TWI239935B - Sintered body, resin particles and method for production thereof - Google Patents

Abstract

The present invention relates to an adsorbent which can adsorb, concentrate, separate, or remove a minor ingredient contained in a liquid or gas at a high water or gas permeation rate without causing impurity dissolution in the liquid or gas. It is a sinter of a mixture of thermoplastic resin particles having no adsorptive functional groups with resin particles having adsorptive functional groups bonded to the surface thereof through graft polymer chains.

Description

1239935 A7 B7 V. Description of the Invention (Technical Field (please read the precautions on the back before filling out this page) The purpose of this invention is to provide for the treatment of liquids such as water, various aqueous solutions or organic solvents, or for gas When processing the mixture, it can be used to adsorb, concentrate, separate and remove the impurities in the liquid or gas, etc. In particular, to provide in the ultrapure water manufacturing process' can be used to remove particles, colloids by adsorption. The purpose is to obtain porous adsorbents that are necessary for the formation of substances, metal ions, and extremely low concentrations. Technical Background In recent years, in order to reduce the impact on the environment, the process of reducing the generation of various wastes or removing impurities has been started. Concerns have risen, and requirements for methods that can adsorb, concentrate, and separate trace substances in liquids or gases have been increased. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, for example, traditionally, water ions are removed during the water treatment process. Ion exchange resin is used. Conventional ion exchange resins generally have a particle size distribution of 3 0 0 // m to 1 2 0 0 // m, filling the resin tower with such resin, so that when the treated water flows through, the gap between the resins (flow path) due to the large relationship, the accuracy of the contact between the resin surface and the ions in the treated water will change. Small, especially water with low ion concentration, such as ultrapure water, its effect of removing ions is very poor. In addition, in the field of ultrapure water, such as the semiconductor industry, the polymerization of ion exchange resin, the resin Internal impurities of organic type (τ 0 C (total organic carbon) detected in ultrapure water) 'dissolves after a long period of time, but the impurities are caused in the treated water. This paper applies Chinese national standards (CNS) A4 specifications (210X 297 mm) -4- 1239935 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. The problem of invention description (2). Try to use sintered bodies for adsorption, removal, and separation methods, such as Japanese Patent Laid-Open No. 5 1-23492, Japanese Patent Publication No. 7-204429, and the like. Japanese Patent Laid-Open No. 5 1-2 3 4 92 describes the use of sorbents such as silicone and alumina, and polyolefins. Resin powder It is a technique of combining, slurrying, spreading and adhering on a support, and heating to make a sintered body. However, the inorganic absorbing bodies such as sand rubber and alumina cannot be connected to each other by contact with the thermoplastic resin. The powder's connection adhesion is also small, which makes the particles of the adsorbed body fall off, which is unsuitable for use. JP-A-Sho 5 1 — 2 3 4 9 2 and Hyohe 7 — 2 0 4 4 2 9 explain The technology of mixing and sintering ion exchange resins and thermoplastic resin particles is used. However, the use of ion exchange resins does not solve the essential problem of mixing impurities with the dissolution of T 0 C, etc. JP 5 7 — Japanese Patent No. 1 0 9 8 3 7 proposes a method for imparting hydrophilicity to a sintered porous body formed by using a sulfonating agent such as oleum and sulfonating a polyolefin resin. However, due to the sulfonated sintered body resin itself, not only the exchange capacity is reduced, but also the sulfonation method such as fuming sulfuric acid or hot concentrated sulfuric acid has inherent problems, such as acidification, dehydration, and other by-products. Many, like the ion exchange resin, the reverse pollution caused by the elution of impurities cannot be solved at all. In addition, due to side reactions such as acidification and dehydration, there is a problem that fine particles fall off from the fragile resin and are mixed into the treated water. (Please read the notes on the back before filling this page)-Order

Fm, this paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -5-1239935 A7 B7 V. Description of invention (Θ (Please read the precautions on the back before filling this page) In the field of water treatment In order to respond to the requirement of TOC to dissolve ultra-pure water with low and high purity, we have developed a new deionization technology for manufacturing ultrapure water system with absorbing film (Japanese Patent Application Laid-Open No. 5-2 0 9 0 7 1 Japanese Patent Application Laid-Open No. 7-4 1 5 7 4). Compared with ion exchange resins, this ion-adsorbing membrane has a higher efficiency of removing ions and less T 0 C dissolution. Its advantages include flat membranes, fibers, and hollow filaments. However, from the viewpoint of the balance of separation function, water permeability, mechanical strength, etc., the range of pore diameter and film thickness that can be manufactured is limited. In order to increase the film area, the flat film is folded into a crepe in a tube It is necessary to process the hollow fiber into bundles and re-mold it. It is necessary to be an adsorbent. Although the adsorption performance is the first requirement, when the adsorbent is used to treat water or gas, the water permeability 2. Gas permeability is not high, it is not practical enough. And it is preferable that the thickness of the film is large and the pore diameter is large, which makes the technique of manufacturing the above-mentioned ion absorbing film difficult. The present invention provides that impurities such as T 0 C hardly occur, and the processed liquid or gas is not polluted. In particular, absorbing structures that can remove impurities to extremely low concentrations. Description of invention printed by the Consumers 'Cooperative of Intellectual Property Bureau of the Ministry of Economics The present invention is to' use functional groups that have sorption energy by graft polymerization chain bonding Resin particles' aim to obtain an adsorbate with less elution of impurities, and a porous sintered body having this adsorption energy. As a result of diligent research, it was found that they can satisfy adsorption performance, water and air permeability, and low elution of impurities. The material of any one of these properties has reached the result of the invention. That is, the present invention is described as follows. This paper size applies the Chinese National Standard (CNS) A4 specification (21〇 > < 297 Gonglu) -6-1239935 A7 B7 ___ V. Description of the invention (j (1) is a sintered body of thermoplastic resin particles, which is bonded to a porous sintered body based on its surface by a graft polymer chain and has a function of adsorption energy. (Please read the precautions on the back before filling this page) (2) The sintered body as described in (1) above, the voids are voids formed when the thermoplastic resin particles are dissolved and bonded, and the average void diameter is 1 Am The above is less than 100 // m. (3) The sintered body according to the above (1) has a porosity of 20% or more and less than 60%. (4) As described in the above (1) The sintered body has a function of absorbing energy based on a concentration in the sintered body of 0 · 3 mm ο 1 / g or more and less than 1 Ommo 1 / g. (5) The sintered body according to the above (1), wherein The functional group having an adsorption energy is spread on the surfaces of the thermoplastic resin particles constituting the sintered body. (6) The sintered body as described in the above (1), wherein the thermoplastic resin particles are polyolefin resins. (7) The sintered body according to the above (1), wherein the functional group having an adsorption energy is an ion exchange group. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (8) A porous sintered body containing a mixture of thermoplastic resin particles and resin particles with functional sorption energy based on the surface of the resin particles. (9) The sintered body according to the above (8), wherein the pores are voids formed when the particles of the sintered body are dissolved in the bond structure, and the average pore diameter is 1 // m or more and less than 100 // m . (1 0) The sintered body as described in (8) above, the porosity of this paper is the same as the standard of Chinese paper (CNS) A4 (210'〆297 mm) 1239935 Μ B7 V. Description of the invention (5) Above 20%, less than 60%. (1 1) The sintered body according to the above (8), wherein the thermoplastic resin particles are formed of a polyolefin. (1 2) The sintered body according to the above (8), wherein the function having an absorption energy is based on a concentration in the sintered body of 0 · 3 m m ο 1 / g or more and less than 10 mmo 1 / g. (1 3) The sintered body according to the above (8), wherein the resin particles based on the surface of the sintered body are functionally bonded to each other with a function of absorbing energy by graft polymerization, and the proportion of the entire sintered body is 10% by weight or more. 70% by weight or less (14) The sintered body according to the above (8), wherein the functional group having an adsorption energy is distributed on the surface of the resin particles. (1 5) The sintered body according to the above (8), wherein the functional group having an adsorption energy is a resin particle bonded to its surface by graft polymerization chain, and the resin particle has an adsorption by graft polymerization chain bonding. The energy function is based on the polyalkene resin particles on its surface. (16) The sintered body according to the above (8), wherein the functional group having an adsorption energy is an ion exchange group. (17) Resin particles having a functional group having an adsorption energy are bonded by graft polymerization. (18) The resin particles according to the above (17), wherein the functional group having an adsorption energy is distributed on the surface of the resin particles. (19) The resin particles according to (17) above, wherein the resin particles are made of a polyalkene. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling this page). Printed by the Consumer Cooperative of the Property Bureau 1239935 A7 B7 V. Description of the invention (β) (2 0) The resin particles as described in (1 7) above, in which the concentration of the functional group having adsorption energy is 0.3 mm0 1 / g or more , 1 Ommo 1 / g is not full. (2 1) The resin particle according to (17), wherein the functional group having an adsorption energy is an ion-exchange group. (2 2) The resin particle according to the above (17), wherein the particle diameter is 300 // m or less. (2 3) A method for producing a sintered body, which comprises sintering thermoplastic resin particles having a particle diameter of 300 # m or less, and bonding with a functional group having a particle diameter of 300 // m or less that can have adsorption energy The particle mixture made of the crosslinked resin particles is made into a porous resin matrix, and the functional groups are bonded to each other with adsorption energy. (2 4) The production method according to the above (2 3), wherein the mixing ratio of the crosslinked resin particles having a functional group bond having adsorption energy can be 10% by weight or more of the entire mixture, 70 % Weight is not full. (2 5) The production method according to the above (2 3), wherein the thermoplastic resin particles are formed of a polyolefin. (2 6) The production method according to the above (2 3), wherein the crosslinked resin particles are resin particles having a crosslinked layer formed by a graft polymerization reaction. (2 7) The production method according to the above (2 3), wherein the crosslinked resin particles are resin particles that form a crosslinked layer on a polyolefin. (28) The production method according to the above (2), wherein the functional group having an adsorption energy is an ion exchange group. This paper size applies to China National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before filling this page)

-9-1239935 A7 B7 V. Description of the invention (7) (Please read the precautions on the back before filling out this page) (2 9) Manufacturing method of sintered body, including thermoplastic resin with sintered particle size below 3 0 0 β m The particles are a particle mixture formed by grafting and polymerizing a resin particle having a functional group having an adsorption energy with a particle size of 300 // m or less. (3 0) The manufacturing method according to the above (2 9), wherein the mixing ratio of the resin particles having a functional group having an absorption energy is bonded by graft polymerization, and the mixing ratio is 10% by weight or more of the entire mixture, 7 0% by weight or less (3 1) The production method according to the above (2 9), wherein the thermoplastic resin particles are formed of a polyolefin. (3 2) The manufacturing method according to the above (2 9), wherein the resin particles having a functional group having an adsorption energy are bonded by graft polymerization, and the resin particles having an adsorption energy are bonded by graft polymerization. Polyolefin resin particles with functional groups. (3 3) The production method according to the above (2 9), wherein the functional group having an adsorption energy is distributed on the surface of the resin particles. The consumer property cooperation printed by the Intellectual Property Bureau of the Ministry of Economic Affairs (3 4) The manufacturing method as described in (2 9) above, wherein the metal is salted before the functional group with absorbing energy is sintered. (3 5) The production method according to the above (2 9), wherein the functional group having an adsorption energy is an ion exchange group. (3 6) A method for manufacturing a sintered body based on the surface of a sintered body having a function of bonding energy based on bonding, which is included on the surface of the sintered body of thermoplastic resin particles to form a crosslinked body layer, followed by the Functional groups with sorption energy. This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) — -10- 1239935 A7 ________ V. Description of invention (g) (Please read the precautions on the back before filling this page) (3 7) The manufacturing method described in (3 6) above, wherein the particle diameter of the thermoplastic resin particles forming the sintered body of the thermoplastic resin particles is 3 0 0 // m or less. (38) The production method according to the above (36), wherein the thermoplastic resin particles are formed of a polyolefin. (39) The manufacturing method according to the above (36), wherein the thermoplastic resin particle sintered body is irradiated with radiation, and is contacted with a reactive monomer under stirring in a solvent that does not swell the thermoplastic resin particles to form The crosslinked layer is followed by a function in the liquid phase that enables the reaction with the crosslinked layer to have a function of adsorption energy. (40) The production method according to (36) above, wherein the functional group having an adsorption energy is an ion-exchange group. (41) A method for manufacturing a resin particle having a function of bonding energy based on its surface, which is included on the surface of the resin particle to form a crosslinked body layer, and the second is to make the reaction with the crosslinked body layer having an absorption energy Functional group reaction. (4 2) The manufacturing method described in (4 1) above, wherein the particle size of the lipid particles printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is 3 0 0 // m or less. (4 3) The production method according to (4 1) above, wherein the resin particles are formed of a polyolefin. (4 4) The manufacturing method according to the above (4 1), wherein the resin particles are irradiated with radiation, and then stirred in a solvent that does not swell the resin particles, and contacted with a reactive monomer to form a crosslinked body layer, followed by The function with sorption energy that enables the reaction with the crosslinked body layer is based on the reaction in the liquid phase. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -11-1239935 A7 __B7 __ V. Description of the invention (g) (4 5) The manufacturing method described in (4 1) above, where The functional group having an adsorption energy is an ion exchange group. (Please read the precautions on the back before filling out this page.) Brief description of the drawing Figure 1 shows the manufacturing flow chart of the sintered compact in the present invention. Fig. 2 is a schematic diagram showing a cylindrical filter using a sintered compact in the present invention. Best Mode for Carrying Out the Invention In the present invention, in order to introduce an absorbing function based on the sintered body itself, an absorbing group is present on the surface of the sintered body, so that an absorbing body having excellent absorbing property and hardly eluting impurities is obtained. The sintered body of the present invention controls the pore diameter according to the particle size obtained by sintering the thermoplastic resin and the resin particles introduced with the absorbing functional group, and controls the thickness of the sintered body by filling the particles with the voids of the metal device, so it is easy to form The sintered body with a large pore size can maintain the porosity of the sintered body even if many absorbing bases are introduced without blocking its pores. It can improve the adsorption capacity, water permeability and air permeability. It is produced by the employee's intellectual property bureau of the Ministry of Economic Affairs. This invention is explained in more detail. <Thermoplastic resin particle> The thermoplastic resin particle (henceforth a thermoplastic resin particle) in this invention is a granular material containing the following. Vinyl chloride resins including polyvinyl chloride, polyvinyl chloride, etc .; Polyolefin resins represented by polyethylene and polypropylene storage; Polyethylene terephthalic acid as representative

1239935 Α7 Β7 V. Description of the invention (Shi ester resin; including polystyrene, polyamidoamine, polyoxymethylene, polycarbonate, polyethylene master class, polyether master (PES), polyphenylene sulfide (PPS), polymethyl (Please read the precautions on the back before filling out this page) So-called engineering plastics such as methyl methacrylate (P Μ Μ A), polyether ether ketone (PPE), etc .; polyvinylidene fluoride (PVDF), ethylene 1-4 A fluorine resin such as a fluoroethylene copolymer. In the sintering process of the present invention, the thermoplastic resin particles are heated to the vicinity of the melting point, and after melting, the functional group having an adsorption energy is bonded with the graft polymerization chain. Resin particles (hereinafter referred to as absorbing resin particles), when the particles are in contact with each other, are melted and bonded to each other to form a structure of a sintered body having pores formed by voids between the particles. For heat resistance, it is important to choose a thermoplastic resin with a suitable melting point. Especially at high temperatures above 180 ° C, the thermal decomposition of functional groups will become fierce. Therefore, it is recommended to use them below 180 ° C. Temperature, between particles It is advisable to melt and bond the resins. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. In addition, when the thermoplastic resin has a large melt flow, during the sintering step, flow deformation will occur to destroy the voids or cover the holes. The problem of the surface of the bonding functional group is that it is suitable to use a resin that is difficult to flow. The index of the fluidity of the molten thermoplastic resin is, for example, M I (Melting Index) measured according to ASTM D 1 2 3 8 8, 0.5 g / 10 points or less is preferable, and 0 · 1 g / 10 points or less is more preferable. It is not even possible to measure the hard-flowing thermoplastic resin of MEMS. Among the thermoplastic resins, the price is cheap. In terms of excellent chemical resistance, excellent processability, material hygroscopicity, and low water absorption, etc., polyethylene, this paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) -13-1239935 Ministry of Economic Affairs Printed by the Intellectual Property Bureau Staff Consumer Cooperative A7 B7

V. Description of the invention (A Representative of polypropylene: Polyolefin resin or fluorine resin with low melting point polyfluorinated vinylidene is suitable. Examples of polychain hydrocarbon resins include polyethylene, polypropylene, and ethylene. -Propylene copolymer, ethylene-butene-1 copolymer 'ethylene-hexene-1 copolymer, ethylene-pentene-1 copolymer, ethylene-octene-1 copolymer, ethylene-4 methylpentene-1 1 copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, etc. Among them, it is easy to obtain particles used in sintering, easy to sinter, and to resist For reasons such as excellent chemical properties, polyethylene is preferred. From the viewpoint of fluidity in the sintering molding step described above, a 'high molecular weight polyethylene having a weight average molecular weight of 100,000 or more' has low fluidity and particles. Interstices are easy to form voids, so it is satisfactory. Polyethylene with a high molecular weight of more than 1 million by weight is more preferred. The shape of the thermoplastic resin particles used in the present invention is not particularly limited. It does not matter whether it is spherical or irregular, formed by primary particles, formed by a plurality of primary particles integrated into an integrated secondary particle, or formed by pulverizing secondary particles. On the other hand, the particle size is 3 0 0 // m or less is preferred. Above 1 0 // m, preferably less than 1 0 // // m. The so-called particle diameter in the present invention is the average particle diameter. The enlarged photo of resin particles is used to measure 5 The individual short and long diameters of more than 0 particles are represented by their average 値. When the particle size is greater than 3 0 0 // m, the size of the pores of the obtained sintered body also becomes larger, which reduces the amount of adsorbed substances and The combination frequency of the absorbing functional groups makes the absorbing efficiency worse. Conversely, if the particle size is less than 10 // m, the size of the pores of the sintered body also becomes smaller, reducing the water and air permeability without practicality. . This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

-14-1239935 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention ("<crosslinked particles and adsorbed resin particles>) As the adsorbed resin particles in the present invention, the resin removal fiber system In addition to natural resins such as phenol resin, urea resin, melamine resin, unsaturated polyester resin, allyl resin and other typical thermosetting resins; polyvinyl chloride, polyvinyl chloride, etc. Chlorinated vinyl resins; Polyolefin resins typified by polyethylene and polypropylene; Polyester resin typified by polyethylene terephthalic acid; Polystyrene, polyamide, polyoxymethylene, and polycarbonate , Plastics, polyethers, polyphenylene sulfide, polymethyl methacrylate, polyether ether ketones, etc. so-called engineering plastics; polyfluorinated ethylene fluorene, ethylene-tetrafluoroethylene copolymers and other fluorine Plain resins; thermoplastic resins, etc. Among these resins, they are cheap, excellent in chemical resistance, little leachables, low hygroscopicity, low dissolution, and easy introduction of functionalities based on the surface of resin particles. In terms of less thermal decomposition than the absorbing functional group during sintering, it is preferable to use polyethylene, a representative polyolefin resin or a fluorine resin, which has a lower melting point, and polyfluoroethylene. Polychain Examples of the olefin resin include polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-hexene-1 copolymer, ethylene-pentene-1 copolymer, ethylene-octene-1 1 copolymer, ethylene-4 methylpentene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, etc. Among them, it is easy to obtain It has excellent particle shape, chemical resistance, and the use of radiation as one of the methods to introduce absorbing functional groups, so that the free basic paper size when graft polymerization is applied to the Chinese National Standard (CNS) A4 specification (210X 297 mm)

(Please read the notes on the back before filling this page)

-15- 1239935 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Α7 Β7

V. Description of the invention (A is superior to polyethylene in terms of excellent retention. As with thermoplastic resins, when the melt fluidity of the resin used is large, flow deformation occurs during sintering and the surface is formed. The problem that the absorbing functional group sneaks into the inside and damages the pores of the sintered body is therefore a resin that is difficult to flow. For example, the M I 値 of the flowability index is preferably 0. 5 g / 10 minutes or less. 0 · 1 g / 10 points or less is preferred. Even resins that are difficult to flow can not be measured. The high molecular weight polyethylene with a weight average molecular weight of 100,000 or more has small fluidity and does not have the above problems. Therefore, it is satisfactory. Polyethylene with a high molecular weight of more than 1 million by weight is more preferred. The absorbing resin particles of the present invention are based on these resin particles and are introduced with functional groups having absorbing energy (hereinafter (Referred to as adsorbed functional group) particles. The method of introducing the adsorbed functional group is preferably a method that can uniformly introduce the surface of these resin particles. For example, the resin particles that become the basic material are made uniform It is suitable to generate free radicals, and to graft-polymerize the monomers with the free radicals as the starting point and the cross-linking agent to form a crosslinked body layer, and then the method of introducing an adsorbing functional group is appropriate. Alternatively, a monomer having an adsorbing functional group The method of direct graft polymerization of the bulk, the method of joint bonding and the formation of the crosslinked layer, etc. The method of freely generating uniformly based on the entire surface includes a plasma zone method, a light irradiation method, a radiation method, or a method using various radical initiators. Especially When you want to ensure uniformity, the method of generating free radicals by irradiation with radiation is the most suitable. This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm). --- (Please read the precautions on the back first Fill in this page) Order -16- 1239935 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (▲ To introduce a large amount of absorbing functional groups, suitable ionizing radiation used in radiation graft polymerization, For example, α, / 5, 7 rays, electron rays, and ultraviolet rays can be used, but in order to generate uniform free radicals, r rays are suitable. During graft polymerization, the obtained A sufficient amount of free radicals to be generated without causing unnecessary cross-linking or partial decomposition. The economical radiation dose is 10k Gy to 300kGy, preferably 50kGy to 100kGy. Radiation grafting on resin particles Polymerization methods include coexistence of resin particles and monomers, simultaneous irradiation with radiation, and irradiation with resin particles before irradiation with radiation before contacting with the monomers, but before the formation of individual polymers of monomers is small. The irradiation method is suitable. As the crosslinked layer formed by graft polymerization, for example, a copolymer layer of styrene and divinylbenzene as a monomer, a polymer layer of epoxypropylmethacrylic acid, and epoxypropylmethyl Copolymer layer of acrylic acid and acrylonitrile, copolymer layer of epoxypropylmethacrylic acid and divinylbenzene. Among them, a copolymer layer of styrene and divinylbenzene is most suitable for easily controlling the reaction. The ratio of the crosslinked layer formed by the graft polymerization is preferably 50% by weight or more and less than 150% by weight based on the weight of the resin particles. When it is less than 50% by weight, the introduction amount of the absorbing functional group cannot be increased, while when it is more than 150% by weight, the particle size of the crosslinked body is too large, which increases the pore diameter of the sintered body, resulting in a decrease in the adsorption capacity. . The ratio is preferably 60% by weight or more, and preferably less than 120% by weight. Therefore, crosslinked particles (hereinafter, referred to as crosslinked particles) capable of introducing and adsorbing a functional group are obtained. This paper size applies Chinese National Standard (CNS) A4 specification (2 丨 〇 &gt; &lt; 297 mm) (Please read the precautions on the back before filling this page)

-17- 1239935 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (whether it can uniformly introduce the surface of the adsorption functional resin-based particles, grafting in the reaction solvent, that is, in the liquid phase The polymerization reaction and the functional group introduction reaction are suitable. In addition, in order to allow the reaction to proceed near the surface of the resin particles, it is preferable to use a solvent having a small swelling property with respect to the resin used. Specifically, the resin used as a material is A solvent having a swelling degree of 10% or less is preferable. For example, alcohols such as methanol, ethanol, and isopropanol, or a dispersion liquid in which monomers are dispersed in water can be used. The so-called swelling degree is [ The difference between the particle diameter of the resin particles after immersion in the solvent for 1 hour] and the [particle diameter of the resin particles before immersion] is divided by the [particle diameter of the resin particles before immersion]. Adsorbed particles with functional groups spread on the surface of the particles, unlike conventional ion-adsorbed resins, can provide an adsorbed material with a small amount of dissolution. In addition, the surface referred to in this application The depth of the surface to the surface layer of 5 // m. The extent to which the adsorbing functional group is distributed on the surface is indicated by the following method to determine the distribution of the adsorbing functional group. After the adsorbed resin particles are embedded in the resin, Use a slicer, etc., to cut the exposed section of the particles. Mount the exposed section of the sample on a scanning electron microscope, enlarge it to an appropriate magnification, and then absorb specific elements in the functional group, and use an energy dispersive X-ray analysis device. (EDX), X-ray analysis is performed from the surface to the center of the particle. The line profile of the X-ray analysis is read from the intensity of the surface portion and the intensity of the center portion, and obtained from the line profile The known strength can be used as the ratio of the element amount in the sample. The dimensions of this paper are applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). ---- Ί. (Please read the precautions on the back before filling this page ) Order -18-1239935 A7 B7 V. Explanation of the invention (The functional group distribution index is [the intensity of the EDX line contour of the particle center (the height of the wave peak)] divided by [the EDX line wheel of the particle surface part] The intensity of the profile (the height of the wave peak)] is the obtained 値. That is, as long as the functional groups are uniformly distributed from the surface to the center, the intensity of the EDX line profile is equal, so it is roughly 1, if the functional groups are mostly When distributed on the surface, the strength of the surface portion is increased, and its chirp is smaller than 1. For the adsorbed particles of the present invention, the chirp is preferably less than 0 · 9. It is preferably less than 0 · 8. In addition, the so-called The specific element in the absorbing functional group refers to, for example, S (sulfur) when the sulfonic acid group is included in the background resin. If the absorbing functional group and the resin are substantially composed of the same element, the After the functional group absorbs metal ions, etc., the analysis may be performed in the manner described above. The concentration of the introduced functional group is such that the total weight of the resin is 0. 3mmo Ι / g or more, and 10mmo Ι / g is less than Preferably, it is more than 0 · 5mmo 1 / g, and preferably less than 5mmo 1 / g. When it is less than 0.3 mmoI / g, the concentration of the absorbing functional group is too low, and the absorbing ability is insufficient in practical use. W Μ 'Iron-like ions with low selectivity to protons are at the level of lPPt (ie, 〇-1Qm〇l / L level). At the time of ion exchange, the concentration of protons competing for the same time (about 1 〇- 7 m 〇1 / 1 level), the utilization efficiency of ion exchange groups is extremely reduced. Therefore, at an ion exchange capacity of less than 0.3 mm / g / g, a considerable amount of ion-adsorbing resin was not used, and almost no ion-removing effect was observed. On the other hand, if it exceeds 1 Ommo Ι / g, if you want to introduce absorbing functional groups, the paper size is applicable to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page) ▼ Order Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-19- 1239935 A7 B7

V. Description of the invention (A is not only on the resin surface, but also on the inside of the resin, and the by-products remain with the reaction. For example, when treating water, dissolve these as impurities (please read the precautions on the back before filling in this Page), it is not suitable. Specific examples of adsorption functional groups are shown below. Among the ion exchange groups, the sulfonic acid group, carboxylic acid group, and phosphate group as cation exchange groups, and the fourth-order ammonium salt group as anion exchange groups. , Pyridinium salt and 3 to 2 amino groups, iminodiacetic acid group, hydrogenthio group and ethylenediamine group as chelating group, etc. Cibacron Blue F 3 G -A as group-specific affinity absorbing group Concanavalin A (abbreviated as c ο η A), heparin, tannin, metal chelating groups, etc. can be introduced into the antigen or antibody as affinity sorbent groups. These can not only be individually bonded, but also It can form a plurality of absorbing groups, or further introduce other functional groups such as hydroxyl groups to form a bond. The employee cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the thermal stability of the absorbing functional groups during sintering, In a practical environment From the viewpoint of the stability of thermochemistry, it is preferable that the cation exchange group is a strong acid sulfonic acid type, and the anion exchange group is a strong basic quaternary ammonium salt type or a pyridinium salt type. It is also suitable. Metal salts as these functional groups are used to replace metals with protons after forming the sintered body. Generally, the use of metal salts can improve the heat resistance of functional groups, and can reach higher sintering temperatures than when no replacement is used. To expand the range of usable conditions. In addition, halogen replacement methods such as chlorine can also be used in the same way. Specifically, for example, when contacting with sodium hydroxide solution, sulfonic acid groups in the form of sodium sulfonate can be used. This paper standard applies China National Standard (CNS) A4 specification (210X 297 mm 1 '-20-1239935 A7 B7 V. Description of the invention (There is no particular limitation on the method for introducing an adsorbed functional group. For example, an ion-exchange group can be introduced as follows.) Please read the notes on the back before filling this page.) For cation exchange groups, use sulfonation reagents to replace the reaction, introduce sulfonic acid based on aromatic compounds, or add sulfurous acid. Method, etc. For example, 'After irradiating the resin particles with r-rays, graft polymerization of styrene or epoxypropylmethacrylic acid and a cross-linking agent, use chlorosulfonic acid on styrene, and use a basic sulfite solution on Glycidyl methacrylic acid is reacted to introduce a sulfonic acid group. There is also a method of directly graft-polymerizing a monomer having a sulfonic acid group such as a styryl sulfonate. For an anion exchange group, for example, by irradiating with r rays After passing through the resin particles, chloromethylstyrene or epoxypropylmethacrylic acid is graft-polymerized, and then a level 4 ammonium group is introduced. In the case of chloromethylstyrene, trimethylamine is treated for the treatment. In the case of methyl methacrylic acid, a fourth-grade ammonium group is introduced to react with trimethylamino hydrochloride. There are also monomers having a fourth-grade money group which are directly polymerized on resin particles such as styryl dimethyl mirror salt. Method. When printing the chelate exchange group in the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, for example, after the resin particles irradiated with r-rays were graft-polymerized with an ethanol solution in which epoxypropylmethacrylic acid and divinylbenzene were dissolved, A method of reacting with a dimethyl subcode containing sodium iminodiacetate and a 1: 1 mixed solution with water to introduce a chelate exchange group. In the present invention, instead of directly bonding and adsorbing functional resin-based particles, a graft polymerized chain is introduced to form a layer. For example, compared with a direct method of introducing a sulfonic acid based polyalkene such as using hot concentrated sulfuric acid, the reaction is stable and easy. Control, and fewer products associated with side reactions. The shape of the absorbing resin particles obtained in this manner is not particularly limited. This paper size applies to China National Standard (CNS) A4 (210X297 mm) -21-1239935 A7 B7

V. Description of the invention (A is perfectly spherical or irregular, it does not matter whether the primary particles are formed, the primary particles are aggregated into secondary particles, or the secondary particles are pulverized. It does not matter. It is better to be less than 3 ◦ 0 // m. More than 1 〇 # m is better than 1 0 0 // m is less than full. When the particle size is greater than 3 0 0 // m, the size of the pores of the sintered body obtained It also becomes larger, lowering the frequency of convergence of the substance to be adsorbed and the adsorbable functional group, which deteriorates the adsorption efficiency. Conversely, if the particle diameter is less than 1 0 // m, the size of the pores of the sintered body also becomes smaller. It is not practical to reduce the water permeability and air permeability. <Method for manufacturing sintered sintered body> The sintered body (hereinafter, referred to as sintered sintered body) having sinterability of the present invention can be prepared by the following method. One method is a method of sintering a mixture of thermoplastic resin particles and resin particles forming a crosslinked layer capable of introducing an adsorbing functional group to form a porous resin matrix, and then reacting the adsorbing functional group. The two methods are: sintering and mixing by introducing The method of mixing functional resin particles with thermoplastic resin particles. The third method is to sinter the thermoplastic resin particles to form a sintered body, and then to form a crosslinked layer on the surface, followed by enabling and crosslinking Bulk layer reaction method with functional group with adsorption energy. Figure 1 shows the finishing of these processes. The first method has the advantage of introducing the sintered body that has formed the crosslinked layer based on the sintering step at the end of the sintering step. The functional group will not be exposed to this paper size. Applicable to China National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling this page). Ding * 8— · II ....... illlsl · _ϋϋ Βιαιι · Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-22- 1239935 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Α7 Β7 V. Description of the invention (4 High temperature during sintering, even if the thermal stability is poor It is not necessary to worry about the thermal decomposition of the functional group and the generation of impurities accompanying the thermal decomposition. The second method has the advantage of being in the liquid phase beforehand. Introducing the functional group based on resin particles by graft polymerization makes it easy to uniformly introduce the absorbing functional group onto the surface. The third method has the advantage that the steps are the simplest. As can be seen from FIG. 1, the elements when producing the absorbing and burning body In order to mix particles and particles filled with metal appliances, sinter, form a crosslinked body layer, and introduce an adsorbing functional group, the methods for forming a crosslinked body layer and introducing an adsorbed functional group are as described above. The following is a description of mixed particles '' A method for filling particles into metal appliances and sintering. Mixing thermoplastic resin particles and absorbing resin particles, and mixing thermoplastic resin particles with resin particles that form a crosslinked layer capable of introducing absorbing functional groups, can be mixed using a drum. Machines, precision mixers, high-speed flow mixers, and V-type mixers. However, it is desirable to select devices and mixing conditions where particles are not charged during mixing. When the particulate matter is charged, it is easy for the particles to aggregate and it is difficult to uniformly mix them. Use an appropriate ground wire of the mixer. When supplying and removing particles from the mixer, it is advisable to remove static electricity with a blower type static elimination device. The mixing ratio of the resin particles adsorbing the resin particles or the resin particles forming a crosslinked layer capable of introducing an adsorption functional group to the thermoplastic resin particles is preferably 10% by weight or more and less than 70% by weight in total. It is more preferably in a range of 30% by weight or more and less than 60% by weight. In order to obtain practicality, this paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) (Please read the precautions on the back before filling in this page)

-23- 1239935 A7 B7 V. Description of the invention (2) | (Please read the precautions on the back before filling this page) Sufficient adsorption capacity, the ratio of adsorbed resin particles must be 10 wt% Μ ±. However, if it exceeds 70% by weight, the ratio of the thermoplastic resin particles becomes small. 'Because of the incomplete dissolution bonding between the particles, sufficient strength of the sintered compact cannot be obtained. For filling particles into metal appliances, for example, a vibration-type filling device such as a vibration-type packer can be used. The amplitude of vibration during charging is relatively not to affect the particles, and the vibration charging time of the charging device is the minimum necessary. The burden of long-term vibration will cause the particles with small particle size to sink to the lower part, that is, the redistribution of the particles, which has to lose the meaning of uniform mixing. There are no particular restrictions on the materials of metal appliances, including iron, stainless steel, sheet copper, and brocade. In terms of durability, small heat capacity, light weight and easy operation, aluminum is preferred. The shape of metal appliances, such as two flat plates in parallel, cylindrical objects with different diameters, and double-layered cylindrical objects, are not particularly limited as long as they can fill particles. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The heating method of the particle mixture filled in metal appliances is performed by any controlled heating method. There are hot air dryers or electric induction heating and electric resistance heating methods. The heating temperature is near the melting point of the resin, which is a temperature at which the particles can fully dissolve and bond, and the temperature is selected to allow the thermoplastic resin to flow without burying the voids between the particles. For example, polyethylene is more preferably 110 ° C or more and less than 180 ° C, and more preferably 120 ° C or more and less than 150 ° C. The adsorption function is based on high temperature, which can easily cause decomposition, especially for paper sizes above 180 ° C. The Chinese paper standard (CNS) A4 specification (21〇 &gt; &lt; 297 mm) is applicable. -24-1239935 A7 ___________________ B7 V. Description of the invention (4 temperature, this tendency is particularly strong, so the heating temperature during sintered body forming should be less than 180 ° C. (Please read the precautions on the back before filling this page) The present invention The shape of the absorptive sintered body is flaky, massive, tubular, cylindrical, or spherical, and is not particularly limited. Any shape can be used. The average pore diameter of the absorptive sintered body of the present invention is Above 1 // m, 1 0 0 // m is less than adequate. 1 // m is less than the empty aperture, sufficient water permeability and air permeability cannot be obtained, and if it exceeds the range of 1 00 // m, suction The frequency of meeting the absorbing substance and the absorbing functional group is reduced, and the absorbing ability is insufficient from the early stage of use, which causes the impure substance to be absorbed. In addition, the average pore diameter is the enlarged photo of the surface and the section, and 50 or more are measured. Individual short and long diameters of adjacent holes The average 値 indicates. The porosity of the sintered body of the present invention is preferably more than 20% and less than 60%, preferably more than 30% and less than 50%. When less than 20%, the water permeability and air permeability It is small, not practical, and more than 60% makes the strength of the sintered body insufficient. In addition, the porosity is based on the quality difference between the state of impregnation with water and the state of drying, and it is obtained by the method described later. Wisdom of the Ministry of Economic Affairs The invention is printed by the Consumer Cooperative of the Property Bureau. The present invention is to provide resin particles with high concentration of various absorbing functional groups on the surface, and to provide a large number of pore diameters controlled by the particles and a thickness that cannot be obtained with conventional film materials. The adsorbed sintered body can provide the base block for adsorption, concentration and separation to remove trace components in liquid or gas. Especially the adsorbed sintered body with ion-absorbing functional group introduced can remove fine particles, cationic components, Anionic ingredients, alkali metals and alkaline earth metals. The paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) -25- 1239935 A7 __ B7 V. Description of the invention Very low concentration, which is complementary to high water permeability, suitable for use in the production of ultrapure water, etc. (Please read the precautions on the back before filling out this page) The following is a specific example of an ion-exchange group as an absorbing functional group The present invention will be described in detail. <Measurement method> (1) The melt flowability of thermoplastic resin particles is measured in accordance with ASTM D 1 2 3 8 (Ml (melt index)). (2) The particle size is enlarged by the resin particles. In the photograph, the individual short and long diameters of 50 or more particles were measured and expressed as the average 値. (3) The introduction amount of the crosslinked layer The weight of the resin particles to be introduced into the parent connected layer is measured in advance. The weight of the obtained crosslinked particles is subtracted from the weight of the resin particles, and then divided by the weight of the resin particles. Out. (4) Adsorption functional group distribution index Printed by Xiao Gong Consumer Cooperative, Bureau of Intellectual Property, Ministry of Economic Affairs After absorbing resin particles is embedded in the resin, it is cut with a slicer or the like to expose the cross section of the particles. The cross section of the exposed sample was mounted on a scanning electron microscope and enlarged to an appropriate magnification. The specific elements in the functional group were absorbed by an energy dispersive X-ray analysis device (EDX) from the surface of the particles to the center. X-ray analysis. From the intensity of the surface part and the intensity of the center part, the line contours of the X-ray analysis (N n e p r 0 f i 丨 e) were read. And the intensity obtained from the spectral line profile can be used as the ratio of the element amount in the sample. Paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) — -26- 1239935 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (The functional group distribution index is [Particle Center The intensity of the part of the EDX line contour (the height of the wave crest)] is divided by [the intensity of the contour of the EDX line of the particle surface (the height of the wave crest)], and the obtained pyrene is an indicator of the distribution of the adsorption functional group. (5 ) The amount of cation exchange group introduced was quantitatively 10 g of the cation exchange group-adsorbed resin, impregnated with pure water, and then filled in a glass chromatographic tube, with a 1 N Na 〇Η solution, pure water, 1 Rinse the nitric acid solution and pure water in order. Then flow through 1 N N aq solution, and the obtained filtrate is titrated with 1 N N a 0 H solution to determine the ion exchange capacity. After that, the sorbent resin was replaced with ethanol and vacuum-dried at 50 ° C for 2 hours, and the dry weight was calculated to calculate the amount of cation exchange group introduced per weight unit. (6) The amount of anion exchange group introduced was 10 g. Introduction of anion exchange group After filling the resin with a 1 N NaOH solution, the ion-exchange group was formed into a 0H type, and then passed through a 1 N NaC1 aqueous solution, so as to absorb C1 ions, and then with 1 N The potassium nitrate solution was flowed through, and the filtrate obtained by titration was precipitated to determine the C 1 ion adsorption amount. After that, the adsorption resin was replaced with ethanol and dried under vacuum at 50 ° C for 2 hours. Dry weight, calculate the amount of anion exchange group introduced per weight unit. (7) Chelate exchange group introduction amount The sintered body into which the chelate exchange group is introduced, and then made into hydrazone with 1 N hydrochloric acid, then copper sulfate with 100 ppm After the solution flows through, it absorbs Cu ions and desorbs with 1 N hydrochloric acid. The desorbed solution is used to determine copper ions by atomic absorption method. The paper size is applicable to Chinese National Standard (CNS) A4 (210X 297 mm) (please (Read the notes on the back before filling out this page)

-27- 1239935 A7 B7 V. Description of the invention (4 concentration. After that, the adsorption resin was replaced with ethanol and dried under vacuum at 50 ° C for 2 hours. The dry weight was calculated and the chelate exchange group per weight unit was calculated. Introduced amount. In addition, the atomic absorption device used is SAS-72 7 type manufactured by Seiko Denshi Kogyo Co., Ltd. (8) Average pore diameter The average pore diameter is measured from the enlarged photo of the surface and cross section. The individual short and long diameters of adjacent voids are calculated by calculating the average 値. (9) The porosity is immersed in ethanol for 1 hour, then immersed in pure water, repeated 5 times, and drained. The mass of the dried sintered body was determined by measuring its mass. After that, it was immersed in ethanol again, and then dried at 50 ° C for 10 hours. The mass after drying was measured, and the difference a was calculated in cm 3 units. On the one hand, the size of the sintered body was measured, and its volume b was obtained in cm 3 units. The porosity was calculated as a / b.

(10) T 0 C The sample water was introduced into a TOC meter—A 1 000 × P manufactured by A ante 1 company, and its content was measured. In addition, △ T〇C is ultrapure water

When the flow passes through an ion-exchange-based adsorbent (or a column filled with adsorbent resin), the difference in TOCTO in the sample water is measured at the entrance and exit ([TOC at the exit]) 1 [t0C at the entrance]) ° (11) Number of microparticles Lead sample water into UltraDI — 5 0 made by PMS Co., Ltd. This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) (please first Read the precautions on the back and fill in this page) Gather one --- Order ---- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics -28- 1239935 A7 B7 V. Description of the Invention (Measurement, 0 · 1 # m The total number of underfilled particles is an indicator. In addition, △ Micro (please read the precautions on the back before filling this page) For particles, measure the number of microparticles in the sample water at the entrance and exit of the scorched body 値([Number of fine particles at the exit]-[Number of fine particles at the entrance]). (1 2) Permeate the ultra-pure water through the ion-exchange group and burn by a pressure difference of 9 · 8 N / cm2. Body to measure the weight of permeated water to determine its permeation amount. (13) The metal content in the water was cleaned in a clean room, and the sample water was concentrated by 10 to 100 times, and measured by ICP-MS manufactured by Yokogawa Chemical Analvsis. (14) The resistivity of the treated water was manufactured by Toya DKK Company. Type AQ-1 1 directly measures the resistance of treated water. <Example of resin particles adsorbed> Example 1 Printed by Asahi Kasei Co., Ltd., which is an employee consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The polyethylene powder "Safain UH90l" (trademark) was sieved through a metal mesh with a mesh of 2000 to obtain a polyethylene powder with a particle size of 8 3 // m. The M I of the resin was almost 0. 250 g of powder was put into an aluminum steamer polyethylene bag, sealed with nitrogen, and irradiated with 1000 k G ray. Dissolved 300 g of styrene and 4 3.6 g of divinylbenzene. (Purity: 55%) in 1 L of isopropanol, at 50 t for 30 minutes, the paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 / ^ &quot; &quot;] ~ 一-- ~ -29- 1239935 A7 B7 V. Explanation of the invention (4 Soothing bubble flow to remove dissolved oxygen. After irradiating r-ray "SafajnuH901" was put into the monomer solution under a stream of nitrogen gas. After stirring for 3 hours, the reaction slurry was filtered through a Buchner filter, washed with 3 L of dichloromethane, and dried in vacuum. The yield was 410 g, and the amount of the crosslinked layer formed was 64%. A reaction solution in which 71 g of chlorosulfonic acid was dissolved in 1 L of dichloromethane was put into the graft, and stirred for 3 hours. 500 ml of isopropanol was added to this reaction solution, and after stirring slightly, it was filtered through a Buchner filter, washed with 1 L of isopropanol and 10 L of pure water, and dried in vacuo. The yield of the obtained cationic ion-adsorbing resin was about 240 g. The particle size of the resin is 8 4 // m, and the ion adsorption capacity is 2 · 4 m m ο 1 / g. The index of the absorption functional group distribution of E D X measured for S (sulfur) was 0 · 7. Example 2 100 g of the ion-adsorbing resin obtained in Example 1 was charged into a 15 mm% glass tube column with an inner diameter of 15 mm%, and was regenerated with 1 N nitric acid. After pure water was passed at a flow rate of 100 m L / mi η for 48 hours, Δ TOC was determined. The ATOC at the initial stage of washing was about 500 PPb ', but it was about 20 P P b after 24 hours, and it was stable. After that, the ultra-pure water at room temperature has an ATOC of 1 p p b or less. The Δ fine particles were 0.05 particles / mL. Comparative Example 1 This paper size applies the Chinese National Standard (CNS) A4 specification (210 &gt; &lt; 297 mm) (Please read the precautions on the back before filling this page) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives -30 -1239935 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (4 The ion absorption resin of Example 2 was changed to use ion exchange resin "D iai ο η PK 2 1 2" manufactured by Mitsubishi Chemical Corporation (Trademark), and others are the same as in Example 2, and evaluated △ Τ Ο C of the ion-adsorbed resin. After hot ultrapure water was passed for 48 hours, its △ T ◦ C was 120 to 150 ppb. After that, △ τ ° C after ultra-pure water flowing at room temperature is 10 to 15 ppb or less. In addition, △ fine particles are 0.3 particles / m L, and the ratio 1 is 10 times larger. Example 3 Similar to Example 1, the weight was changed. The 250 g polyethylene powder "SafainSH801" (trademark) manufactured by Asahi Kasei Co., Ltd. with an average molecular weight of 200,000 was irradiated with r-rays of 100 k G y. The M I of the resin was 0.88 g / 10 minutes, particle size is 86 // m. Dissolve 300g of chloroethylstyrene and 4 3 · 6 g of divinylbenzene (purity 5 5%) in 1 L of isopropanol reaction solution, at 50 ° C, nitrogen gas flow for 30 minutes, and then put into 250 g of r-ray irradiation Polyethylene powder. After stirring for 3 hours, it was filtered with a Buchner filter, washed with 1 l of methyl chloride, and then dried under vacuum. The yield was 480 g, and the amount of crosslinked layer formation was 92%. The obtained crosslinked particles were immersed in isopropyl alcohol in which 30% of trimethyl ammonia was dissolved, and reacted at 35 ° C for 50 hours to make them grade 4 ammonium. The obtained anionic ions The adsorption resin was washed with water, washed with water, and replaced with ethanol, and then dried in a vacuum dryer. The ion exchange capacity of the anion ion adsorption resin obtained was 3.26 mm 0 / g. The particle size of the obtained particles was 8 8 // m. Replace the basic paper size with C 1 (chlorine) for China National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before filling out this page} Order -31-1239935 A7 B7 V. Description of the invention (4 The measured index of the functional group distribution of the absorber is 0.6. The same method as in Example 2 was used to evaluate The TOC of the anion ion adsorption resin was eluted, and the ATOC after washing with 80% of its ultra-pure water for 48 hours was 1 ppb or less. In addition, the △ fine particles were 0.07 particles / mL. Example 4 As in Example 1, 250 g of a polyethylene powder (SafainSH801 manufactured by Asahi Kasei) was irradiated with r-rays of 1,000 k G y. The resin had a MI of 0.08 g / l0 and a particle size of 86 // m. Dissolve 300 g of epoxypropylmethacrylic acid and 4 3 · 6 vinylbenzene (55% purity) in a reaction solution of 1 L of isopropanol, and perform a nitrogen bubble flow for 30 minutes to remove the dissolution. Existing oxygen, polyethylene powder after irradiated with 250 g of r-ray. After the reaction was performed for 0.5 hours, the resin powder after the graft polymerization was taken out and washed with isopropyl alcohol. The obtained graft polymerized copolymer 'was put into a mixed solution in which a volume ratio of 1: 1 of dimethyl subcode to water in which 10% by weight of sodium iminodiacetate was dissolved and a ratio of 1: 1 was carried out at 80 t for 7 2 Hour response. The ion exchange capacity of the thus obtained chelate ion-adsorbing resin was 0.886 mmo I / g. In the same manner as in Example 2, the 'TOC of this chelate ion-adsorbing resin was evaluated for dissolution, and the ATOC after washing with 8Ot of hot ultrapure water for 48 hours was 1 ppb or less. △ Fine particles: 0 · 05 / m L 〇 This paper size applies Chinese National Standard (CNS) A4 specifications (21〇 &gt; &lt; 297 mm) (Please read the precautions on the back before filling this page) Order economy Printed by the Ministry of Intellectual Property Bureau's Consumer Cooperatives-32-1239935 A7 B7 i. Invention Description (4 Example 5 (Please read the precautions on the back before filling this page) The cationic ion absorbing resin synthesized in Example 1 Blended with polyethylene powder ("SafainUH901", sieved with a metal mesh with a mesh size of 20 and a particle size of 8 4 # m) at a mass ratio of 50/50. Installation outer diameter / inner diameter = 8 Omm ^ / 7 Omm ^ Zhiming's extruded tube and aluminum extruded tube with outer diameter / inner diameter = 6 Omme / 5 Omm0, made into concentric metal utensils, using a vibration packer to fill the above powder mixture in the space, at 1 5 Sintered in a hot air dryer at 0 ° C for 10 minutes. The average pore diameter of the obtained sintered body was 2 2 // m and the porosity was 4 2%. A flat plate made of polyethylene and The filtering water outlet is a cylindrical filter as shown in FIG. 2 above and below the manufactured cylindrical sintered body. This filter was installed in a commercially available PFA cylindrical filter box, and after regenerating with 1 N nitric acid, T ◦ C was evaluated in the same manner as in Example 2. In addition, the flow direction is the so-called outside The direction of pressure filtration is the direction from the outside to the inside of the cylinder shown in Figure 2. The Intellectual Property Bureau of the Ministry of Economic Affairs (industrial and consumer cooperatives prints hot ultrapure water at 80 ° C, which is washed after 48 hours △ T〇C is 1 ppb or less. In addition, the ion exchange capacity is 0.72 mmo 1 / g. △ fine particles are -0.3 3 / mL, which means that there is less water treatment. The water permeability is 2100 000 L / m2 · hr.Mpa Example 6 The cationic ion-adsorbent resin synthesized in Example 1 was changed to this paper size to apply Chinese National Standard (CNS) A4 specification (2 丨 〇 &gt; &lt; 297 mm)- 33- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1239935 A7 B7 V. Description of the invention (4 The anionic ion absorbing resin synthesized in Example 3 was used, and the other steps were performed in the same manner as in Example 5 to obtain an anionic sintered body. .The average pore diameter is 2 1 // m, and the pore ratio is 40%. 5 The same method was used to evaluate the TOC dissolution of this anionic ion sorbent. After washing with 80 ° ultrapure water for 48 hours, △ τ ° C was 1 ppb or less. △ fine particles were -0 · 04 / mL, almost 0. In addition, the ion exchange capacity of the obtained anionic porous ion sorbent was 0 ♦ 96 mm / g. The water permeability was 2000000 million L / m 2 · hr · M pa 〇 Example 7 The cationic ion absorbing resin synthesized in Example 1 was replaced with the integrated ion absorbing resin synthesized in Example 4. Example 5 was performed in the same manner to obtain a chelate-type porous ion adsorbent. The average void diameter is 2 3 // m, and the void ratio is 4 2%. In the same manner as in Example 5, the TOC dissolution of this chelated porous ion sorbent was evaluated, and the ATOC after washing with hot ultrapure water at 80 ° C for 48 hours was 1 ppb or less. The number of △ fine particles is 10 · 2 / m L, which indicates that the number of fine particles at the exit is small. The ion exchange capacity of the obtained porous ion sorbent was 0.36 inmo I / g. Example 8 In order to measure the water quality before and after the filters of Examples 5 and 7, the model pure water containing trace metals was passed through, and the analysis of the supply water and the filtration were performed according to the Chinese National Standard (CNS) A4 specification (210X 297). Mm) (Please read the notes on the back before filling in this page)

-34- 1239935 A 7 B7 V. Description of the invention (4 (Please read the precautions on the back before filling this page) for the treatment of metal ions in water. Pass pure water at 20 L / min through Example 5 and Examples The filter of 7 was performed for 50 days. The results are shown in Table 1. Table 1 Filtered water of the cationic sintered body of Example 5 before filtration The Zn ion concentration of the filtered water of the chelated sintered body of Example 7 0.2 ND ND (PPb) Na ion concentration 0.97 0.45 (ppt) Printed on the cationic porous ion adsorbent and chelated porous ion adsorbent by the Consumer Cooperative of the 4th Bureau of Wisdom and Finance of the Ministry of Economic Affairs. Reduce the concentration of Z η in ultrapure water. Also reduce the concentration of Na in cationic sorbents. That is, metal ions are adsorbed in the ion-adsorbed sintered body. Sintered body (sintering with metal salt as the functional group) Example> Example 9 The cationic ion-adsorbing resin synthesized in Example 1 was immersed in a 1 N NaOH solution, and filtered and washed with na-type. The Na-type cationic ion-absorbing resin was dried in vacuum. After the machine is dried, with polyethylene powder ( ^ Paper scale applicable Chinese National Standard (CNS) A4 size (210X297 mm) - -35- 1239935 A7 _______B7 V. invention will be described (What

SafainUH901 "was sieved with a metal mesh with a mesh size of 200, the particle size was 8 3 β m), and mixed at a mass ratio of 50/50. Installation outer diameter / inner diameter = (Please read the precautions on the back before filling in this page) 8 Omm ^ / 7 Omm0 aluminum extrusion tube and outer diameter / inner diameter = 6 Omm0 / 5 Omm0 aluminum extrusion tube, into Concentrically round metal utensils, put the powder mixture mentioned above into the gaps, fill it with a little vibration. Sinter in a hot air dryer at 180 ° C for 20 minutes. The average void diameter of the sintered body was 2 3 // m, and the void ratio was 43%. A flat plate made of polyethylene and a filtered water outlet are installed above and below the manufactured cylindrical sintered body, as shown in the cylindrical filter shown in FIG. 2. This filter was installed in a commercially available cylindrical filter box made of PFA, and was regenerated with 1 N nitric acid, and T 0 C eluted was evaluated. After washing with hot ultrapure water at 80 ° C for 48 hours, △ TOC was 1 p p b or less. In addition, the ion exchange capacity of the porous ion-adsorbent was 0 ♦ 9 3 mmo 1 / g. Even if the sintering is performed at a relatively high temperature, it is considered that there is no decomposition of the occluding group, and the TOC component is not increased by thermal decomposition. The number of △ fine particles was 0.1 · mL / mL, indicating that there was a small amount of treated water. Water permeability is 2 2 0 0 0 0 0 0 0 L / m 2 · hr · M pa 〇 Example of “Sintered body (sintered by halogenating functional groups) and printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy” Example 1 0 The anion-type ion absorbing resin synthesized in Example 3 was immersed in a 1 N hydrochloric acid solution, and filtered to wash into a C 1 form. This C 1 type anion ion-absorbing resin was dried in a vacuum dryer, and then carried out in the same manner as in Example 9 to obtain an anionic porous ion-adsorbing body. The average pore size is 2 1 // m This paper size is in accordance with Chinese National Standard (CNS) A4 (210X 297 mm) -36- 1239935 A7 B7 V. Description of the invention (4 'pore size is 39%. (Please Read the precautions on the back before filling this page.) Evaluate the T ◦ C of this anionic porous ion adsorbent. Dissolve in hot ultrapure water at 80 ° C for 4 to 8 hours. △ T〇C is 1 PP b or less. In addition, the ion exchange capacity of the ion-adsorbed body was 0. 65mmo 1 / g. △ fine particles were -0.04 particles / mL. "No fine particles derived from the sintered body were generated. The water permeation amount was 1950. 0〇0L / m2 · hr-Mpa 〈Example of sintered body (sintered mixture of crosslinked resin particles and thermoplastic resin, functional group introduced) Example 1 1 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Polyethylene powder, Safain UH901 manufactured by Asahi Kasei Co., Ltd., was sieved through a metal mesh with a mesh of 200 to obtain polyethylene particles having a particle size of 8 6 // m. The 250 g particles were put into aluminum. Steam in a polyethylene bag, seal with nitrogen, and irradiate with 100 k G y ray. Dissolve 3 7 5 g Styrene and 54 · 5 g of divinylbenzene (purity 55%) in 1 L of isopropanol at 50 t under nitrogen gas flow for 30 minutes to remove dissolved oxygen. Under the nitrogen gas flow, the "Safain UH901" after r-ray irradiation was put into this monomer solution. After stirring for 3 hours, the reaction slurry was filtered through a Buchner filter, washed with 3 L of dichloromethane, and dried in vacuum. The yield is 4 1 0 g, and the amount of cross-linked layer formation is 64%. In addition, the particle size is 87 // m. Example 1 2 This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -37- 1239935 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (4 The crosslinked particles synthesized in Example 1 1 and a metal mesh with a mesh size of 20 ◦ were passed through the sieving Safain UH901 to obtain particles. Polyethylene particles with a diameter of 8 5 // m are mixed in a weight ratio of 50/50. Metal utensils filled with grooved aluminum disks in the shape of disks of 25 mm ^ x 3 mm t. Sintering was carried out in a hot air dryer at 180 ° C for 30 minutes. The average pore diameter of the obtained sintered body was 2 2 // m, with a porosity of 41%. In a 500 m 1 separation flask, put 2,000 m 1 of methyl chloride and the sintered body made of 2.5 mm 0 x 3 mm t. After cooling to 5 ° C or lower, 0.26 g of chlorosulfonic acid was added while stirring. After the addition, raise the liquid temperature to 30 ° C for 3 hours. After adding 20 ml of ethanol for 30 minutes, the sintered body was taken out, washed with ethanol and water, and dried under vacuum. The pore size of the sintered body introduced with a cation exchange group was 2 1 // m, and the porosity was 41%. The ion exchange capacity is 0 · 87mmo 1 / g °. △ T ◦ C measured by pure water flowing through the holder is 1 P P b or less. The number of △ fine particles was almost 0 / mL. Comparative Example 2 50 g of the crosslinked particles obtained in Example 11 and 200 m 1 of methyl chloride were placed in a separation flask, and after cooling to 5 ° C, dripped 1 7 with stirring. 5 g of chlorosulfonic acid. After dropping, the temperature of the solution was raised to 30 ° C and maintained for 3 hours. After adding 50 ml of ethanol for 30 minutes, it was filtered through a Buchner furnace, washed with ethanol and water, and dried under vacuum. The size of this sulfonated paper is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) ^ „—! (Please read the precautions on the back before filling this page) Order-38- 1239935 A7 ____ B7 V. Description of the invention ( &amp; (Please read the precautions on the back before filling in this page) Resinized resin particles and sieved Safain UH901 with a metal mesh of 2 0 0 to obtain particles with a particle size of 8 4 / zm and weight of 5 0/5 0 The specific mixing has an ion exchange capacity of 0.8 2 mmo 1 / g. This mixture is filled in the aluminum metal device of Example 9 and heated in a hot air dryer at 180 π for 30 minutes to form a sintered body. The ion exchange capacity of the obtained sintered body was 0.5 5 mmo / g. This means that the ion exchange capacity was reduced due to sintering, which was about 70% before sintering. Example 1 3 Same as Example 1 1 and 2 5 0 g of polyethylene particles (Safa inU Η 901 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics and Industry of Asahi Kasei, sieved with a metal mesh with a mesh size of 2 0 〇, particle size of 8 6 // m), with 1 0 0 k G y r-ray irradiation. Dissolve 3 7 5 g of chloromethylstyrene and 5 4 · 5 g of divinyl (Purity: 55%): 1 L of isopropyl alcohol was used to form a reaction solution. At 50 ° C., a nitrogen gas bubble flow was performed for 30 minutes, and the polyethylene particles after r-ray irradiation were introduced. After 3 hours, they were subjected to Brinell filtration. Filtered with a bucket, washed with 1 L of acetone, and dried under vacuum. The yield of the obtained crosslinked particles was 470 g. The formation of the crosslinked layer was 88%. In addition, the particle size was 87 // in Example 14 The crosslinked particles synthesized in Example 13 and a metal mesh with a mesh size of 200 sieving Safai nUH9 0 1 were used to obtain polyethylene particles having a particle size of 8 5 // m. 5 〇 / 5 〇 weight ratio mixing. The paper size filled with the particles in a disc-shaped grooved aluminum disc at 25mm0x 3mm t applies the Chinese National Standard (CNS) A4 specification (210X 297 mm)- 39-1239935 A7 B7 V. Description of the invention (Metal utensils, heated in a hot air dryer at 180 ° C for 30 minutes to sinter. (Please read the precautions on the back before filling out this page) At 50 0 〇 In a m 1 separation flask, put 200 m 1 of isopropyl alcohol in which 30% of trimethyl ammonia was dissolved, and the 25 mm 0X 3 mmt prepared above. The aggregate was reacted at 35 ° C for 50 hours to make it grade 4 ammonium. After the reaction, the sintered body was taken out, washed with ethanol and water, and dried under vacuum. The obtained anionic porous ions were adsorbed The volume ion exchange capacity was 0.95 mmo 1 / g. Comparative Example 3 The crosslinked particles synthesized in Example 13 were immersed in isopropyl alcohol in which 30% of trimethyl ammonia was dissolved, and reacted at 35 ° C for 50 hours to make it a grade 4 Ammonium. The obtained anion absorbing resin was washed with ethanol and water and dried under vacuum. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed this grade 4 ammonium resin particles and sieved Safain UH901 with a metal mesh of 200 to obtain polyethylene particles with a particle size of 8 5 // m. 0 weight ratio mixing has an ion exchange capacity of 0.93 mmo 1 / g. This mixture was filled in the same metal utensil as in Example 9, and heated in a hot air dryer at 180 ° C for 30 minutes to form a sintered body. The ion exchange capacity of the obtained sintered body was 0 · 2 8 m m ο 1 / g. This means that the ion exchange capacity is reduced due to sintering, which is about 30% before sintering. This paper size is applicable to Chinese National Standard (CNS) A4 (210X 297 mm) -40-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1239935 A7 B7 V. Description of the invention (4 Example 15 Same as Example 1 1) 2,500 g of polyethylene particles (SafainSH801 manufactured by Asahi Kasei, sieved through a metal mesh with a mesh size of 2 0, 8 4 / / m), irradiated with 100 k G y ray. Dissolve 300 g of epoxypropylfluorenyl acrylic acid and 4 3.6 g of divinylbenzene in 1 L of isopropanol. At 30 ° C, a nitrogen bubble flow was performed for 30 minutes to remove dissolved oxygen, and 250 g of polyethylene particles were irradiated after being irradiated with R. Ray. At 30 ° C, it was performed for 0.5 hours. After the reaction, the graft-polymerized crosslinked body was taken out and washed with isopropanol. The yield of the obtained graft copolymer was 395 g, the amount of the crosslinked body formed was 5 8%, and the particle size was 8 4 // m. This graft copolymer is sieved with Safain UH901 with a metal mesh of 2 0 0 to obtain polyethylene particles with a particle size of 8 5 // m. 50 weight ratio mixing. Fill the particle mixture in a disc-shaped grooved aluminum disc metal appliance of 25 mm 0 X 3 mm t. Heat in a hot air dryer at 1 8 0 ° C for 3 hours. Sintering was performed in 0 minutes. The average pore diameter of the obtained sintered body was 20 // m, and the porosity was 39%. In a 50-m1 separation flask, 10% by weight of sodium iminodiacetate was placed. The mixed solution of the volume ratio of dimethyl subcode to water of 1: 1, and the sintered body formed as described above with a shape of 25 mm 0 x 3 mm t was reacted at 80 ° C for 7 2 hours. After the reaction, the sintering was taken out Body, washed with water, and dried under vacuum. The introduced amount of the chelate exchange group of the obtained chelated porous ion sorbent was 1.7 5mmo Ι / g. This paper size applies to Chinese national standards (CNS ) A4 size (210X297mm) (Please read the notes on the back before filling this page)

-41-1239935 Printed by the Consumer Cooperatives of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (4 <Example of sintered body (radiation-graft resin sintered body, introduction of functional groups)> Example 16 6 1 0 0 The sintered body of flaky polyethylene particles was irradiated with k G y, and Sunfine AQ — 800 (made by Asahi Kasei Co., Ltd. (pore diameter: 20 / zm, film thickness: 2 mm, porosity: 35%). Dissolved 80 g of Styrene and 6 g of divinylbenzene (55% purity) in 1 L of isopropanol were heated at 70 ° C, and a nitrogen bubble flow was performed for 30 minutes to remove dissolved oxygen. 7-ray irradiation The subsequent SunfineAQ — 80 0 was cut into a disk shape of 0 4 7 mm, all of which were 60 g, and put into this monomer solution. The reaction was carried out under stirring for 5 hours, and the sintered body was taken out and washed with isopropyl alcohol. Dry in a vacuum dryer at 50 ° C for 2 hours. The total weight after drying is 109 g, and the amount of crosslinked layer formation is 82%. The pore diameter of the sintered body forming the crosslinked layer is 2 0 // m, porosity is 3 4% 〇 After dipping the obtained sintered body in dichloroethane, it was dissolved by dripping A 10% by weight solution of chlorosulfonic acid in dichloroethane was reacted in an ice-cooled state for 1 hour, and then reacted at room temperature for 30 minutes, and chlorosulfonic acid was introduced. The anion sorbent obtained The ion-exchange capacity was 1.87mmo Ι / g. The water permeability was 2400000 000 L / m2 · hr.Mpa. The average void diameter was 19 // m and the void ratio was 33%. A part was cut out and analyzed to form a sintered body. As a result of the distribution of the sulfonic acid groups in the cross-sectional direction of the particles, the absorption functional group distribution index is 0 · 8. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) (Please read the precautions on the back first (Fill in this page again)

-42-1239935 A7 _____ B7

V. Description of the invention (A Example 17 (Please read the precautions on the back before filling in this page) Irradiate SunfineAQ — 8 0 0 with 100 k G y rays. Dissolve 1 20 g of chloromethyl Styrene and 6 g of divinylbenzene (55% purity) in 1 L of isopropanol were heated at 50 ° C, and a nitrogen gas bubble flow was performed for 30 minutes to remove dissolved oxygen. R-rays were irradiated The next SunfineAQ — 80 0 is cut into a circular plate shape of 4 7 mm, all of which are 60 g, and put into this monomer solution. The reaction is carried out under stirring for 2 hours. The sintered body is taken out and washed with isopropanol. Dry in a vacuum dryer at 50 ° C for 2 hours. The total weight after drying was 105 g, and the amount of crosslinked layer formation was 75%. The pore diameter of the sintered body forming the crosslinked layer was 19 // m, the porosity is 30%. The obtained sintered body is immersed in isopropyl alcohol in which 30% by weight of trimethyl ammonia is dissolved, and the reaction is performed at 35 ° C for 50 hours to introduce the chlorine Methylmethylstyrene is graded 4. The anion sorbent obtained is washed with ethanol and water, replaced with ethanol, and dried with a vacuum dryer. The amount of cation exchange groups introduced by the ion sorbent (printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the Ion Exchange Capacity) was 3.26 mmOg / g, and the water permeability was 19000000 L / m2 · hr.Mpa. The pore diameter is ig ^ m, and the porosity is 3%. The sintered body is immersed in an aqueous solution of Na C 1 so that the c 1 ions are adsorbed on the anion exchange group, and then the C 1 DEX analysis. The result is that the distribution index of the anion exchange group is 0 · 7 5. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -43- 1239935 A7 _ B7 V. Description of the invention (4 Examples 18 (Please read the precautions on the back before filling in this page) Install the sintered body with cationic anion exchange group synthesized in Examples 16 and 17 in a special holder and pass it with ultrapure water. Measure the resistance rate of the treated water side and the concentration of TO C. After 24 hours from the start of the circulation, measure the resistance rate 値 with respect to the supplied water: 1 8 · 1, the cationic adsorbent: 1 8 · 2, and the anion absorbent. Attention: 1 8 · 1. In addition About TOC, with respect to the supplied water: 2.0 ppm, cationic sorbate: 2.0, and anionic sorbent: 1.1, no dissolved ionic impurities and TOC were found. Example 1 9 Implementation The cation-absorbing sintered body of Example 16 was measured in the same manner as in Example 18 to determine the adsorption properties of Z η and Na. The results are shown in Table 2. Table 2 Water before filtration Zn ion concentration (ppb) of filtered water of type sintered body 0.19 0.01 Na ion concentration (ppt) 0.98 0.44 Printed on the cationic sorbent by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, it is believed that the cation absorbing body is significantly reduced. From the concentrations of Z η and Na, it can be seen that they have excellent ion adsorption performance. This paper size applies to Chinese National Standard (CNS) A4 specification (2 丨 〇X 297 mm) -44-1239935 Α7 Β7 V. Description of the invention (comparative example 4 (Please read the precautions on the back before filling this page) No A comparative example in which a cation-exchange group was introduced through a crosslinked body layer, and SunfineAQ-800 used in Example 17 was immersed in concentrated sulfuric acid heated at 8 ° C for 8 hours to obtain a sulfonated sintered body. The sintered body is brown overall, and some of them are blackened. When touched by hand, visible particles are peeled off by the sintered body. Made of 47 mm 0, connected to a special holder, the water is circulated, and ATOC and As a result of fine particles, ATOC is 2 5 ppb, which is equivalent to more than 25 times that of the sintered body of the present invention. △ Fine particles are 1 · 8 pieces / mL, which is 100 times higher. In addition, when the treated water is filtered by a non-woven fabric, Filter out the possibility of use of black objects visible to the naked eye. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy. And Excellent absorbent structure that can remove impurities to a very low concentration. In particular, it provides an absorbent sintered body that can reduce metal ions in ultrapure water to a very low concentration. This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -45-

Claims (1)

1239935 Announcement A8 B8 C8 D8 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs VI. Application for Patent Scope 1 No. 9 1 1 1 7484 Chinese Patent Application Scope Amendment 1 May 17, 1994 Amendment 1 · One A porous sintered body is characterized in that the sintered body of the polyolefin particles is ion-exchanged and / or a group-specific affinity group is locally bonded to the surface thereof via a graft polymer chain. 2 · For the sintered body according to item 1 of the patent application, the pores are voids formed when the polyolefin resin particles are dissolved and bonded, and the average pore diameter is 1 // 1ΊΊ or more ′ 1 Q 〇 # m is not full. 3. If the sintered body in item 1 of the patent application scope, its porosity is more than 20% and less than 60%. 4. The sintered body according to item 1 of the patent application scope, wherein the ion exchange group and / or group-specific affinity is based on a concentration in the sintered body of 0.3 mm ο 1 / g or more, 10 mM 11 〇 1 / g full. 5 · A porous sintered body characterized by containing a mixture of thermoplastic resin particles and polyolefin resin particles with ion exchange groups and / or group-specific affinity groups partially bonded to the surface thereof via a graft polymer chain. 6 · The sintered body according to item 5 of the patent application, wherein the pores are voids formed when dissolving the bond structure into particles of the sintered body, and the average pore diameter is 1 // m or more, and 100 m // is not full. 7 · If the sintered body in item 5 of the patent application scope, its porosity is more than 20% and less than 60%. 8. The sintered body according to item 5 of the patent application scope, wherein the thermoplastic resin particles are formed of polyolefin. This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back ^^ Fill in this page) -Packing · 丨 -Order embroidery 1239935 A8 B8 C8 D8 __ VI. Patent Application Scope 2 (Please read the note on the back ^ 8 ^ before filling out this page) 9 · If the sintered body of the scope of application for item 5 of the patent, the ion exchange group and / or group specific affinity is based on the concentration in the sintered body is 0 · 3 mm ο 1 / g or more, 1 〇 ^ m ο 1 / g is less than full. 1 〇 • The sintered body according to item 5 of the scope of the patent application, in which the ion-crosslinking Ms and / or group-specific affinity group is bonded to the surface of the sintered body through a graft polymerization chain, and the proportion of the total sintered body is 1 〇 More than 70% by weight. 1 1 · A polyolefin resin particle, characterized in that an ion exchange group and / or a group-specific affinity group is locally bonded via a grafting / polymerizing chain, and is selected from the group consisting of polyethylene, polypropylene, ethylene-propylene copolymer, and ethylene butylene. Ene-1 copolymer, ethylene-hexene-1 copolymer, ethylene-pentene-1 copolymer, ethylene-octene-1 copolymer, ethylene-4-methylpentene-1 copolymer, ethylene-vinyl acetate copolymerization Polymers, ethylene- (meth) acrylic acid copolymers and ethylene- (meth) acrylic acid ester copolymers. 1 2. The resin particles according to item 11 of the scope of patent application, wherein the concentration of the ion-exchange group and / or group-specific affinity group is 0.3 1Ή 1Ώ 〇1 / g or more, and 10 mm ο 1 / g is less than . Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1. If the resin particle in item 11 of the patent application scope has a particle size of less than 300 // m. 1 4 · A method for producing a sintered body, comprising a polyolefin resin particle having a sintered particle size of 300 0 // m or less, and an ion-exchange group with a particle size of 300 V m or less and / or The particle mixture of the group-specific affinity group-bound parent conjoined resin particles is formed into a porous resin matrix, and then bonded to an ion-exchange group and / or a group-specific affinity group. The paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) ~-: ----:-1239935 A8 B8 C8 D8: 、 Applicable patent scope 1 2 3 1 5 In the manufacturing method, the mixing ratio of the crosslinked resin particles capable of bonding the ion-exchange group and / or the group-specific affinity group is 10% by weight or more of the whole mixture, and the Q% weight is less than. 16. The manufacturing method according to item 14 of the scope of patent application, wherein the crosslinked resin particles are resin particles having a crosslinked layer formed by a graft polymerization reaction. 1 7 · According to the manufacturing method of item 14 in the scope of patent application, where the crosslinked resin particles are resin particles that form a crosslinked layer on a polyalkene, please read the precautions at the back first, and then the staff of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by a consumer cooperative 18 · A method for manufacturing a sintered body, characterized in that it comprises polyolefin resin particles with a sintered particle size of 3 0 0 // m or less, ion-exchange groups with a particle size of 3,000 m or less, and / or A particle mixture of group-specific affinity groups of resin particles locally bonded to the surface via a grafted polymeric chain. 19. The manufacturing method according to item 18 of the scope of patent application, wherein the mixing ratio of the resin particles bonded to the parent group and / or the group-specific affinity group via graft polymerization is 10% of the entire mixture Above weight, less than 70% weight. 20 · The manufacturing method according to item 26 of the patent application, wherein the ion exchange group and / or the group-specific affinity group are polymerized with resin particles to which hydrocarbon resin particles are bonded via a graft polymerization chain. 3 2 1 · The manufacturing method according to item 18 of the scope of patent application, which further comprises salting the metal before sintering the ion exchange group and / or group-specific affinity group. 1239935 Α8 Β8 C8 D8 VI. Patent application scope 4 2 2 · —A method for manufacturing a sintered body in which ion exchange groups and / or group-specific affinity groups are bonded to its surface, which is characterized by being contained in a polyolefin resin particle sintered body The surface 'forms a crosslinked layer, followed by a reaction with an ion exchange group and / or a group-specific affinity group capable of reacting with the crosslinked layer. 2 3 · The manufacturing method according to item 22 of the scope of patent application, wherein the particle size of the fine-polycarbonate resin particles constituting the sintered body is 30 m / m or less. 2 4 · The manufacturing method according to item 22 of the patent scope, wherein the sintered body of polyolefin resin particles is irradiated with radiation and then contacted with a reactive monomer while being stirred in a solvent that does not swell the polycarbonated hydrocarbon resin particles. To form a crosslinked layer, followed by ion-exchange groups and / or group-specific affinities that enable reaction with the crosslinked layer based on reactions in the liquid phase. 2 5 · —A method for producing resin particles having an ion exchange group and / or a group-specific affinity group bonded to the surface thereof, which is characterized in that it comprises a material selected from the group consisting of polyethylene, polypropylene, ethylene-propylene copolymer, and ethylene-butene. _ 1 copolymer, ethylene-hexene-1 copolymer, ethylene-pentene-1 copolymer, ethylene-octene-1 copolymer, ethylene-4-methylpentene-1 copolymer, ethylene-vinyl acetate copolymer 2. The surface of polyolefin resin particles formed by ethylene- (meth) acrylic acid copolymer and ethylene- (meth) acrylic acid ester copolymer forms a crosslinked layer, followed by ion exchange that enables reaction with the crosslinked layer And / or group-specific affinity groups. 2 6 · The manufacturing method according to item 25 of the scope of patent application, wherein the particle size of the resin particles is 3 0 0 // m or less. 2 7 · The manufacturing method according to item 25 of the scope of patent application, wherein after the resin particles are irradiated with radiation, the paper size is stirred in a solvent that does not swell the resin particles. 】 0 Father 297 mm) -4-Please read the precautions before printing by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1239935 A8 B8 C8 D8 Six, apply for the scope of patent 5 Mix, contact with reactive monomers, Formation of a crosslinked body layer, followed by ion-exchange groups and / or group-specific affinity capable of reacting with the crosslinked body layer based on the corresponding anti-III ^-(please read the notes on the back first and fill in this page) The paper size printed by the Intellectual Property Bureau employee consumer cooperative is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm)