as in the example was performed. The ammonia concentration after 30 minutes was 2.5 ppm.

  From Example 4 and Comparative Example 3, it was found that the fibrous adsorbent with an increased polymer brush ratio is effective not only in the liquid phase but also in improving the adsorption performance of ammonia gas in the gas phase.

[Example 11]
Deodorization and removal of cigarette smoke with strong acid and strongly basic anion exchange fibers A fibrous adsorbent is installed in the order of fibrous adsorbent A2 and fibrous adsorbent A3 from the upstream in a deodorizing test evaluation apparatus having a filter mounting part of 50 mmφ. The deodorization test was conducted by the flow method shown in FIG. In the filter mounting part, 6 g of each of the fibrous adsorbents A2 and A3 was cut to 0.5 to 1 cm and filled so as to have a layer thickness of 1 cm. The test gas was ammonia (basic gas) and acetic acid (acid gas) using a permeator for gas generation. Tobacco smoke was evaluated by a sensory test in which tobacco was actually burned and smelled on the secondary side (exit). The analysis of the gas concentration was performed by inserting the tip of a Kitagawa type gas detector tube (manufactured by Komyo Chemical Co., Ltd.) from the sampling ports attached before and after the filter mounting portion and sucking it, and judging it by the degree of coloring of the detector tube. The results are shown in Table 1.

[Comparative Example 10]
An experiment similar to Example 11 was performed using the fibrous adsorbents B2 and B3. The results are also shown in Table 1.

  Ammonia and acetic acid were removed in both Examples and Comparative Examples. There was no difference in tobacco odor in the sensory test. However, when 3 minutes passed from the start of the test, a slight odor was felt in the comparative example. When the filter part was disassembled after the test was completed, in Example 11, the fibrous adsorbent A2 had a brown nicotine and a dark tar color and no discoloration was observed in the fibrous adsorbent A3. On the other hand, in the comparative example, the discoloration of the fibrous adsorbent B2 was thinner than that of the example, and color transfer was recognized up to the fibrous adsorbent B3. From this, it was found that the fibrous adsorbent having a high polymer brush ratio is excellent in adsorbing tobacco smoke particles such as tobacco odor, nicotine, and tar with very fine particle diameter. Most other airborne particulates, viruses and aerosols are charged, and it is found that the fibrous adsorbent with an increased polymer brush ratio removes air in the same way as in the case of colloid removal in water. It was.

[Example 12]
BSA adsorption of fibrous adsorbent produced by vapor phase graft polymerization (production of fibrous adsorbent A8 by vapor phase graft polymerization)
The irradiated fiber of Example 1 was loaded into a 3 L flanged glass ampule (inner diameter: 120 mm, trunk length: 250 mm) and evacuated to 10 ⁻⁵ torr with a vacuum pump. In this glass ampule, a plastic mesh frame is installed at a height of 50 mm from the bottom of the ampule with a wire so that irradiated fibers do not fall. A petri dish to which 30 mL of GMA was added was placed under the gantry, and the evaporated GMA passed through the mesh so that it could contact the irradiated fibers. The evacuated ampule was left in a thermostatic bath at 50 ° C. for 4 hours to perform gas phase graft polymerization. After 4 hours, the ampoule was taken out from the thermostat and the gas phase graft polymerization was stopped by releasing the vacuum. The grafted fiber was immersed in 300 mL of dimethylformamide at 50 ° C., and the homopolymer was washed and removed, followed by replacement with methanol and measurement of the dry weight to obtain a graft ratio of 36%. Next, DEA was introduced by the same method as in Example 1 to obtain 1.1 mmol / g of weakly basic anion exchange fiber from the weight increase rate.

(BSA adsorption test)
A BSA adsorption test was conducted in the same manner as in Example 1 to obtain a dynamic adsorption capacity of 21 g / L-filled volume (70 mg / g-fiber).

[Comparative Example 11]
(Production of fibrous adsorbent B8 by liquid phase graft polymerization)
In the method for producing the fibrous adsorbent B2 of Comparative Example 1, liquid phase graft polymerization was performed at 45 ° C. for 1 hour while the irradiated nylon fibers were immersed in a 5% GMA / methanol solution. The GMA graft fiber after the reaction was washed and dried in the same manner to obtain a graft rate of 39%. Next, DEA groups were similarly introduced to obtain 1.0 mmol / g DEA-introduced fiber.

(BSA adsorption test)
Using this fibrous adsorbent B8, the same BSA adsorption test as in Example 1 was conducted. As a result, BSA leaked from the beginning of the liquid passage, and the dynamic adsorption capacity was 1.5 g-BSA / L-filled volume ( 5 mg / g-fiber) and a small value.

  Comparing the example and the comparative example, the polymer brush of the fibrous adsorbent obtained by the gas phase graft polymerization method has the same graft ratio because the BSA adsorption capacity of the example is large despite the same graft ratio. It was found that the ratio was higher than the polymer brush ratio of the fibrous adsorbent obtained by the liquid phase graft polymerization method.

[Example 13]
Virus removal with strong basic anion exchange fiber (production of fibrous adsorbent A9 by emulsion graft polymerization)
The fibrous adsorbent A3 in Example 4 was immersed in a 1% aqueous solution of potassium iodide and converted to the iodide ion type.

(Antiviral test)
Antiviral test against influenza virus was performed by 50% tissue culture infectious dose (TCID ₅₀ ) measurement method. Viral infectivity after 10 minutes (TCID ₅₀₎ was 10 ^2.

[Comparative Example 12]
(Production of fibrous adsorbent B9 by liquid phase graft polymerization)
The fibrous adsorbent B3 was converted to the iodide ion type in the same manner as in Example 12.

(Antiviral test)
Was carried antiviral testing for similar influenza virus as in Example 13, viral infectivity after 10 minutes (TCID ₅₀₎ was 10 ^4.

The antiviral test is performed for a predetermined time after the test virus is inoculated into the fiber. Thereafter, the virus is washed out from the fiber with a washing solution, and the host cells are infected to measure the virus infectivity. The virus infectivity value means the dilution rate when the virus solution is diluted 10-fold, 100-fold, 1000-fold, 10000-fold and 10-fold in order, and this solution infects 50% of cells. Therefore, a virus infectivity titer of 10 ² TCID50 means that 50% of cells were infected with a virus diluted to the square of 10. Looking at the virus infectivity values of the examples and comparative examples, the comparative examples are two orders of magnitude larger and have 50% of infectivity to cells despite being diluted 100 times than the examples. I understand. On the contrary, the virus solution inoculated into the fibrous adsorbent A9 of Example 13 did not infect at the same dilution factor of 10 4 as in Comparative Example 5, but infection occurred at a concentration of 100 times, confirming the antiviral effect. It was done.

[Example 14]
Moisture absorption / desorption test (production of fibrous adsorbent A10 by emulsion graft polymerization)
The GMA graft-polymerized fiber in Example 1 was immersed in 1% sulfuric acid and heated at 70 ° C. for 1 hour. In this reaction, two hydroxyl groups are introduced by ring opening of the epoxy group to form a diol. By measuring the weight increase, 2.1 mmol / g of hydroxyl groups of nonionic hydrophilic groups were introduced.

(Moisture absorption / desorption test in air)
The fibrous adsorbent A10 was placed in a hot air dryer at 80 ° C. to remove moisture. It was taken out from the dryer and left in a room at a temperature of 25 ° C. and a humidity of 75%, and the rate of weight increase was measured. It was 6% at 1 minute, 10% at 2 minutes, and 12% after 10 minutes. Then, when put into an 80 degreeC drying machine for 5 minutes and the weight measurement, the weight increase rate returned to 0%.

[Comparative Example 13]
(Production of fibrous adsorbent B10 by liquid phase graft polymerization)
The GMA graft-polymerized fiber in Comparative Example 1 was subjected to hydroxyl group introduction reaction by opening an epoxy group in the same manner as in Example 13. As a result, the amount of hydroxyl group introduced was 2.2 mmol / g.

(Moisture absorption / desorption test in air)
The same test as in Example 13 was performed. The weight increase after removal from the dryer was 3% in 1 minute, 6% in 2 minutes, and 8% in 10 minutes. Moreover, when it put into the 80 degreeC drying machine for 5 minutes, the weight increase rate returned to 0%.

  As a result of the moisture adsorption / desorption test, it was found that the rate of adsorbing moisture in the air was higher when the ratio of the polymer brush was higher.

[Example 15]
Application to polyethylene fiber
(Production of fibrous adsorbent A11 by emulsion graft polymerization method)
In Example 1, except that the fiber base material was changed to polyethylene having a diameter of about 20 μm, graft polymerization was performed under the same conditions to obtain a graft fiber having a GMA graft ratio of 133%. Next, DEA was introduced, and a 1.7 mmol / g DEA-introduced fiber was obtained from the weight increase rate.

(BSA adsorption test)
The same BSA adsorption test as in Example 1 was performed to obtain a dynamic adsorption capacity of 63 g-BSA / L-filled volume (220 mg / g-fiber) of BSA.

[Comparative Example 14]
(Production of fibrous adsorbent B11 by liquid phase graft polymerization)
In Comparative Example 1, graft polymerization was performed under the same conditions except that the fiber base material was changed to polyethylene having a diameter of about 20 μm to obtain a graft fiber having a GMA graft ratio of 140%. Next, DEA was introduced to obtain 1.8 mmol / g of DEA-introduced fiber based on the weight increase rate.

(BSA adsorption test)
The same BSA adsorption test as in Example 1 was performed to obtain a BSA dynamic adsorption capacity of 4 g-BSA / L-filled volume.

  When the fiber substrate was changed to polyethylene and a BSA adsorption test was performed, 63 was obtained for the emulsion graft polymerization method, and 1 g-BSA / L-filled volume (3 mg / g-fiber) and the emulsion graft polymerization method were used for the liquid phase graft polymerization method. The ratio of the polymer brush obtained in (1) was 70 times larger than that of the liquid phase graft polymerization method. The base polyethylene was more hydrophobic than nylon, and the results suggested that the ratio of polymer brushes would be higher in the oil-in-water emulsion graft polymerization method using hydrophobic monomers.

[Example 15]
(Measurement of tensile strength of fibers used in Examples and Comparative Examples)
When the tensile strength of the fibrous adsorbents A1 and A3 used in the examples was measured in the state of twisted yarn, it was 7 kgf / one twisted yarn. The tensile strength was 50% or more larger than the 4 kgf / one twisted yarn of the fibrous adsorbents B1 and B3 used in the comparative example. Therefore, it was found that the tensile strength of the adsorbent with the increased ratio of the polymer brush was higher than that of a normal liquid phase graft polymerization method in which graft polymerization was performed uniformly to the center of the fiber.

  According to the present invention, it becomes possible to greatly improve the separation functionality of the fibrous adsorbent using the radiation graft polymerization method, the size of the adsorption speed, the ease of molding processing, the pressure loss when passing water is small, etc. Various applications that take advantage of the characteristics of the fiber are possible, and the processing is stabilized. For example, it can be used in various industrial fields such as improving water quality stability during high flow rate processing, removing fine colloidal substances that were difficult to filter with filters, and removing large molecules such as proteins and viruses. Became. In addition, by increasing the ratio of the polymer brush, it is possible to concentrate the graft polymerization on the peripheral edge of the base fiber as a result, increasing the physical strength and having an excellent effect on the molding process. It was.

DESCRIPTION OF SYMBOLS 1 ... Amorphous part 2 ... Crystal part 3 ... Polymer root 4 ... Polymer brush 5 ... Syringe pump 6 ... Syringe 7 ... Adsorbent filling layer 8 ... Outflow liquid 9 ... Fiber cross section 10 ... Charge layer 11 of fiber cross section ... Sodium ion 12 ... perforated core 13 ... adsorption fiber 14 ... core 15 ... bovine serum albumin 16 ... fiber surface 17 ... substrate fiber

Claims (15)

  A separation functional fiber having a functional functional group introduced into a graft chain, wherein the ratio of the polymer brush is 5 mg / bottle on the basis of the bovine serum albumin adsorption amount than the ratio of the polymer brush of the adsorbent obtained by the liquid phase graft polymerization method. An adsorbent in which the ratio of the polymer brush is increased so that the adsorption capacity is not less than g-fiber and not more than 500 mg / g-fiber.   The adsorbent with an increased ratio of a polymer brush according to claim 1, wherein the functional functional group is selected from at least one of an ion exchange group, a chelate group, a nonionic hydrophilic group, and a hydrophobic group.   3. The polymer brush according to claim 1, wherein the shape of the separation functional fiber is selected from fiber, single fiber, twisted yarn that is an aggregate of fibers, woven fabric, non-woven fabric, cut fiber, hollow fiber, or a processed product thereof. Adsorbent with increased ratio.   4. The adsorbent with an increased ratio of polymer brush according to claim 1, wherein the graft chain is provided by a method selected from a pre-irradiation gas phase graft polymerization method or a pre-irradiation emulsion graft polymerization method.   The ratio of the polymer brush according to any one of claims 1 to 4, wherein the pre-irradiation emulsion graft polymerization method uses an oil-in-water emulsion solution containing a non-hydrophilic monomer, a surfactant and water, and the graft ratio is 20 to 200%. Adsorbent with increased resistance.   The adsorbent with an increased ratio of the polymer brush according to claim 1, wherein the non-hydrophilic monomer used in the emulsion graft polymerization method includes glycidyl methacrylate.   The adsorbent with an increased ratio of a polymer brush according to claim 1, wherein a support is supported between the polymer brushes of the adsorbent with an increased ratio of the polymer brush.   The supported material is a ferrocyanate metal salt insolubilized material, hydrous titanium oxide, a titanate metal salt, at least one of silver and a silver compound, at least one of a platinum group element and a platinum group element compound, a transition metal element and a transition metal The adsorbent with an increased ratio of the polymer brush according to claim 1, wherein the adsorbent contains at least one of elemental compounds, an extraction reagent, and an enzyme.   A method for treating a fluid, wherein the adsorbent having an increased ratio of the polymer brush according to claim 1 and a fluid containing a useful substance or a harmful substance are brought into contact with each other.   The contact material is brought into contact with a fluid containing useful substances or harmful substances according to claim 9, wherein ions and colloidal particles in the liquid are simultaneously removed by the adsorbent having an increased ratio of the polymer brush according to claim 1. Processing method   The material removed from the liquid by the adsorbent with the increased ratio of the polymer brush according to claim 1 is a metal ion, halide ion, ionic or colloidal radioactive cesium, radioactive strontium, radioactive iodine The method for treating a fluid in contact with a fluid containing a useful substance or a harmful substance according to claim 10, comprising a colored substance containing humic substances, a virus, or a microorganism.   The fluid containing the useful substance or harmful substance according to claim 9, wherein malodorous substances and suspended particulate substances in the air are simultaneously removed by the adsorbent having an increased ratio of the polymer brush according to claims 1 to 8. Treatment method for fluid contact.   The substance removed from the air by the adsorbent with the increased ratio of the polymer brush according to any one of claims 1 to 8 is selected from basic gas acidic gas, infectious virus, pollen, and aerosol. A method for treating a fluid, which is brought into contact with a fluid containing the useful substance or harmful substance according to claim 12.   The substance adsorbed or purified by the adsorbent having an increased ratio of the polymer brush according to any one of claims 1 to 8 is selected from proteins, enzymes, viruses, antigens, antibodies, and biochemical related substances. Item 10. A method for treating a fluid, wherein the fluid is brought into contact with a fluid containing the useful or harmful substance according to Item 9.   The fluid containing the useful substance or harmful substance according to claim 9, wherein the substance to be treated is an oxidizing / reducing substance by the adsorbent in which the ratio of the polymer brush according to claim 1 is increased. Processing method of fluid to be contacted.