JP2003200173A - Water cleaning material of water tank such as cooling tower containing inorganic antibacterial agent or the like and water cleaning method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water cleaning material having high antibacterial effect and antifungal effect, low in cost, enabling easy work, reducing environmental load and obtaining safe antibacterial and antifungal action and cleaning water of a water tank, a cooling tower, a bath, a pool, an agricultural field (paddy field), a fishing field (breeding basin, breeding ground), rivers, lakes and marshes, a reservoir, a pet breeding water tank or the like, and a water cleaning method using the same. <P>SOLUTION: The water cleaning material contains an inorganic antibacterial agent containing at least one of metal ions of Ag, Mn, Fe, Co, Ni, Cu and Zn and has a specific gravity of below 1.00 and a void ratio of 20% or more. The maximum length of this water cleaning material is not less than 1 cm. The water cleaning method for cleaning water by floating the water cleaning material on water is also disclosed. Antibacterial and antifungal treatment can be easily applied to water by an inexpensive method reducing the generation of an offensive smell, facilitating disposal and reducing environmental load and the recovery and reutilization of the antibacterial agent becomes possible. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

The present invention relates to a water purification material for water in a water tank, cooling tower, bathhouse, pool, agriculture (paddy field), fishery (culture pond, farm), river, lake, pond, pet breeding tank, etc. And to provide a water purification method.

[0002]

2. Description of the Related Art Propagation of bacteria, bacteria, fungi, and algae in stored water and circulating water has become a big problem such as poisoning by Legionella bacteria, diseases of the local military, and the like, rather than merely impairing the feeling of cleanliness. Conventionally, it has been known and used that chlorine-based bactericides, organic agents and metal ions are effective for controlling the growth of these bacteria, bacteria, mold and algae in stored water or circulating water. It was Conventionally, such chemicals and antibacterial agents have been used to sterilize stored water such as cooling water in a cooling tower or circulating water.

However, when these agents and antibacterial agents are used as water purifying agents, not only the bactericidal action and antibacterial action are generally insufficient, but also the bactericidal effect and the antibacterial effect are not sustained, and the sterilization is repeated many times in a short period of time. It had to be repeated, and the burden of labor and cost was great. In addition, these sterilization methods have a chlorine odor, or the safety of the human body due to organic agents,
Especially there was the problem of sick house syndrome. Electrolyzed water has been proposed as a chlorine-based sterilizing solution. Electrolyzed water does not have sufficient bactericidal power, and it is necessary to increase the effective chlorine concentration in order to obtain sufficient bactericidal power.Therefore, there is a drawback that the metal parts of equipment are easily corroded. It has a drawback that it is difficult to use because it may generate gas.

It has been conventionally known that Legionella spp. Are generated and proliferate in water use facilities such as bathtubs and pools in which hot water or water is circulated through a flow path by a filtration circulation device. The Legionella spp. Sterilization of Legionella spp. Is important for water use facilities because it may cause pneumonia etc. when it enters the human body. It is one of the microorganisms, such as algae, mold, and rust on metal parts such as iron. And if these algae, molds, rust, etc. are formed, they are not only unpleasant and unclean, but also worsen the distribution of water, change the water quality, and change the material of the constituent parts, and finally Often impaired the function of the cooling tower. In particular, water flowing through a cooling tower (cooling tower) in a facility such as a building or a waterway system such as a fountain generates blue powder consisting of microalgae and changes its color to green-blue, especially when used for a long time. I have something to do. However, the water in these artificial facilities causes the generation of blue powder for hygiene reasons, from the viewpoint of preventing clogging of the water treatment system, and for maintaining good appearance. It should be almost completely prevented, colorless and transparent, and kept as pure as possible. Since it can be treated so as not to generate algae and plankton in the water by contacting with water such as cooling tower, fountain, aquaculture pond, aquarium, fishbowl, natural pond, lake, marine, etc., generation of blue powder and red tide can be prevented. There is a real benefit that can be prevented.

In this way, the water tank, the cooling tower,
In the management of baths, pools, agriculture (paddy fields), fisheries (culture ponds, farms), rivers, lakes, reservoirs, and pet tanks, it is important to prevent the growth of harmful bacteria and fungi. Although these organic antibacterial agents have been used for the purpose of antibacterial, there are problems such as environmental pollution, safety, especially human health, and deterioration of antibacterial effect due to generation of resistant bacteria. There has been a demand for an antibacterial agent that replaces an organic system and a water purification method that has a small environmental load, can be collected, and is inexpensive.

[0006]

[Problems to be Solved by the Invention] The antibacterial effect and antifungal effect are large, the cost is low, the work is easy, and the environmental load is small.
Retrievable, safe antibacterial and antifungal water storage tanks, cooling towers, baths, pools, agriculture (paddy fields),
It is intended to provide a water purification material and a water purification method for water in fisheries (culture ponds, farms), rivers, lakes, reservoirs, pet tanks, etc.

[0007]

Means for Solving the Problems The present inventors have found that Ag, M
It has a specific gravity of less than 1.00 containing an inorganic antibacterial agent containing at least one of metal ions consisting of n, Fe, Co, Ni, Cu and Zn, and a porosity of 20% or more. It has been found that the above-mentioned problems can be achieved by the characteristic water purification material. Moreover, the above-mentioned subject was able to be better achieved by the size of the above-mentioned water purifying material, which has a maximum crossover length of 1 cm or more. Further, the above-mentioned problems can be better achieved by a water purification method in which the above water purification material is floated on water. By using the sterilizing method using a sterilizing solution containing chlorine ions such as hypochlorous acid and chlorine dioxide, and the above water purification method together, the above-mentioned problems can be better achieved. In the present invention, the terms antibacterial and purified water are used as terms including the concepts of antibacterial, antifungal, antifungal, disinfecting, sterilizing, sterilizing, sterilizing and deodorizing.

The water purification material preferable in the present invention will be described.
The specific gravity of the water purification material of the present invention is preferably 1.00 or less,
98 or less is more preferable, and 0.90 or less is still more preferable. This is because it can float on the water surface and exert an antibacterial action for a long period of time. The water purification material can be of any shape and size, but if it is too small, it will be submerged in soil and dust, will be submerged in the water, will be blown away by the wind, and will be difficult to collect after use. I have a problem. If it is difficult to recover after use, it may accumulate on the spot and cause environmental problems, which is not preferable. Therefore, a water purification material having a maximum passage of 1 cm or more is preferable. This maximum crossover is the larger value of either diameter or length for a cylindrical shape, the maximum value of vertical, horizontal, and height for a rectangular parallelepiped. To the furthest end, which is the maximum length value of the various combinations. The maximum distance is more preferably 2 cm or more, and particularly preferably 10 cm or more.

In the water purifying material of the present invention, an inorganic antibacterial agent may be used alone, but in order to reduce the specific gravity and to adjust the content to an appropriate range, a substance having a low specific gravity, especially a porous substance is used. It is preferable to use it by supporting it on. The antibacterial agent of the present invention may be integrated with the porous substance by means such as sintering, adhesion, molding or the like, or may be supported on the porous substance by means such as impregnation. It is preferable to process these into an appropriate shape and use them as a water purification material. The porosity of this water purification material is preferably 20% or more, more preferably 30 to 95%, and 40 to 90.
% Is most preferred.

The non-combustible porous material of the present invention includes sand, clay, zeolite, mineral powder such as bentonite, silica gel, aerosil, white carbon, high silica clay, silica sol, porous glass, Silica fiber, diatomaceous earth, colloidal silica type such as calcium silicate, natural zeolite, zeolite type such as synthetic zeolite, activated alumina, alumina type such as alumina, bone charcoal, natural apatite, apatite type such as synthetic apatite, frass earth, There are activated clay, activated bauxite, activated magnesium oxide, etc. These porous materials are described in "Science of Adsorption" (Seiji Kondo, Maruzen Publishing Co., Ltd. 2001 2
Issued March) pp. 183-217, "Design of Adsorbent / Adsorption Operation" (Hiroshi Yanai, Gihodo Publishing, January 1982) 4
It is described on pages 8-53. Among them, porous glass,
Zeolites such as natural zeolite and synthetic zeolite, and alumina such as slag, activated alumina and alumina are preferable. Of these, zeolite and slag are most preferred.

Examples of combustible porous materials include coal, charcoal, fir shell charcoal, coconut shell charcoal, coke, activated carbon, charcoal, carbon nanotubes and other carbonaceous materials, cellulose, wood, wood flour, pulp powder, cotton. Powder, grain of paper, synthetic fiber, natural fiber, non-woven fabric, especially non-woven fabric made of polyethylene, polypropylene, wood chips, sawdust, corn core chips, coffee bean meal, okara, defatted soybeans, beer meal, sake lees, Shochu lees and soy sauce lees are preferred. If necessary, these may be mixed with a binder and granulated to obtain granules having an appropriate size. As the binder, starch, guar gum, carboxymethyl cellulose, hydroxymethyl cellulose, methyl cellulose, ethyl cellulose, sodium alginate, xanthan gum, bean gum, color ginnan, gluten and the like can be used alone or in combination. When a non-combustible porous material is used, it is preferable that the antibacterial property can be restored by firing after use and recovery.

Further, when the inorganic antibacterial agent of the present invention is used in combination with a porous substance, the porous substance adsorbs bacteria, harmful gas and the like, and the antibacterial agent beside it decomposes these bacteria and gas. The antibacterial effect is exerted more effectively.

The BET surface area of the porous material is preferably 10 m2 / g or more, more preferably 100 m2 / g or more, 2
00 m2 / g or more is more preferable, and 600 m2 / g or more is the most preferable. The average size of the porous material is 0.01
˜100 μm is preferred, 0.05 to 30 μm is more preferred, and 0.1 to 10 μm is most preferred.

These porous substances may be particles of any shape such as spherical, plate-like, and lump-like, and those formed by sintering into a certain size are also preferable. When an antibacterial agent is supported on these porous materials, especially zeolite, it is disclosed in JP-A-11-
It can be carried out by a method according to Reference Example 1 of No. 246322. In addition, JP-A-6-72816 and JP-A-6-65.
011, JP-A-8-291011, JP-A-8-48
No. 606, JP-A-11-123385, JP-A-11-
180808, JP-A-11-209258, JP-A-2
In the method of the antibacterial agent described in No. 000-63219, it is also preferable that the carrier is allowed to coexist during the synthesis.

As a method for supporting the antibacterial agent, it is also preferable to incorporate the antibacterial agent of the present invention into the nonwoven fabric. The non-woven fabric may be any, for example, “Manufacturing and application of non-woven fabric”
(Edited by Yoshio Nakamura, CMC Co., Ltd., 2000 April
The non-woven fabric described in (issued on March 30th) can be used. Among these, the dry method is preferable, and the hydroentangling method and the spinning method are more preferable. As the spinning type, a spunbond method, a meltblowing method, a net-like method and a film method are preferable, a spunbonding method and a meltblowing method are more preferable, and a spunbonding method is most preferable. Further, the spunlace method is most preferable as the hydroentangling method. Regarding the melt-blowing method, the above-mentioned "Manufacturing and application of non-woven fabric" 80-85
The method described on pages 86 to 102 of the same book can be used for the spunbond method. Regarding the spunlace method, the method described on pages 70 to 79 of the same book can be used.

The material used for the nonwoven fabric or film of the present invention is not particularly limited as long as it is a melt-spinnable thermoplastic resin. Crystalline random copolymers of propylene with other α-olefins, such as polyethylene, polypropylene, linear low density polyethylene, propylene / ethylene or propylene / ethylene / butene-1 binary or ternary copolymers. , Etc. Polyolefin, nylon-6, nylon-66, etc. Polyamide, polyethylene terephthalate, polybutylene terephthalate, poly (ethylene terephthalate-co-isophthalate), etc. low melting point polyester, polyester Polyesters such as elastomers, fluorine resins, polyphenylene sulfide, and ester fibers such as polyethylene terephthalate, polybutylene terephthalate, and polyhexamethylene terephthalate are preferably used, with isophthalic acid as the third component, Sulfoisophthalic acid, it can also be used those obtained by copolymerizing such methemoglobin oxy polyoxyethylene glycol. Further, as the polyamide fiber, nylon 6, nylon 66, nylon 61
0. Nylon 12, etc., and vinyl chloride are preferably used. Examples thereof include a mixture of the above resins, and a spinnable thermoplastic resin. Among them, polyethylene and polypropylene are preferable.

Double core / sheath structure in which polyethylene is the sheath and polypropylene is the core, or double core / sheath structure in which polypropylene is the sheath and polyethylene is the core, and polyethylene and polypropylene A laminated fiber is also preferably used.

The combination of thermoplastic resins for the mixed fiber spunbond spinning is a combination of resins having melting points of 10 ° C. or more. For example, high density polyethylene / polypropylene, low density polyethylene / polypropylene, propylene / ethylene / butene-1 crystalline copolymer / polypropylene, propylene / ethylene crystalline copolymer / polypropylene, high density polyethylene / polyethylene terephthalate, low Melting point polyester / polyethylene terephthalate, polypropylene / polyethylene terephthalate,
Examples thereof include propylene / ethylene / butene-1 crystalline copolymer / polyethylene terephthalate, polyvinylidene fluoride / polyethylene terephthalate, a mixture of low density polyethylene and high density polyethylene / polypropylene and the like. Among them, high density polyethylene / polypropylene,
A low density polyethylene / polypropylene combination is preferred.

In the mixed fiber spunbonded non-woven fabric, the mixed fiber ratio of the low melting long fibers and the high melting long fibers is 10 to 10 for the low melting long fibers.
90% by weight, high melting point long fibers 90 to 10% by weight.
The low melting point long fibers are preferably 30 to 70% by weight, and the high melting point long fibers are preferably 70 to 30% by weight.

A non-binder thermal bond non-woven fabric using rayon and heat-fusible fibers having a double core / sheath structure is also used.
A spunlace-based non-woven fabric in which polyester and rayon are entangled (by a stream of water) is also preferable.

As the material of the porous film of the present invention, polyethylene and polypropylene are preferable, and polyethylene is particularly preferable. The diameter of the hole is preferably 0.1 to 2 mm,
0.2-1 mm is more preferable. The ratio of the area of the holes to the area of the film (aperture ratio) is preferably 1 to 80%.
-20% is more preferable. The cross-sectional shape of the hole is preferably funnel-shaped.

The fibers constituting the long-fiber non-woven fabric used in the present invention may be any of mixed fibers or composite fibers of polyethylene terephthalate, polyamide, polypropylene, polyethylene, or a combination thereof, and the single yarn denier is 0.2 to 40 denier. Is preferable, and 0.2-2
0 denier is more preferred, 0.2 to 10 denier is still more preferred, and 0.2 to 5 denier is most preferred. As the flame retardant, for example, a halogen type, a nitrogen type, an organic phosphorus type or a combination thereof is used.

The inorganic antibacterial agent will be described. Ag, M
An inorganic antibacterial agent containing at least one kind of metal ions consisting of n, Fe, Co, Ni, Cu and Zn is preferable. However, Ag-based antibacterial agents react with chlorine ions and sulfur compounds to lose their antibacterial action, and are expensive, so the above metal ions are Mn, Fe, Co, Ni, Cu and Zn.
Is more preferable. Furthermore, since the antibacterial cost is high, the above metal ions are more preferably Cu and Zn.
Is most preferred. Also, oxides of these metal ions,
Hydroxides are preferred. The content of the metal ion in these inorganic antibacterial agents is preferably 2 to 82% by weight.
It is more preferably 20 to 82% by weight.

As the oxides and hydroxides used as these inorganic antibacterial agents, those represented by the following formulas (1) to (6) and ZnO are more preferable, and the following formulas (1) to (6) are more preferable. The following formulas (1), (4) and (5) are more preferable. (1) is the most preferable. M _x N _1-x O (1) (In the formula, N represents Mg and / or Ca, and M represents M.
It represents at least one kind of metal ion selected from the group consisting of n, Fe, Co, Ni, Cu and Zn, and x is 0.
02 <x <a _{0.8) M y N 1-x} (OH) 2 (2) ( wherein, M, N, x is the formula (1) is the same as) (MO) · _(L 2 O ) _Y (3) (wherein M is the same as in formula (1), L represents an alkali metal ion, and y is 0.0001 <y <0.1) (MO) · (Al ₂ O ₃ ) _a · (SiO ₂ ) _b (4) (where M and M are the same as in formula (1). A is 0.00 ≦ a <5.
At 0, b is 0.00 ≦ b <80. However, a = 0
In the case of, b is 0.001 ≦ b <80, and in the case of b = 0, a is 0.001 ≦ a <50. ) (MO) · (XO ₂ ) _c (5) (In the formula, M is the same as the formula (1). X represents Ti and / or Zr. C represents 0.001 <c <0.2. .) (MO). (NO) _d. (Al ₂ O ₃ ) _e (6) (In the formula, M and N are the same as those in the formula (1). D is 0.05 ≦ d <
5, b is 0.01 ≦ b <5. ) In the above formulas (1) to (6), M is Cu or Zn.
Is more preferable, and Zn is further preferable. Further, N in the formulas (1) and (2) is more preferably Mg. It is preferable that L in the above formula (3) is Na or K. Further, a and b in the above formula (4) are more preferable, and a is 0.00 ≦ a <
In 2, b is 0.00 ≦ b <50. However, a = 0
In the case of, b is 0.001 ≦ b <50, and in the case of b = 0, a is 0.001 ≦ a <2. More preferably, a is 0.00 ≦ a <0.2 and b is 0.00 ≦ b <1. However, when a = 0, b is 0.001 ≦ b <1, and when b = 0, a is 0.001 ≦ a <0.2. )

Examples of preferred inorganic antibacterial agents of the present invention are shown below, but the invention is not limited thereto. (
Numbers in parentheses are BET surface area (m ² / g), particle size D 50% (μm), Zn or Cu content (wt%)
Represents Represent ) (1) _{(A-1) Zn 0.14 Mg} 0.86 O (15,0.5,19.
9) (A-2) Zn _0.05 Ca _0.95 O (12, 0.6, 19.
9) (A-3) Cu _0.05 Ca _0.95 O (18, 0.2, 5.
7) (A-4) Cu _0.14 Mg _0.86 O (30, 0.3, 19.
4) (2) Formula (A-5) Zn _0.14 Mg _0.86 (OH) ₂ (19,0.
4, 19.6) (3) Formula (A-6) ZnO. (K ₂ O) _0.005 (12
0, 0.3, 80) (A-7) ZnO. (Na ₂ O) _0.005 (9
0, 0.3, 80) (4) Formula (A-8) ZnO. (Al ₂ O ₃ ) _0.04 (30, 0.
3, 76.5) (A-9) An antibacterial agent in which the surface of A-8 is modified with sodium laurate (30, 0.3, 76.5) (A-10) (CuO). (Al ₂ O ₃ ) _2.5 · (Si
_{O2) 40 · 12.5H 2 O (} 15,0.2,2.3) (A-11) ZnO · (SiO 2) 0.05 (2
5, 0.2, 77.5) (5) Formula (A-12) ZnO. (TiO ₂ ) _0.05 (1
5, 0.4, 76.6) (6) Formula (A-13) ZnO. (MgO) _1.5. (Al ₂ O ₃ ).
_1.25 (60, 0.3, 24.3) Others (A-14) ZnO (30, 0.3, 80.3) (A-15) Antibacterial surface of A-14 modified with sodium laurate Agent (30, 0.3, 80.3)

The inorganic antibacterial agent of the present invention is preferably surface-treated. The following is an example of one that is preferably used as the surface treatment agent. Higher fatty acids having 10 or more carbon atoms such as stearic acid, erucic acid, palmitic acid, lauric acid and behenic acid; alkali metal salts of the higher fatty acids; sulfuric acid ester salts of higher alcohols such as stearyl alcohol and oleyl call; polyethylene glycol ether Sulfate ester salt, amide bond sulfate ester salt, ester bond sulfate ester salt, ester bond sulfonate, amide bond sulfonate, ether bond sulfonate, ether bond alkylallyl sulfonate,
Anionic surfactants such as ester-bonded alkylallyl sulfonates and amide-bonded alkylallyl sulfonates; mono- or diesters of orthophosphoric acid and oleyl alcohol, stearyl alcohol, etc., or a mixture of both, and their acid form or Phosphates such as alkali metal salts or amine salts; vinylethoxysilane,
Vinyl-tris (2-methoxy-ethoxy) silane, gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, beta (3,4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltri Silane coupling agents such as methoxysilane and gamma-mercaptopropyltrimethoxysilane; isopropyltriisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate,
Titanate coupling agents such as isopropyl tridecylbenzene sulfonyl titanate; aluminum coupling agents such as acetoalkoxyaluminum diisopropylate; esters of polyhydric alcohols and fatty acids such as glycerin monostearate and glycerin monooleate. Among these, among the surface treatment agents selected from the group consisting of higher fatty acids, anionic surfactants, phosphoric acid esters, coupling agents (silane-based, titanate-based, aluminum-based) and esters of polyhydric alcohols and fatty acids. Surface treatment with at least one of, preferably stearic acid, erucic acid, palmitic acid, lauric acid,
Particularly preferred are higher fatty acids having 10 or more carbon atoms such as behenic acid, and alkali metal salts of the higher fatty acids. The surface treatment can be performed by a method similar to the method described in Example 1 of JP 2001-123071A.

The particle size D50% of the inorganic antibacterial agent of the present invention is preferably 0.05 to 20 μm, more preferably 0.05 to 10 μm, and further preferably 0.05 to 5 μm. The particle size is ultrasonically dispersed for 5 minutes or more,
It is the value measured by the laser scattering method. The BET surface area of antibacterial agents is an important indicator. Generally, an extremely large BET surface area is preferable in order to rapidly exert an antibacterial effect. However, on the other hand, in order to maintain the antibacterial effect, it is necessary to set the value below a certain level. Therefore, the BET surface area is preferably 1 to 300 m2 / g, more preferably 5 to 150 m2 / g, and further preferably 10 to 150 m2 / g. Methods for producing these inorganic antibacterial agents include JP-A-6-72816, JP-A-6-65011, and JP-A-8-
-291011, JP-A-8-48606, JP-A-1
1-123385, JP-A-11-180808, JP-A-11-209258, 2000-63219.
The method described in No. can be used.

The sterilizing solution of the present invention will be described. The sterilizing solution of the present invention is preferably used as long as it contains chlorine ions. Particularly, a sterilizing solution containing hypochlorous acid and chlorine dioxide is preferable. The hypochlorous acid-containing sterilizing solution preferably has an effective chlorine concentration of 0.2 to 1000 ppm. 0.5-300 ppm is more preferable, 1-1
Most preferred is 50 ppm. The pH is 2.0 to 8.0.
Is preferred, 4.0-7.2 is more preferred, and 4.5-
6.5 is most preferred. It is desirable that the effective chlorine concentration is the minimum required concentration to exert the bactericidal effect. If the concentration is high, there is an unfavorable effect such as chlorine odor, and if the concentration is low, a sufficient bactericidal effect cannot be obtained. The bactericidal effect varies with temperature. At temperatures near room temperature, higher temperatures have a greater bactericidal effect. pH is an important factor that determines the concentration of undissociated hypochlorous acid. When the pH is 8 or more, hypochlorous acid is dissociated and the bactericidal effect is significantly reduced. When the pH is 2 or less, chlorine is generated, which is harmful to the human body.

Hypochlorous acid is supplied as a hypochlorite or an aqueous solution of hypochlorous acid. The hypochlorite is not particularly limited, but sodium hypochlorite and potassium hypochlorite are preferable.

The pH of the sterilizing solution of the present invention is preferably adjusted by adding an inorganic acid such as hydrochloric acid, phosphoric acid, sulfuric acid or nitric acid, or an organic acid such as acetic acid, formic acid, citric acid or tartaric acid. Although not usually required, an alkali such as sodium hydroxide can be added when the pH becomes too low. As the acid, hydrochloric acid, phosphoric acid, acetic acid, citric acid and tartaric acid are more preferable, hydrochloric acid and acetic acid are further preferable, and hydrochloric acid is particularly preferable. When adjusting these pHs, it is preferable to dilute both the acid and the alkali with water. In particular, p
When adjusting between H5.0 and 7.0, it is preferable to use a sufficiently diluted acid.

Further, an aqueous solution of acid and alkali, an aqueous solution of hypochlorous acid (preferably an aqueous solution of sodium hypochlorite) and water are mixed to prepare an aqueous solution of hypochlorous acid having a predetermined concentration and pH. It does not matter whether this preparation is carried out well before use or just before use. However, since hypochlorous acid in the aqueous solution of hypochlorous acid is unstable with respect to heat, light and an oxidizing agent, it is preferable to put it in a closed container, shield it from light and store it at a low temperature. It is preferable to use a sufficiently washed container. Further, in order to accurately adjust the concentration of each composition to a predetermined value, it is preferable to use a mixing device capable of adjusting the addition amount with high precision. With this device, the hypochlorous acid aqueous solution can be prepared immediately before use. In that case, an aqueous solution of acid or alkali, an aqueous solution of hypochlorous acid (preferably an aqueous solution of sodium hypochlorite) and water can be mixed, or an aqueous solution of acid or alkali and / or It is also preferable to use an aqueous solution of chlorous acid (preferably an aqueous solution of sodium hypochlorite) diluted with water to a predetermined concentration in advance. The method for adjusting the hypochlorous acid-containing sterilizing solution of the present invention is not particularly limited, but a sodium hypochlorite aqueous solution on one side of the container separated by a porous filter, water on the other side. A continuous mixing apparatus in which hydrochloric acid diluted with is added, and both solutions are gradually mixed through a filter to adjust to a predetermined pH is preferable. As these methods, the method described in Japanese Patent No. 2852461 is preferably used. Further, these solutions are preferably stored in a closed container, and more preferably in the form of a cartridge which can be easily attached and detached.

The pH of the sterilizing solution of the present invention can be adjusted with a pH buffer. Also, the pH of the aqueous solution of hypochlorous acid
It is also preferred to use a pH buffer to adjust the pH. The pH buffer solution is a solution in which a change in pH (hydrogen ion concentration) when an acid or a base is added to the solution is smaller than a change in pH when an acid or a base is added to pure water. The pH buffer solution can be obtained by mixing an acid, a base, or a salt thereof. As an example of the pH buffering agent, any of those described in the second edition, pages 336 to 339, of the revised fourth edition of the Chemical Handbook (September 1993, Maruzen Publishing Co., Ltd.) is preferably used. it can.

Specific examples of the present invention will be described below.

Example 1 Synthetic zeolite (particle size 0.8 m
m, BET surface area 700 m2 / g) and inorganic antibacterial agent A-
1 was mixed (A-1 is 40% by weight) and baked at 600 ° C. (in the present invention, this is referred to as being integrated with or carrying a porous substance). The particle size of the fired product was 3 mm.
Add paper powder and methyl cellulose aqueous solution to the stirrer, and
Stir for ~ 5 minutes. 35 parts by weight of bleached pulp powder,
15 parts by weight of wood flour and 10 parts by weight of methyl cellulose were added and stirred with a stirrer. The agitated product is mixed with the above antibacterial agent A.
-1 was added to the burned material in an amount of 3% by weight of the total solid content, and the mixture was stirred and molded to have a diameter of 2 cm and a length of 5 c.
A cylindrical water purification material of m was obtained (H1-1). Specific gravity is 0.9
At 0, the porosity was 43%.

[Example 2] The size of the molded product is 8 mm in diameter and 7 mm in length.
H1-1 was repeated except that the above was used to obtain H2-1. The specific gravity was 0.90 and the porosity was 43%.

Example 3 H1-1 was repeated except that the inorganic antibacterial agents were A-4 and A-8 and the zeolite-containing silver antibacterial agent was used.
3-1 to 4 were obtained. In each case, the specific gravity was 0.90 and the porosity was 43%.

[0034]

Example 4 Water purification materials H1-1, H2-1, H3 of the present invention
-1 to 4 were floated on a water tank in the circulating water system of the cooling tower so as to cover 5% of the water surface, the cooling tower was operated, and water was collected after 2 weeks to measure the number of Legionella bacteria. The measurement results are H1-1, H1-2
-1 <H3-1, 2 << H3-3 << water purification material was not added. All of the samples of the present invention are not added water purification material,
The number of bacteria was small and it was preferable. However, H3-3, which uses a silver-based antibacterial agent, is not preferable because the number of bacteria is larger than that of the other water purification materials of the present invention. Moreover, the water purification material was recovered after the end of the experiment, but the recovery rate of H2-1 was about 30% of that of the other water purification materials of the present invention. It was difficult to collect. (Test method for detection of Legionella spp.) 400 mL of sample water was cooled to 10 rpm by centrifugation at 6000 rpm for 30 minutes.
Concentrate to 0 times and heat at 50 ° C. for 20 minutes. Then, 50 μL of the W having the compounding composition shown in Table 1 is used.
Apply to YOα medium and culture aerobically at 37 ° C. On the 7th day of culturing, several colonies determined to be Legionella spp. Were picked from the colony condition, and BCYEα was added to each colony.
Subculture into two types of medium, a plate medium and a 5% blood agar medium, and culture aerobically at 37 ° C. BCYE on the second day of culture
Colonies that grew on the α plate medium but did not grow on the 5% blood agar medium were determined to be Legionella spp. from the L-cysteine requirement, and the number of the same type of colonies on the WYOα medium was counted. The limit of detection by this method is 20/100 mL.

(WYOα medium) Pure water 1000 mL Yeast extract 10.0 g ACES buffer 10.0 g L-cysteine monohydrochloride 0.4 g Soluble iron pyrophosphate 0.25g α-ketoglutaric acid 1.0 g Glycine 3.0 g Amphotericin B 80.0 mg Polymyxin B 100000 U Vancomycin 5.0 mg Activated carbon powder 1.5 g Agar 15.0 g pH 6.9

Comparative Example 1 Using antibacterial agent particles A-8 having a specific gravity of 1.6,
The same experiment as in Example 4 was conducted. The water purification material sank to the bottom of the water after stirring. The number of Legionella bacteria was lower than that of the water purification agent not added, but the antibacterial effect was obviously smaller than that of the water purification agent of the present invention, which was not preferable.

[0036]

Example 5 A sodium hypochlorite aqueous solution was added to one side of a container separated by a porous filter, and hydrochloric acid diluted with water was added to the other side, and both solutions were gradually mixed by passing through a filter to adjust the pH. Adjusted to 5.6, effective chlorine concentration is 2ppm
The hypochlorous acid aqueous solution of the present invention was prepared. The cooling tower of the building was sterilized with this sterilizing solution. Water was observed daily to observe the generation of algae, slime and odor. The earliest odor was produced, and the odor was produced 14 days later. On the other hand, in the case of only washing with tap water, odor was generated after 4 days. When the water purification material H1-1 of the present invention was used for this, when an antiseptic solution was used, odor was generated after 40 days, and in the case of tap water after 7 days. The combination of the water purification material of the present invention and the chlorine-containing sterilizing solution was preferable because it significantly delayed the generation of odor.

Example 6 Inorganic antibacterial agent A- of the present invention was added to polyethylene.
3% by weight of 1 was kneaded with a three roller mill to uniformly disperse the antibacterial agent in polyethylene. This was spun by a predetermined method to obtain a polyethylene fiber. A mixed-fiber spunbonded non-woven fabric was prepared by a predetermined method of heat-sealing these fibers. The amount ratio of polyethylene to polypropylene of this nonwoven fabric was 50:50. This is 2cm thick and 10c each in length and width
It was cut into m (Sample H6-1). The specific gravity is 0.5,
The porosity was 70%. This is H1-1 of Example 4.
Was used instead of to measure the occurrence of Legionella. The number of bacteria generated was almost the same as that of H1-1, and favorable results were obtained.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C02F 1/50 C02F 1/50 520J 520K 520L 531 531D 531E 531F 531M 540 540B 540C 540F A01G 16/00 A01G 16/00 67/00 A01K 67/00 C A01N 59/08 A01N 59/08 Z 59/16 59/16 A Z 59/20 59/20 Z F28G 13/00 F28G 13/00 A

Claims (4)

[Claims] 1. A water purification material containing an inorganic antibacterial agent containing at least one kind of metal ions consisting of Ag, Mn, Fe, Co, Ni, Cu and Zn, the specific gravity of which is less than 1.00. A water purification material having a porosity of 20% or more. 2. The water purification material according to claim 1, wherein the maximum crossover length is 1 cm or more. 3. A water purification method characterized by floating the water purification material according to claim 1 on water. 4. A water purification method characterized in that the sterilization method using a sterilizing solution containing chlorine ions such as hypochlorous acid and chlorine dioxide is combined with the water purification method according to claim 3.