JP2022034389A - Alkali aqueous solution having superior performance of sterilization, deodorization and the like - Google Patents

Abstract

To provide a solution that has much superior performance of sterilization and deodorization to those of the conventional one including calcined calcium materials, and also boasts superior biological safety.SOLUTION: An alkali aqueous solution has a calcium oxide-containing fired product produced by a specific method, which is dissolved in water.SELECTED DRAWING: None

Description

The present invention relates to an alkaline aqueous solution having excellent sterilizing and deodorizing properties.

In recent years, the demand for sterilizing or deodorizing products has increased significantly due to the improvement of the idea of hygiene in the general society. In addition, diseases caused by bacteria and viruses, including in-hospital infections, have become major social problems. For this reason, various sterilizing and deodorizing products are supplied to the market, and a wide variety of sterilizing and deodorizing agents are widely available.

Here, as these sterilizing and deodorizing agents, those derived from natural materials using scallops baked at high temperature have been proposed. For example, in Patent Document 1, coarsely crushed scallop shells are calcined at 1000 ° C to 1100 ° C for 2 to 4 hours, and finely calcined to an average particle size of 0.5 to 3 μm using a crushing device such as a wet bead mill crusher. The antiviral effect of the ground product is disclosed. Patent Document 2 discloses application of a supernatant of a 100-500 nm calcined nanopowder mixture obtained by calcining washed scallop shells at 1100 ° C. for 2 hours as an antiviral agent.

Prior patent documents

Japanese Unexamined Patent Publication No. 2008-179555 Japanese Unexamined Patent Publication No. 2012-066257

By the way, the present inventors conducted a verification test of a bactericidal deodorizing effect on various natural calcium materials including the above-mentioned patent documents, which were calcined and made into an aqueous solution. However, it was found that a sufficient sterilizing and deodorizing effect cannot be obtained with a conventional product that is simply fired. Therefore, it is an object of the present invention to provide an alkaline aqueous solution having far superior bactericidal and deodorant properties as compared with the case where a conventional calcined calcium material is used. In addition, it is also an object of the present invention to provide a liquid that is safe even when applied to the human body as a disinfectant / bactericidal agent, despite the damage of strong alkalis.

The present invention (1) is
A primary firing step of calcining a starting material containing calcium carbonate and / or calcium hydroxide to obtain a primary calcined product.
A fine crushing process for finely crushing the primary fired product,
The secondary firing step of re-baking the primary fired product to obtain the secondary fired product,
A secondary cooling process that cools the secondary fired product to the outside air temperature under a vacuum atmosphere or an inert gas atmosphere, and
An alkaline aqueous solution having a pH of 12 or more, which is obtained by dissolving the calcined product containing calcium oxide obtained in the above method in water.
When the alkaline aqueous solution is stirred in a beaker at a rotation speed of 100 rpm or more and 700 rpm or less for 1 hour under air at 25 ° C., it becomes cloudy, and when it is stirred under air at 25 ° C. for 24 hours, the pH drops to a safe range of 10 or less, and The causative substance of the cloudiness and the decrease in pH is an alkaline aqueous solution characterized by being calcium carbonate. Here, when the alkaline aqueous solution is sprayed on metal, plastic, wood, or paper under air at 25 ° C., it is preferable that the surface pH drops to a safe range of 10 or less within 20 minutes.
The present invention (2) is
The alkaline aqueous solution of the invention (1), wherein the starting material is a shell.
The present invention (3) is
The alkaline aqueous solution of the invention (2), wherein the shell is a scallop shell or an oyster shell.
The present invention (4) is
It has a cocoon-like dense particle surface structure and has a cocoon-like dense particle surface structure.
The calcium oxide content measured by differential thermogravimetric analysis (TG-DTA) is 95% by weight or more, and the calcium hydroxide content is 5% by weight or less.
The calcium element content measured by X-ray fluorescence analysis (XRF) is 95 atom% or more.
The calcium oxide content measured by X-ray diffraction analysis (XRD) is 95% by mass or more.
The average particle size is 20 μm or less,
A calcium oxide-containing calcined product obtained by calcining shells having a BET specific surface area of 0.5 m ² / g or more and 3.0 m ² / g or less is dissolved in water with an alkaline aqueous solution having a pH of 12 or more. There,
When the alkaline aqueous solution is stirred in a beaker at a rotation speed of 100 rpm or more and 700 rpm or less for 1 hour under air at 25 ° C., it becomes cloudy, and when it is stirred under air at 25 ° C. for 24 hours, the pH drops to a safe range of 10 or less.
Moreover, the causative substance of the cloudiness and the decrease in pH is an alkaline aqueous solution characterized by being calcium carbonate. Here, when the alkaline aqueous solution is sprayed on a metal, plastic, wood, or paper under air contact at 25 ° C., it is preferable that the surface pH drops to a safe range of 10 or less within 20 minutes.
The present invention (5)
The alkaline aqueous solution of the invention (4), wherein the shell is a scallop shell or an oyster shell.
The present invention (6) is
It is an alkaline aqueous solution according to any one of the above inventions (1) to (5), which is a disinfectant, a disinfectant or a deodorant.
The present invention (7) is the alkaline aqueous solution of the invention (6), wherein the object of application is a finger, skin or oral cavity.

According to the present invention, by using a special calcined calcium material, it is possible to provide an alkali having far superior sterilizing and deodorizing properties as compared with the case where a conventional calcined calcium material is used. Further, according to the present invention, it is possible to provide an alkaline aqueous solution that is safe even when applied to the human body as a disinfectant / bactericidal agent, despite the damage of strong alkalis.

It is an SEM photograph of Example 1. It is a deodorant test result of an Example. It is a sterilization test result of an Example / comparative example. It is a sterilization test result when the Example product was attached to the mask surface. Frozen-SEM image of alkaline aqueous solution and dry SEM image of alkaline aqueous solution and element mapping according to Examples. Specifically, the particle surface structure of the dried nanoparticles of the nanoparticles in the liquid at 12,000 times magnification (upper row) and the alkaline aqueous solution at 7,000 times magnification (lower row) was examined with an electro-decomposition scanning electron microscope. It was observed with the SEM image taken in. The upper right photo shows carbon, the lower left photo shows oxygen, and the lower right photo shows elemental mapping of calcium. It is the result of X-ray analysis showing the content of CaCO ₃ in the white powder generated from the dried alkaline aqueous solution. It is a figure showing that when a strong alkaline aqueous solution (pH = 12.8) is sufficiently exposed to air by stirring, the pH decreases to about 10 after 24 hours. It is the figure which showed the pH change at the time of spraying on the substance surface of an alkaline aqueous solution. The pH on the surface of each substance immediately after spraying was about 12.45, which was clearly lower than that of the original aqueous alkaline solution (pH = 12.8), and it is shown that the pH decreased rapidly with time thereafter. It is the figure which showed the pH change when the alkaline aqueous solution was sprayed on the palm and when the mouth was rinsed. The pH of the palm immediately after spraying was about 12.45, which was clearly lower than that of the original alkaline aqueous solution, and the pH after 1, 3 and 5 minutes decreased rapidly over time at 12, 11 and 10, respectively. Shows. In addition, the pH immediately after being put in the mouth was about 12.3, and the pH after 1, 3 and 5 minutes was 11.5, 10.6 and 10 or less, respectively, indicating that the pH decreased rapidly with time. It is a figure which showed the bactericidal effect of a test sample against contaminated water. It is a figure which showed the bactericidal effect of the test sample against the contaminated wood piece.

The alkaline aqueous solution according to the present invention can be obtained by dissolving a specific calcined calcium oxide product in water. Hereinafter, the fired product, the method for producing the fired product, the method for producing the alkaline aqueous solution, and the use of the alkaline aqueous solution (sterilizing deodorant) will be described in this order.

≪Baked product≫
The starting material for producing the baked product according to the present invention is a shell. The shell refers to a material containing calcium carbonate, which is formed as an outer shell by an organism generally called a shellfish and similar organisms (many of which belong to the subphylum Conchifera).

Shellfish are generally classified into single shellfish, bivalve shellfish, and snails. Examples of single shells include abalone, tokobushi and the like, examples of bivalves include scallops, oysters, freshwater clams, clams and clams, and examples of snails include turban shells, clams and clams. Any shell can be used as a starting material, but bivalve shells are preferred because they are easy to clean and reduce the risk of contamination. Among the bivalve shells, scallop shells and oyster shells are more preferable, and scallop shells are particularly preferable.

The average particle size of the fired product according to the present invention is preferably 20.0 μm or less, 15.0 μm or less, 10.0 μm or less, 8.0 μm or less, 6.0 μm or less, 5.0 μm or less, or 2.0 μm. It is as follows.

The average particle size of the fired product according to the present invention may be measured using a particle size distribution measuring device. Examples of such a device include CILAS (Aisin Nano Technologies Co., Ltd.). Further, the shape and surface structure of the fired product of the present invention can be obtained from an SEM image having an arbitrary magnification of 2000 to 10000 times.

The ratio of calcium element to the elements that can be measured by wavelength dispersive fluorescent X-ray analysis (XRF) of the fired product is 90 atom% or more, 91 atom% or more, 92 atom% or more, 93 atom% or more, 94 atom% or more, 95 atom%. As mentioned above, 96 atom% or more, 97 atom% or more, 98 atom% or more, and 99 atom% or more may be used.

In addition to calcium, fluorescent X-ray analysis (XRF) can measure the content of trace amounts of potassium, sulfur, phosphorus, magnesium, sodium, aluminum, silicon, strontium, and the like. Carbon and oxygen are not measured by the wavelength dispersive fluorescent X-ray analysis method (XRF).

As an apparatus for wavelength dispersive fluorescent X-ray analysis (XRF), RIX3100 (manufactured by Rigaku Denki Kogyo Co., Ltd.) can be mentioned.

The calcium oxide, calcium hydroxide, and calcium carbonate content ratios of the calcined product according to the present invention are estimated using a differential calorific value gravimetric analyzer. By differential thermal calorimetric analysis, the water content is estimated from the weight change around 300 ° C, the calcium hydroxide content is estimated from the weight change around 350 ° C, and the calcium carbonate content is estimated from the weight change around 600 ° C. can.

The weight retention ratio (also referred to as calcium oxide content ratio) at 30 to 1000 ° C. measured by the differential calorific value weight analysis (TG-DTA) of the fired product according to the present invention is preferably 75.0% by weight or more. , 80.0% by weight or more, 85.0% by weight or more, 90.0% by weight or more, 95.0% by weight or more, 99.0% by weight or more, 99.3% by weight or more, or 99.5% by weight or more. Is. The weight retention ratio is a percentage of the weight at 1000 ° C. to the weight at 30 ° C.

As an apparatus for differential thermogravimetric analysis (TG-DTA), for example, TGA851e (manufactured by METTLER TOLEDO) can be mentioned. The measurement of the differential thermogravimetric analysis is performed by raising the temperature from 30 ° C. to 1000 ° C. at a heating rate of 10 ° C./min in a nitrogen 100 mL / min air flow.

The purity measured by the X-ray diffraction analysis method (XRD) of the calcined product according to the present invention is preferably 90.0% by mass or more, 92% by mass or more, 94% by mass or more, 96% by mass or more, and 98% by mass. % Or more, 99% by mass or more, or 99.5% by mass or more.

As an apparatus for X-ray diffraction analysis (XRD), for example, X'Pert-PRO (Philips) can be mentioned.

The BET specific surface area of the fired product according to the present invention is preferably 0.2 m ² / g or more, 0.3 m ² / g or more, 0.4 m ² / g or more, 0.5 m ² / g or more, 0. 6 m ² / g or more, 0.7 m ² / g or more, 0.8 m ² / g or more, 0.9 m ² / g or more, or 1.0 m ² / g or more. On the other hand, preferably, 3.0 m ² / g or less, 2.8 m ² / g or less, 2.6 m ² / g or less, 2.4 m ² / g or less, 2.2 m ² / g or less, or 2.0 m. It is ² / g or less.

As an apparatus for analyzing the BET specific surface area, for example, ChemBET3000 manufactured by Quantachrome can be mentioned. The method for measuring the BET specific surface area is not particularly limited and may be measured under normally used conditions.

When the calcined product according to the present invention is hydrated with water vapor or the like, the surface structure changes due to the formation of calcium hydroxide and the formation of crevices and pores, and the surface structure changes due to the formation of calcium hydroxide. Occurs. In fact, the calcined shells having a calcium oxide content of 99% or more and an average particle size of 5 μm or less measured by the X-ray diffraction analysis method (XRD) are calcium oxide measured by the X-ray diffraction analysis method (XRD). Compared to shell-baked products with a content of 75 to 95%, a calcium hydroxide content of 5 to 20%, and an average particle size of 5 μm or less, the hydrophilicity and water suspension are poor at the beginning when water is added, and more. A large amount of precipitation occurs.

≪Manufacturing method of fired product≫
An example of the method for producing the above-mentioned fired product will be described below. As a matter of course, the above-mentioned fired product may be produced by a modified method of the following method or a completely different method.

The manufacturing method is executed in the order described in the following steps (1) to (6).
(1) Primary firing process for firing shells,
(2) A process of naturally cooling the fired primary fired product to the outside air temperature.
(3) The primary fired product is passed through each filter (air filter, micro mist filter, activated charcoal filter) to remove impurities, and is used as a high-pressure gas by a dry ultrafine crushing system (nanojet mizer) and / or a bug or cyclone dust collector. A process of uniformly pulverizing and collecting dust while injecting inert gas nitrogen gas or argon gas to replace and remove carbon dioxide and water vapor, in addition to dried air.
(4) Secondary firing step of secondary firing of the primary fired product,
(5) A step of naturally cooling the secondary fired product to the outside air temperature under low pressure conditions of 10 ³ Pa or less and / or under inert gas atmosphere conditions.
(6) The cooled fired product is carried out while the firing furnace opening / closing door is placed in a nitrogen gas or argon gas atmosphere (the outside of the firing furnace opening / closing door is also placed in an argon gas atmosphere) and filled with vacuum and / or nitrogen gas or argon gas. Packaging process

Hereinafter, each step will be described by taking the case where a scallop shell is used as a shell as an example.

In the present invention, the "outside air temperature" means the temperature of the surrounding environment in which the firing device (firing furnace) is placed. The temperature of the surrounding environment fluctuates depending on the area and place where the firing furnace is located, the time and the season, and although it cannot be defined uniformly, it is less than 100 ° C, less than 80 ° C, less than 60 ° C or less than 50 ° C. It may be interpreted as temperature.

The step (1) is a step of primary firing the starting material. In this firing, carbon and hydrogen derived from proteins and the like contained in the starting material are released, and calcium carbonate, which is the main component, is transformed into calcium oxide.

The firing temperature is preferably 1200 ° C. or higher, 1400 ° C. or higher, or 1600 ° C. or higher. By raising the temperature above these temperatures, organic substances can be sufficiently removed and the purity of calcium oxide becomes high. On the other hand, the upper limit of the firing temperature is not particularly limited as long as it is below the melting point of calcium oxide (about 2600 ° C.), but from the viewpoint of the load on the firing furnace and the energy cost, it is 1650 ° C. or lower, 1600 ° C. or lower, and 1550 ° C. or lower. , Or 1500 ° C. or lower is preferable. As a matter of course, the firing temperature may be constant or variable throughout the firing step as long as it is within the above range.

The firing time is preferably 3 hours or more, 4 hours or more, or 5 hours or more. On the other hand, the upper limit of the firing time is preferably 8 hours or less, 7.5 hours or less, 7 hours or less, or 6.5 hours or less.

Step (1) is carried out in an oxygen-containing atmosphere (usually in an air atmosphere) in order to remove organic substances. Carbon and hydrogen contained in proteins and the like react with oxygen to become carbon dioxide and water, which are released from the starting material.

The rate of raising the temperature from the outside air temperature to the firing temperature is not particularly limited, but is usually 100 to 500 ° C./hour, 150 to 450 ° C./hour, 200 to 400 ° C./hour or 250 to 350 ° C./hour. ..

The step (2) is a step of cooling the primary fired product fired by the step (1). Instead of actively cooling, the heating is stopped and the heat is dissipated to naturally cool the outside air temperature. The time required for the step (2) is considered to be affected by the temperature of the outside air temperature and the starting material, but is about 10 hours or more, 15 hours or more, and 20 hours or more.

The step (2) may be performed in any atmosphere. For example, it may be in an atmosphere of an inert gas (helium, nitrogen gas, etc.) or an atmosphere. Further, it may be the same as or different from the atmosphere of the step (1). It is preferable to cool in a low humidity environment to prevent hydration reaction.

It is understood that calcium oxide is cooled while maintaining high crystallinity in the process of gentle natural cooling.

In step (3), impurities are removed from the powdered calcined product through filters such as an air filter, micro mist filter, and activated carbon filter, and the particles are accelerated by high-pressure gas energy that is extremely dried by a special compressor. Fine pulverization is performed using a device (nanojet mizer; NJ-300-D) capable of realizing ultrafine pulverization by collision. In addition to dried air as a high-pressure gas, nitrogen gas or argon gas, which are inert gases, can also be used.

The step (4) is a secondary firing step of further firing the fired product. After firing the primary calcined product, it is considered that the proportion of calcium oxide decreases by reacting with water vapor in the atmosphere and carbon dioxide, which is a gas produced by calcining. Therefore, in order to maintain and improve the purity of calcium oxide, recalcination is performed.

The firing temperature in the secondary firing step is preferably 600 ° C. or higher, 700 ° C. or higher, 800 ° C. or higher, 850 ° C. or higher, 900 ° C. or higher, and 950 ° C. or higher. By firing at these temperatures or higher, calcium carbonate and calcium hydroxide can be sufficiently converted into calcium oxide. The firing temperature in the secondary firing step is about 2600 ° C. (melting point of calcium oxide) or less, and usually 1500 ° C. or lower, 1200 ° C. or lower, 1000 ° C. or lower.

The firing time in the secondary firing step is preferably 1 hour or longer, 1.5 hours or longer, or 2 hours or longer. On the other hand, from the viewpoint of the load on the firing furnace and the energy cost, 7 hours or less, 6 hours or less, 5 hours or less, 4 hours or less, and 3 hours or less are preferable.

The step (5) is a cooling step after the secondary firing. Natural cooling is performed under low pressure conditions of 10 ³ Pa or less and / or under inert gas conditions.

In the step (6), the inert gas is injected into the firing furnace to open and close the firing furnace. In this case, it is desirable to use a sliding door instead of a double door. It is easy to cover the inside state under the atmosphere of inert gas. Further, the fired product is vacuum-packed in this inert gas atmosphere.

The inert gas in the present invention is not particularly limited as long as it is a gas that does not react with calcium oxide, and examples thereof include helium gas, argon gas, nitrogen gas, and oxygen gas.

The above-mentioned one is only an example, and for example, the step (5) may be executed instead of the step (2). Step (5) may be omitted, and step (3) and step (6) may be continuously executed.

≪Manufacturing method of alkaline aqueous solution≫
The alkaline aqueous solution according to the present invention can be obtained by dissolving the calcium oxide-containing calcined product in water. At this time, it is preferable to gradually add the calcium oxide-containing calcined product while stirring the water so that the water does not boil, from the viewpoint of further enhancing the sterilizing / deodorizing effect. The alkaline aqueous solution may contain other components. For example, the addition of ethanol can be expected to improve volatility and bactericidal activity.

Here, the amount of the calcined product containing calcium oxide added is preferably 0.5% by mass or more, more preferably 3% by mass or more, based on the total mass of the aqueous solution. It is more preferable that it is by mass or more, and it is particularly preferable that it is 15% by mass or more. The upper limit is not particularly limited, and is, for example, 30% by mass. Further, it can be repeated 50 times or more, 100 times or more, and 200 times or more while maintaining the strong alkalinity of the aqueous solution consisting of the operation of adding water to the produced precipitate so as to have the same mass%.

Further, it is preferable to produce the alkaline aqueous solution at a low temperature (<10 ° C., the lower limit is, for example, 0 ° C.) under a substantially non-air contact state. The "substantially non-contact state with air" here means that the air in the system is reduced (for example, the volume of the system) by, for example, under reduced pressure or by introducing nitrogen or an inert gas (for example, argon). Refers to a state in which 10% by volume or less, 5% by volume or less, and 1% by volume or less) are applied. When the filtration step is included, the filtration is preferably pressure filtration or vacuum filtration. In this case, in the case of pressure filtration, it is preferable to pressurize with nitrogen or an inert gas (for example, argon).

≪Physical characteristics of alkaline aqueous solution≫
The pH of the alkaline aqueous solution according to the present invention is preferably 12.0 or more and 13.5 or less, and more preferably 12.5 or more and 12.9 or less. Here, the pH is a value measured with a pH meter at a temperature of 25 ° C. (for example, Monotaro Co., Ltd. waterproof handy pH meter PH-6011A-OM).

Further, the alkaline aqueous solution according to the present invention becomes cloudy when the alkaline aqueous solution is stirred in air at 25 ° C. for 1 hour, and after 24 hours, the pH is 1 or more (for example, 1.25 or more, 1.5 or more, 1). .75 or more; for example, 5 or less, 4 or less, 3 or less, 2 or less) has the property of decreasing (for example, pH is 11 or less, 10.5 or less, 10.25 or less, 10 or less) (the lower limit is particularly limited). For example, 7.0 or more, 8.0 or more). Here, when the alkaline aqueous solution is sprayed on metal, plastic, wood, or paper under air at 25 ° C., it is preferable that the surface pH drops to a safe range of 10 or less within 20 minutes. Here, "metal", "plastic", "wood" and "paper" are materials having a surface pH of 10 or less when the alkaline water at 25 ° C. is applied for 20 minutes. Further, "stirring" as used in the present specification and claims is, for example, by stirring with a Corning Digital Stirrer / Hotplate at room temperature (about 25 ° C.), a rotation speed of 500 rpm, and an AS ONE stirrer (diameter 5 mm × 50 mm). be. Here, the causative substance of the cloudiness and pH decrease is calcium carbonate. It can be said that such a property is excellent in biosafety from the following viewpoints. First, even if the alkaline aqueous solution according to the present invention is sprayed on various materials or the surface of the palm, or the alkaline aqueous solution according to the present invention is put in the mouth to clean the oral cavity, regardless of the strong alkali of the original alkaline aqueous solution. Instead, by reacting Ca ²⁺ (see Examples below), which is presumed to be present in an alkaline aqueous solution, with CO ₂ in the air to generate calcium carbonate, it is safe to drop to a safe pH region in a short time. It suggests that. Incidentally, the generated calcium carbonate is used as a gastric antacid and the like, and it is safe if swallowed in a small amount. Even if it is inhaled, it is presumed that there is no danger because it further reacts to form soluble calcium hydrogen carbonate.

≪How to use and use alkaline aqueous solution≫
The alkaline aqueous solution according to the present invention can be used, for example, as a bactericide or a deodorant in the form of a spray, foam, high-pressure mist injection, or the like. The object to be sterilized using the alkaline aqueous solution according to the present invention is not particularly limited, and can be used for any pathogen. More specifically, it can be used for eubacteria, archaea, fungi and viruses. Examples of eubacteria include gram-negative bacteria such as Escherichia coli, Pseudomonas aeruginosa, and Salmonella, and gram-positive bacteria such as staphylococcus. Examples of the fungus include Trichophyton, Candida and the like. Examples of the virus include influenza virus, norovirus, coronavirus and the like. Furthermore, since it is safe to apply to the human body, it may be applied to a bactericide or the like whose target is fingers, skin or oral cavity. In addition, in the claims and the present specification, detoxification of virus (antiviral activity) is also collectively referred to as "sterilization". Further, in the present invention, sterilization is a concept that not only means completely or almost completely detoxifying / removing an object, but also includes "bacteriostatic" that reduces the growth of the object. As described above, the alkaline aqueous solution according to the present invention can be used for virus removal, sterilization, and deodorization of general living spaces and daily necessities. For example, hand wash, entrance, toilet, bathroom, washroom, kitchen (washing dishes after washing with detergent, disinfecting sponge, etc.), dining table, food waste, disinfecting deodorant of trash can, water for humidifier, removing pet supplies It can be used for deodorizing bacteria, irrigating, rinsing the mouth, etc.

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

≪Manufacturing of calcined calcium oxide body≫
(Example 1)
The scallop shells were calcined at 1450 ° C. for 6 hours and naturally cooled to the outside air temperature. Impurities were removed from this through an air filter, a micro mist filter, and an activated carbon filter, and the mixture was finely pulverized by a dry ultrafine pulverization system (nanojet mizer). Then, it was calcined at 950 ° C. for 2 hours. This secondary fired product was naturally cooled to the outside air temperature under low pressure conditions (10 ^-4 Pa or less).

(Example 2)
The scallop shells were calcined at 1450 ° C. for 6 hours and naturally cooled to the outside air temperature. Impurities are removed through an air filter, a micro mist filter, and an activated carbon filter, and an inert gas such as nitrogen gas or argon gas is injected by a dry ultrafine pulverization system (nanojet mizer) to replace and remove carbon dioxide and water vapor. Finely ground.

(Example 3)
The scallop shells were calcined at 1100 ° C. for 4 hours and naturally cooled to the outside air temperature.

(Average particle size)
The average particle size of each powder was measured using a particle size distribution measuring device (CILAS; Aisin Nano Technologies Co., Ltd.).

(Calcium element content ratio)
The calcium element content ratio of each powder was measured using a fluorescent X-ray analyzer (RIX3100; manufactured by Rigaku Denki Co., Ltd.).

(Calcium oxide content ratio)
The calcium oxide content and the calcium hydroxide content of each powder were measured using a differential calorific value gravimetric analyzer (TGA851e; METTLER TOLEDO) and an X-ray diffractometer (X'Pert-PRO (Philips)). ..

(BET specific surface area)
The BET specific surface area of Examples 1 to 3 was measured using ChemBET3000 manufactured by Quantachrome.

(Electron microscope observation)
The fired product was coated with osmium metal with a neo-osmium coater (Neoc-STB; Meiwaforsis Co., Ltd., Tokyo) and then 3000 times using an electric field deradiation scanning electron microscope (JSM-6340F; JEOL Ltd., Tokyo). The surface shape in the dry powder state was analyzed based on the 10000 times SEM image.

In Examples 1 and 2, a cocoon-like dense surface structure was observed, and the BET ratio area was observed to be inversely proportional to the average particle size of the powder. Further, in the fired products according to Examples 1 and 2, adjacent particles are firmly fused to each other, cocoon-shaped dense crystals and particles are grown, and the reaction boundary area is reduced due to the blockage of pores. Observed (Fig. 1).

<< Preparation of alkaline aqueous solution according to Examples >>
200 g of the calcined product containing calcium oxide produced in Example 1 was added to 1 liter of water. At the time of this addition, the calcined product containing calcium oxide was gradually added while stirring the water so that the water did not boil, and an alkaline aqueous solution (BiSCaO Water) was prepared.

≪Deodorant effect of BiSCaO Water≫
1 wt% Brain Heart Infusion Bouillon (Nissui Pharmaceutical Co., Ltd.) was placed in the remaining hot water of the bath and cultured at 37 ° C. for 24 hours. At this point, the general viable bacteria and coliform bacteria were 7 × 10 ⁷ / mL and the coliform bacteria were 9 × 10 ⁶ / mL, respectively, and they were prepared as deodorant targets that generate a strong rotting odor. For an experiment on the deodorizing effect of BiSCaO Water, 25 mL of BiSCaO Water (stock solution, 2-fold, 4-fold diluted solution) was added to 25 mL of the above-mentioned contaminated water in a tube with a cap (50 mL), and the cap was closed. The cells were cultured at room temperature (23-27 ° C.) for 1 hour. The deodorizing effect on the deodorized object after the addition was measured and evaluated by using an odor meter (Handheld Odor Meter, OMX-SR, manufactured by Shinei Technology Co., Ltd.). As for the deodorizing effect on this deodorizing object, all deodorants had deodorizing activity. In particular, the deodorizing effect of CaO Water (stock solution) was excellent (Fig. 2).

≪Bactericidal effect of BiSCaO Water≫
1 w% of Brain Heart Infusion Bouillon (Nissui Pharmaceutical Co., Ltd.) was placed in the remaining hot water of the bath and cultured at 37 ° C. for 24 hours. At this point, the general viable bacteria and coliform bacteria were about 8 × 10 ⁷ / mL and about 7 × 10 ⁶ / mL, respectively, and were prepared as highly organic environment-contaminated water that generated a putrid odor. For experiments on the bactericidal effect of BiSCaO, etc., 25 mL of BiSCaO Water (stock solution, 2-fold, 4-fold diluted solution), isodine (0.05 wt%, (0.2 wt%, 0.8 wt% solution) was added, the cap was closed, and the mixture was cultured at room temperature (23-27 ° C.) for 1 hour. For each sample, the general viable cell count and coliform group count (Fig. 3) were used using a medium kit for measuring the general viable cell group and large intestine group number (compact dry "Nissui" TC and CF, manufactured by Nissui Pharmaceutical Co., Ltd., respectively). ) Was measured. As for the bactericidal effect on the sterilized object, all the bactericidal agents tested had bactericidal activity. In particular, BiSCaO Water (stock solution, 2-fold diluted) was sterilized below the detection limit for both general viable bacteria and coliform bacteria.

≪Bactericidal effect by BiSCaO Water spray on mask surface≫
1 w% of Brain Heart Infusion Bouillon (Nissui Pharmaceutical Co., Ltd.) was placed in the remaining hot water of the bath and cultured at 37 ° C. for 24 hours. At this point, the general viable bacteria and coliform bacteria were about 8 × 10 ⁷ / mL and about 7 × 10 ⁶ / mL, respectively, and were prepared as highly organic environment-contaminated water that generated a putrid odor. Using a spatula, 100 μL of highly contaminated water was applied to the front surface of a medical mask (Singer Surgical Mask ST, Utsunomiya Seisakusho Co., Ltd.) and left at room temperature for 1 hour (without spray). Before applying the contaminated water, 1 mL BiSCaO Water stock solution was sprayed on the coated portion and left at room temperature for 30 minutes to dry, then 100 μL of highly contaminated water was applied and left at room temperature for 30 minutes (pre-spray). After applying 100 μL of highly contaminated water and leaving it at room temperature for 30 minutes, 1 mL BiSCaO Water stock solution was sprayed on the coated part and left at room temperature for 30 minutes to dry (post-spray). Before applying the contaminated water, 1 mL BiSCaO Water stock solution was sprayed on the coated portion and left at room temperature for 30 minutes to dry, then 100 μL of highly contaminated water was applied and left at room temperature for 30 minutes. Then, 1 mL BiSCaO Water stock solution was further sprayed on the coated portion before application of contaminated water and left at room temperature for 30 minutes to dry, then 100 μL highly contaminated water was applied and left at room temperature for 30 minutes (pre- and post-spray). Each part was cut with scissors, 10 mL of pure water was added, and the mixture was vigorously stirred for 1 minute. For each sample, the general viable cell count and coliform group count (Fig. 4) were used using a medium kit for measuring the general viable cell group and large intestine group count (compact dry "Nissui" TC and CF, manufactured by Nissui Pharmaceutical Co., Ltd., respectively). ) Was measured. As a result, the post-spray was observed to have an almost complete sterilizing effect. Contaminated masks can also be almost completely sterilized by spraying BiSCaO Water, suggesting the possibility of reusing disposable masks.

≪Safety verification≫
<Preparation of BiSCaO Water>
100 g of the calcined calcium oxide according to Example 1 was added to 1100 mL of cold water (<10 ° C.), mixed gently, and left to stand for 30 minutes to prepare. The supernatant (1000 mL) was collected and transferred to a 100 L water tank. Another chilled 1000 mL of clean water was gently poured and mixed with the remaining calcium oxide calcined precipitate and the supernatant was collected in a tank. This process was repeated 50 times or more. The calcined calcium oxide (100 L in total) produced was colorless and transparent, and had a pH of about 12.8.

<Test method>
(SEM, element mapping test and CaCO ₃ content test)
Freezing SEM and element mapping tests were performed on the above BiSCaO Water and dry powders. Briefly, the above BiSCaO Water was frozen in liquid nitrogen, sheared, and observed under vacuum at −90 ° C. using a JEOL JSM 7100F SEM. The acceleration voltage was 10 KV, and a backscattered electron image was used as the detection signal. Element mapping was also performed using a JEOL JSM 7100F SEM-EM device. The CaCO ₃ content test in the dry powder of BiSCaO Water was carried out using an X-ray analyzer (Philips X'Pert-PRO; Philips Japan, Ltd. Japan).

(PH change test of BiSCaO Water in agitation under air)
200 mL of the above BiSCaO Water was placed in a 500 mL beaker and stirred at room temperature for 24 hours at a rotation speed of 350 rpm. After stirring at 0, 1, 2, 4, 8, 12 and 24 hours, each pH was measured using a tabletop meter (F-52, HORIBA, Ltd., Kyoto, Japan).

(Test of pH change of BiSCaO Water sprayed on the application target)
The BiSCaO Water (about 2 mL) was sprayed on the surface of a culture plate, an iron plate, a piece of wood and paper {Kimwipe ™} (about 5 x 5 cm). The pH of each wet surface was measured every minute for 20 minutes by a tabletop meter (LAQUA pH meter, F-74, HORIBA, Ltd., Kyoto) equipped with a strongly resistant microelectrode (9618S-10D; HORIBA, Ltd.). , Japan). Similarly, the above BiSCaO Water (about 1 mL each) was sprayed on the palm, and the pH of the skin surface was measured every 1 minute for 5 minutes. Further, the BiSCaO Water (about 7 mL) diluted 2-fold was contained in the mouths of 3 persons, and the mouths were rinsed for 5 minutes. A small amount (about 0.5 mL) was spit out every minute, and the pH was measured using a tabletop meter equipped with a highly resistant microelectrode as described above.

(Microbial killing activity test)
The microbial killing activity against coliform bacteria (CF) and general viable bacteria (TC) in the highly contaminated liquid and contaminated wood pieces of the diluted BiSCaO Water, which was stirred for 12 hours and brought into contact with air, was compared and examined. Equal volumes of test sample and highly contaminated water were mixed and incubated for 15 minutes at room temperature before colony forming units (CFU / mL) were measured. In the disinfection assay for contaminated wood pieces, add wood pieces to each 10 mL of disinfectant, gently vortex for 15 minutes, then vigorously vortex for 2 minutes to TC with 10 mL of clean water from the contaminated wood pieces. Released CF. To count the number of minimum colony forming units (CFU), 1 mL of each mixture was added to a TC or CF simple dry medium plate (Nissui Pharmaceutical Co. Ltd., Tokyo, Japan) and the plate was added at 37 ° C. Incubator (A1201; Ikuta Sangyo Co., Ltd., Ueda, Nagano Prefecture) was incubated for 24 hours. Seeding and counting were performed as a set of four technical replicas (N = 4).

<Result>
(SEM, element mapping test and CaCO ₃ content test)
The above BiSCaO Water, which is colorless and transparent and has a pH of about 12.8, was sprayed onto a smooth metal, plastic or wood surface and dried to obtain a white fine powder. No tinder phenomenon was observed in the BiSCaO Water at the time of production, and nanoparticles were not present in the BiSCaO Water even in the frozen-SEM. When the BiSCaO Water was exposed to air for one week or longer, nanoparticles (100-200 nm) appeared in the BiSCaO Water and they aggregated to form larger fine particles (400-800 nm) (Fig. 5.). Upper photo). When further dried, a large number of fine particles are aggregated and exist (Fig. 5. Lower photo). Elemental mapping revealed that both particles consisted primarily of calcium, oxygen and carbon. When the dry powder was suspended in pure water, the powder was insoluble and the pH of the supernatant was less than 10.0, suggesting that the fine particles were calcium carbonate produced by the interaction of Ca ²⁺ and CO ₂ . Furthermore, most of the white fine powder generated in the dried BiSCaO Water was found to be calcium carbonate (CaCO ₃ ) by the X-ray analysis system (Fig. 6).

(PH change test of BiSCaO Water in agitation under air)
When the BiSCaO Water placed in a beaker is stirred and brought into contact with air, turbidity is generated after one hour, turbidity is generated over time, and the pH drops from 12.8 over time as shown in FIG. I started. After 24 hours, the pH was 10.1. The dry powder was insoluble and the pH of the supernatant was 9.6, suggesting that the fine particles were calcium carbonate (CaCO ₃ ) produced by the interaction of Ca ²⁺ and CO ₂ .

(Test of pH change of BiSCaO Water sprayed on the application target)
The BiSCaO Water was sprayed on the surface of a plastic plate, an iron plate, lumber, and paper {Kimwipe ™}, and the change in pH was measured (FIG. 8). The pH was measured using a tabletop pH meter equipped with a microToug pH electrode. On all surfaces, the pH immediately after spraying was 12.62 ± 0.2, which was clearly lower than that of the undiluted solution (= 12.8), and after 3 minutes, the pH was well below 12. After 10 minutes, the pH was well below 11 on all surfaces. After an additional 17 minutes, the pH was all below 10 on the surface. Similarly, 2 mL of the undiluted solution of BiSCaO Water was sprayed on the palm, and immediately after that, the pH was measured every minute for 5 minutes using a tabletop pH meter equipped with a microToup electrode. The pH immediately after spraying was 12.45, which was clearly lower than that of the undiluted solution, and after 1 minute, the pH was 12. After 3 minutes, the pH was about 11 and after 5 minutes, the pH was 10 (FIG. 9, left). In this way, when the undiluted solution of BiSCaO Water is sprayed on the palm, it shows strong alkalinity with a pH exceeding 12 only for the first minute, and after that, there is a great risk even in a damp state before drying. It became clear that the amount of alkaline water was reduced. As a result of using the undiluted solution of BiSCaO Water for disinfecting the hands on the monitor, no side effects such as rough skin have been reported. Furthermore, 7 mL of BiSCaO Water (pH 12.5) diluted twice with tap water was contained in the mouth, and a part (about 1 mL) was taken out every minute immediately after that, and the pH was a tabletop pH equipped with a microToup electrode. It was measured using a meter. The pH immediately after being put in the mouth was 12.3, which was clearly lower than that of the undiluted solution, and after 1 minute, the pH was 11.5. After 3 minutes, the pH was 10.6, and after 5 minutes, the pH was 10 or less (Fig. 9, right).

(Microbial killing activity test)
When the remaining bath water is cultured in 10% DMEM + BSA (0.1 wt%) for 24 hours at 37 ° C, TC and CF are 80 ± 11 CFU / mL and 32 ± 7 CFU / mL to 9.8 ± 3.1 (× 10 ⁷ ), respectively. ) CFU / mL and 2.1 ± 0.5 (× ¹⁰⁷ ) CFU / mL increased contaminated water was obtained. Undiluted and 2-fold diluted (finally 2-fold and 4-fold, respectively) The sterilization of contaminated water with BiSCaO Water drastically reduced the amount below the detection limit. However, sterilization of contaminated water by 4-fold dilution (finally 8-fold dilution) of BiSCaO Water left a considerable amount of growth TC and CF, although each showed weak sterilization ability (FIG. 10). In contrast, BiSCaO Water, which was agitated for 12 hours and brought into contact with air, showed sterilizing ability even when undiluted (eventually 2-fold diluted), but left a considerable amount of growing TC and CF. (Fig. 10). The count was performed as a set of four technical replicas (n = 4). Furthermore, the TC and CF released from the contaminated wood pieces were 2.5 ± 0.6 ( ^x107 ) CFU / mL and 2.9 ± 1.4 ( ^x106 ) CFU / mL, respectively. Undiluted and 2-fold diluted (finally 2-fold and 4-fold, respectively) sterilization of contaminated wood pieces with BiSCaO Water left a small amount of growth TC and CF, respectively, showing sterilization ability (FIG. 11). In contrast, BiSCaO Water, which was agitated for 12 hours and brought into contact with air, showed sterilizing ability even when undiluted (eventually 2-fold diluted), but left a considerable amount of growing TC and CF. (Fig. 11). The count was performed as a set of four technical replicas (n = 4).

≪Summary (safety) ≫
To summarize the above, BiSCaO Water is colorless and transparent, and has a pH of 12.8. A smooth surface of metal or plastic can be sprayed to dry and a white powder coating can be applied. Dry scanning electron microscope (SEM) images of BiSCaO Water showed images of fine particles (1-2 μm) agglomerated with each other. Freezing-SEM observations showed that CaO nanoparticles (100-200 nm) aggregated to produce larger particles (400-800 nm) in BiSCaO Water. In addition, the composition of the micro / nanoparticles generated in BiSCaO Water exposed to air and the white fine powder generated when air-dried by the element mapping method is composed of oxygen, carbon and calcium, and is calcium carbonate. Was suggested (Fig. 5). Furthermore, although this white fine powder is insoluble, the pure water suspension has a pH <10, and the results of X-ray analysis also showed that it was calcium carbonate (FIG. 6). BiSCaO Water becomes cloudy in one hour when stirred and sufficiently exposed to air. After another 24 hours, the pH drops to about 10 (Fig. 7). This result indicates that the produced insoluble fine particles are calcium carbonate (CaCO ₃ ) produced by the reaction of Ca ²⁺ in BiSCaO Water and CO ₂ in the air. Also, an important concern in the bioapplication of BiSCaO Water is the strong alkalinity with a pH above 12.7. BiSCaO Water was sprayed on the surface of a material such as a plastic plate, an iron plate, lumber or paper, and the pH of the moist surface was measured with a tabletop pH meter using a micro tough electrode. The pH of the surface immediately after spraying is 12.6 ± 0.02 on the entire surface, which is much lower than the pH of the original BiSCaO Water (12.8). Further, after 3 minutes and 10 minutes, the pH was below 12 and 11, respectively, and after 20 minutes, the pH was below 10 on the entire surface (FIG. 8). Similarly, when BiSCaO Water was sprayed on the palm, it became about 12 after 1 minute, which was much lower than the pH (12.8) of the original BiSCaO Water (FIG. 9, left). Then, after 5 minutes, the pH dropped to 10. Also, double the amount of BiSCaO Water (pH = 12.3) in the mouth with tap water, and after 1 minute, 3 minutes and 5 minutes when rinsing the mouth, the pH is 11.5, 10.6 and 10 or less, respectively. Decreased (Fig. 9, right). No side-effect disorders were observed in the hands or mouth in this experiment. This result shows that even if BiSCaO Water is sprayed on various materials or the surface of the palm or put in the mouth to wash the oral cavity, it is efficiently contained in BiSCaO Water despite the strong alkalinity of the original BiSCaO Water. By producing calcium carbonate by the reaction of Ca ²⁺ and CO ₂ in the air, it drops to a safe pH range in a short time, suggesting that it is safe. Further, as for the generated calcium carbonate, the calcium carbonate powder is used as a gastric antacid or the like, and it is safe if swallowed in a small amount. It is also understood that even if inhaled, there is no danger because it further reacts to form soluble calcium hydrogen carbonate.

Claims (7)

A primary firing step of calcining a starting material containing calcium carbonate and / or calcium hydroxide to obtain a primary calcined product.
A fine crushing process for finely crushing the primary fired product,
The secondary firing step of re-baking the primary fired product to obtain the secondary fired product,
A secondary cooling process that cools the secondary fired product to the outside air temperature under a vacuum atmosphere or an inert gas atmosphere, and
An alkaline aqueous solution having a pH of 12 or more, which is obtained by dissolving the calcined product containing calcium oxide obtained in the above method in water.
When the alkaline aqueous solution is stirred in a beaker at a rotation speed of 100 rpm or more and 700 rpm or less for 1 hour under air at 25 ° C., it becomes cloudy, and when it is stirred under air at 25 ° C. for 24 hours, the pH drops to a safe range of 10 or less and 25 ° C. When sprayed on metal, plastic, wood, or paper under the above atmosphere, the surface pH drops to a safe range of 10 or less within 20 minutes, and the causative substance of the cloudiness and pH drop is calcium carbonate. Alkaline aqueous solution. The alkaline aqueous solution according to claim 1, wherein the starting material is a shell. The alkaline aqueous solution according to claim 2, wherein the shell is a scallop shell or an oyster shell. It has a cocoon-like dense particle surface structure and has a cocoon-like dense particle surface structure.
The calcium oxide content measured by differential thermogravimetric analysis (TG-DTA) is 95% by weight or more, and the calcium hydroxide content is 5% by weight or less.
The calcium element content measured by X-ray fluorescence analysis (XRF) is 95 atom% or more.
The calcium oxide content measured by X-ray diffraction analysis (XRD) is 95% by mass or more.
The average particle size is 20 μm or less,
A calcium oxide-containing calcined product obtained by calcining shells having a BET specific surface area of 0.5 m ² / g or more and 3.0 m ² / g or less is dissolved in water with an alkaline aqueous solution having a pH of 12 or more. There,
When the alkaline aqueous solution is stirred in a beaker at a rotation speed of 100 rpm or more and 700 rpm or less for 1 hour under air at 25 ° C., it becomes cloudy, and when it is stirred under air at 25 ° C. for 24 hours, the pH drops to a safe range of 10 or less and 25 ° C. When sprayed on metal, plastic, wood, or paper under the air, the surface pH drops to a safe range of 10 or less within 20 minutes, and the causative agent of cloudiness and pH drop is calcium carbonate. Aqueous solution. The alkaline aqueous solution according to claim 4, wherein the shell is a scallop shell or an oyster shell. The alkaline aqueous solution according to any one of claims 1 to 5, which is a disinfectant, a disinfectant or a deodorant. The alkaline aqueous solution according to claim 6, wherein the application target is fingers, skin or oral cavity.

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