JP2000007514A - Granulated antimicrobial material and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a granulated antimicrobial material excellent in durability and suitable for purifying bath water for domestic and business uses, tap water, water in an elevated cistern, water in a swimming pool, cooling water in a cooling tower, etc., without requiring large-scale facilities and running cost, and to provide a method for producing the same material. SOLUTION: This granulated antimicrobial material in which an antimicrobial agent of the formula MLaAbM2c(PO4)d.nH2O [ML is a (L)-valent metal ion (L is a positive integer) from silver, copper, zinc, or the like; A is a (m)-valent ion ((m) is a positive integer) such as an alkali metal ion or the like; M2 is a tetravalent metal ion; 0<=(n)<=6; (a) and (b) are a positive number meeting the requirement of (L) (a)+(m) (b)=1 or 2; (c)=2 and (d)=3 when (L) (a)+(m) (b)=1; (c)=1 and (d)=2 when (L) (a)+(m) (b)=2] is supported on the surface of granulated ceramic and is produced by blending the antimicrobial agent with granulated ceramic and a binder and then by heating the mixture to soften or cure the binder and to make the antimicrobial agent be supported on the surface of the granulated ceramic through the binder.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a granular antibacterial material carrying an inorganic antibacterial agent and a method for producing the same. In particular, household and commercial bath water, tap water and elevated water layers,
The present invention relates to a granular antibacterial material used for purifying water of a pool, cooling water of a cooling tower, and the like.

[0002]

2. Description of the Related Art Conventionally, as a method for purifying bath water for home or business use, tap water, water in an elevated water layer, water in a pool, cooling water in a cooling tower, etc., a method using adsorption by activated carbon, ozone and There are a method of sterilizing with ultraviolet rays, a method of sterilizing with a chlorine-based germicide, and the like. Activated carbon has a low disinfection efficiency and is black, which may contaminate water. The method using ozone or ultraviolet rays has a disadvantage that it is limited to a specific application because the equipment cost is high and the running cost such as electric power is high. In the method using a salt-based disinfectant, chlorine is smelled because chlorine remains after the treatment.

[0003] In order to improve these disadvantages, there is a method of using an inorganic antibacterial agent containing a metal having antibacterial properties. However, since most of the inorganic antibacterial agents are fine powders, when added to water, turbidity occurs. It is also difficult to remove them. A method of filling the column with an inorganic antibacterial agent and passing water through the column is also conceivable, but it is not practical due to a large pressure loss and a low water passing speed.

[0004] In order to solve these problems, it has been proposed to use an inorganic antibacterial agent in the form of granules. JP 5
No. 176976 proposes a method of supporting an inorganic antibacterial agent on the surface of a synthetic resin serving as a base material. This method is a method in which an inorganic antibacterial agent is carried on the surface of a synthetic resin that has been melted by heating. However, since the base material particles are synthetic resin, the durability is poor and the inorganic antibacterial agent particles may fall off.

JP-A-6-126285 discloses that Ag ₂ O or
A bath water purification apparatus using a column filled with phosphoric acid-based glass particles containing CuO has been proposed. The antibacterial agent used in the present invention exerts a bactericidal effect by eluting Ag ions and Cu ions. Therefore, in applications where a large amount of flowing water is treated, such as bath water, tap water, water in an elevated water layer, water in a pool, cooling water in a cooling tower, etc., the sustainability of the effect is limited. In applications that enter the human mouth, such as bath water and pool water, as well as the water in the elevated water layer, there is a problem that Ag ions and Cu ions are taken into the body.

[0006]

SUMMARY OF THE INVENTION The present invention does not require large-scale facilities and running costs, has almost no pollution of water to be treated, and furthermore, bath water, tap water and elevated water layers for home and business use. It is an object of the present invention to provide a granular antibacterial material having excellent durability suitable for purifying water, water of a pool, cooling water of a cooling tower, and the like, and a method for producing the same.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a granular antibacterial material having a specific phosphate compound having an antibacterial metal supported on the surface of a granular ceramic. Alternatively, a granular antibacterial material in which at least one metal oxide selected from zinc oxide and titanium dioxide and a specific phosphate compound having an antibacterial metal are supported on the granular ceramic surface has excellent antibacterial effect and durability. The present inventors have found that they can be manufactured efficiently and economically, and have completed the present invention. That is,
The present invention provides an antimicrobial agent represented by the following general formula [1], or at least one metal oxide selected from zinc oxide and titanium dioxide and an antimicrobial agent represented by the following general formula [1] on a granular ceramic surface. It is a granular antibacterial material characterized by having been made. Further, at least one metal oxide selected from zinc oxide and titanium dioxide and the following general formula [1]
Or an antibacterial agent represented by the following general formula [1] is mixed with a binder and a granular ceramic,
Manufacturing of a granular antibacterial material characterized in that the binder is softened or cured by heating at a temperature higher than the softening temperature or the curing temperature of the binder, and the antibacterial agent is supported on the surface of the granular ceramic via the binder. Is the way. M ¹ _{a Ab} M ² _c (PO ₄ ) _d · nH ₂ O [1] (M ¹ is silver, copper, zinc, tin, mercury, lead, iron, cobalt,
At least one l-valent (l is a positive integer) metal ion selected from nickel, manganese, arsenic, antimony, bismuth, barium, cadmium, and chromium, and A is an alkali metal ion, an alkaline earth metal ion, or ammonium At least one selected from ions and hydrogen ions
A species of m-valent (m is a positive integer) ion, M ² is a tetravalent metal ion, n is a number satisfying 0 ≦ n ≦ 6,
a and b are both la + mb = 1 or la + mb = 2
Where c and d are la + mb = 1,
c = 2, d = 3, and when la + mb = 2, c = 1, d
= 2. )

Hereinafter, the present invention will be described in detail. -Antibacterial agent The antibacterial agent in the present invention is represented by the following general formula [1]. M ¹ _{a Ab} M ² _c (PO ₄ ) _d · nH ₂ O [1] (M ¹ is silver, copper, zinc, tin, mercury, lead, iron, cobalt,
At least one l-valent (l is a positive integer) metal ion selected from nickel, manganese, arsenic, antimony, bismuth, barium, cadmium, and chromium, and A is an alkali metal ion, an alkaline earth metal ion, or ammonium At least one selected from ions and hydrogen ions
A species of m-valent (m is a positive integer) ion, M ² is a tetravalent metal ion, n is a number satisfying 0 ≦ n ≦ 6,
a and b are both la + mb = 1 or la + mb = 2
Where c and d are la + mb = 1,
c = 2, d = 3, and when la + mb = 2, c = 1, d
= 2. )

The compound represented by the general formula [1] is a crystalline compound or an amorphous compound having a layered structure or a three-dimensional knitted structure belonging to the space group R3C. As the antibacterial agent in the present invention, a crystalline compound having a three-dimensional network structure is preferable because there is little change in physical properties. M ¹ in the above general formula [1] is known as a metal having antifungal, antibacterial and antialgal properties, and among these, silver is not only safe but also antifungal and antibacterial. It is particularly effective as a metal capable of enhancing algal resistance.

A in the general formula [1] is at least one ion selected from the group consisting of an alkali metal ion, an alkaline earth metal ion, an ammonium ion and a hydrogen ion. Preferred examples thereof include lithium, sodium and potassium. And alkaline earth metal ions such as magnesium and calcium or hydrogen ions. Among these, potassium, sodium and hydrogen ions are preferred ions in view of the stability of the compound and availability at low cost.

M ² in the general formula [1] is a tetravalent metal ion, and preferred examples thereof include zirconium and
There are titanium and tin, and considering the safety of the compound, zirconium and titanium are particularly preferred tetravalent metal ions.

Preferable specific examples of the antibacterial agent represented by the general formula [1] are as follows. Ag _0.001 Li _1.999 Zr (PO ₄ ) ₂ Ag _0.01 Na _1.99 Zr (PO ₄ ) ₂ Ag _0.01 K _1.99 Sn (PO ₄ ) _{2 1.2} H ₂ O Ag _0.1 (NH ₄ ) _1.9 Ti (PO ₄ ) _2. Ag in each of the above formulas was changed to Z while maintaining the same charge as the charge of silver ions per mole of 4H ₂ O and compound.
It is a compound substituted with n, Mn, Ni, Pb, Hg, Sn, or Cu. The following antibacterial agents are also preferable. Ag _0.005 Li _0.995 Zr ₂ (PO ₄ ) ₃ Ag _0.01 (NH ₄ ) _0.99 Zr ₂ (PO ₄ ) ₃ Ag _0.05 Na _0.95 Zr ₂ (PO ₄ ) ₃ Ag _0.2 K _0.8 Ti ₂ (PO ₄ ) ₃ Ag _0.1 H _0.9 Zr ₂ (PO ₄ ) ₃ Ag _0.40 H _0.15 Na _0.45 Zr ₂ (PO ₄ ) ₃ Ag _0.60 H _0.10 Na _0.30 Zr ₂ (PO ₄ ) ₃ and the same charge amount as silver ion per mole of compound In each of the above equations, Ag is changed to Z
Compounds substituted with n, Mn, Ni, Pb, Hg, Sn, or Cu.

The antibacterial agent of the present invention is obtained by supporting an antibacterial metal ion on a phosphate compound, and the method for synthesizing the phosphate compound includes a baking method, a wet method, a hydrothermal method and the like. And can be easily obtained, for example, as follows. When synthesizing a network-structured phosphate by a firing method, a compound containing an alkali metal such as lithium carbonate (Li ₂ CO ₃ ) or sodium carbonate (Na ₂ CO ₃ ), or zirconium oxide (ZrO ₂ ) A compound containing zirconium and a compound containing a phosphate group such as ammonium dihydrogen phosphate (NH ₄ H ₂ PO ₄ ) are mixed at a molar ratio of about 1: 4: 6, By firing at 1400 ° C., the general formula [2] A ^′ _x Zr ₂ (PO ₄ ) ₃ [2] (A ^′ is at least one metal selected from alkali metal ions, alkaline earth metal ions and ammonium ions) And x is 1 when A ^′ is monovalent and ２ when A ^′ is divalent. This is immersed in an aqueous solution containing silver ions at an appropriate concentration at room temperature to 100 ° C. to obtain the compound represented by the general formula [1].

The compound represented by the general formula [2] wherein the A ion is a hydrogen ion in the general formula [1] can be obtained by converting the compound represented by the general formula [2] into an aqueous solution of an inorganic acid such as nitric acid, sulfuric acid and hydrochloric acid at room temperature to 100 ° C. By immersion in the general formula H
_(1-z) A ^′ _z M ₂ (PO ₄ ) ₃ (z is 0 or less than 1) to obtain a compound [3], which is further added to an aqueous solution containing silver ions at an appropriate concentration. By immersing, the compound represented by the general formula [1] is obtained.

In the case of synthesizing by a wet method, oxalic acid is added to the aqueous solution of zirconium oxychloride while stirring, and phosphoric acid is further added thereto. The pH of the reaction solution was adjusted to 3 with an aqueous sodium hydroxide solution, and after heating and refluxing for 10 hours,
The precipitate is filtered, washed with water, dried and pulverized to obtain network zirconium phosphate [NaZr ₂ (PO ₄ ) ₃ ]. By immersing this in an aqueous solution containing an antibacterial metal at an appropriate concentration, the compound represented by the general formula [1] is obtained.

In order to exhibit the fungicidal, antibacterial and antialgal properties, the value of a in the general formula [1] is preferably large,
When the value of a is 0.001 or more, it is possible to sufficiently exhibit fungicide, antibacterial properties and antialgal properties. However, if the value of a is less than 0.001, it may be difficult to exhibit the fungicide, antibacterial properties and anti-algal properties for a long time, so the value of a is set to 0.01 or more. Is preferred.
Further, in order to obtain an effect by adding a small amount, the value of a is 0.1
It is more preferable to make the above. The preferred particle size of the antimicrobial agent in the present invention is 0.1 to 10 μm, more preferably 0.1 to 3 μm, since the particle size is easily adhered to the surface of the granular ceramic.

The antimicrobial agent of the present invention is stable to heat and light exposure, and is 500 ° C., and sometimes 800 ° C.
Even after heating at １1300 ° C., the structure and composition do not change at all, and no discoloration occurs even when irradiated with ultraviolet rays. In addition, the phosphate used in the present invention does not come into contact with water in a liquid state or change in skeletal structure even in an acidic solution. Therefore, when used after processing into granular antibacterial material,
Extremely few restrictions on use environment.

Metal oxide The metal oxide in the present invention is at least one selected from zinc oxide and titanium dioxide, and may be a natural product or a synthetic product. There are no particular restrictions on the shape or particle size, but the finer the particle size is preferably 10 μm or less in order to process the surface of sand. Zinc oxide and titanium dioxide may be used alone or in combination.

Binder The binder used in the present invention is not particularly limited as long as it has an ability to bind the granular ceramic and the antibacterial agent by firing. For example, glassy powder, clay, sol substances such as silica sol and alumina sol, water glass and the like can be mentioned. Glassy powder is easy to mix with antibacterial agent because it is a powder,
Further, the softening temperature is preferably several hundred degrees which is easy to handle in production, and the antibacterial agent can be firmly supported on the granular ceramics.
Any known glassy powder can be employed, and is not particularly limited. Preferred specific examples include, for example, frit,
Although there is a drug, etc., it is also possible to use crushed glass waste from industry and home.
However, leaded glass containing harmful substances is not suitable from the viewpoint of safety. Preferred vitreous powder is a frit having a flow temperature of 1000 ° C. or less because the excellent antibacterial property of the antibacterial agent can be exhibited. In general, it is known that soda-based vitreous material starts to soften at a temperature of about 500 to 700 ° C., gradually becomes a fluid state, and changes to a liquid state as the temperature rises. It is preferable to use a vitreous material, and specific examples include the following.

Lead-free transparent soda glass softening temperature 540 ° C Flow start temperature 635 ° C Flow temperature 670 ° C Melting temperature 695 ° C Lead-free transparent borate glass softening temperature 550 ° C Flow start temperature 710 ° C Flow temperature 770 ° C Melting temperature 795 ° C Zircon milky white glass softening temperature 610 ° C Flow starting temperature 810 ° C Flowing temperature 840 ° C Melting temperature 950 ° C Zircon milky lime glassy softening temperature 700 ° C Flow starting temperature 940 ° C Flowing temperature 990 ° C Melting temperature 1110 ° C The preferred particle size of the vitreous powder used is preferably from 0.1 to 100 μm, more preferably from 1 to 20 μm, and still more preferably, from the viewpoint that mixing is easy and an appropriate bonding force can be exhibited. 3-10
μm.

Granular ceramic The granular ceramic referred to in the present invention refers to a natural or artificially produced inorganic solid material and a granular glass. In other words, ceramics, which are generally said in the public,
Refers to ceramic products and glass. For example, silica, alumina, zirconia, mullite, glass beads, balls, or the like can be used, but is not particularly limited as long as the softening temperature is equal to or higher than the firing temperature required for supporting. The shape is not particularly limited, such as a sphere, a column, a disk, a cube, a rectangular parallelepiped, and an irregular shape. The particle size of the granular ceramic is not particularly limited, but is preferably from 0.1 mm to 50 mm. If it is less than 0.1 mm, handling becomes complicated, and
When packed in a column or the like, the pressure loss increases. 50mm
If it is larger, the surface area per unit weight of the granular antibacterial material carrying the antibacterial agent is reduced, and the efficiency of the antibacterial property is reduced.
The component, color, specific gravity and the like of the granular ceramic in the present invention are not particularly limited, and the physical properties may be appropriately selected according to the application.

Mixing and heating The order of mixing the components of the antimicrobial agent, metal oxide, binder and granular ceramic is not limited, and it is sufficient that these components are uniformly mixed. However, in order to uniformly mix a relatively small amount of the antibacterial agent with the granular ceramic, it is desirable to preliminarily mix the antibacterial agent, the metal oxide, and the binder, and then mix this with the granular ceramic. In the present invention, the temperature at which the vitreous powder is softened is equal to or higher than the softening temperature of the vitreous, and is preferably equal to or lower than the melting temperature of the vitreous. In the present invention, “softening” is a concept including “liquefaction”.

A preferred specific process for obtaining a granular antibacterial material will be described below in the case where a vitreous powder is used as a binder. When a liquid or solution binder is used, a step of dehydrating at several tens to about 100 ° C. may be added before the firing step. (Process Example 1) An antimicrobial agent or a metal oxide and an antimicrobial agent are mixed and stirred with a vitreous powder. Granular ceramic is added to the mixed and stirred, and further mixed and stirred, and the surface of the granular ceramic is dusted with the blended antibacterial agent and glassy powder. These are heated in a firing furnace at a temperature equal to or higher than the softening temperature of the vitreous powder to soften the vitreous powder, and then cooled to room temperature. In this example, although the mixing and stirring process of the raw materials is complicated, the antibacterial agent can be sprinkled on the glassy powder moderately, so that the antibacterial agent can be efficiently supported on the granular ceramic. Can be. (Step Example 2) An antimicrobial agent or a metal oxide and an antimicrobial agent are mixed and stirred with a vitreous powder and a granular ceramic. The mixed and stirred material is heated in a firing furnace at a temperature equal to or higher than the softening temperature of the vitreous powder to soften the vitreous powder, and then cooled to room temperature. In this example, since the raw materials are mixed and stirred at once, there is an advantage that the complexity of the manufacturing process can be eliminated. (Step Example 3) The vitreous powder and the granular ceramic are mixed and stirred. The mixed and stirred product is heated in a firing furnace at a temperature equal to or higher than the softening temperature of the vitreous powder to soften the vitreous powder. An antibacterial agent or an antibacterial agent and a metal oxide are added to the softened glass, and then the mixture is allowed to cool to room temperature. In this example, when adding the antibacterial agent, there is the complexity of controlling the viscous state of the glass according to the heating conditions, but there is an advantage that the antibacterial agent has excellent binding ability. (Process Example 4) A binder, for example, a synthetic resin adhesive is applied to the surface of the granular ceramic, and a vitreous powder is adhered through the binder. The mixed and stirred material is appropriately heated in a furnace at a temperature equal to or higher than the softening temperature of the vitreous powder to soften the vitreous powder. An antibacterial agent or an antibacterial agent and a metal oxide are added to the softened glass, and then the mixture is allowed to cool to room temperature. In this example, the vitreous powder is preliminarily bound to the granular ceramic by a binder, and then, when adding an antibacterial agent, the viscosity state of the vitreous is complicated. Since the antibacterial agent can be supported, there is an advantage that the antibacterial agent is effectively used.

The compounding ratio of the antibacterial agent and the metal oxide, and the compounding ratio of these components and the granular ceramic can be appropriately changed depending on the use application, the use method, the production method and the like. For example, in order to obtain a stable antibacterial activity, the mixing ratio of the metal oxide is 1 to the total weight of the antibacterial agent and the metal oxide.
It is preferably 0 to 90% by weight, and in order to exhibit excellent supporting force, the mixing ratio of the antimicrobial agent or the total amount of the antimicrobial agent and the metal oxide to the total weight of the antimicrobial agent, the metal oxide and the binder is preferable. It is preferably 20 to 60% by weight, and in order to obtain a granular ceramic having excellent antibacterial properties, an antibacterial agent,
The mixing ratio of the metal oxide and the binder is preferably 0.05 to 5% by weight based on the total weight of these components and the granular ceramic.

In the granular antibacterial material thus obtained, the antibacterial phosphate, which is an antibacterial agent component, has excellent chemical and physical stability, and zinc oxide or titanium dioxide contains the antibacterial phosphate. Since the effect is more stabilized and improved, it has excellent antibacterial properties, safety and processability. In addition, it does not deteriorate when the antibacterial agent and the granular ceramic are mixed and when the granular antibacterial material is used, and has long-term antifungal, antibacterial and antialgal properties even under severe environments.

When the granular antibacterial material is used, its use method or amount may be appropriately selected depending on the application. For example, as for water purification, there is a method of adding an appropriate amount of granular antibacterial material to water to be treated as it is, or passing water through a column packed with granular antibacterial material.

Use The particulate antibacterial material of the present invention is effective as a particulate antibacterial material for purifying various types of water requiring sanitary control, and is particularly useful for bath water, tap water, and elevated water for home and business use. It is effective in purifying water in the water layer, water in the pool, cooling water in the cooling tower, and the like. In addition, the granular antibacterial material of the present invention can be used in various fields requiring sanitary management in addition to water purification, for example, sandboxes such as parks or schools, kindergartens, stadiums, sports fields, racetracks, and golf courses. It is useful as a granular antibacterial material for building materials such as pet sand, earth and sand for agricultural and horticultural use, mortar for exterior, etc., and exhibits stable antibacterial power by being compounded with these building materials and molded as necessary for use It can also be done.

[0028]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. Reference Example 1 (Preparation of Zirconium Phosphate Antibacterial Agent) An aqueous solution of zirconium sulfate and an aqueous solution of phosphoric acid were mixed so that the atomic ratio of zirconium to phosphorus was 2: 3, thereby forming a precipitate, and After adjusting the pH to 2 using an aqueous solution of sodium, the solution was heated to 130 under hydrothermal conditions.
° C., to obtain a crystalline zirconium phosphate _{[N a Zr 2 (PO 4)} 3 ] by heating for 12 hours. The crystalline zirconium phosphate obtained above was thoroughly washed with water, added to three types of aqueous solutions having different silver nitrate concentrations, stirred at 60 ° C. for 4 hours, thoroughly washed with water, and dried. This is lightly pulverized to obtain the following three kinds of antibacterial agents in which the weight percentage of silver is 4% by weight (antibacterial agent A), 7% by weight (antibacterial agent B) or 11% by weight (antibacterial agent C). Was.

[Antimicrobial agent A]: Ag _0.2 Na _0.8 Zr ₂ (PO ₄ ) ₃ [Anti-microbial agent B]: Ag _0.4 Na _0.6 Zr ₂ (PO ₄ ) ₃ [Anti-microbial agent C]: Ag _0.55 Na _0.45 Zr ₂ ( PO ₄ ) _{3 The} resulting antimicrobial agent is a white powder with an average particle size of 0.78 microns.

Reference Example 2 (Preparation of zeolite-based antibacterial agent) The content of silver was determined in the same manner as in Reference Example 1 except that commercially available zeolite 4A was used instead of the crystalline zirconium phosphate synthesized in Reference Example 1. Was 4% by weight to obtain an antibacterial zeolite [Antibacterial Agent D].

Example 1 (Preparation of granular antibacterial material) A metal oxide, glassy powder and granular ceramic were mixed with the antibacterial agent obtained in Reference Example 1 in various mixing ratios shown in Table 1, and each mixture was fired. After heating to 700 ° C. in a furnace to soften the vitreous powder, it was allowed to cool to room temperature to prepare granular antibacterial materials (Samples I to H). The zinc oxide and titanium dioxide used as metal oxides are commercially available for pigments, and the vitreous powder is lead-free transparent soda glass. Further, together with the antibacterial agent obtained in Reference Example 1, a metal oxide, silica sol or alumina sol (both having a solid content of 20% by weight) and granular ceramic were mixed at various mixing ratios shown in Table 1, and each mixture was placed in a firing furnace. 50
By heating to 0 ° C. and allowing to cool to room temperature, a granular antibacterial material was prepared (samples 、 and ヌ). The zinc oxide used as the metal oxide is commercially available for pigments, and the process example in the production method is the process example described in the section of “Mixing and heating”, and the silica sol shown in the table is used. Alternatively, the proportion of the alumina sol was shown as the amount of solid content.

[0032]

[Table 1]

Comparative Example 1 A granular antibacterial material was obtained in the same manner as in Sample A except that Antibacterial Agent D was used in place of Antibacterial Agent A in Sample A prepared in Example 1. ).

Comparative Example 2 An appropriate amount of a polyester ball (7 mmφ) and toluene were added to a high-speed mixer and rotated. When the ball surface was melted, 1 part by weight of the antibacterial agent A was added to 99 parts by weight of the polyester ball and rotated to obtain a granular antibacterial material having the antibacterial agent A carried on the polyester ball surface (Table 2). Of the sample ヲ).

[0035]

[Table 2]

Test Example 1 (Evaluation of Antibacterial Property) The antibacterial activity of the granular antibacterial materials produced in Example 1, Comparative Examples 1 and 2 was evaluated by the following method. That is, Escherichia coli and Staphylococcus aureus were used as test bacteria, and about 10 g of a granular antibacterial material was added to 75 mm of a bacterial solution adjusted to have a bacterial count of about 10 ⁴ and shaken at 25 ° C. for 1 hour or 3 hours. I'm sorry. The viable cell count of these test liquids was measured by a pour plate culture method (37 ° C. for 2 days) using a medium for cell count measurement. The results of the antibacterial test obtained as described above are shown in Table 3 below. The initial number of bacteria in the antibacterial test and the number of bacteria in a control test in which the same operation was performed on a porcelain ball (7 mmφ) not carrying an antibacterial agent are also shown.

[0037]

[Table 3]

Test Example 2 (Evaluation of antibacterial properties after durability test) About 100 g of the granular antibacterial material (samples I and D) prepared in Example 1 or the granular antibacterial material (sample No. 2) prepared in Comparative Example 2 The mixture was placed in a container, 1 liter of water was added, and the mixture was shaken at 60 ° C for 24 hours. The same operation was repeated seven times while replacing the water. The granular antibacterial material was taken out, and the antibacterial properties were evaluated in the same manner as above. Table 4 shows the results.

From the results in Table 3 above, it can be seen that the sample loaded with a substance other than the specific antibacterial agent of the present invention has poor antibacterial properties, whereas the sample antibacterial materials of the present invention, Samples (1) to (4), have excellent antibacterial properties. It can be seen that

[0040]

[Table 4]

From the results shown in Table 4, it can be seen that although the sample A using the polyester ball as a carrier has a problem in durability, the samples A and D, which are the granular antibacterial materials of the present invention, have excellent durability.

Test Example 3 (Evaluation of antibacterial activity against Legionella spp.) The granular antibacterial material (sample a or sample b) prepared in Example 1
0 cells are placed in a 100 ml Erlenmeyer flask, and a bacterial solution adjusted so that the number of Legionella bacteria is 1 × 10 ⁶ is added,
Shake at 30 ° C. for up to 3 hours. For these test solutions, a plate smear culture method (37 ° C., 5
Days). As a result, the viable count is
5.0 × 10 ⁴ (sample b) and 1.0 × 10 ⁴ (sample b), and the granular antibacterial material of the present invention has a problem in a 24-hour bath or a commercial bath other than Escherichia coli and Staphylococcus aureus. It has been confirmed that it also has an antibacterial effect against Legionella spp.

[0043]

The granular antibacterial material of the present invention has excellent durability,
It is effective for purifying various types of water that require hygiene, particularly for purifying bath water for home use or business use, tap water, water in an elevated water layer, water in a pool, and cooling water in a cooling tower. The particulate antibacterial material of the present invention can be used in various fields where sanitary properties are required in addition to water purification, for example, parks, schools, kindergartens, sandboxes, stadiums, sports fields, racetracks, golf courses, pet sands. It is also effective in purifying earth and sand for agricultural and horticultural use and mortar for exterior use. According to the production method of the present invention, a granular antibacterial material having excellent durability can be easily obtained.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Takao Kuramoto 2-38-8 Meieki Station, Nakamura-ku, Nagoya City, Aichi Prefecture Moriroku Co., Ltd. (72) Noriyuki Yamamoto 1 Funamicho, Minato-ku, Nagoya City, Aichi Prefecture Nagoya Research Institute, Toagosei Co., Ltd. (72) Inventor Koji Sugiura 1 Togosei Gosei Co., Ltd. Nagoya Research Institute, Minato-ku, Nagoya City, Aichi Prefecture (72) Inventor Hideki Kato Nagoya, Aichi Prefecture 1F, Funami-cho, Minato-ku F-term (reference) in the Nagoya Research Laboratory, Toagosei Co., Ltd. 4H011 AA02 BA01 BB18 BC18

Claims (5)

[Claims] 1. A granular antibacterial material comprising an antibacterial agent represented by the following general formula [1] supported on the surface of a granular ceramic. M ¹ _{a Ab} M ² _c (PO ₄ ) _d · nH ₂ O [1] (M ¹ is silver, copper, zinc, tin, mercury, lead, iron, cobalt,
At least one l-valent (l is a positive integer) metal ion selected from nickel, manganese, arsenic, antimony, bismuth, barium, cadmium, and chromium, and A is an alkali metal ion, an alkaline earth metal ion, or ammonium At least one selected from ions and hydrogen ions
A species of m-valent (m is a positive integer) ion, M ² is a tetravalent metal ion, n is a number satisfying 0 ≦ n ≦ 6,
a and b are both la + mb = 1 or la + mb = 2
Where c and d are la + mb = 1,
c = 2, d = 3, and when la + mb = 2, c = 1, d
= 2. ) 2. The granular antibacterial material according to claim 1, wherein at least one metal oxide selected from zinc oxide and titanium dioxide is supported on the surface of the granular ceramic. 3. The particulate antibacterial material according to claim 1, wherein the particle size of the particulate antibacterial material is 0.1 mm to 50 mm. 4. A granular antibacterial material according to claim 1, wherein a vitreous powder is used as a binder for supporting the antibacterial agent on the surface of the granular ceramic. 5. An antibacterial agent represented by the above general formula [1] or at least one metal oxide selected from zinc oxide and titanium dioxide together with a binder together with a particulate ceramic, and heating the mixture. A method for producing a granular antibacterial material, wherein a binder is softened or hardened, and an antibacterial agent is carried on the surface of the granular ceramic via the binder.