JP2002003320A - Bactericidal agent and method for sterilization - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a bactericidal agent excellent in chemical resistance and heat resistance, and having a high sterilization efficiency per hour even having a small heavy metal loading amount, and to provide a recycling technology of the above bactericide. SOLUTION: This bactericidal agent contains a compounded material consisting of a complex metal hydroxide containing copper ion or zinc ion exhibiting a bactericidal or an antibacterial activity as a bactericidal element and calcium phosphates as active ingredient, and a method of sterilization by using the above bactericide and a method for regenerating the above bactericide are also provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to sterilization or antibacterial
A specific heavy metal ion-containing composite metal hydroxide (hereinafter, simply abbreviated as "composite metal hydroxide") containing copper ions or zinc ions exhibiting properties (hereinafter simply referred to as "sterilization") as a sterilization element. The present invention relates to a bactericide containing a complex comprising calcium and calcium phosphates as an active ingredient, a bactericidal method using the bactericide, and a method for regenerating the bactericide.

More specifically, a composite metal hydroxide containing at least one selected from the group consisting of copper ions or zinc ions has an affinity for harmful microorganisms (including phages and virus particles in the present specification). The present invention relates to a technique for regenerating a bactericide by decomposing cells killed by a cell desorbing solution or baking while further improving the bactericidal property of the composite metal hydroxide by complexing calcium phosphates having high properties. .

[0003]

2. Description of the Related Art In recent years, Escherichia coli, Pseudomonas aeruginosa, Salmonella, Klebsiella pneumoniae, Staphylococcus aureus, Micrococcus, MRS have been developed.
A, bacteria such as Corynebacterium and Bacillus subtilis, phages such as T-type phage and λ phage, influenza virus, HIV, rabies virus, herpes virus, yellow fever virus, polio virus, tobacco mosaic virus, and viruses such as pox virus, Black mold fungus,
Contamination of the living environment by harmful microorganisms such as Cladosporium, ketomium and blue mold as phage and protozoa has caused serious social problems. With the spread and fluidization of marine organisms, it has become increasingly important to suppress the generation of these harmful microorganisms and protozoa, and to maintain the safety and cleanliness of the living environment.

On the other hand, in recent years, components such as nitrogen and phosphorus contained in rivers, various industrial wastewaters, or domestic wastewaters have promoted the generation of algae such as blue-green algae, causing water pollution in lakes and marshes and the generation of red tide in the near seas. Therefore, there is a demand for the development of a fungicide that suppresses the generation of these algae because it promotes eutrophication that leads to the occurrence of algae.

Conventionally, as an inorganic bactericide or antibacterial agent, a metal ion or metal having a bactericidal action, such as silver, zinc or copper, carried by an impregnation method, an adsorption method, an ion exchange method or the like is known. Used.

As typical examples, zirconium phosphate containing silver ions (JP-A-3-83905, JP-A-6-330)
No. 285) and a zeolite containing silver ions (JP-A-63-2).
65809, JP-A-1-286913), copper / zinc-containing composite metal oxides / hydroxides (JP-A-8-48606)
JP-A-8-291011) and silver-containing hydroxyapatite (JP-A-4-300975, JP-A-5-300975)
No. 78218) and the like. In particular, the production of an antibacterial resin or an antibacterial fiber by utilizing the fact that the chemical resistance and heat resistance, which are the characteristics of inorganic disinfectants, are superior to those of organic disinfectants. Are widely used as additives.

[0007]

It has been conventionally known that copper ions and zinc ions exhibit bactericidal properties, and metal salts or metal salt aqueous solutions containing these metal ions have been used as germicides. However, since these ions are heavy metal ions and are harmful to the human body, the amount and method of use thereof are currently limited.

In general, it has been pointed out that an inorganic bactericide has a lower sterilization rate than an organic bactericide or the like.
Therefore, it is an important issue how to reduce the amount of heavy metal ions used and increase the sterilization efficiency including the improvement of the sterilization rate. Given the process of disinfecting harmful microorganisms with fungicides, sterilization is based on how harmful microorganisms are phage-killed by contact with bactericidal metal ions (eg, copper or zinc ions) in the germicide. Efficiently increasing the number of times of contact between the bactericide and the harmful microorganisms is also important from the viewpoint of improving the bactericidal effect in a short time. Furthermore, from the viewpoint of effective utilization of resources, it is important to obtain a high sterilizing effect with a small amount of heavy metal ions carried, and there is a strong demand for the development of a sterilizing method in consideration of recycling of the sterilizing agent itself.

[0009] The present invention provides a bactericide which has excellent chemical resistance and heat resistance and has a high bactericidal efficiency per hour even if the amount of heavy metal ions carried is small. The purpose is to provide recycling technology.

[0010]

Means for Solving the Problems The present inventors have conducted intensive studies focusing on the above-mentioned problems, and as a result, as heavy metal ions having a sterilizing ability, at least one selected from the group consisting of copper ions or zinc ions. Incorporating calcium phosphates, which do not have a bactericidal action but have a high affinity for bacteria, into a composite metal hydroxide containing, forms a bactericide containing these inorganic compounds as active ingredients, and the interaction between the two Can increase the sterilization rate against bacteria, and the addition of calcium phosphates makes it possible to relatively reduce the amount of heavy metal ions per unit weight of the fungicide, effectively sterilizing even small amounts of heavy metal ions. I found what I could do.

Further, the sterilizing agent after the sterilizing treatment is subjected to a desorbing treatment using an appropriate cell desorbing agent or a baking treatment to separate and remove dead cells and to sterilize the surface by renewing the surface of the sterilizing agent. It has been found that the agent itself can be recycled.

That is, the present invention provides the following disinfectant, disinfecting method and regenerating method. Item 1. A fungicide comprising, as an active ingredient, a composite comprising a compound represented by the following general formula [1] and calcium phosphates. ((M ₁ ²⁺ ) _y (M ₂ ²⁺ ) _1-y ) _1-x (M ³⁺ ) _x (OH ⁻ ) _{2 + xy} (A ⁿ⁻ ) _{y / n} [1] ₁ ²⁺ represents at least one selected from the group consisting of Zn ²⁺ and Cu ^2+, M ₂ ^2+, Mg ^2+,
It represents at least one selected from the group consisting of Fe ²⁺ and Ca ^2+, M ³⁺ represents at least one selected from the group consisting of Cr ^3+, Al ³⁺ and Fe ^3+, A
^n- represents an n-valent anion, and the subscript in the formula is 0 <x ≦
0.5, 0 <y ≦ 1, and n is 1 or 2. Item 2. A disinfectant containing, as an active ingredient, a calcined product obtained by calcining the composite according to item 1 at 400 to 1000 ° C. Item 3. Item 3. A sterilization method comprising bringing a gas or liquid containing harmful microorganisms into contact with the sterilizing agent according to Item 1 or 2. Item 4. Item 3: A fungicide according to item 1 or 2, wherein a gas or a liquid containing harmful microorganisms is brought into contact with the fungicide to sterilize the fungicide, followed by separating and removing dead cells from the fungicide by a cell desorbing agent or baking. how to.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The fungicide of the present invention is effective against bacteria, phages, viruses and fungi. Specific examples of bacteria include Escherichia coli, Pseudomonas aeruginosa, Salmonella, Klebsiella pneumoniae, Staphylococcus aureus, Micrococcus, MRSA, Corynebacterium, Bacillus subtilis, and the like. Phages include T-type phage, λ phage, and the like. Examples of the virus include influenza virus, HIV, rabies virus, herpes virus, yellow fever virus, poliovirus, tobacco mosaic virus, poxvirus, and the like, and as molds black mold (cladosporium), black koji mold (Aspergillus), Examples include Ketama mold (ketomium), blue mold (penicillium), black mold (Rhizopus), red mold (Fusarium), scabi (Altanaria), Tsukaio mold (Gliocladium), and black yeast-like bacteria (Aureopasidium).

[0014] In the above general formula (1), M ₁ ²⁺ is, Z
It shows at least one selected from the group consisting of n ²⁺ and Cu ²⁺ .

In the above general formula (1), M ₂ ²⁺ is, M
at least one selected from the group consisting of g ²⁺ , Fe ²⁺ and Ca ²⁺ , preferably Mg ²⁺ ;

In the above general formula [1], M ³⁺ represents Cr
³⁺ represents at least one selected from the group consisting of Al ³⁺ and Fe ^3+, preferably Al ^3+.

In the general formula [1], A ^n- represents an n-valent anion (n = 1 or 2). That is, A
^n- is composed of only a monovalent or divalent anion, or is composed of both a monovalent anion and a divalent anion. The monovalent ^{anion, OH -, Cl -, NO} 2 -, NO 3 -,
_{^{F -, Br -, HCO 3}} - and the like, preferably Cl ^-
Or HCO ₃ ^- is. As the divalent anion, SO 2
₄ ^2-, CO ₃ ^2-, include SO ₃ ^2-like, preferably CO ₃
^2- .

In the above general formula [1], 0 <x
≤ 0.5, preferably 0.1 ≤ x ≤ 0.4, more preferably 0.15 ≤ x ≤ 0.35.

In the general formula [1], generally, 0 <y
≦ 1, preferably 0.3 ≦ y ≦ 0.95,
More preferably, 0.45 ≦ y ≦ 0.85.

The calcium phosphates used in the present invention are:
Especially limited if it is a compound mainly composed of acid and calcium
There is no. For example, hydroxyapatite (Ca_Ten(PO_Four)₆
(OH) _Two), Tribasic calcium phosphate (Ca_Three(PO_Four)_Two), 2nd re
Calcium phosphate (CaHPO_Four), Octacalcium phosphate
(Ca₈H_Two(PO_Four)₆), Tetracalcium phosphate
(Ca_FourO (PO_Four)_Two) And the like.

For example, hydroxyapatite is an amphoteric ion
It is known to be a heat exchanger and has the composition formula Ca_Ten(PO_Four)₆(OH)_Two
Among the elemental species that constitute²⁺Instead of Na⁺, K⁺, S
r²⁺, Ba²⁺, Pb²⁺, Zn²⁺, Cd²⁺, Cu²⁺, Mg²⁺, Fe²⁺, Mn
²⁺Etc., PO_Four ^3-Instead of SO_Four ^2-, CO_Three ^2-, HPO_Four ^2-, AsO
_Four ^2-, SiO_Four ^Four-Etc., OH^-Instead of F^-, Cl^-, Br^-, CO_Three ^Two
-Hydroxyapatite-like compound partially converted by e.g.
A substance can also be used as calcium phosphates.

The bactericide of the present invention is a bactericide containing, as an active ingredient, a complex comprising a specific copper ion or zinc ion-containing composite metal hydroxide represented by the general formula [1] and calcium phosphates. Not restricted. The fungicide can be prepared, for example, by the following method.

An acidic aqueous solution in which calcium phosphates are dissolved in an acid, or an acidic aqueous solution in which a phosphate compound and a calcium compound are dissolved in a desired chemical composition, and an alkaline aqueous solution are prepared by suspending a composite metal hydroxide. The desired disinfectant can be prepared by simultaneously dropping the solution into the liquid, successively filtering and washing the obtained precipitate, and then drying or firing at a predetermined temperature.

The acidic aqueous solution is preferably an acidic aqueous solution obtained by dissolving calcium phosphate in an acid. By temporarily dissolving calcium phosphates in acid and reacting with the composite metal hydroxide suspension, the first is that the specific surface area of the regenerated calcium phosphate itself is large, and the adsorption capacity for harmful microorganisms is also large. This is advantageous in that the dispersibility of heavy metal ions in the fungicide is also increased.

Examples of the acid used for dissolving calcium phosphates in acid include hydrochloric acid, nitric acid and the like, more preferably hydrochloric acid. On the other hand, examples of the alkaline aqueous solution include aqueous solutions of potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like, more preferably potassium hydroxide, An aqueous sodium hydroxide solution may be used.

The firing temperature at the time of preparing the fungicide is as follows:
About 400 to 1000 ° C, preferably 400 to 800 ° C
Degree, more desirably about 400 to 600 ° C. The firing time varies depending on the firing temperature, but is usually 2 to 2.
6 hours, preferably 3 to 5 hours.

The germicide thus obtained is considered to be in a state where the composite metal hydroxide having excellent bactericidal ability is uniformly dispersed on its base calcium phosphate.
It is thought that the synergistic effect of the affinity of calcium phosphates for harmful microorganisms and the bactericidal action of the sterilizing element itself effectively kills harmful microorganisms. Therefore,
In order to effectively carry out the present invention, by increasing the content of calcium phosphates, the affinity for microorganisms is increased, but the bactericidal effect is reduced, and conversely, by increasing the content of the composite metal hydroxide. Although the bactericidal effect increases, the affinity for microorganisms decreases. Therefore, it is extremely important to determine an appropriate mixing ratio of the two.

The compounding ratio of the composite metal hydroxide in the composite is about 30 to 90% by weight, preferably about 40 to 90% by weight when compounding a composite metal hydroxide containing 6.94% as copper. , More preferably 50-80 wt
%, And from this result, when compounding a composite metal hydroxide having a different copper content, the compounding amount may be appropriately adjusted.

At this time, the amount of the sterilizing element in the composite is not particularly limited, but is usually 2.0 to 7.0 watts.
It can be used by blending about t%, preferably about 2.5 to 6.5 wt%, more preferably about 3.5 to 5.5 wt%.

The fungicide of the present invention may be used as a powder, and may be used as an additive to a matrix of resin, paper, hydraulic cement, or the like, or as a molded product and a filter medium by adding a binder. Is also possible.

When added to the resin, the disinfectant may be added to an existing fatty acid, an alkali metal salt of a fatty acid, a silane-based, an aluminum-based or a titanate-based cup, if necessary, in order to improve the compatibility between the disinfectant and the resin. After performing a surface treatment with a surface treating agent such as a ring agent or an anionic surfactant, a resin molded article may be obtained.

The binder is not particularly limited, but polyacrylic resins such as polyacrylic acid hydrazide, aminated polyacrylamide such as styrene / acrylic resin, celluloses such as ethyl cellulose, carboxymethyl cellulose, cellulose acetate, and carrageenan. Such as polysaccharides, polyamide / epichlorohydrin resin, organic binders such as vinyl acetate / vinyl versatate copolymer, inorganic binders such as alumina sol and silica sol, and preferably aminated polyacrylamide. Can be The amount of the binder is about 1 to 50% by weight, preferably 5
About 30% by weight, more preferably about 10 to 25% by weight.

In the sterilization method of the present invention, the gas to be subjected to the sterilization treatment includes air and air in the living environment. A sterilizing agent is installed at a location where the gas flows, and sterilization is performed by contact with air. . In the case of liquids, the target is septic tank treated water, rainwater, lakes and marshes, rivers and other environmental waters, water supply, middle water supply, sewerage, etc. However, in order to increase the processing efficiency, sterilization is performed by filling the column with a bactericide and passing the target liquid through the column. At this time, the amount of the germicide used, the gas flow rate or the liquid flow rate may be appropriately adjusted depending on the processing conditions.

In the method for regenerating the fungicide of the present invention,
By treating the sterilizing agent after sterilization with a single component or a mixed aqueous solution of two or more phosphates as a cell desorbing solution,
Dead cells are detached from the surface of the germicide, and the germicide itself can be recycled. As the cell detachment liquid, an aqueous solution of a phosphate such as sodium phosphate, sodium hydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, ammonium phosphate, ammonium hydrogen phosphate can be used. , Sodium hydrogen phosphate, potassium phosphate and potassium hydrogen phosphate are preferred.

The concentration of phosphate ions in the cell detachment solution at the time of cell detachment can be used in the range of 1 mol / m ³ as PO ₄ ³⁻ ion to the saturation concentration of each phosphate, preferably 5 mol. It is desirable to carry out treatment at a phosphate ion concentration of at least / m ³ .

Desorption of dead cells can also be carried out by baking. That is, the disinfectant subjected to disinfection is not particularly limited, but is fired at 200 to 1000 ° C., preferably 400 to 600 ° C., thereby burning dead cells attached to the disinfectant surface and renewing the disinfectant surface. The fungicide can be reused.

[0037]

According to the present invention, a bactericide for microorganisms is obtained by complexing calcium phosphates with a copper or zinc ion-containing composite metal hydroxide having excellent chemical resistance and heat resistance to form a bactericide. Has improved affinity and microorganisms can be efficiently killed with a relatively small amount of copper ions or zinc ions carried.

Further, by using an aqueous phosphate solution as a cell desorbing solution, dead cells can be detached from the surface of the sterilizing agent after the sterilization treatment, and the surface of the sterilizing agent can be recycled by renewing the surface. It is also very useful as a low environmental load fungicide.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

[0040]

EXAMPLES Example 1 Hydroxyapatite (trade name: HA-300BP, manufactured by Tomita Pharmaceutical Co., Ltd.) as a calcium phosphate compound;
100 g of 2N-HCl 1,000 c
It was dissolved in m ^3, to prepare a CaP solution.

[0041] Next, prepare the ion exchange water 2,500cm ³ in a beaker (5,000cm ^3), Mg-Cu-
Al-type composite metal hydroxide (Mg _0.736 Cu _0.087 Al
₂₅₈ g of _0.177 (OH) _1.877 Cl _0.128 (CO ₃ ) _0.086 ; Cu content 6.94%) was added to form a suspension. At room temperature under a CaP solution 1,000 cm ³ in suspension, 6.25N
The reaction solution was added dropwise while maintaining the pH of the reaction solution alkaline with an aqueous solution of NaOH. The resulting coprecipitate was filtered, washed with water, and dried (80 ° C., 24 hours), and then pulverized to obtain a bactericide (Cu content: 4.83%).

Example 2 500 g of CaP was added as a calcium phosphate compound.
N-HCl was dissolved in 5000 cm ³ to prepare a CaP solution.

[0043] Subsequently, the beaker (20000 cm ³⁾ to prepare the ion-exchanged water 4000 cm ^3, Zn-Al type composite metal hydroxide _{(Zn 0.730 Al 0.270 (OH)} 1.875 Cl
_0.015 (CO ₃ ) _0.190 ) was added to form a suspension.
5. Add 5000 cm ³ of CaP solution in the suspension at room temperature.
The reaction solution was added dropwise while maintaining the pH of the reaction solution at neutral with a 25N-NaOH aqueous solution. The resulting coprecipitate was filtered, washed with water, and dried (80 ° C., 24 hours), and then pulverized to obtain a bactericide.

Example 3 A fungicide was prepared by baking the fungicide obtained in Example 1 at 500 ° C. for 3 hours.

Example 4 The bactericidal ability of the bactericide was evaluated according to the following test method.

That is, Escherichia coli IAM
12119: hereinafter abbreviated as E. coli) at 37 ° C.
After culturing in Broth liquid medium, E. coli was weighed at 9 kg / m ^3.
During -NaCl aqueous solution, the initial cell concentration (N ₀₎ 1 × 10
¹¹ cells / m ³ were added, and this was used as an E. coli sample solution.

Next, in an E. coli sample solution (10 dm ³ ),
A disinfectant was added so as to be 0.5 kg / m ^3, and the mixture was transferred to an L-shaped tube, and then sterilized by shaking at 25 strokes / min under dark conditions. 0, 15, 30, 6
Sampling was performed at 0, 90, and 120 minutes, and the sample and 20 μg of L-cysteine were spread on a Nutrient Broth agar medium, and a colony counting method (Ind. Eng. Chem.
Res., 34, 3920-3926, 1996).

The obtained E. coli survival rate change over time of 120
The following formula was applied to all data up to the minute, and the number of lethal reactions n and the apparent bactericidal rate constant (k ″) were calculated by the nonlinear least squares method.

[0049]

(Equation 1)

[N _t : number of bacteria (cells) after sterilization time t minutes (cells / m ³ ) N ₀ : number of bacteria (cells) at start of experiment (cells / m ³ ) N _t / N ₀ : Bacterial (cell) survival rate after t minutes k ″: Apparent sterilization rate constant (min ⁻¹ ) t: sterilization experiment time (min) As a result of fitting a lot of data, the value of n was determined to be 1. In evaluating the bactericidal properties of the bactericide against bacteria, the larger the value of the bactericidal rate constant k ″, the higher the bactericidal ability can be evaluated.

The disinfectant obtained in Example 1 and Mg-Cu
-Al-type composite metal hydroxide (Mg _{0. 736} Cu _0.087 Al
_0.177 (OH) _1.877 Cl _0.128 (CO ₃ ) _0.086 )
FIG. 1 shows the change over time in the survival rate of E. coli. The disinfectant and the amount of the composite metal hydroxide used were 0.36 respectively.
kg / m ³ and 0.25 kg / m ³ , in order to confirm the combined effect, in order to make the same amount of copper added to both samples. The apparent sterilization rate constant (k ″) was determined from FIG. 1, and as a result, k ″ was obtained for the sterilizing agent (Example 1).
= 4.51 × 10 ⁻¹ min ⁻¹ , k ″ for composite metal hydroxide
= 9.08 × 10 ⁻² min ⁻¹ , it was confirmed that the bactericide of the present invention had a high bactericidal rate and that a composite of calcium phosphates provided an excellent bactericidal effect.

Example 5 The content of the Mg—Cu—Al type composite metal hydroxide in the fungicide was 27.2, 44.0, 64.4, 78.7 and 8
A bactericide was obtained in the same manner as in Example 1 except that the amount was changed to 9.8% by weight. Using the obtained bactericide, an apparent bactericidal rate constant was determined in the same manner as in the above test method. FIG. 2 shows the relationship between the composite metal hydroxide content and the apparent sterilization rate constant. FIG. 2 shows that the composite metal hydroxide content was about 65%.
Since the maximum rate constant was obtained in weight%, Mg-Cu
It is understood that it is most desirable to mix the Al-type composite metal hydroxide at about 60 to 70% by weight.

Example 6 The bactericide obtained in Example 3 was evaluated for an apparent bactericidal rate constant in the same manner as in the above test method.
2.38 × 10 ⁻¹ min ⁻¹ , and the apparent sterilization rate constant (k ″ = 9.0) of the Mg—Cu—Al type composite metal hydroxide
8 × 10 ^-2 min ^{- 1)} as compared with, it can be seen that obviously fungicidal properties are improved.

Example 7 The method for regenerating the fungicide of the present invention can be carried out according to the following procedure.

A glass column having a diameter of 5 mm was filled with glass wool as a filter medium, and a fungicide (140 mg) was filled thereon, and a 0.9 wt% -NaCl aqueous solution (35 cm ³⁾ adjusted to a concentration of 1 × 10 ¹³ cells / m ³ of E. coli was prepared. Loading. The number of viable cells and the total number of cells in the eluate were measured at each time, and when the adsorption of Escherichia coli by the bactericide reached saturation, the pH was adjusted to 30 mM-NaH ₂ PO ₄ /
Elution of Escherichia coli adsorbed on the bactericide is performed by adding 25 ml of Na ₂ HPO ₄ buffer solution to the column. After elution of E. coli, the E. coli-containing NaCl aqueous solution is loaded again. By repeating the cycle of adsorption of E. coli, sterilization, and elution of E. coli, the germicide can be reused.

The total number of cells was determined by measuring the number of cells with an optical microscope using a hemocytometer for phase difference.
Measure by the following method. Measurement of the number of viable cells: 0.1 cm ³ of the sample solution was collected, and 9.0 was collected.
It was diluted to a predetermined concentration using an aqueous solution of kg / m ³ -NaCl. 0.1 cm ³ of this diluted solution was spread on Nutrient Broth agar medium. Subsequently, the agar medium is cultured at 37 ° C. for 24 hours in a constant temperature room, and the number of viable cells is calculated by measuring the number of formed colonies.

[Brief description of the drawings]

FIG. 1 shows the fungicide obtained in Example 1 and Mg-Cu-A.
It is a graph which shows the relationship between the survival rate of bacteria (cells) of l-type composite metal hydroxide and time.

FIG. 2 is a graph showing the relationship between the Mg—Cu—Al type composite metal hydroxide content during sterilization and an apparent sterilization rate constant.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C02F 1/50 531 C02F 1/50 531J 531S (72) Inventor Takuro Nishimura No. 1 Machikaneyamacho, Toyonaka-shi, Osaka No. 3 Osaka University Graduate School of Engineering Science (72) Inventor Akira Okubo 85-1 Maruyama, Seto-cho, Naruto City, Tokushima Prefecture Tomita Pharmaceutical Co., Ltd. (72) Inventor Yuhiro Kawamoto Seto, Naruto City, Tokushima Prefecture 85-1 Maruyama, Mt. Myojin Character Tomita Pharmaceutical Co., Ltd. (72) Inventor Mikiko Mihara 85-1 Maruyama, Setocho Myojin, Naruto City, Tokushima Pref. F-term (reference) 4H011 AA02 BA01 BA02 BB18 BC18 DA02 DC08 DC11 DE04

Claims (4)

[Claims] 1. A fungicide comprising, as an active ingredient, a composite comprising a compound represented by the following general formula [1] and calcium phosphates. ((M ₁ ²⁺ ) _y (M ₂ ²⁺ ) _1-y ) _1-x (M ³⁺ ) _x (OH ⁻ ) _{2 + xy} (A ⁿ⁻ ) _{y / n} [1] ₁ ²⁺ represents at least one selected from the group consisting of Zn ²⁺ and Cu ^2+, M ₂ ^2+, Mg ^2+,
It represents at least one selected from the group consisting of Fe ²⁺ and Ca ^2+, M ³⁺ represents at least one selected from the group consisting of Cr ^3+, Al ³⁺ and Fe ^3+, A
^n- represents an n-valent anion, and the subscript in the formula is 0 <x ≦
0.5, 0 <y ≦ 1, and n is 1 or 2. ] 2. The composition according to claim 1, wherein
A fungicide containing a fired product obtained by firing at 000 ° C. as an active ingredient. 3. A sterilization method comprising bringing a gas or a liquid containing harmful microorganisms into contact with the sterilizing agent according to claim 1 or 2. 4. A method of contacting a germicide according to claim 1 or 2 with a gas or liquid containing harmful microorganisms for sterilization, followed by separating and removing dead cells from the germicide by a cell desorbing agent or baking. A method of regenerating a fungicide.