TW201138638A - Antibacterial treating agent for processing water, method for producing antibacterial treating agent for processing water and method for processing water - Google Patents

Abstract

Provided of this invention are an antibacterial treating agent, which can dissolve out the decided proper concentration of silver ions and give antibacterial treatments for fresh water such as drinking water or circulating water etc., and sustain the ability for dissolving out the silver ions chronically, and a method for processing water, which used the said antibacterial treating agent. An antibacterial treating agent for processing water, characterized in consisting of resin compositions, which contain resins having a standard moisture percentage of 1 to 10 weight% ruling by JIS L 0105: 2006, and 1 to 30 weight% of silver substituted phosphoric acid zirconium represented by formula [1] as antibacterial agent, AgaMbZrcHfd(PO4)3.NH2O [1] in formula [1], M is at least one ion choose from the group, which consists of alkali metal ions, alkali earth metal ions, ammonium ions, hydrogen ions, and oxonium ions, a, b, and c are independent integers individually, d is 0 or a integer, n is 0or a integer smaller than 2, all a, b, c, and d satisfy the relationships of the formula [A], when the valence number of M is 1, they satisfy the formula [B], when the valence number of M is 2, they satisfy the formula [C]. 1.75 < c+d < 2.25 [A] a+b+4 (c+d)=9 [B] a+2b+4(c+d)=9 [C]

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial treatment agent for water treatment and a method for producing the same, and the antibacterial treatment agent for water treatment characterized by a resin containing a specific standard moisture percentage and A resin composition of a specific silver-based inorganic antibacterial agent. Further, a water treatment method for performing an antibacterial treatment of water by bringing the antibacterial treatment agent for water treatment of the present invention into contact with various kinds of water. [Prior Art] As an antibacterial agent for water treatment, various applications have been proposed depending on the use, the target water, and the amount of water to be used. For example, as a water treatment, a silver-loaded antibacterial agent for water treatment is proposed, which is supported in a treatment liquid having a pH which does not impair the crystal structure of the zeolite, and supports silver ions in a zeolite of any size capable of solid-liquid separation. The pellet or the zeolite is processed (see, for example, Patent Document 1). Further, it has been proposed to add a glass water treatment agent to a cooling tower, a water storage tank, a swimming pool, a solar energy system, and irrigation water by using a soluble glass containing monovalent silver ions in the composition. The occurrence of aquatic bacteria and aquatic organisms such as slime or algae is prevented (see, for example, Patent Document 2). Further, there has been proposed an antibacterial water treatment medium which is obtained by a fiber block in which a plurality of short fibers containing an antibacterial agent are intertwined with each other, and the antibacterial agent supports a metal or metal ion having an antibacterial property. It is obtained by phosphate (refer to, for example, Patent Document 3). Further, there is disclosed a water treatment filter for use in a water treatment filter for decontaminating 201138638 dyed material from water, characterized in that a zeolite supporting activated carbon and an antibacterial metal ion is used. A binder (binde 1·) made of a high molecular weight porous polymer is cured (see, for example, Patent Document 4); or a water purifying agent which is supported by a phosphoric acid compound and activated carbon bonded with silver. It is excellent in antibacterial property (see, for example, Patent Document 5). Others have proposed an antibacterial resin molded article for inhibiting the growth of aquatic bacteria, which is characterized in that a mixture containing a silver-based inorganic antibacterial agent, an alkali metal and/or an alkaline earth metal halide salt, and a polyolefin resin is melt-mixed to form a resin. The composition was subjected to water treatment to make the resin composition finely porous. When silver zeolite is mixed with polyolefin by this technique, a high concentration of silver is continuously eluted as compared with a case where silver zeolite is simply mixed with polyamine (see, for example, Patent Document 6). CITATION LIST Patent Literature Patent Literature 1: Japanese Laid-Open Patent Publication No. 2001-278715; Patent Document 2: Japanese Laid-Open Patent Publication No. Hei. (4) Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2008-174576. DISCLOSURE OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION If zeolite particles described in Patent Document 1 are directly added to water, 201138638 will not be able to withstand long-term use in any case, and in addition to the silver of the active ingredient, there is a powder of zeolite powder. Or shedding, and the silver concentration is not stable due to the large variation in the amount of silver dissolved. On the other hand, the dissolvable glass described in Patent Document 2 is also the same, and in addition to the silver of the active ingredient, the glass component is dissolved, and the concentration of silver in the aqueous solution is difficult to control. Even if the water is not replaced or replaced, the glass continues to dissolve, so that the silver concentration in the treated water is remarkably increased due to the continued dissolution of the silver. For clean water such as drinking water or circulating water, it is preferable to dissolve a small amount of silver ions of the antibacterial component in an appropriate amount, and do not dissolve or dissolve other substances other than necessary. Further, in the invention described in Patent Document 3, even if the silver is supported on the phosphate of the non-ion exchanger which controls the concentration of the eluted silver by the balance between the antibacterial agent and the environment, the silver elution concentration cannot be controlled. Further, the short fibers have a problem that the threads are loosened and mixed into the water. Further, there are proposals for using activated carbon in Patent Document 4 and Patent Document 5. If activated carbon is used, it is not limited to black, and it is also used for adsorption of pollutants. Therefore, the use is limited, and there is a problem that if the adsorption of activated carbon is saturated, the pollutants are released into the water. In the invention described in Patent Document 6, since the hydrophilicity of the polyolefin is low, the fine pores obtained by the water treatment are only very close to the surface of the molded article, so that only the silver in the vicinity of the surface can be utilized, and even if the initial stage can be obtained Sustainability cannot be sustained in the long run. Further, since the fine pores of the silver zeolite are large, the control of the ion exchange property can never be called precision, so the concentration of the dissolved silver can not be strictly controlled. 201138638 In this way, although the antibacterial property is exhibited in the short term, the long-term persistence in water and the control of a certain silver concentration are not easy, so the technique suitable for the antibacterial agent for water treatment has not been disclosed. An object of the present invention is to provide an antibacterial treatment agent for water treatment, which is capable of dissolving a certain concentration of silver ions in a clean water (freshwate 1·) such as drinking water or circulating water, and performing antibacterial treatment. And silver dissolution can be sustained for a long period of time; a method for producing an antibacterial treatment agent for water treatment; and a water treatment method using the antibacterial treatment agent for water treatment. Means for Solving the Problems The above problems of the present invention are solved by the following descriptions of <1>, <6>, and <7>. The <2> to <5> of the preferred embodiment are described below. <1> An antibacterial treatment agent for water treatment, which comprises a resin having a standard moisture percentage of 1 to 1% by weight, and 1 to 30% by weight, as an antibacterial agent, as specified in ns L 0 105 :2006 And a resin composition of a phosphoric acid-substituted phosphoric acid pin represented by the formula [1],

AgaMbZi-cHfd (P〇〇3. nH2〇 [1] In the formula [1], hydrazine is at least one selected from the group consisting of alkali metal ions, alkaline earth metal ions, ammonium ions, hydrogen ions, and ions. ; a, b, and c are independent integers; d is 〇 or an integer; n is 〇 or an integer less than 2; a, b, c, and d are satisfied with the relationship of the formula [a]; , is satisfied by the formula [Β]; when Μ is 2, it satisfies the formula [C]. 1.75 &lt; c + d &lt; 2.25 [A] 201138638 a+b+4(c+d)=9 [B] a+2b+4(c+d) = 9 [ C ) <2> The antibacterial treatment agent for water treatment described in <1> above, the silver content of the chromium phosphate substituted with soft silver is preferably 4 to 13 by weight. %. <3> The antibacterial treatment agent for water treatment described in the above <1>, wherein the pre-% treatment agent has a specific surface area of 5 to 100 cm 2 /g. (4) The antibacterial treatment agent for water treatment described in the above <1>, wherein 50% to 99% by weight of the resin of the resin composition is a polyamine resin. <5> The antibacterial treatment agent for water treatment according to the above <4>, wherein the polyamine resin is nylon 6. The method for producing an antibacterial treatment agent for water treatment according to any one of the above items <1> to <5>, which comprises the step of mixing the antibacterial agent with the resin. (7) A water treatment method comprising the step of bringing the antibacterial treatment agent for water treatment described in any one of the above <1> to <5> into contact with water. Advantageous Effects of Invention According to the present invention, it is possible to provide an antibacterial treatment agent for water treatment which is capable of dissolving a certain concentration of silver ions in an aqueous solution such as hydrazine water or circulating water, and performing antibacterial treatment, and silver. The dissolution can be sustained for a long period of time; a method for producing an antibacterial treatment agent for water treatment; and a water treatment method using the antibacterial treatment agent for water treatment. [Embodiment] Embodiments of the Invention 201138638 Hereinafter, the present invention will be described in detail. Further, in the present invention, the description of the "lower limit to the upper limit" indicating the range of the number is indicated as "above the lower limit and the upper limit"; and the description of the "upper limit to the lower limit" means "the upper limit is equal to or lower than the lower limit". That is, the range including the upper limit and the lower limit is indicated. (Antibacterial treatment agent for water treatment) The antibacterial agent for water treatment of the present invention is characterized in that it contains a resin having a standard moisture percentage of 1 to 10% by weight and 1 to 30% by weight based on the total weight of the resin composition. a specific silver-substituted zirconium phosphate (hereinafter, sometimes referred to as "silver-substituted chromium phosphate j") represented by the following formula [1],

AgaMbZrcHfd(P〇4)3 · nH2〇[1] In the above formula [1], hydrazine is one or more ions selected from the group consisting of alkali metal ions, alkaline earth metal ions, ammonium ions, hydrogen ions, and ions; , b and c are independent integers; d is 0 or an integer; η is an integer of 0 or less; a ' b ' c and d are satisfied with the relationship of the formula [A]; In the formula [B; ]; M is a divalent:: is satisfied by the formula [c]. 1.75 &lt; c + d &lt; 2.25 [ A] a + b + ^ " c + d ) = 9 ( B ] a + 2b + 4( c + d ) = 9 CC] In the present invention, the so-called water treatment, meaning pointer It is required to clean the water (drinking water) that has been ingested into the living body directly after conditioning, mixing, dissolving, etc., or circulating cooling water or a variety of ornamental water, food and medicine, etc., 201138638 water, etc., is required to be harmless, Clean water (purified water) In the present invention, the silver ions which are not dissolved in the above-mentioned water are subjected to antibacterial treatment, and the antibacterial treatment of bacteria is also carried out. The antibacterial treatment agent for water treatment of the present invention The concentration of ions contained in the water is maintained at a certain concentration of silver, and the dissolution of silver is continued. Therefore, for the drinking water or circulating water, even if water is replaced by water or water consumption, it is necessary for the antibacterial effect. Silver ions are not incompatible with the effect of bacteria. The silver-substituted zirconium phosphate-based agent used in the present invention, and preferably the chromium phosphate in its main chain has a crystalline crystal. Crystals and become 2 times 3 It is a crystallized structure of a meta-mesh structure, and it is preferably made of crystalline chromium phosphate which is excellent in heat resistance, chemical resistance, and low thermal expansion property, among which silver is made of chromium crystals by cubic crystals. The silver extraction obtained by ion substitution not only exhibits an excellent antibacterial effect, but also is excellent in discoloration or safety during durability or ion processing, so that it can be further used as a silver-substituted chromium phosphate method used in the present invention. For the zirconium phosphate molar represented by the following formula [2], an aqueous solution containing the coefficient bl of the formula [2] and multiplied by 0.6 to silver nitrate is ion-exchanged and subjected to heat treatment for antibacterial treatment, and a certain concentration is determined. It means suppressing the clean water according to the treatment object and having a long-term basis, in order to achieve long-term anti-silver inorganic antibacterial 3-dimensional mesh structure layer structure or 3-dimensional mesh structure radiation resistance in the water, for six planes Instead of zirconium phosphate, the selectivity, the resin is good, the specific synthesis of the compound, which is obtained for every 0.99 equivalents. -10- 201138638 N ab 丨A c 丨Zr e H fr (P 〇4) 3 · η Η 2 Ο [2] In the formula [2], 'A series ammonium ion and/or hydrogen ion, bl, cl, e, and f are each an independent integer' and 1.75 &lt; (e+f) &lt; 2.25, And a method of synthesizing a phosphoric acid pin compound represented by the formula [2], and a wet method or a hydrothermal method for reacting various raw materials in an aqueous solution The phosphoric acid compound of the A-based ammonium ion in the formula [2] may be sodium hydroxide by using an aqueous solution containing a specified amount of a chromium compound, ammonia or a salt thereof, oxalic acid or a salt thereof, or phosphoric acid or a salt thereof. Hereinafter, it may be referred to as "caustic alkali" or ammonia water, and pΗ is adjusted to about 1 to 4, and then it is synthesized by heating at a temperature of 70 ° C or higher. Further, the heating temperature is preferably 20 or less (TC or less). Further, the zirconium phosphate compound of the A-type hydrogen ion in the formula [2] may contain a specified amount of a pin compound, oxalic acid or a salt thereof, or phosphoric acid or An aqueous solution of a salt or the like is adjusted to have a pH of about 1 to 4 with caustic alkali, and then the phosphoric acid pin obtained by heating at a temperature of the above is further stirred in an aqueous solution of hydrochloric acid, nitric acid or sulfuric acid. The hydrogen ion is supported and synthesized. Further, the heating temperature is preferably 200 ° C or less. Further, the hydrogen ion support may be carried out simultaneously with the support of the silver ion by silver nitrate, or may be performed on the silver ion branch. After the loading, the synthesized chromium phosphate compound is further filtered and washed with water to a predetermined conductivity, dried, and lightly pulverized to obtain a white fine particle zirconium phosphate compound. The hydrothermal method synthesized under the pressure of 100 ° C can synthesize the zirconium phosphate compound represented by the formula [2] without using oxalic acid or a salt thereof. -11 - 201138638 It can be used as a synthetic raw material of the zirconium phosphate compound represented by the formula [2]. Phosphorus used Examples of the chromium compound include water-soluble or acid-soluble zirconium salts, and examples thereof include chromium nitrate, zirconium acetate, chromium sulfate, basic barium sulfate, zirconyl sulfate, and chromium oxychloride, and if reactivity or economy is considered. The oxyzirconium oxychloride is preferred as the compound for use as a synthetic raw material of the zirconium phosphate compound represented by the formula [2], and is a water-soluble or acid-soluble salt, and is exemplified by, for example, chlorinated bell and oxychloride. The compounding bell, the cerium oxide, and the like are also exemplified to contain the compound which is supplied with the compound. The content of the compound contained in the zirconium compound is preferably 〇.丨5 5 mol%, more preferably the oxygen is used in such a manner. The oxalic acid or a salt thereof which can be used as a synthetic raw material of the zirconium phosphate compound represented by the formula [2], and examples thereof include oxalic acid dihydrate, sodium oxalate, ammonium oxalate, sodium hydrogen oxalate, and ammonium hydrogen oxalate, and the like. An oxalic acid dihydrate is preferred. The ammonia or a salt thereof which can be used as a synthetic raw material of the zirconium phosphate compound represented by the formula [2] is exemplified by ammonium chloride, ammonium nitrate, ammonium sulfate, ammonia water, ammonium oxalate, and phosphoric acid. Ammonium, etc., and preferably chlorine Ammonium or ammonia water. Phosphoric acid or a salt thereof which can be used as a synthetic raw material of the zirconium phosphate compound represented by the formula [2] is preferably a soluble or acid-soluble salt, and specific examples thereof include phosphoric acid, sodium phosphate, sodium hydrogen phosphate, and phosphoric acid. Ammonium hydroxide, ammonium phosphate, etc., and more preferably phosphoric acid. Further, an aqueous solution having a concentration of about 60 to 85% by weight is preferably used as the concentration of the phosphoric acid. Phosphoric acid in the case of synthesizing a phosphoric acid compound represented by the formula [2] Or the molar ratio of the salt thereof to the zirconium compound (the chromium compound is ruthenium), preferably more than 1 5 under -12-201138638 2. More preferably 1.51 or more and less than 1.71, further preferably 1.52 or more and 1.67 or less. In particular, it is preferably 1 · 5 2 or more and 1 6 5 or less. Further, the molar ratio of phosphoric acid or a salt thereof to ammonia or a salt thereof in synthesizing a phosphoric acid pin represented by the formula [2] (1 or 6 with ammonia or a salt thereof) Preferably, it is 〇. 3 to 10, more preferably 1 to 1 0 'particularly preferably 2 to 5. The molar ratio of the phosphoric acid or the salt thereof to the oxalic acid or the salt thereof in the synthesis of the hydrazine phosphate represented by the formula [2] (the oxalic acid or the salt thereof is 1), preferably 1 to 6, more preferably 1 to 5 to 5, further More preferably, it is 1.51 to 4, and particularly preferably 1.52 to 3.5. Namely, the chromium phosphate compound represented by the formula [2] can be preferably synthesized by a wet method or a hydrothermal method containing oxalic acid or a salt thereof. In the hydrothermal method, it is not necessary to contain oxalic acid or a salt thereof. On the other hand, the wet method can easily control the particle diameter, and a zirconium phosphate having a uniform particle size distribution in the range of μ. 1 μ m or more and 5 // m or less can be obtained. Crystallization of the compound. When the yttrium phosphate compound represented by the formula [2] is synthesized, the concentration of the solid content in the reaction slurry is preferably 3% by weight or more, and more preferably 7 to 20% by weight in consideration of economy and the like. The pH at the time of synthesizing the phosphoric acid pin compound represented by the formula [2] is preferably 1 or more and 4 or less, more preferably 1⁄3 to 35, still more preferably 1 to 3 Å, and particularly preferably 2.0 to 3.0. In order to adjust this pH, it is preferred to use sodium hydroxide, potassium hydroxide or ammonia water, and it is more preferred to use sodium hydroxide. Further, when the synthesis temperature of the zirconium phosphate represented by the formula [2] is higher, the reaction is faster, and it is preferable to carry out the reaction. However, on the other hand, the cost of the synthesis device or the energy for heating is It is advantageous to set the synthesis temperature lower than -13-201138638. The lower limit is preferably 70 ° C or higher, more preferably 80 t or higher, still more preferably 90 ° C or higher, and particularly preferably 95 ° C or higher. Further, the upper limit ' of the synthesis temperature is preferably 150 ° C or less, more preferably 1201 or less. In the case of synthesizing the zirconium phosphate compound represented by the formula [2], it is preferred that the raw materials are uniformly mixed 'and stirred to allow the reaction to proceed uniformly. The synthesis time of the chromium phosphate compound represented by the formula [2] varies depending on the synthesis temperature. The synthesis time of the acid-storing compound used in the present invention is, for example, preferably 4 hours to 7 2 hours, more preferably 8 hours to 7 2 hours, particularly preferably 1 hour to 48 hours. The particle size of the phosphoric acid pin compound represented by the formula [2] is determined by a volume measurement based on a laser diffraction type particle size distribution analyzer to define a median particle diameter. The zirconium phosphate compound represented by the formula [2] preferably has a ruthenium particle diameter of 0.1 to 4 μm, more preferably 〇 2 to 3 μm, particularly preferably 0.3 to 2 # m. Further, considering the processability of processing into various products, the median diameter is not limited, and the maximum particle size is also important. Therefore, the maximum particle diameter of the chromium phosphate compound represented by the formula [2] is preferably 10 μm or less, more preferably 6 &quot; m or less, and particularly preferably 4 or less. The lower limit 値〇. i is preferably from m or more. The phosphoric acid pin compound which is not used in the formula [2] which is a raw material of the silver-substituted zirconium phosphate compound used in the present invention can be specifically exemplified below.

Na〇.〇7(NH4)〇.85zr2 〇Hf〇 02(p〇4)j , 〇 65H2〇

Na〇.i2(NH4)〇.65zr2 olHf〇 〇3(p〇4)3 # 〇 85H2q

Na〇.i9(NH4)〇.65zr2 〇3Hf〇 0l(p〇4)3 , 0.75H2O

Na〇.2i(NH〇〇.75Zri.”Hf〇.〇2(P〇4)3 · 〇 6H2C) -14- 201138638

Na〇.27(NH4)0.75Zl*l.92Hf〇.15(P〇4)3 · 0.75H2〇

Na〇.29(NH4)0.55Zl-1.92Hf〇.〇5(P〇4)3 · 0·5Η2〇

N a 0 . 5 7 ( N Η 4 ) 0 . 5 5 Z r 1 . 9 5 H f 0 . 0 2 ( P Ο 4 ) 3 · O.35H2O

Na〇.70(NH4)0.85Zr 丨.99Hf〇.〇l(P〇4)3 · O.4H2O N a 0. 07 H 0 . 8 5 Z r 2 . oH f 0 . 0 2 ( P 0 4 3 · 0.65H2〇N a 0 . 1 2 H 0 . 6 5 Z r 2 . 0 1 H f 0 . 0 3 ( P 0 4 ) 3 · O.85H2O Na〇.19H〇.6 5Zr2.03Hf〇 .〇l(P〇4)3 * O.75H2O

Na〇.2lH〇.75Zri.99Hf〇.02(P〇4)3 · 0.6H2〇N a 0 . 2 7 H 0 . 7 5 Z r 1 . 9 2 H f 0 . 1 5 ( P 0 4 ) 3 B 0.75H2〇N a 0 . 29 H 0 . 5 5 Z r 1 - 9 2 H f 0 .0 5 ( P 0 4 ) 3 * 0.5H2〇

N a 0 . 5 7 H 0 . 5 5 Z r 1 . 9 5 H f 0 . 0 2 ( P 0 4 ) 3 # 0.35H2〇N a 0 . 7 0 H 0 . 8 5 Z r 1 . 9 9 H f 0 . 0 1 ( P 0 4 ) 3 · O.4H2O The silver-substituted zirconium phosphate of the formula [1] can be obtained by exchanging silver ions for these zirconium phosphate compounds and then heat-treating them. The silver ion exchange method is a method of immersing a zirconium phosphate compound in an aqueous solution containing silver nitrate. It is preferred that the silver nitrate content of the aqueous solution is increased as the obtained silver-based inorganic antibacterial agent is less likely to be discolored when it is used in the resin. On the other hand, if too much is too much, it will be economically unsatisfactory for excess silver ions to remain in the aqueous solution. Preferably, for every 1 part of the chromium phosphate compound represented by the formula [2], an aqueous solution containing a coefficient bl of the formula [2] and multiplied by 0-6 to 〇99 moles of silver nitrate is used, more preferably for every 1 mole. The zirconium phosphate of the ear is an aqueous solution of silver nitrate containing a coefficient bl of the formula [2] and multiplied by 0-7 to 0.98 moles. The amount of the phosphoric acid-discriminating compound is immersed in the aqueous solution of silver nitrate, and the concentration of the zirconium-containing compound represented by the formula [2] and the aqueous solution can be 'specifically and g' as long as the concentration of the aqueous solution is -15-201138638. It is preferably 20% by weight or less. The adjustment of the aqueous solution containing silver ions is preferably carried out using an aqueous solution in which silver nitrate is dissolved in deionized water. The temperature of the aqueous solution at the time of ion exchange is preferably 0 to 100 ° C, more preferably 20 to 80 ° C. Since the ion exchange system is fast, the immersion time can be within 5 minutes, but it is preferably 30 minutes to 5 hours in order to obtain a uniform silver ion exchange rate. Preferably, after the end of the silver ion exchange, it is washed with water by deionized water or the like. The washing is preferably carried out until the conductivity of the filtrate is 500 μS or less. After the water washing, it is dried, and further heat-treated at a suitable temperature to obtain a silver-based inorganic antibacterial agent represented by the formula [1]. In the formula [1], a represents the content of silver. If a is small, the silver content in the zirconium phosphate substituted by silver becomes low; if a is large, the silver content becomes high. The higher the silver content rate, the more sustainable it is, so it is better. On the other hand, silver ions are unstable to heat and exposure to light, and are immediately reduced to metallic silver to cause coloring, etc., and have a long period of stability. Even in the case of a phosphoric acid cone which can stably hold silver ions, the high silver content rate is still doubtful of discoloration or productivity, and it is necessary to appropriately adjust the silver content. Further, since the silver content in zirconium phosphate varies depending on the type or ratio of other components, it is easier to control the silver content rate instead of a. The silver content in the zirconium phosphate substituted by silver is preferably 2% by weight or more and 15% by weight or less, more preferably 4% by weight or more and 13% by weight or less, particularly preferably 6% by weight or more and 12% by weight or less. Further, at this time, it is preferable that a -16 - 201138638 値 (for the other kind of lithium, the water limit for each of the 10 limits is 0.05 or more 〇.7 or less. In the formula [1], the 'c and d systems satisfy i. 75&lt;c+d&lt;2.25, a+b+4 c + d) = 9 number. c is preferably greater than ι.75 and is 21 or less, more preferably 1.85 or more and 2.07 or less, still more preferably 1.9 or more and 2. 〇3 or less. (1 is 0_005~〇.2, preferably 〇.01~〇2, more preferably 〇.〇15~〇.15. In the formula [1], 'b is 0.01~2, preferably 〇.〇1丨.95. In the formula [丨], Μ can also contain one or more kinds, preferably 1 to 5, more preferably 1 to 3. Preferred μ can be exemplified by sodium ion, potassium ion, ion, Magnesium ions, zinc ions, ammonium ions, hydrogen ions, and cesium ions. In the formula [1], η is preferably 1 or less, more preferably 〇〇丨 〇 〇 5, particularly 0.03 to 0.3. n is greater than 2 When the amount of water contained is large, the amount of water contained in the various materials may be foamed or hydrolyzed during heating, etc. The silver-substituted zirconium phosphate is preferably a white crystal crystallization, and The particle size distribution meter and the particle size measured according to the volume reference are 0.1 to 30//m. More preferably (^~彳m, the step is more preferably 0.2 to 3 m., especially preferably 〇_3) ～2 ym. In addition, considering the processability of processing into a product, it is not only the median particle size, but also the maximum particle size. It is preferable to make the maximum particle size of the phosphoric acid pin compound represented by the formula [2] Below V m More preferably, it is 6 /2 m or less, particularly preferably 4 μm or less. The lower 値0. 1 /zm or more is preferable. The silver-substituted pity acid table used in the present invention is compared with most other carriers due to silver ions. Since the support is high, the cleansing with low ion concentration tends to have less release of silver ions. On the other hand, for contaminated water with a high concentration of ion-17-201138638, silver ions are easily released, so The release amount of silver ions in the degree of water pollution is automatically adjusted, the resistance is good, and it is not easy to cause the silver-substituted phosphoric acid pin in the present invention due to the excess silver ion release, and the silver ion is preferably replaced by silver. The crystallinity of zirconium phosphate is determined by powder X-rays from the peak intensity of the zirconium phosphate crystals substituted by silver, and is measured by powder X-ray diffraction and measured by C u Κ α line at 50 kV/120 mA. The peak intensity attributed to the peak of the six-plane cube is about 20 = 20.2°, preferably upper, more preferably 2,000 cps or more, particularly preferably 2,500 cps. The higher the peak intensity, the higher the crystallinity and the silver ion Supporting force to prevent the release of silver ions The purity of the silver-substituted zirconium phosphate-substituted high-purity silver-substituted zirconium phosphate used in the present invention can be obtained by powder X-rays around a peak other than the peak of the silver-substituted phosphoric acid cone crystal and further It is confirmed by fluorescence X-ray analysis that the total amount of the silver-substituted component detected by the fluorescent X-ray analysis is preferably 96% or more and 1% by mass or less and 100% or less. The specific use of silver substituted chromium phosphate is as follows:

Ag〇.〇5Na〇.22H〇.,(H3〇)〇.5 5 2 r2.〇Hf〇.〇2(P〇4)3 · 〇·

Ag〇.17Na〇.32H〇.35Zr2.03Hf0.0|(p〇4)3 . The characteristics of 0.05H2O are: the discoloration caused by the effect of the bacteria. Crystallinity 13⁄4. Diffraction can be judged. Under the conditions, the crystal zirconium phosphate 1,5 0 0 c p s or more. Because it gets higher before, it gets better. The amount of the component of the impurity is determined by the injection. More preferably, 99% of zirconium phosphate can be exemplified by 15H2〇 -18- 201138638

Ag〇.17Na〇.64H〇.33Zr)-92Hf〇.05(P〇4)3 · 0 15H2〇Ag〇.45Na〇.47H〇.2Zri.95Hf〇.02(P〇4)3 · Q Ag 〇.55Na〇.iH〇.2(H3〇)〇.i5Zri.99Hf〇.01(p〇4)3 . 〇.15H2〇Ag〇.05Na〇.32(NH4)〇.2H〇.35Zr2.〇 Hf〇.〇2(P〇4)3 . 〇15H2〇Ag〇.l〇Na〇.2lH〇.28(H3〇)〇.25Zr2.〇lHf〇.〇3(P〇4)3 . IOH2O AgO.i7Na0.20Li0.i5Ho.3Zl. 1.92Hf〇.l〇(P〇4)3 · Q 15PJ2Q Ag〇.17Na〇.l〇Mg〇.l〇H〇.25Zn.92Hf〇.i5(p 〇4)3 . Q !5f{2〇A g 0 1 7 Zn 0 . 20N a 0 . 2 5 H 0 . 3 Z r 1 . 9 2H f 0 . 0 5 ( P〇4 ) 3 . Q I5H2O A g 0 4 5 Z n 0 . 2 7 K 0 1 H 0 . 3 Z r 1 . 9 5 H f 0 . 0 2 ( P 〇4 ) 3 · Q 1 5 H 2 Q

Ag〇.55K〇.lH〇.l(H3〇)0.25Zri.99Hf〇, OI(p〇4)3 ·〇.15H2〇 by mixing the silver-substituted chromium phosphate used in the present invention with a resin An antibacterial resin composition can be easily obtained. The method for producing an antibacterial treatment agent for water treatment according to the present invention is characterized by comprising a step of mixing the antibacterial agent with the above resin. The method of processing the silver-substituted zirconium phosphate to the resin to form the antibacterial resin molded article may be any conventional method, and examples thereof include the following four production methods (1) to (4). (1) A method in which a silver-substituted zirconium phosphate is easily attached to a resin or a dispersing agent for improving dispersibility, and a nine-shaped resin or a powdery resin is directly mixed by a mixer. (2) A method in which the mixture is mixed as described above and pressed into a nine shape by an extrusion molding machine, and the molded product is mixed with a nine-shaped resin. (3) A method in which a silver-substituted zirconium phosphate is formed into a high-concentration nine shape by using a wax, and the nine-shaped molded product is mixed with a non-formed resin. Ι:ϊ -19- 201138638 (4) A paste-like composition in which a silver-substituted zirconium phosphate is dispersed and mixed with a high-viscosity liquid of a polyol or the like, and then the paste is mixed with a nine-shaped resin. The method. In the method, when a hydrophilic substance such as a dispersing agent or a polyhydric alcohol is used, it is preferred that the hydrophilic substance in the resin composition exceeds 〇% by weight to less than 5%, more preferably more than 0% by weight. weight%. In the present invention, it is necessary to use a resin having a predetermined standard moisture percentage, because when other hydrophilic substances are used, it is feared that the hydrophilicity of the resin composition becomes too high, the amount of silver eluted is increased, or the hydrophilic component is first dissolved. And change the physical properties of the treatment agent. In the present invention, the amount of the silver phosphate-substituted phosphoric acid pin to the resin composition is from 1 to 30% by weight based on the total weight of the resin composition. The mixing amount is preferably a high concentration from the viewpoint of controlling the concentration of silver eluted into water and the continuous highness; however, in terms of dispersibility or ease of processing when kneading into a resin, the mixing amount is less. good. The mixing amount is preferably 2 to 25% by weight, more preferably 3 to 20% by weight. The method for forming the antibacterial treatment agent for water treatment of the present invention is not limited, and an existing method or apparatus can be used. For example, injection molding (machine), extrusion molding (machine), blow molding (machine), and hot press forming (machine) are exemplified. In addition, in addition to the shape stability, injection molding (machine) is preferred because of less heat experience. The heat is less than the heat, and the resin is less thermally degraded, so that no decomposition component of the resin is dissolved in the water. The standard of the resin used in the antibacterial treatment agent for water treatment of the present invention is -20-201138638. The percentage of moisture refers to the dry state of the physical test method for fiber products as specified in ns L 0 1 0 5:2006 (will The weight of the test piece placed in a hot air dryer at 1〇5 °C ± 2 °C in a constant state) is compared with the standard state (temperature 20 °C ± 2 °C, relative humidity 65% ± 4%). The weight difference of the constant amount of the test piece is taken as the standard moisture content, and based on the weight of the above-mentioned dry state, and expressed as a percentage, and the specific moisture percentage of the fiber of Table 1 of IS L 1 03 0-2 : 2005 is used. The same definition. The higher the standard moisture percentage of the resin used in the present invention, the more the silver elution amount is, the easier the antibacterial effect is, but if the amount of dissolution is too large, the problem of discoloration is liable to occur. On the other hand, the lower the moisture content, the lower the elution amount, and the antibacterial effect is not easily expressed, but the discoloration is reduced. This effect is also greatly affected by the combined antimicrobial agent. The resin used in the present invention has a water content of 1.0% by weight or more and 10% by weight or less, preferably 2% by weight or more and 9% by weight or less, more preferably 3% by weight or more and 8.5% by weight or less, particularly preferably 4% by weight. % or more and 8% by weight or less. As a standard moisture percentage of a general resin, polypropylene is 〇.〇, polyethylene 0.0, vinyl chloride 0.0, vinylidene 0·0, polyester 〇·3~0.4, urethane 1, acrylate 1.2 to 2.0, poly Acetal 2.0, polyamine 3.5 to 5.0, acetate 6 to 7, and oxime 12 to 14' are in terms of standard moisture percentage. The most preferred resin is polyamine. Polyamines are also commonly referred to as nylons and are available in nylon 6, 66, 46, MDX 6, 61, 9T, 610, 612, 11, 12, etc. These may be used singly or in combination. Among them, in terms of versatility, formability, and controllability of silver dissolution, it is particularly preferable to be nylon 6. It can also be mixed with other types of 201138638 nylon. In this case, the mixing ratio is preferably 50% or more and 100% or less. Further, the lower density of the same resin is preferred because it is easily eluted. The density of the resin is known to have an influence on the hardness of the resin and the like. As a central crucible of the standard resin density, it is known that polypropylene 0.90 to 0.91, polyethylene 0.92 to 0.93, vinyl chloride 1.30 to 1.35, nylon 1.12 to 1.14, urethane 1.20, acrylate 1.17 to 1.2, polyacetal 1.42. In the case of the above-mentioned range, it has been found that silver having a high density in the same resin is not easily eluted; and silver having a low density tends to be easily eluted. Further, a resin having a standard water percentage percentage not in the range of 1.0 to 10 can be used to the extent that the effects of the present invention are not impaired. The degree of the effect of the damage is preferably 40% by weight or less, more preferably 20% or less, and particularly preferably 10% by weight or less based on the total amount of the resin to be used. A dispersing agent such as a metal soap can be used in the antibacterial treating agent for water treatment of the present invention. Preferred dispersing agents are metal soaps, such as zinc stearate, calcium stearate, magnesium stearate, etc., more preferably magnesium stearate. In the resin composition used for the antibacterial treatment agent for water treatment of the present invention, in order to improve the workability or other physical properties of the kneading to the resin, various additives may be mixed as necessary. Specific examples include pigments such as zinc oxide and titanium oxide, inorganic ion exchangers such as zirconium phosphate or zeolite, dyes, antioxidants, light stabilizers, flame retardants, charge inhibitors, foaming agents, and impact enhancers. , glass fiber, metal soap and other slip agents, anti-wetting agents, extenders, chelating agents, nucleating agents, fluidity improvers, deodorants, wood powder, mildew inhibitors, antifouling agents, rust inhibitors, Metal powder, ultraviolet absorber, and ultraviolet shielding agent. However, -22- 201138638 is used for the antibacterial treatment of clean water, and it is better to exclude such additives as much as possible. For the antibacterial treatment agent for water treatment of the present invention, all conventional processing techniques or instruments can be used in accordance with the characteristics of various resins. It can be easily prepared by mixing, 'mixing or kneading, at the appropriate temperature or pressure, while heating and pressurizing or depressurizing. The specific operations can be carried out according to the usual methods. Further, the shape is not limited, and a spherical shape of a block, a sponge, a film, a plate, a wire, a tube, or a composite thereof can be formed into various forms and can be appropriately designed according to the use. . In the molded article of the antibacterial treatment agent for water treatment of the present invention, the larger the specific surface area ', the faster the elution rate of silver is, and the more the dissolved silver concentration is obtained, and the antibacterial agent which is not far from the deep surface of the contact surface with water is insufficient. It is better to use it. On the other hand, those having a small specific surface area are thick and have high strength, and it is not necessary to worry about overlapping after deformation. Therefore, the specific surface area of the antibacterial treatment agent for water treatment in the present invention is preferably from 3 to 110 cm 2 /g, more preferably from 5 to 100 cm 2 /g. The specific surface area can be calculated using the size of the treating agent as a shaped body. For example, in order to obtain a surface area of 3 c m2 /~5 0 c m2 / g, if the sphere is a sphere, the radius is about 0.05 cm to about 1 cm, and if it is a plate of l〇cm square, the average thickness is from about 3 mm to about 6 mm. Further, when the specific surface area is increased, if the planar shape is increased, the installation area may become large, which may cause interference due to the shape of the water-passing cylinder or the like. However, it can be formed into a vortex type or a molded body which is preferably a new type which does not impair the water permeability even if it is filled. The water treatment method of the present invention is characterized by comprising the step of bringing the above-mentioned antibacterial treatment agent for water treatment into contact with water. &lt;: ί -23- 201138638 The use form of the antibacterial treatment agent for water treatment of the present invention is not particularly limited, and may be used as it is, or may be wrapped in a mesh fabric or a non-woven fabric, or may be filled in a cylindrical container. . The antibacterial treatment agent can be used by immersing the antibacterial treatment agent in the water to be treated or by passing the water to be treated through a container containing the antibacterial treatment agent. It is not necessary to keep the antibacterial treatment agent in the water all the time, and even if it is temporarily dried in the air, there is no large change in the performance of returning it to the water again. The standard of the amount of the antibacterial treatment agent to be used may be appropriately adjusted depending on the silver content or the antibacterial effect of the purpose. The amount of silver eluted when the antibacterial treatment agent for water treatment of the present invention is immersed or passed through the purified water of the object is preferably 5 ppb or more and 200 ppb or less, more preferably 10 ppb or more and 100 ppb or less. The concentration in this range lasts for more than 3 weeks, and it is better if it is likely to be about 1 year. Further, ppb is a weight ppb 0. For example, when a treatment agent is used for immersion, a preferred amount of silver elution can be obtained by using an antibacterial treatment agent for water treatment having a surface area of about 50 cm 2 to about 500 cm 2 with respect to 1 L of water. Compared with the impregnation, the contact time of the water is small, so when the water is used, the surface area is preferably several times to about 1 times of the impregnation. The use of the antibacterial agent for water treatment of the present invention is not particularly limited, and it can be effectively used for water treatment of water in which microbial contamination is a problem. For example, water purifiers for water purifiers, water tanks for water purifiers, circulating water, water for cutting flowers, water pipes or tanks, swimming pools or ponds, ice making water in refrigerators, humidifiers, and cold air drainage. The invention is described below based on the examples, but the invention is not limited thereto. The particle size of the particles in the particles was measured using a laser diffraction type particle size distribution and based on the volume ratio of the body * 24 - 201138638. The amount of chromium contained in the antibacterial agent or its raw material is determined by dissolving the sample using a strong acid, and the liquid is measured by an inductively coupled plasma (ICP) optical emission spectrophotometer. The amount of phosphorus was measured by dissolving the sample using a strong acid, and the liquid was measured by an ICP optical emission spectrometer. The amount of sodium was dissolved in a sample using a strong acid, and this liquid was measured by an atomic absorption spectrometer and calculated. The amount of ammonia was measured by dissolving the sample using a strong acid, and the liquid was measured by the indophenol method and calculated. The amount of lithium ions was measured by thermal analysis and the weight loss of 160 to 190 °C was calculated. The diffraction intensity of the X-ray powder diffraction method (XRD) is the diffraction intensity of the x-rays measured by the Cu ο: line by X-ray 50 kV/120 mA by a powder XRD diffraction apparatus. The number of bacteria was measured by a pour culture using a common agar medium at 37 ° C for 2 days. The silver dissolution concentration was measured by ICP optical emission spectrometry. <Antimicrobial Agent A: Preparation of Chromium Phosphate (a) Substituted by Silver> 0.1 mol of oxalic acid dihydrate, 0.2 mol of zirconia octahydrate containing 7% of Oi, and ammonium chloride 〇 After the ear was dissolved in 3 〇〇 ml of deionized water, 0.3 mol of phosphoric acid was added under stirring. After the solution p Η was adjusted to 2·6 using a 20% aqueous sodium hydroxide solution, the mixture was stirred at 9 8 t for 14 hours. Thereafter, the obtained precipitate was sufficiently washed with deionized water and dried at 1 2 〇 〇c for 4 hours to synthesize a yttrium phosphate compound. -25- 201138638 The amount of each component of the phosphoric acid cone compound was determined and the composition formula was as follows.

Na〇.6(NH4)〇.4Zri.98Hf〇.〇2(P〇4)3 · O.O9H2O In the obtained chromium phosphate 0.09 mol, an ion exchange aqueous solution in which 5 mol of silver nitrate was dissolved was added. 450ml, and by 60. (The silver is supported by stirring for 2 hours. The slurry after the silver is supported is subjected to furnace, washed with water and washed with deionized water until the conductivity of the filtrate becomes 70 yS. Further 'by being used The dried product of the electric furnace after being subjected to heat treatment for 12 hours at TC is broken to obtain silver-substituted zirconium phosphate (A). The silver-substituted chromium phosphate (A) has a median diameter of 1 · 〇vm The silver content is 12.2% by weight' and the composition obtained by measuring the amount of each component is as follows:

Ago.sNao.i H〇.4Zri.98Hf〇.〇2(P〇4)3 <Antibacterial agent B: Preparation of silver-substituted zirconium phosphate (b)> Oxalic acid dihydrate 〇", containing 〇1 8% of zirconium oxychloride octahydrate 0.19 moles, and ammonium chloride 〇.10 moles dissolved in deionized water 3 〇〇 ml, and then add 0.3 mol of phosphoric acid under stirring. After adjusting the pH of the solution to 2·7 using a 20% aqueous sodium hydroxide solution, the mixture was stirred at 9 8 t for 14 hours. Thereafter, the obtained precipitate was sufficiently washed with deionized water and dried at 1,200 ° C to synthesize a zirconium phosphate compound. The amount of each component of the phosphoric acid table compound was determined as follows: Na〇.5(NH4)〇.8Zi·丨'9 丨Hf0.0tl5(P〇4)3 · 〇.11Η2〇 obtained zirconium phosphate In the compound 0.09 mol, 450 ml of an aqueous solution of nitric acid in which 0.019 mol of silver nitrate was dissolved was added, and the silver was supported by stirring at -26-201138638 at 60 °C for 2 hours. Thereafter, it was sufficiently washed with deionized water, and subjected to a drying treatment at 1200 ° C for 4 hours at a high temperature of 670 ° C. After the high-temperature heat-treated powder was gently broken, it was allowed to stand in an atmosphere of a humidity of 5 〇% and a temperature of 110 ° C for 6 hours and subjected to moisture absorption treatment, thereby obtaining a silver-substituted chromium phosphate (B). ). The silver-substituted zirconium phosphate (B) has a median diameter of 〇. 8 m and a silver content of 4.2% by weight, and the composition formula obtained by measuring the amounts of the respective components is as follows:

Ag〇.I9Na〇.37 H〇.21(H3〇)0.43Zl.l.9lHf〇.015(P〇4)3 · 0.1 9 Η 2 Ο <Antibacterial agent C: Zirconium phosphate substituted by silver (c) Preparation> After dissolving 0.18 mol of 0.15 mol of oxychlorinated pin octahydrate and 0.12 mol of ammonium chloride in deionized water, 300 g of deuterated phosphate was added thereto with stirring. The pH of the solution was adjusted to 2.7 using a 20% aqueous sodium hydroxide solution and stirred at a saturated vapor pressure of 1 40 ° C for 4 hours. Thereafter, the obtained precipitate was sufficiently washed with deionized water and dried at 12 ° C to synthesize a chromium phosphate compound. The amount of each component of the phosphoric acid pin compound was determined as follows: Na〇.35(NH4)〇.85Zn.93Hf〇.〇2(P〇4)3 · 0.09Η2〇 The obtained zirconium phosphate 0.09 mole In the middle, 45 ml of ion-exchanged water in which 0-014 mol of silver nitrate was dissolved was added, and silver was supported by stirring at 60 t for 2 hours. Thereafter, it was sufficiently washed with deionized water, and heat-treated at 1,200 ° C for 4 hours at 700 ° C to obtain silver-substituted zirconium phosphate (C ). -27- 201138638 The silver-substituted zirconium phosphate (C) has a median particle size of 〇. 8 # m, a silver content of 3 · 丨 by weight, and the composition of each component is determined as follows:

Ag〇.l4Na〇.24 H〇.46Zr2.03Hf〇.02(P〇4)3 <Antibacterial agent D: Preparation of chromium phosphate (D) substituted by silver> 0.18 % of chromium oxychloride is added After hydrate 0.15 mol and ammonium chloride 0.12 mol dissolved in deionized water 3 〇〇 ml, add phosphoric acid under stirring ο. 旲 ear. This solution ρ η was adjusted to 2.7 using a 20% aqueous sodium hydroxide solution and stirred at 1 40X: saturated vapor pressure for 4 hours. Thereafter, the precipitate obtained was sufficiently washed with deionized water and dried at 12 (r) to synthesize a bismuth phosphite compound. The components of the phosphoric acid compound were determined to have the following composition:

NaZr 1 9 8 5 Hf〇.〇i 5(P〇4)3 . O.09H2O Into the obtained zirconium phosphate 〇〇9 molar, 450 ml of ion-exchanged water in which silver nitrate 〇.〇8 mol was dissolved was added. The silver was supported by stirring for 2 hours at 6 〇t. It is then thoroughly washed with deionized water and passed through a crucible. The dry-drying treatment was heat-treated at 700 C for 4 hours, thereby obtaining silver-substituted zirconium phosphate (D). The amount of each component of the silver-substituted chromium phosphate (D) was determined as follows:

Ag〇.79Na〇.u H〇.28Zn 98sHf〇〇)5(p〇4)3 and the silver-substituted chromium phosphate (D) has a median particle size of 1. 〇&quot; m, silver content 15.3 wt%. •28- 201138638 <Antibacterial agent E: Preparation of zeolite-based silver-based inorganic antibacterial agent (e)> 5. A commercially available A zeolite 2〇g is added with an ion exchange aqueous solution in which potassium potassium nitrate is dissolved. The silver was supported by stirring at 6 〇t: for 2 hours. After washing with water, the zeolite-based silver-based inorganic antibacterial agent (E) obtained after drying at 1201 was crushed, and had a medium ruthenium size of 4 μm and a silver content of 42% by weight. <Anti-caries agent F: Preparation of zeolite-based silver-based inorganic antibacterial agent (F)> 100 g of an ion-exchanged aqueous solution in which 36 g of silver nitrate was dissolved was added to 20 g of a commercially available type A zeolite, and stirred by 6 〇t. Silver is supported for hours. After washing, '1 2 〇. (: After the zeolite-based silver-based inorganic antibacterial agent (F) obtained after drying is crushed, the median particle size is m and the silver content is 1〇2% by weight. <Anti-caries agent G: silver glass-based antibacterial agent ( g) Preparation> Mix the glass materials to make Ag2〇 (2% by weight), K2〇 (7% by weight), B2〇3 (45% by weight), Si〇2 (46% by weight) and heat at 1200 C. Melting. After melting, 'cooling is performed using a metal cooling forming roll' and the obtained glass is further crushed by a ball mill to obtain a medium-sized particle size of 9 V m and a silver content of 1.9% by weight. Silver glass-based antibacterial agent (G). <Examples 1 to 9 and Comparative Examples 1 to 9> Various silver-based inorganic antibacterial agents A to G® obtained by the above method were combined in various resins as shown in Table 1. The antibacterial treatment agents of Examples 1 to 9 and Comparative Examples 1 to 9 were formed by using Nylon 6 (manufactured by UBE INDVSTRIES, LTD.; trade name 1011FB) having a standard moisture percentage of 4.4 -29 to 201138638% by weight. , a standard moisture percentage of 3.9 wt% of nylon 66 (manufactured by UBE INDVSTRIES, LTD.; trade name 2020B), Polyacetal resin (manufactured by P〇iypiastics Co., Ltd.; trade name Duraeon) having a water content of 1.8% by weight, and an acrylic resin having a standard moisture content of 1.4% by weight (manufactured by MITSUBISHI RAYON CO., LTD.: trade name Acrypet a polyacrylic resin (manufactured by Prime Porypro Co., Ltd.; trade name J105G) having a standard moisture percentage of 0.0% by weight, a polyester resin (manufactured by UNITKA, LTD.; trade name: NEH-2030) having a standard moisture percentage of 0.3% by weight as a resin, and The antibacterial agent powder is directly mixed into various resins and then molded. When the treatment agent is formed into a flat plate, when the injection molding machine is used to form a plate having a thickness of 1 cm, the specific surface area (calculated by size) is about 14 cm 2 . / g ; a plate having a thickness of 4 mm, a specific surface area of about 3 cm 2 / g; and a specific surface area of about 110 cm 2 / g when the thickness is 0.15 mm. The treatment agent is formed into a conical shape having a diameter of 4 mm and a height of 1 mm by using a hot-cut extrusion molding machine. The combination of the resin type and the antibacterial agent, the antibacterial ratio, the mixing ratio of the treating agent, and the specific surface area of the treating agent are described in Table 1. However, Comparative Examples 8 and 9 caused significant foaming and discoloration. The specific surface area was not measured, and the treatment agent was not used. -30- 201138638 Table 1 Resin type Resin standard moisture percentage (% by weight) Antibacterial agent type Antibacterial agent mixing ratio ( % by weight) specific surface area (cm2/g) of the shape treating agent of the treating agent Example 1 Wheel resistant 6 4.4 A 10 Plate shape 14 Example 2 Nylon 6 4.4 A 10 臓 3 Example 3 Nylon 6 4.4 A 10 plate Example 110 Example 4 Nylon 6 4.4 A 10 Nine-shaped 9 Example 5 Nylon 6 4.4 B 10 Nine-shaped 9 Example 6 Wheel-resistant 6 4.4 C 10 Nine-shaped 9 Example 7 Nylon 66 3.9 A 10 尬9 Implementation Example 8 Polyacetal resin 1.8 A 10 Nine form 9 Example 9 Acrylate resin 1.4 A 10 Nine form 9 Comparative Example 1 Polypropylene resin 0.0 A 10 Nine form 9 Comparative Example 2 Polyester resin 0.3 A 10 Nine form 9 Comparative Example 3 Nylon 6 4.4 A 0.8 ΛΜ 9 Comparative Example 4 Nylon 6 4.4 D 0.5 Nine 9 Comparative Example 5 Polypropylene resin 0.0 E 33 9 Comparative Example 6 Polypropylene resin 0.0 F 10 Nine shape 9 Comparative Example 7 Resistance wheel 6 4.4 G 10 Nine 9 Comparative Example 8 Nylon 6 4.4 E 33 尬Comparative Example 9 Nylon 6 4.4 F 10 Nine-shaped _ (in the table, one is not measured) -31 - 201138638 <Evaluation of antibacterial treatment using natural water for drinking> Each of the antibacterial treatment agents for water treatment obtained in Examples 1 to 9 and Comparative Examples 1 to 7 was measured. 30 g, immersed in 1 L of water supplemented with commercially available drinking natural water (hereinafter referred to as natural water) and sodium nitrate and adjusted to a sodium concentration of 500 ppm in natural water, and stored at a water temperature of about 15 ° C. The silver concentration in the water was measured after the day. Further, for the natural water, the silver concentration in the water after 21 days of direct storage and only the water was changed again every day and stored for 21 days. The results of the dissolved silver concentration measured by ICP optical emission spectrometry are shown in Table 2. Table 2 Silver concentration after 1 day of storage (Ray ppb) Silver concentration after 21 days of storage. (Weight ppb) Water quality of the sample Natural water Natural water + Na 500ppm Natural water Natural water exchange Μ κκ Μ /\ w Yes ( Daily) Example 1 25 899 25 27 Example 2 7 390 22 10 Example 3 128 3093 198 98 Example 4 44 912 54 32 Example 5 11 569 20 33 Example 6 6 239 14 9 Example 7 18 701 28 18 Example 8 11 333 20 11 Example 9 6 471 19 5 Comparative Example 1 3 155 32 .1 Comparative Example 2 4 87 45 1 Comparative Example 3 2 62 21 4 Comparative Example 4 12 56 21 1 Comparative Example 5 12 59 28 3 Comparative Example 6 19 64 19 2 Comparative Example 7 562 540 6192 122 -32- 201138638 Examples 1 to 9 show that the silver concentration after 1 day is 5 ppb or more, and has nothing to do with whether or not there is water change, even after 2 1 days. When the concentration of silver is increased or decreased, the dissolution of silver occurs. Further, the meaning of the dissolution test at a high concentration of Na concentration of 500 ppm is based on the idea that ion exchange between Na ions and silver ions occurs rapidly, and silver ions eluted from the test piece are eluted and the concentration thereof is measured. It can reflect the amount of silver that it is dissolved. In this test, a test piece having a high silver concentration can be obtained, and since it is capable of dissolving a large amount of silver, it is sufficient to judge that it is highly sustained under normal use conditions. On the other hand, in Comparative Examples 1 to 3, the amount of elution after one day was small, and it took time to reach the silver concentration at which the antibacterial effect was obtained. Further, in Comparative Examples 1, 2 and 4, it was revealed that the silver concentration was lowered due to water exchange, and under the condition of exchange of water, the sufficient silver concentration at which the antibacterial effect was obtained could not be achieved. Comparative Examples 3 to 6: Since the silver concentration under the condition of a Na concentration of 50,000 p p m is low, the amount of silver eluted is small, and sustainability cannot be expected. Comparative Example 7: Since the concentration of silver after 21 days without water change was higher than the desired concentration, discoloration due to an excessively high concentration of silver ions was observed, and a certain concentration of silver ions could not be eluted. <Evaluation of long-term life> In addition, in order to investigate the long-term life' in the two types of Examples 3 and 4', the daily water exchange test was extended to 90 days. Thus, the silver ion concentration in the water on the 90th day was 13 PPb in Example 3, and 24 ppb' in Example 4 was opposite to the first day and the 21st day. Example 4 was higher than Example 3. This result shows that, compared with Example 3, the amount of silver eluted in the initial stage of Example 4 was less than -33-201138638, but the concentration variation was small and it was excellent in dissolution over a long period of time. <Evaluation of water treatment using industrial water> 100 g of each of the test pieces of Examples 3 and 4 and Comparative Examples 1, 3 and 7 were respectively placed in a water purifier, and the average number of bacteria was about 100 pieces/m. Industrial water having a water temperature of about 15 ° C was passed at 0.1 liter/min. According to the injection culture method using a general agar medium, the results of measuring the total number of bacteria in 1 ml of industrial water after 10 minutes and one day after passing water, and the results of measuring the concentration of dissolved silver at this time by ICP optical emission spectrometry In Table 3. Table 3 General bacteria number (cfu/ml) Silver concentration (mass ppb) Water time 1 minute after 1 day 1 minute after 1 minute 1 Example 3 Less than 1 Less than 1 42 3 1 Example 4 Less than 1 less than 1 12 18 Comparative Example 1 47 94 2 0 Comparative Example 3 29 73 9 3 Comparative Example 7 18 98 7 1 No antibacterial agent 98 1 10 — —— (The table is not measured) Example 3 and After 4, 10 minutes and 1 day, the antibacterial effect was confirmed, and the silver dissolution concentration was confirmed. On the other hand, in Comparative Examples 1, 3 and 7, the antibacterial effect and the silver elution concentration were significantly lowered after one day after 10 minutes. Since the molded article used in Comparative Example 7 showed that silver was continuously eluted and was not related to ion exchange, in the evaluation of the water exchange method shown in Table 2, it was confirmed that -34-201138638 even if the high concentration 'silver was reached, the dissolution continued. The result. On the other hand, in the test results of Table 3 of the water treatment evaluation, it was found that since the dissolution rate of silver was not high for water passage, it was found that the silver concentration after i 〇 minutes was not so high, and the dissolution rate after one day was not high. Then further decrease. Industrial Applicability The antibacterial treatment agent for water treatment of the present invention maintains a constant silver concentration and has long-term sustainability. Therefore, for clean water such as drinking water or circulating water, even if water is replaced by water or consumption, it can be adjusted to a certain amount of silver in the necessary amount of water, and the antibacterial effect is maintained for a long period of time. [Simple description of the diagram] Μ . ^\\\ [Main component symbol description] None. -35-

Claims (1)

201138638 VII. Patent application scope: 1. An antibacterial treatment agent for water treatment, characterized by comprising: a resin having a standard moisture percentage of 1 to 10% by weight as specified in JISL 0105:2006, and 1 to 30% by weight The antibacterial agent is a resin composition of the silver-substituted chromium phosphate represented by the formula [1], and AgaMbZrcHfd(P〇4)3 · nHaO [1] wherein, in the formula [1], at least one selected from the group consisting of alkali metals An ion, an alkaline earth metal ion, an ammonium ion, a hydrogen ion, and a group of ions formed by ions; a, b, and c are independent integers; d is 0 or an integer; η is an integer of 0 or less; a, b, c, and d are satisfied with the relationship of the formula [Α]; Μ is 1 valence, satisfying the formula [Β]; Μ is 2 valence, satisfying the formula [C], 1.75 &lt; c + d &lt; 2.25 [ A] a + b + 4 (c + d) = 9 [B] a + 2b + 4 (c + d) = 9 [C]. 2. The antibacterial treatment agent for water treatment according to the first aspect of the invention, wherein the silver content of the silver-substituted zirconium phosphate is 4 to 13% by weight. 3. The antibacterial treatment agent for water treatment according to the first aspect of the invention, wherein the treatment agent has a specific surface area of 5 to 100 cm 2 /g. 4. The antibacterial treatment agent for water treatment according to claim 1, wherein 50 to 100% by weight of the resin constituting the resin composition is a polyamide resin. 5. For the antibacterial treatment agent for water treatment according to item 4 of the patent application, the poly-amide resin described in the former -36-201138638 is nylon 6. The method for producing an antibacterial treatment agent for water treatment according to any one of claims 1 to 5, which comprises the step of mixing the antibacterial agent with the aforementioned resin. A water treatment method comprising the step of bringing the antibacterial treatment agent for water treatment according to any one of claims 1 to 5 into contact with water. -37- 201138638 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 4^: 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: