JP4576026B2 - Disinfectant and disinfecting method - Google Patents

Description

【００５０】
[上記数式中、
Ｎ_t：殺菌時間ｔ分後の細菌（細胞）数（cells／m³）
Ｎ₀：実験開始時の細菌（細胞）数（cells／m³）
Ｎ_t／Ｎ₀：ｔ分後の細菌（細胞）生存率
ｋ''：みかけの殺菌速度定数（min^-1）
ｔ：殺菌実験時間（min）である。]
なお多くのデ−タをフィッティングさせた結果、ｎの値を１と決定した。殺菌剤の菌に対する殺菌特性を評価する上で、殺菌速度定数ｋ''値は、大きな値を示す場合ほど、殺菌能力が高いと評価できる。
【００５１】
実施例１で得られた殺菌剤と、Ｍｇ−Ｃｕ−Ａｌ型複合金属水酸化物（Ｍｇ_0.736Ｃｕ_0.087Ａｌ_0.177(ＯＨ)_1.877Ｃｌ_0.128(ＣＯ₃)_0.086）とについてE. coli生存率の経時変化を図１に示した。なお、殺菌剤及び複合金属水酸化物の使用量は、それぞれ０．３６ｋｇ／ｍ³及び０．２５ｋｇ／ｍ³であり、これは複合効果を確認するために、両試料における銅としての添加量を同じとするためである。
図１よりみかけの殺菌速度定数（ｋ''）を求めた結果、殺菌剤（実施例１）ではｋ''＝４．５１×１０^-1min^-1、複合金属水酸化物ではｋ''＝９．０８×１０^-2min^-1と求められたことから、本発明殺菌剤の殺菌速度が高く、リン酸カルシウム類の複合により優れた殺菌効果が得られることが確認された。
【００５２】
実施例５
殺菌剤中のＭｇ−Ｃｕ−Ａｌ型複合金属水酸化物の含有率を、２７．２、４４．０、６４．４、７８．７及び８９．８重量％とした以外は、実施例１と同様にして殺菌剤を得た。得られた殺菌剤を用い、上記試験方法と同様にして、みかけの殺菌速度定数を求めた。複合金属水酸化物の含有率とみかけの殺菌速度定数との関係を図２に示した。図２より、複合金属水酸化物の含有率が約６５重量％で最大速度定数が得られたことから、Ｍｇ−Ｃｕ−Ａｌ型複合金属水酸化物を６０〜７０重量％程度で配合することが最も望ましいことがわかる。
【００５３】
実施例６
実施例３で得られた殺菌剤について、上記試験方法と同様にして、みかけの殺菌速度定数を求めた結果、ｋ''＝２．３８×１０^-1min^-1となり、Ｍｇ−Ｃｕ−Ａｌ型複合金属水酸化物のみかけの殺菌速度定数（ｋ''＝９．０８×１０^-2min^-1）と比較して、明らかに殺菌特性が向上していることがわかる。
【００５４】
実施例７
本発明の殺菌剤の再生方法としては、以下の手順にて実施することができる。
【００５５】
直径５ｍｍのガラスカラムにろ材としてガラスウールを詰め、その上に殺菌剤１４０ｍｇを充填し、大腸菌濃度として１×１０¹³ｃｅｌｌｓ／ｍ³に調整した０．９重量％−ＮａＣｌ水溶液３５ｃｍ³をローディングする。各時間毎に溶出液の生細胞数と全細胞数を測定し、殺菌剤による大腸菌吸着が飽和に達した時点において、ｐＨ６に調整した３０ｍＭ−ＮａＨ₂ＰＯ₄／Ｎａ₂ＨＰＯ₄緩衝溶液２５ｍｌをカラムに添加して、殺菌剤に吸着された大腸菌の溶出を実施する。大腸菌溶出後、再度、大腸菌含有ＮａＣｌ水溶液をローディングする。このように大腸菌吸着、殺菌、大腸菌溶出のサイクルを繰り返すことにより、殺菌剤を再利用することができる。
【００５６】
なお全細胞数は、位相差用血球計算盤を用いて光学顕微鏡で細胞数を測定し、生細胞数の測定は、次の方法にて測定を行う。
生細胞数の測定：
試料液０．１ｃｍ³を採取し、９．０ｋｇ／ｍ³−ＮａＣｌ水溶液を用いて所定の濃度に希釈した。この希釈液０．１ｃｍ³をNutrient Broth寒天培地上に塗布した。続いて寒天培地を恒温室にて３７℃で２４時間培養し、形成されたコロニー数を測定することにより、生細胞数を算出する。
【図面の簡単な説明】
【図１】実施例１で得られた殺菌剤及びＭｇ−Ｃｕ−Ａｌ型複合金属水酸化物の細菌（細胞）生存率と時間の関係を示すグラフである。
【図２】殺菌在中のＭｇ−Ｃｕ−Ａｌ型複合金属水酸化物含有率とみかけの殺菌速度定数との関係を示すグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a specific heavy metal ion-containing composite metal hydroxide (hereinafter simply referred to as “composite metal water”) containing copper ions or zinc ions exhibiting sterilization or antibacterial (hereinafter simply referred to as “sterilization”) properties as a sterilization element. The present invention relates to a bactericidal agent comprising a composite comprising calcium oxides as an active ingredient, a bactericidal method using the bactericidal agent, and a method for regenerating the bactericidal agent.
[0002]
More specifically, the composite metal hydroxide containing at least one selected from the group consisting of copper ions or zinc ions has high affinity for harmful microorganisms (including phages and virus particles in the present specification). The present invention relates to a technique for further improving the bactericidal properties of the composite metal hydroxide by complexing calcium phosphates and reusing a bactericidal agent by detaching cells killed by a cell desorption solution or baking.
[0003]
[Prior art]
In recent years, bacteria such as Escherichia coli, Pseudomonas aeruginosa, Salmonella, Klebsiella pneumoniae, Staphylococcus aureus, Micrococcus, MRSA, Corynebacterium, Bacillus subtilis, T-type phage, phage such as λ phage, influenza virus, HIV, rabies virus Of living environment by harmful microorganisms such as herpes virus, yellow fever virus, poliovirus, tobacco mosaic virus, pox virus, black mold, molds such as cladosporium, ketomium, blue mold, protozoa, etc. Contamination has caused serious social problems, and in the future, with the diversification of our lifestyle and the expansion and fluidization of the range of living behavior, the occurrence of these harmful microorganisms and protozoa will be suppressed, and the living environment will be safe. Maintaining sexuality and cleanliness has become an increasingly important issue.
[0004]
On the other hand, in recent years, components such as nitrogen and phosphorus contained in rivers, various industrial effluents and domestic effluents have promoted the generation of algae and other algae, leading to water pollution in lakes and red tides in the nearby seas. Development of a bactericidal agent that suppresses the generation of these algae is desired because it promotes nutrition.
[0005]
Conventionally, as an inorganic disinfectant or antibacterial agent, a metal ion such as silver, zinc or copper having a bactericidal action or a metal supported by a method such as an impregnation method, an adsorption method or an ion exchange method has been used. Yes.
[0006]
Typical examples include silver ion-containing zirconium phosphate (JP-A-3-83905, JP-A-6-330285), silver ion-containing zeolite (JP-A 63-265809, JP-A-1-286913), copper Known are zinc-containing composite metal oxides / hydroxides (JP-A-8-48606, JP-A-8-291011) and silver-containing hydroxyapatite (JP-A-4-3000097, JP-A-5-78218). In particular, it is widely used as an additive in the production of antibacterial resins or antibacterial fibers, taking advantage of the superior chemical resistance and heat resistance that are characteristic of inorganic fungicides compared to organic fungicides. ing.
[0007]
[Problems to be solved by the invention]
It is conventionally known that copper ions and zinc ions exhibit bactericidal properties, and metal salts or metal salt aqueous solutions containing these metal ions are used as bactericides. 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.
[0008]
In general, it has been pointed out that inorganic bactericides have a slower bactericidal rate than organic bactericides. Therefore, how to increase the sterilization efficiency including the reduction of the amount of heavy metal ions and the improvement of the sterilization rate is an important issue. Considering the sterilization process of harmful microorganisms with a bactericidal agent, how sterilization is carried out as phages by contacting harmful microorganisms with bactericidal metal ions (for example, copper ions or zinc ions) in the bactericide, Efficiently increasing the number of contact between the bactericide and harmful microorganisms is also important in terms of improving the bactericidal effect in a short time. In addition, from the viewpoint of effective use of resources, it is important to obtain a high sterilization effect with a small amount of heavy metal ions supported, and development of a sterilization method in consideration of recycling of the sterilizer itself is strongly desired.
[0009]
As a bactericidal agent that can satisfy these demands, the present invention provides a bactericidal agent that is excellent in chemical resistance and heat resistance and has a high sterilizing efficiency per hour even with a small amount of heavy metal ions, and a recycling technology for the bactericidal agent. The purpose is to provide.
[0010]
[Means for Solving the Problems]
As a result of intensive studies focusing on the above problems, the present inventors have developed a composite metal hydroxide containing at least one selected from the group consisting of copper ions or zinc ions as heavy metal ions having sterilizing ability. On the other hand, by adding calcium phosphates that have no bactericidal action but high affinity for bacteria, a bactericidal agent containing these inorganic compounds as an active ingredient can be formed, and the bactericidal rate against bacteria can be improved by their interaction. In addition, by adding calcium phosphates, it has been found that the amount of heavy metal ions per unit weight of the bactericide can be relatively reduced, and it can be effectively sterilized even with a small amount of heavy metal ions.
[0011]
Further, the disinfectant after the disinfection treatment is detached by using an appropriate cell desorbing agent or subjected to a baking treatment, thereby separating and removing dead cells and renewing the disinfectant surface. I found out that it could be recycled.
[0012]
That is, the present invention provides the following disinfectant, disinfecting method and regenerating method.
Item 1. A bactericidal agent comprising a compound composed of a compound represented by the following general formula [1] and calcium phosphates as an active ingredient.
((M ₁ ²⁺ ) _y (M ₂ ²⁺ ) _1-y ) _1-x (M ³⁺ ) _x (OH ⁻ ) _{2 + xy} (A ⁿ⁻ ) _{y / n} [1]
[ ^Wherein M ₁ ²⁺ represents at least one selected from the group consisting of Zn ²⁺ and Cu ²⁺ , and M ₂ ²⁺ represents a group consisting of Mg ²⁺ , Fe ²⁺ and Ca ^2+. represents at least one selected, M ³⁺ is Cr ³⁺ represents at least one selected from the group consisting of Al ³⁺ and Fe ^3+, a ^n-represents an n-valent anion, in the formula The subscripts are 0 <x ≦ 0.5, 0 <y ≦ 1, and n is 1 or 2. ]
Item 2. The disinfectant which uses the baked product obtained by baking the composite of claim | item 1 at 400-1000 degreeC as an active ingredient.
Item 3. Item 3. A sterilization method comprising bringing the gas or liquid containing harmful microorganisms into contact with the sterilizer according to item 1 or 2.
Item 4. A germicide that regenerates a germicide characterized by separating and removing dead cells from the germicide by cell desorption or firing after contacting the germicide according to item 1 or 2 with a gas or liquid containing harmful microorganisms and sterilizing how to.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The fungicides of the present invention are effective against bacteria, phages, viruses and molds. Specific examples of bacteria include Escherichia coli, Pseudomonas aeruginosa, Salmonella, Klebsiella pneumoniae, Staphylococcus aureus, Micrococcus, MRSA, Corynebacterium, Bacillus subtilis and the like. Examples include viruses such as influenza virus, HIV, rabies virus, herpes virus, yellow fever virus, poliovirus, tobacco mosaic virus, pox virus, and molds such as black mold (Cladosporium), black mold mold (Aspergillus), Examples include Ketama mold (Ketomium), Blue mold (Penicillium), Kumonosukabi (Rhizopus), Red mold (Fusarium), Susukabi (Alternaria), Astragalus (Glyocradium), Black yeast-like fungus (Aureopasidium), and the like.
[0014]
In the general formula [1], M ₁ ²⁺ represents at least one selected from the group consisting of Zn ²⁺ and Cu ²⁺ .
[0015]
In the general formula [1], M ₂ ²⁺ represents at least one selected from the group consisting of Mg ²⁺ , Fe ²⁺ and Ca ²⁺ , and is preferably Mg ²⁺ .
[0016]
In the general formula [1], M ³⁺ represents at least one selected from the group consisting of Cr ³⁺ , Al ³⁺ and Fe ³⁺ , and is preferably Al ³⁺ .
[0017]
In the general formula [1], A ⁿ⁻ represents an n-valent anion (n = 1 or 2). That is, A ⁿ⁻ consists of only a monovalent or divalent anion, or consists of both a monovalent anion and a divalent anion. Examples of the monovalent anion include OH ⁻ , Cl ⁻ , NO ₂ ⁻ , NO ₃ ⁻ , F ⁻ , Br ⁻ , HCO ₃ ^{− and the} like, preferably Cl ⁻ or HCO ₃ ⁻ . The divalent anions, SO ₄ ^2-, CO ₃ ^2-, SO ₃ ^2- and the like, preferably CO ₃ ^2-.
[0018]
In the general formula [1], usually 0 <x ≦ 0.5, preferably 0.1 ≦ x ≦ 0.4, and more preferably 0.15 ≦ x ≦ 0.35.
[0019]
In the general formula [1], usually 0 <y ≦ 1, preferably 0.3 ≦ y ≦ 0.95, and more preferably 0.45 ≦ y ≦ 0.85.
[0020]
The calcium phosphates used in the present invention are not particularly limited as long as they are compounds mainly composed of phosphoric acid and calcium. For example, hydroxyapatite (Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ ), tricalcium phosphate (Ca ₃ (PO ₄ ) ₂ ), dicalcium phosphate (CaHPO ₄ ), octacalcium phosphate (Ca ₈ H ₂ (PO _{4 6} ), tetracalcium phosphate (Ca ₄ O (PO ₄ ) ₂ ) and the like.
[0021]
For example hydroxyapatite is known to be amphoteric ion exchanger, in the element species constituting the composition formula _{Ca 10 (PO 4) 6 (} OH) 2, in place of ^{Ca 2+, Na +, K +} , Sr ²⁺ , Ba ²⁺ , Pb ²⁺ , Zn ²⁺ , Cd ²⁺ , Cu ²⁺ , Mg ²⁺ , Fe ²⁺ , Mn ²⁺ etc., instead of PO ₄ ^3- , SO ₄ ^{2- _{, CO 3 2-, HPO 4 2-}} , AsO 4 2-, in SiO ₄ ^4-like, OH ^- instead ^{of, F -, Cl -, Br} -, and composition partially converted CO ₃ ^2-, etc. hydroxy Apatite-like compounds can also be used as calcium phosphates.
[0022]
The disinfectant of the present invention is not particularly limited as long as it is a disinfectant containing a composite composed of a specific copper ion or zinc ion-containing composite metal hydroxide represented by the above general formula [1] and calcium phosphates as an active ingredient. The disinfectant can be prepared, for example, by the following method.
[0023]
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 placed in a suspension in which a composite metal hydroxide is suspended. The desired disinfectant can be prepared by simultaneously dripping and subsequently filtering and washing the resulting precipitate, followed by drying or baking at a predetermined temperature.
[0024]
As the acidic aqueous solution, an acidic aqueous solution in which calcium phosphate is dissolved in an acid is preferable. First, by dissolving calcium phosphates in acid and reacting with the composite metal hydroxide suspension, firstly, the regenerated calcium phosphate itself has a large specific surface area and a large adsorption capacity for harmful microorganisms. This is advantageous in that the dispersibility of heavy metal ions in the bactericide is also increased.
[0025]
Examples of the acid used for dissolving calcium phosphates with acid include hydrochloric acid, nitric acid and the like, and 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 more preferably potassium hydroxide, A sodium hydroxide aqueous solution is mentioned.
[0026]
Moreover, as a calcination temperature at the time of preparation of a disinfectant, about 400 to 1000 ° C., desirably about 400 to 800 ° C., more desirably about 400 to 600 ° C. is desirable. The firing time varies depending on the firing temperature, but is usually 2 to 6 hours, preferably 3 to 5 hours.
[0027]
The thus obtained bactericidal agent is considered to be in a state in which the composite metal hydroxide having an excellent bactericidal ability is uniformly dispersed on the base calcium phosphate, and the affinity of the calcium phosphates for harmful microorganisms, It is considered that harmful microorganisms are efficiently sterilized by a synergistic effect with the sterilizing action of the sterilizing element itself. Therefore, in order to effectively carry out the present invention, increasing the content of calcium phosphates increases the affinity for microorganisms but decreases the bactericidal effect, and conversely increases the content of composite metal hydroxides. As a result, the bactericidal effect increases, but the affinity for microorganisms decreases, so it is extremely important to determine the appropriate blending ratio of the two.
[0028]
The blending ratio of the composite metal hydroxide in the composite is about 30 to 90 wt%, desirably about 40 to 90 wt%, more desirably when blending the composite metal hydroxide containing 6.94% as copper. Can be used by blending about 50 to 80 wt%. From this result, when blending composite metal hydroxides having different copper contents, the blending amount may be appropriately adjusted.
[0029]
At this time, the compounding amount of the sterilizing element in the composite is not particularly limited, but is usually about 2.0 to 7.0 wt%, desirably about 2.5 to 6.5 wt%, more desirably 3.5 to 5%. About 5 wt% can be blended.
[0030]
The disinfectant of the present invention may be used as a powder, and can also be used as an additive to a matrix of resin, paper, hydraulic cement, etc., or as a molded body and a filter medium by adding a binder. is there.
[0031]
When adding to the resin, in order to improve the familiarity between the fungicide and the resin, if necessary, the fungicide is an existing fatty acid, an alkali metal salt of a fatty acid, a silane-based, aluminum-based and titanate-based coupling agent, After the surface treatment with a surface treatment agent such as an anionic surfactant, a resin molded product may be used.
[0032]
The binder is not particularly limited, but polyacrylic hydrazide, polyacrylic resins such as aminated product of polyacrylamide including styrene / acrylic resin, celluloses such as ethylcellulose, carboxymethylcellulose, and cellulose acetate, and many kinds such as carrageenan. Examples thereof include organic binders such as saccharides, polyamide / epichlorohydrin resin, vinyl acetate / vinyl versatate copolymer, and inorganic binders such as alumina sol and silica sol, and preferably an aminated product of polyacrylamide. The blending amount of the binder is about 1 to 50% by weight, preferably about 5 to 30% by weight, and more preferably about 10 to 25% by weight with respect to the disinfectant.
[0033]
In the sterilization method of the present invention, examples of the gas used for the sterilization treatment include 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, examples include septic tank treated water, rainwater, lakes, rivers, and other environmental waters, waterworks, sewers, sewers, etc., and a bactericidal agent is added directly to the target liquid and processed in a batch system. However, from the viewpoint of increasing the processing efficiency, the column is filled with a bactericidal agent, and sterilization is performed by passing the target liquid through the column. What is necessary is just to adjust suitably the usage-amount of the disinfectant used in this case, the amount of gas ventilation, or the amount of liquid flow according to process conditions.
[0034]
In the method for regenerating a bactericide according to the present invention, the bactericidal agent after sterilization is treated with a single component or a mixed aqueous phosphate solution of two or more components as a cell desorbing solution, thereby detaching dead cells from the bactericidal surface The disinfectant itself can be recycled.
As the cell detachment solution, an aqueous phosphate solution such as sodium phosphate, sodium hydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, ammonium phosphate, ammonium hydrogen phosphate can be used, preferably sodium phosphate. Sodium hydrogen phosphate, potassium phosphate, and potassium hydrogen phosphate are preferred.
[0035]
As the phosphate ion concentration of the cell desorption solution at the time of cell desorption, PO ₄ ³⁻ ions can be used in the range from 1 mol / m ³ to the saturated concentration of each phosphate, but preferably 5 mol / m ^3. It is desirable to treat with the above phosphate ion concentration.
[0036]
Desorption of dead cells can also be performed by firing. That is, the bactericidal agent used for sterilization is not particularly limited, but is burned at 200 to 1000 ° C., preferably 400 to 600 ° C., to burn dead cells adhering to the surface of the bactericide and renew the surface of the bactericide. The disinfectant can be reused.
[0037]
【The invention's effect】
According to the present invention, the affinity of a bactericide for microorganisms is improved by combining calcium phosphates with a composite metal hydroxide containing copper ions or zinc ions having excellent chemical resistance and heat resistance to form a bactericide. In addition, microorganisms can be sterilized efficiently with a relatively small amount of copper ions or zinc ions.
[0038]
In addition, by using a phosphate aqueous solution as a cell desorption solution, it is possible to detach dead cells from the surface of the sterilizing agent after sterilization treatment and recycle the sterilizing agent surface to recycle it. It is also very useful as a mold fungicide.
[0039]
EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to this Example.
[0040]
【Example】
Example 1
As a calcium phosphate compound, 100 g of hydroxyapatite (trade name: HA-300BP; hereinafter abbreviated as CaP) manufactured by Tomita Pharmaceutical Co., Ltd. was dissolved in 1,000 cm ³ of 2N HCl to prepare a CaP solution.
[0041]
Subsequently, the beaker (5,000 cm ³⁾ to prepare the ion-exchanged water 2,500cm ^3, Mg-Cu-Al type composite metal hydroxide _{(Mg 0.736 Cu 0.087 Al 0.177 (} OH) 1.877 Cl 0.128 (CO 3) _{258 g of 0.086} ; Cu content of 6.94%) was added to form a suspension. To the suspension, 1,000 cm ³ of a CaP solution was added dropwise at room temperature while maintaining the pH of the reaction solution alkaline with a 6.25N-NaOH aqueous solution. The produced coprecipitate was filtered, washed with water, dried (80 ° C., 24 hours), and then pulverized to obtain a disinfectant (Cu content: 4.83%).
[0042]
Example 2
As a calcium phosphate compound, 500 g of CaP was dissolved in 2N-HCl 5000 cm ³ to prepare a CaP solution.
[0043]
Then, prepare the ion-exchanged water 4000 cm ³ beaker (20000cm ^3), Zn-Al type composite metal hydroxide of _{(Zn 0.730 Al 0.270 (OH)} 1.875 Cl 0.015 (CO 3) 0.190) was added 151g suspended Liquid. To the suspension, 5000 cm ³ of a CaP solution was added dropwise at room temperature while maintaining the pH of the reaction solution neutral with 6.25N-NaOH aqueous solution. The produced coprecipitate was filtered, washed with water, dried (80 ° C., 24 hours), and then pulverized to obtain a disinfectant.
[0044]
Example 3
A fungicide was prepared by firing the fungicide obtained in Example 1 at 500 ° C. for 3 hours.
[0045]
Example 4
The disinfecting ability of the disinfectant was evaluated according to the following test method.
[0046]
That is, after culturing Escherichia coli IAM12119 (hereinafter abbreviated as E. coli) at 37 ° C. in a Nutrient Broth liquid medium, E. coli was cultured in a 9 kg / m ³ -NaCl aqueous solution at an initial cell concentration ( N ₀ ) 1 × 10 ¹¹ cells / m ³ was added to obtain an E. coli sample solution.
[0047]
Next, a bactericidal agent is added to the E. coli sample solution (10 dm ³ ) to a concentration of 0.5 kg / m ³ , the mixture is transferred to an L-shaped tube, and then at 25 strokes / minute in the dark. Sterilized by shaking. Sampling was performed at 0, 15, 30, 60, 90, and 120 minutes, and the sample and 20 μg of L-cysteine were plated on Nutrient Broth agar medium, and colony counting method (Ind. Eng. Chem. Res., 34, 3920- 3926, 1996), the number of viable E. coli was calculated.
[0048]
The following formula is applied to all the data of the obtained E. coli survival rate up to 120 minutes, and the number of lethal reactions n and the apparent bactericidal rate constant (k ″) are applied by nonlinear least square method. Was calculated.
[0049]
[Expression 1]

[0050]
[In the above formula,
N _t : number of bacteria (cells) after sterilization time t minutes (cells / m ³ )
N ₀ : Number of bacteria (cells) at the start of the experiment (cells / m ³ )
N _t / N ₀ : Bacterial (cell) survival rate after t minutes k ″: Apparent bactericidal 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 bactericidal agent against bacteria, the larger the bactericidal rate constant k ″ value, the higher the bactericidal ability.
[0051]
Time course of E. coli survival rate for the bactericide 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 ) The change is shown in FIG. Incidentally, the amount of fungicide and composite metal hydroxides are each 0.36 kg / m ³ and 0.25 kg / m ^3, this amount of in order to verify the combined effect, as the copper in both samples Is the same.
As a result of obtaining the apparent sterilization rate constant (k ″) from FIG. 1, k ″ = 4.51 × 10 ⁻¹ min ^{−1 for} the bactericide (Example 1), and k ″ for the composite metal hydroxide. = 9.08 × 10 ⁻² min ⁻¹ , it was confirmed that the bactericidal rate of the bactericidal agent of the present invention is high, and that an excellent bactericidal effect can be obtained by combining calcium phosphates.
[0052]
Example 5
Example 1 except that the content of Mg—Cu—Al type composite metal hydroxide in the disinfectant was 27.2, 44.0, 64.4, 78.7 and 89.8% by weight. A fungicide was obtained in the same manner. Using the obtained bactericidal agent, the apparent bactericidal rate constant was determined in the same manner as in the above test method. The relationship between the content of the composite metal hydroxide and the apparent sterilization rate constant is shown in FIG. From FIG. 2, the maximum rate constant was obtained when the content of the composite metal hydroxide was about 65% by weight, so the Mg—Cu—Al type composite metal hydroxide was blended at about 60 to 70% by weight. Is the most desirable.
[0053]
Example 6
For the bactericidal agent obtained in Example 3, the apparent bactericidal rate constant was determined in the same manner as in the above test method. As a result, k ″ = 2.38 × 10 ⁻¹ min ⁻¹ and Mg—Cu—Al Compared with the apparent sterilization rate constant (k ″ = 9.08 × 10 ⁻² min ⁻¹ ) of the type composite metal hydroxide, it can be seen that the sterilization characteristics are clearly improved.
[0054]
Example 7
The method for regenerating a bactericide of the present invention can be carried out according to the following procedure.
[0055]
A glass column with a diameter of 5 mm is filled with glass wool as a filter medium, 140 mg of a bactericide is filled thereon, and a 0.9 wt% -NaCl aqueous solution 35 cm ³ adjusted to 1 × 10 ¹³ cells / m ³ as E. coli concentration is loaded. . The viable cell count and total cell count of the eluate were measured every time, and when the E. coli adsorption by the bactericide reached saturation, 25 ml of 30 mM NaH ₂ PO ₄ / Na ₂ HPO ₄ buffer solution adjusted to pH 6 was added. Elution of E. coli adsorbed on the bactericide is performed by adding to the column. After elution of E. coli, the NaCl-containing NaCl aqueous solution is loaded again. Thus, the bactericidal agent can be reused by repeating the cycle of E. coli adsorption, sterilization, and E. coli elution.
[0056]
The total number of cells is measured with an optical microscope using a phase difference hemocytometer, and the number of living cells is measured by the following method.
Viable cell count:
A sample solution of 0.1 cm ³ was taken and diluted to a predetermined concentration using 9.0 kg / m ³ -NaCl aqueous solution. This diluted solution 0.1 cm ³ was spread on a Nutrient Broth agar medium. Subsequently, the number of viable cells is calculated by culturing the agar medium in a thermostatic chamber at 37 ° C. for 24 hours and measuring the number of colonies formed.
[Brief description of the drawings]
1 is a graph showing the relationship between the bacterial (cell) survival rate and time of the bactericide and Mg—Cu—Al type composite metal hydroxide obtained in Example 1. FIG.
FIG. 2 is a graph showing the relationship between the content of Mg—Cu—Al type composite metal hydroxide during sterilization and the apparent sterilization rate constant.

Claims (6)

A bactericide containing a compound in which a compound represented by the following general formula [1] is uniformly dispersed on a base calcium phosphate as an active ingredient.
((M ₁ ²⁺ ) _y (M ₂ ²⁺ ) _1-y ) _1-x (M ³⁺ ) _x (OH ⁻ ) _{2 + xy} (A ⁿ⁻ ) _{y / n} [1]
[ ^Wherein M ₁ ²⁺ represents at least one selected from the group consisting of Zn ²⁺ and Cu ²⁺ , and M ₂ ²⁺ represents a group consisting of Mg ²⁺ , Fe ²⁺ and Ca ^2+. At least one selected, 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, The subscripts are 0 <x ≦ 0.5, 0 <y ≦ 1, and n is 1 or 2. ] The fungicide according to claim 1, wherein 6.94 wt% of copper is contained in the compound represented by the general formula [1], and 30 to 90 wt% of the compound represented by the general formula [1] is contained in the composite. . The disinfectant according to claim 1 or 2, wherein the compounding amount of the compound represented by the general formula [1] in the composite is 2.0 to 7.0 wt% in terms of the amount of copper and / or zinc. . A disinfectant containing a fired product obtained by firing the composite according to any one of claims 1 to 3 at 400 to 1000 ° C as an active ingredient. A sterilization method comprising bringing the gas or liquid containing harmful microorganisms into contact with the bactericidal agent according to any one of claims 1 to 4 . A sterilizing agent according to any one of claims 1 to 4 is contacted with a gas or liquid containing harmful microorganisms and sterilized, and then dead cells are separated and removed from the sterilizing agent by cell desorption or firing. A method of regenerating disinfectant.

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