Antibacterial and antiviral aqueous solutions, and methods for producing the aqueous solutions.

Abstract

The present invention provides an aqueous solution that does not discolor when used in products, has sufficient long-term stability, and possesses at least one of high antibacterial and antiviral properties, as well as a method for producing the same. [Solution] This aqueous solution contains metallic elements belonging to groups 11 to 15 of the periodic table and water-soluble organic matter. The pH of this aqueous solution is 2.0 to 9.0. The metallic elements belonging to groups 11 to 15 of the periodic table contained in this aqueous solution have at least one of antibacterial and antiviral properties.

Description

[Technical Field]

[0001] This invention relates to an aqueous solution containing a metal element, and also to a method for producing the aqueous solution. [Background technology]

[0002] Traditionally, various problems have been pointed out regarding the living environment. In Japan, with its high temperature and humidity, food poisoning caused by bacteria and diseases caused by bacteria and viruses in living spaces are frequent occurrences. Our living environment contains many items that are touched not only by individuals but also by a large number of people, such as clothing, tableware, cutting boards, furniture, home appliances, smartphones, ATMs, ticket machines and other touch-panel displays, doorknobs, and handrails on trains and buses. The problem is that the surfaces of these items are contaminated with bacteria such as E. coli and Staphylococcus aureus, as well as various viruses, and from a hygienic standpoint, antibacterial and antiviral properties are required.

[0003] Regarding the imparting and removal of antibacterial and antiviral properties to these products, it has been conventionally known to apply antibacterial or antiviral agents to the surface of the products, or to clean or remove them with cleaning agents or wet wipes containing antibacterial or antiviral properties. For example, with organic antibacterial or antiviral agents, the application itself is relatively easy, but there is a risk that the coating may be damaged by solvents, and there are problems with the durability of the antibacterial performance in terms of adhesion to the coating and scratch resistance. On the other hand, with inorganic antibacterial or antiviral agents, if they are present in the product, the durability of the antibacterial and antiviral performance can be expected.

[0004] For this reason, precious metals have long been known as antibacterial materials, and among them, silver and copper have high antibacterial properties and are used as antibacterial agents in a wide range of applications. In particular, when present as silver ions, they can exhibit very high antibacterial and antiviral properties. However, in the form of silver ions, discoloration occurs due to reactions with other materials when mixed with other materials, and morphological changes occur due to the deposition of silver oxide or silver hydroxide due to oxidation. In addition, antibacterial compositions are known in which antibacterial active metal components such as silver, zinc, and copper with antibacterial properties are supported on powders such as silica gel, composite oxides, and titanium oxide, or on colloidal particles. Specifically, antibacterial compositions in which silver ions and zinc ions are exchanged on zeolite particles (for example, Patent Document 1), and compositions in which silver, etc., is supported on silica alumina or silica alumina zirconia composite oxide particles (for example, Patent Documents 2 and 3) are known. In addition to these particles, other known antimicrobial materials include liquid compositions of silver ion complexes using cationic polymers having multiple amine structures within the molecule as ligands (for example, Patent Document 4), and organometallic complexes using organic substances having carbonyl groups, such as β-diketones, as ligands (for example, Patent Document 5). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2008-001557 [Patent Document 2] Japanese Patent Application Publication No. 7-033616 [Patent Document 3] Japanese Patent Publication No. 2010-273698 [Patent Document 4] Japanese Patent Publication No. 2020-007277 [Patent Document 5] Japanese Patent Publication No. 2014-084300 [Overview of the project] [Problems that the invention aims to solve]

[0006] In products and cleaning agents containing antibacterial particles or ions, if the particle size is large, such as around micrometers, a large amount of particles must be included to obtain the desired antibacterial performance, which may reduce the stability of the coating solution for processing the products or the cleaning agent for the products containing the particles or ions (for example, Patent Document 1). On the other hand, if the size of antibacterial particles is smaller than the micrometer order, such as on the nanometer order, they have higher dispersibility and a larger number of particles per unit amount, so sufficient antibacterial performance can be easily achieved even with a small amount of particles. However, if silver, a metallic element exhibiting antibacterial properties, is present in the particles as Ag2O, there is a risk that when mixed with tap water containing chlorine, etc., or with surfactants, the Ag2O may react with other compositions and cause discoloration, or the particles may aggregate during solvent dispersion due to their non-uniformity. Furthermore, considering the recent concerns about nanomaterial risks, there is hesitation in introducing such products to the market (for example, Patent Documents 2 and 3). On the other hand, liquid compositions of silver ion complexes using cationic polymers having multiple amine structures in the molecule as ligands exhibit high dispersibility and a large number of silver ions per unit amount, thus easily demonstrating antibacterial properties. However, when mixed with other materials, there is a risk of discoloration due to reactions with other materials, or morphological changes due to the precipitation of silver oxide or silver hydroxide accompanying oxidation (for example, Patent Document 4). Furthermore, antibacterial materials using organometallic complexes with organic substances having carbonyl groups, such as β-diketones, as ligands may have excessively high stability, resulting in insufficient antibacterial properties, or they may form discolored complexes (for example, Patent Document 5).

[0007] Therefore, there is a demand for aqueous solutions that do not cause discoloration when used in supplies or cleaning agents, have sufficient storage (over time) stability, and possess high antibacterial and antiviral properties. [Means for solving the problem]

[0008] To solve these problems, we discovered the following aqueous solution.

[0009] This aqueous solution contains a metal element belonging to Groups 11 to 15 of the periodic table and an organic substance soluble in water. The pH of this aqueous solution is 2.0 to 9.0.

[0010] This aqueous solution has high dispersibility and at least one of high antibacterial performance and antiviral performance. According to a coating solution containing such an aqueous solution, coloring is suppressed, and a film having at least one of high antibacterial performance and antiviral performance can be obtained.

[0011] In order to obtain this aqueous solution, the following production method was found. First, an aqueous solution of a metal compound containing a metal element belonging to Groups 11 to 15 of the periodic table and an aqueous solution of an organic substance soluble in water are prepared. Next, the two are mixed at 10 to 50°C.

Mode for Carrying Out the Invention

[0012] The aqueous solution according to the present invention (hereinafter, the aqueous solution according to the present invention may be simply referred to as "aqueous solution") contains a metal element belonging to Groups 11 to 15 of the periodic table and an organic substance soluble in water. The pH of this aqueous solution is 2.0 to 9.0. The metal element belonging to Groups 11 to 15 of the periodic table has at least one of antibacterial property and antiviral property (hereinafter, the property of "at least one of antibacterial property and antiviral property" according to the present invention may be simply referred to as "antibacterial / antiviral property").

[0013] Among the metallic elements of groups 11 to 15 of the periodic table, examples of metallic elements with high antibacterial and antiviral properties include Cu, Ag, Zn, Ga, Sn, Pb, and Bi. These metallic elements may exist individually or in combination in aqueous solutions. Of these metallic elements, Cu, Ag, Zn, Sn, and Bi are more preferred, and Cu, Ag, and Zn are even more preferred. Ag is particularly preferred from the viewpoint of wastewater regulations and toxicity. These metallic elements are preferably present as ions or complexes. In such forms, their antibacterial and antiviral properties can be effectively exhibited. Here, examples of raw materials for the ions include metallic salts of these metallic elements, such as nitrates, sulfates, acetates, and carbonates. Among these, nitrates and sulfates, which have high solubility in water, are preferred.

[0014] These metal elements are preferably present in the aqueous solution at a concentration of 0.0001 to 1.2% by mass, in terms of metal equivalent. If the content of metal elements is less than 0.0001% by mass, sufficient antibacterial and antiviral performance may not be obtained. Conversely, if it exceeds 1.2% by mass, the antibacterial and antiviral performance will not further improve, and in some cases, the metal elements and organic matter may become unstable, making it easier for the metal elements to be released from the complex or for discoloration to occur. The content of these metal elements is more preferably 0.005 to 1.2% by mass, and even more preferably 0.05 to 1.0% by mass.

[0015] Examples of organic substances included in the aqueous solution include organic substances and their salts, heterocyclic compounds, or mixtures thereof. Furthermore, it is preferable that the structure of the organic substance contains at least one of a hydroxyl group and a carboxyl group. When such organic substances are included in the aqueous solution together with the aforementioned metal elements, the organic substances act as protective agents for the metal elements, suppressing oxidation of the metal elements and reducing their antibacterial and antiviral properties. These organic substances may exist individually or in combination in the aqueous solution.

[0016] Examples of these organic substances include gelatin, polyvinyl alcohol, polyvinylpyrrolidone, vinyl acetate, polyacrylic acid, and carboxylic acid compounds. Examples of carboxylic acid compounds include anthic acid, hydroxyanthracenecarboxylic acid, hydroxynaphthoic acid, gallic acid, cresotic acid, parahydroxybenzoic acid, ortho-acetylsalicylic acid, malic acid, mandelic acid, gluconic acid, citric acid, tartaric acid, lactic acid, benzenecarboxylic acid, formic acid, acetic acid, butanoic acid, propionic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, 9-hexadecenoic acid, heptadecanoic acid, octadecanoic acid, glycolic acid, L-ascorbic acid, fumaric acid, maleic acid, adipic acid, ethylenediaminetetraacetic acid, and their salts. Among these, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, ligluconic acid, citric acid, tartaric acid, lactic acid, L-ascorbic acid, ethylenediaminetetraacetic acid, and their salts are preferred as substances that form complexes with the aforementioned metal elements.

[0017] The ratio (L / M) of the molar concentration (L) of the "water-soluble organic matter" to the molar concentration (M) of the aforementioned metal element in this aqueous solution is preferably 0.1 to 30. When the ratio (L / M) is within this range, the metal element and the organic matter can exist stably. Furthermore, they can also exist stably as a complex of the metal element and the organic matter. Therefore, high antibacterial and antiviral properties can be achieved simultaneously with the suppression of discoloration due to oxidation of the metal element.

[0018] Here, if the ratio (L / M) is less than 0.1, the metal element is in excess of the organic matter, resulting in insufficient protection of the metal element by the organic matter, which may cause the metal element to oxidize and discolor. Also, if the complex formation between the metal element and the organic matter is insufficient, the metal element may oxidize and discolor. Furthermore, if organic matter other than the aforementioned organic matter is present in the aqueous solution, the metal element may become unstable, which may cause the metal element to oxidize and discolor. Conversely, if it exceeds 30, the protective effect of the organic matter on the metal element may be too high, which may result in insufficient antibacterial and antiviral properties. This ratio (L / M) is more preferably 0.3 to 10, even more preferably 1.0 to 10, and particularly preferably 1.0 to 5.0.

[0019] The pH of the aqueous solution is between 2.0 and 9.0. This allows metal elements and organic substances to exist stably. Furthermore, they can also exist stably as complexes between metal elements and organic substances. Therefore, it is possible to achieve both high antibacterial and antiviral properties and suppress discoloration caused by the oxidation of metal elements.

[0020] Here, if the pH of the aqueous solution is less than 2.0, the metal elements tend to exist as metal ions, and although antibacterial and antiviral properties are exhibited, complex formation between the metal elements and organic substances may become difficult. Also, if organic substances other than those mentioned above are present in the aqueous solution, the metal elements may become unstable and oxidize, causing discoloration. Conversely, if the pH exceeds 9.0, the metal elements may oxidize and discolor, or precipitate as hydroxides. The pH is preferably 2.0 to 8.5, more preferably 3.8 to 7.0.

[0021] The aqueous solution preferably has a dissolved oxygen content of 3.0 mg / L or less. When the dissolved oxygen content is within this range, the precipitation of metal elements as hydroxides and oxidation causing discoloration are suppressed, thereby improving stability.

[0022] If the dissolved oxygen level exceeds 3.0 mg / L, there is a risk that metal elements may precipitate as hydroxides or oxidize and become discolored. The dissolved oxygen level is more preferably 2.0 mg / L or less, and even more preferably 1.0 mg / L or less.

[0023] The aqueous solution preferably contains non-oxidizing bubbles with an average bubble diameter of 40 nm to 10 μm. These bubbles include at least one of so-called nanobubbles with a bubble diameter of 40 to 100 nm (0.1 μm) and so-called microbubbles with a bubble diameter of 0.1 to 10 μm, and preferably both. When the average bubble diameter is within this range, bubbles accumulate around metal elements and organic matter, improving the stability of the aqueous solution. Furthermore, when the bubbles come into contact with bacteria or viruses, they burst, and the resulting impact makes it easier to kill the bacteria and viruses.

[0024] Here, if the average bubble diameter is less than 40 nm, the bubbles are small and have a high surface area, which may prevent them from existing stably. Furthermore, even if they do exist, when the bubbles burst, there is a risk of decomposition of organic matter as well as bacteria. Conversely, if the average bubble diameter exceeds 10 μm, it is difficult for the bubbles to exist around metal elements and organic matter, and stability is not enhanced. Also, because the surface area of ​​the bubbles is small, the frequency of contact with bacteria and viruses is low, which may reduce the effectiveness of killing bacteria and viruses. The lower limit of this average bubble diameter is more preferably 50 nm, even more preferably 60 nm, and particularly preferably 65 nm. The upper limit of the average bubble diameter is more preferably 500 nm, even more preferably 350 nm, and particularly preferably 200 nm.

[0025] The gas used to form the bubbles is preferably a non-oxidizing gas in order to suppress the oxidation of metal elements. Specifically, nitrogen, hydrogen, and at least one of a noble gas are preferred.

[0026] The amount of bubbles contained in the aqueous solution is 1.0 × 10⁻⁶. 3 ~1.0×10 11It is preferably 1.0×10 11 particles / mL. When the content of the air bubbles is within this range, air bubbles gather around metals and organic substances, improving the stability of the aqueous solution. Also, when air bubbles come into contact with bacteria or viruses, the air bubbles burst, and due to the impact, it becomes easier for the bacteria and viruses to die.

[0027] Here, when the content of the air bubbles is less than 1.0×10 3 particles / mL, the amount of air bubbles gathering around metals and organic substances is small, and the stability of the aqueous solution does not particularly improve. Also, there is a possibility that the effect of making it easier for bacteria and viruses to die due to the impact of the bursting of air bubbles when they come into contact with bacteria or viruses becomes low. Conversely, when the content of the air bubbles exceeds 1.0×10 11 particles / mL, since the number of air bubbles per unit volume is excessive, air bubbles gather around metals and organic substances, and although the stability of the aqueous solution is high, when air bubbles come into contact with bacteria or viruses, the air bubbles burst, and the effect of making it easier for the bacteria and viruses to die due to the impact does not increase further. Rather, there is a possibility that an increase in production cost due to using such air bubbles becomes a problem. The lower limit of the content of these air bubbles is more preferably 1.0×10 4 particles / mL or more, still more preferably 1.0×10 5 particles / mL or more, particularly preferably 1.0×10 8 particles / mL or more. The upper limit is more preferably 5.0×10 10 particles / mL, still more preferably 1.0×10 10 particles / mL, particularly preferably 1.0×10 9 particles / mL.

[0028] The average bubble diameter and the number of air bubbles are determined by analyzing the Brownian motion migration speed of the air bubbles in the liquid using the nanoparticle tracking analysis method (NTA). For example, it can be measured using "NanoSite NS300" manufactured by Malvern.

[0029] ​​​​​​​​​​​​​​​​The solid content concentration of the aqueous solution is not particularly limited as long as it has antibacterial and antiviral properties and high stability over time, but it is preferably, for example, 0.01 to 5.0% by mass. If it is less than 0.01% by mass, the antibacterial and antiviral properties may not be sufficiently expressed. Conversely, if it exceeds 5.0% by mass, the antibacterial and antiviral properties will be expressed, but the stability will be low, and discoloration or precipitation may occur. This solid content concentration is more preferably 0.01 to 3.0% by mass, and even more preferably 0.01 to 1.0% by mass.

[0030] The alkali metal content of an aqueous solution is not particularly limited as long as it has antibacterial and antiviral properties and high stability over time. However, it is preferable that the total amount of alkali metals, based on metal content, is less than 1.00% by mass relative to the solid content of the aqueous solution. If it is 1.00% by mass or more, the stability will be low and precipitates may form. This alkali metal content is more preferably less than 0.50% by mass, even more preferably less than 0.10% by mass, and most preferably no alkali metals are present. Incidentally, if the aqueous solution contains alkaline earth metals, the above-mentioned "alkali metal content" should be read as "total content of alkali metals and alkaline earth metals". Alkali metals refer to Li, Na, K, Rb, Cs, and Fr, and alkaline earth metals refer to Be, Mg, Ca, Sr, Ba, and Ra.

[0031] The antibacterial activity test of the aqueous solution shall be conducted in accordance with the shake method specified by the Society of International Antimicrobial Agents for Products. A value of 2.0 or higher is preferable. A value of 2.0 or higher indicates that the solution possesses antibacterial properties. A value of 3.0 or higher is more preferable.

[0032] The antiviral activity test of the aqueous solution shall be conducted in accordance with the antiviral activity test method for antiviral processing agents specified by the Society of International Antimicrobial Agents. It is preferable that the antiviral activity value be 2.0 or higher. A value of 2.0 or higher indicates that the product possesses antiviral properties. More preferably, the antibacterial activity value is 3.0 or higher.

[0033] Conventional known products can be used as the aqueous solution of the present invention. For example, it can be added to cleaning agents, detergents, wet wipes, air conditioner filters, antibacterial and antiviral sprays, etc. Furthermore, as processed products on base materials, it is preferable to impart antibacterial and antiviral properties to resins such as glass, chemical fibers, plastics, polycarbonate, acrylic resin, urethane resin, polyethylene terephthalate (PET), triacetylcellulose (TAC), polyimide, polymethyl methacrylate (PMMA), and cycloolefin polymer (COP).

[0034] [Method for producing aqueous solution] The present invention relates to a method for producing an aqueous solution, which involves mixing an aqueous solution of a metal compound containing metal elements belonging to groups 11 to 15 of the periodic table with an aqueous solution of a water-soluble organic substance at 10 to 50°C.

[0035] Among the metallic elements of groups 11 to 15 of the periodic table, examples of metallic elements with high antibacterial and antiviral properties include Cu, Ag, Zn, Ga, Sn, Pb, and Bi. Examples of metallic compounds containing these metallic elements include nitrates, sulfates, carbonates, acetates, and hydrates thereof. These may be used individually, or multiple types of the same metallic element may be used, or multiple types of different metallic elements may be used. Among these metallic compound compounds, for example, silver nitrate, silver sulfate, silver acetate, copper nitrate, copper sulfate, and copper acetate are preferred due to their high solubility in water.

[0036] It is preferable that aqueous solutions of these metal element compounds are contained in the aqueous solution at a concentration of 0.0001 to 1.2% by mass, in terms of metal equivalent.

[0037] Examples of water-soluble organic substances include gelatin, polyvinyl alcohol, polyvinylpyrrolidone, vinyl acetate, polyacrylic acid, and carboxylic acid compounds. Examples of carboxylic acid compounds include anthic acid, hydroxyanthracene carboxylic acid, hydroxynaphthoic acid, gallic acid, cresotic acid, parahydroxybenzoic acid, ortho-acetylsalicylic acid, malic acid, mandelic acid, gluconic acid, citric acid, tartaric acid, lactic acid, benzenecarboxylic acid, formic acid, acetic acid, butanoic acid, propionic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, 9-hexadecenoic acid, heptadecanoic acid, octadecanoic acid, glycolic acid, L-ascorbic acid, fumaric acid, maleic acid, adipic acid, ethylenediaminetetraacetic acid, and salts thereof. Among these, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, gluconic acid, citric acid, tartaric acid, lactic acid, L-ascorbic acid, ethylenediaminetetraacetic acid, and their salts are preferred as they form complexes with the aforementioned metal elements. These may be used individually or in combination.

[0038] These water-soluble organic substances are preferably present in the aqueous solution at a solid content concentration of 0.001 to 20% by mass.

[0039] In mixing an aqueous solution of the aforementioned metal element compound with an aqueous solution of a water-soluble organic substance, the ratio (L / M) of the molar concentration (L) of the "water-soluble organic substance" to the molar concentration (M) of the aforementioned metal element is preferably 0.1 to 30. This allows the metal element and organic substance to exist stably in the final aqueous solution. Furthermore, complex formation between the metal element and organic substance is facilitated. Therefore, it is possible to achieve both high antibacterial and antiviral properties and suppression of discoloration due to oxidation of the metal element.

[0040] Here, if the ratio (L / M) is less than 0.1, the protective effect of the organic matter on the metal element will be insufficient, and the metal element may oxidize and become discolored. Also, if the complex formation between the metal element and the organic matter is insufficient, the metal element may oxidize and become discolored. Conversely, if it exceeds 30, dissolution in water may become difficult, or the antibacterial and antiviral properties may decrease due to the excessive presence of organic matter in the aqueous solution. This ratio (L / M) is more preferably 0.3 to 10, even more preferably 1.0 to 10, and particularly preferably 1.0 to 5.0.

[0041] When mixing an aqueous solution of a metal element compound with an aqueous solution of a water-soluble organic substance, the mixture should be heated to a temperature of 10-50°C. This ensures high solubility of the metal salt and organic substance, allowing them to exist stably in the solution. It also facilitates the formation of complexes between the two substances.

[0042] If the temperature of the mixture is below 10°C, the solubility of the metal salt and organic matter may be low, and they may not dissolve sufficiently. Conversely, if the temperature of the mixture exceeds 50°C, oxidation-reduction reactions may occur between the metal salt and organic matter, making complex formation between the two difficult. The temperature of this mixture is preferably 10 to 40°C, more preferably 10 to 30°C, and even more preferably 10 to 20°C.

[0043] The pH of this mixture is preferably between 2.0 and 9.0. Within this pH range, metal elements and organic substances can exist stably. Furthermore, complex formation between metal elements and organic substances becomes easier. Therefore, it is possible to achieve both high antibacterial and antiviral properties and suppress discoloration due to oxidation of metal elements. A stable antibacterial and antiviral aqueous solution can be obtained.

[0044] Here, if the pH of the mixture is less than 2.0, complex formation between the metal element and the organic substance may become difficult. Conversely, if the pH exceeds 9.0, the metal element may oxidize and become discolored, or precipitate as a hydroxide. The pH is more preferably between 2.0 and 8.5, and even more preferably between 3.8 and 7.0.

[0045] When mixing an aqueous solution of a metal element compound with an aqueous solution of a water-soluble organic substance, the presence of oxidizing gases such as oxygen in the mixture may cause the metal to oxidize. Therefore, it is desirable to reduce the amount of oxidizing gases as much as possible in each aqueous solution, the mixture, and the space in which the mixtures come into contact. To suppress the inclusion of oxidizing gases, it is preferable to mix the solutions under purging conditions with non-oxidizing gases such as N2 gas or noble gases. Furthermore, to suppress the inclusion of oxidizing gases, it is preferable to bubble the aqueous solutions of the metal element compounds, the water-soluble organic substances, and the aqueous solutions (mixtures) obtained by mixing them with a non-oxidizing gas. It is also particularly preferable to use a liquid containing bubbles (including a bubbling liquid containing bubbles), as described later. Examples of oxidizing gases include oxygen, ozone, carbon dioxide, nitric oxide, dinitrogen monoxide, nitrogen dioxide, fluorine, chlorine, chlorine dioxide, nitrogen trifluoride, chlorine trifluoride, silicon tetrachloride, oxygen difluoride, and perchloryl fluoride.

[0046] When preparing aqueous solutions of the aforementioned metal element compounds and aqueous solutions of water-soluble organic substances, it is preferable to pre-bubble at least one of the waters with a non-oxidizing gas to reduce the dissolved oxygen content to 3.0 mg / L or less. Here, the non-oxidizing gas is preferably at least one of nitrogen, hydrogen, and a noble gas. When the dissolved oxygen content is within this range, oxidation of the metal element is suppressed during mixing of the two solutions and in the mixed solution.

[0047] Here, if the dissolved oxygen content exceeds 3.0 mg / L, oxidation of metal elements may proceed during mixing and in the mixture. The dissolved oxygen content is more preferably 2.0 mg / L or less, and even more preferably 1.0 mg / L or less.

[0048] It is preferable that at least one of the waters used in the aqueous solution of the aforementioned metal element compound and the aqueous solution of a water-soluble organic substance contains non-oxidizing bubbles with an average bubble diameter of 40 nm to 10 μm. These bubbles include at least one of so-called nanobubbles with a bubble diameter of 40 to 100 nm (0.1 μm) and so-called microbubbles with a bubble diameter of 0.1 to 10 μm, and it is preferable that they include both. When the average bubble diameter is within this range, bubbles accumulate around the metal element and organic substance, resulting in a highly stable aqueous solution.

[0049] Here, if the average bubble diameter is less than 40 nm, the bubbles are small and have a high surface area, making it difficult for them to exist stably, and thus it is not possible to obtain bubbles of this average diameter. Furthermore, even if they are obtained, the bubbles are prone to bursting, which may decompose organic matter during the production of the aqueous solution, resulting in the failure to obtain the desired aqueous solution. Conversely, if the average bubble diameter exceeds 10 μm, the bubbles are unlikely to exist around metal elements and organic matter during production, which may prevent the acquisition of a highly stable aqueous solution. The lower limit of this average bubble diameter is more preferably 50 nm, even more preferably 60 nm, and particularly preferably 65 nm. The upper limit of the average bubble diameter is more preferably 500 nm, even more preferably 350 nm, and particularly preferably 200 nm.

[0050] The gas used to form the bubbles is preferably a non-oxidizing gas in order to suppress the oxidation of metal elements. Specifically, nitrogen, hydrogen, and at least one of a noble gas are preferred.

[0051] Furthermore, the amount of bubbles in the water used for at least one of the aqueous solutions of the aforementioned metal element compounds and the aqueous solutions of water-soluble organic substances is 1.0 × 10⁻⁶. 3 ~1.0×10 11 A bubble content of 1 / mL is preferable. When the bubble content is within this range, bubbles tend to accumulate around metals and organic materials, making it easier to produce a highly stable aqueous solution.

[0052] Here, the bubble content is 1.0 × 10 3If the bubble content is less than 1.0 × 10¹⁶ / mL, the amount of bubbles that accumulate around metals and organic materials will be small, and a highly stable aqueous solution may not be obtained. Conversely, if the bubble content is 1.0 × 10¹⁶ 11 If the number of bubbles exceeds 10¹ / mL, the number of bubbles per unit volume is excessive, and although the improvement in the stability of the aqueous solution is high, it plateaus. The lower limit of this bubble content is more preferably 1.0 × 10¹⁶ 4 More than 1.0 × 10¹ / mL, more preferably 1.0 × 10¹ 5 More than 1.0 × 10¹ / mL, particularly preferably 1.0 × 10¹ 8 The concentration is 5.0 × 10¹⁶ or more. The upper limit is more preferably 5.0 × 10¹⁶. 11 pieces / mL, more preferably 1.0 × 10 10 pieces / mL, particularly preferably 1.0 × 10 9 The concentration is cells / mL.

[0053] The method for mixing the aqueous solution of the aforementioned metal element compound with the aqueous solution of a water-soluble organic substance is one that ensures uniform mixing, and uniform mixing generally leads to a more stable aqueous solution. Among these, a method of obtaining a uniform aqueous solution by stirring with a magnetic stirrer or an impeller-equipped agitator is preferred, a method of mixing in laminar flow, such as with a static mixer, is more preferred, and a method of instantaneous mixing in laminar flow, such as with micromixing, is even more preferred. However, in all cases, it is preferable to mix each aqueous solution, the mixture, and the space in which the mixtures come into contact in an atmosphere where oxidizing gases are reduced as much as possible by using a non-oxidizing gas such as N2 gas or a noble gas.

[0054] It is preferable to wash the resulting mixture with a washing solution. This washing removes the salts. Here, salts refer to impurities contained in the mixture and ions generated when the aforementioned metal elements and organic substances form complexes. Specifically, examples include metal ions such as sodium and iron, as well as boron ions, chloride ions, nitrate ions, sulfate ions, and organic acid ions.

[0055] The cleaning solution is preferably water containing the aforementioned bubbles. Furthermore, the mixed solution after cleaning is also preferably an aqueous solution containing bubbles.

[0056] Examples of cleaning methods include those using ion exchange resins, ultrafilms, or ceramic membranes. Cleaning with a cleaning solution containing air bubbles can prevent metal oxidation and suppress discoloration of the aqueous solution.

[0057] Furthermore, it is preferable that the total content of alkali metals and alkaline earth metals, based on oxides, be less than 1.0% by mass.

[0058] Furthermore, the physical properties and preferred range of the aqueous solution ultimately obtained by this manufacturing method are the same as those described above.

[0059] The following describes embodiments of the present invention.

[0060] [Example 1] <Preparation of metal compound aqueous solution> In a constant temperature bath set to 20°C, 99.21 g of pure water and 0.79 g of silver nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 99.8% by mass) were added to a 200 mL stainless steel beaker. The mixture was stirred with a magnetic stirrer for 30 minutes and then mixed to prepare an aqueous solution of silver compound with an Ag equivalent concentration of 0.5% by mass.

[0061] <Preparation of organic solution> In a constant temperature bath set to 20°C, 89.06 g of pure water and 10.94 g of citric acid monohydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 99.8% by mass content) were added to a 200 mL stainless steel beaker. The mixture was stirred with a magnetic stirrer for 30 minutes and then mixed to prepare an organic aqueous solution with a solid content of 10% by mass.

[0062] <Manufacturing of antibacterial and antiviral aqueous solutions> In a constant temperature bath set to 20°C, 71.03 g of pure water and 8.97 g of the prepared organic solution were added to a 200 mL stainless steel beaker, and the mixture was stirred with a magnetic stirrer for 30 minutes. Next, 20.0 g of the prepared silver compound solution was added over 30 minutes, and the mixture was stirred with a magnetic stirrer for 30 minutes to produce an antibacterial and antiviral aqueous solution.

[0063] The following methods were used to measure the properties of aqueous solutions of metal compounds, organic substances, and antibacterial / antiviral substances. The characteristics of the production of the antibacterial / antiviral substances and the properties of the solutions are shown in Tables 1 and 2 (the same applies to the following examples and comparative examples).

[0064] (1) Solid content concentration The solid content concentration of organic aqueous solutions and antibacterial / antiviral aqueous solutions was measured by the following method. First, 1.0 g of the sample was taken and dried at 120°C for 3.0 hours. The ratio of the mass of the dried sample to the mass of the sample before drying was determined and defined as the solid content concentration.

[0065] (2) Metal element concentration The content of each metal element was measured by the following method. First, a sample equivalent to approximately 0.2 g of solid content was placed in a platinum dish. To this, 3 mL of phosphoric acid, 5 mL of nitric acid, and 10 mL of hydrofluoric acid were added and heated on a sand bath. After drying, a small amount of water and 50 mL of nitric acid were added to dissolve the sample, and this was transferred to a 100 mL volumetric flask, where water was added to make a total volume of 100 mL. Alkali metals such as Na were measured using an atomic absorption spectrometer (Hitachi, Ltd. Z-2310) with this solution. Next, metals such as Ag, Cu, and Zn were measured using an ICP plasma emission spectrometer (SII Corporation SPS5520) with a solution taken from this 100 mL solution.

[0066] (3) pH The pH was measured using a pH meter (Horiba F-2000, manufactured by Horiba, Ltd.) after adjusting the aqueous solution to 25°C.

[0067] (4) Dissolved oxygen The dissolved oxygen content was measured using a DO meter (WQ-300, manufactured by Horiba, Ltd.) after adjusting the target water or aqueous solution to 25°C.

[0068] (5) Average bubble diameter and bubble content of nanobubbles and microbubbles The Brownian motion velocity of bubbles in a liquid was measured using nanoparticle tracking analysis. Specifically, approximately 20 mL of the sample (water or an antibacterial / antiviral aqueous solution) was injected into the measuring instrument (Malvern's "NanoSight NS300") while being aspirated, and the velocity was measured using nanoparticle tracking analysis.

[0069] (6) Antimicrobial evaluation Antimicrobial activity was evaluated according to the shake method procedure established by the Society of International Antimicrobial Agents. Staphylococcus aureus was used as the bacterial species. The inoculum was prepared by diluting NB medium 500 times with sterile purified water and adjusting the pH to 7.0 ± 0.2 to create "1 / 500 NB medium," into which the pre-cultured bacteria were uniformly dispersed, resulting in a bacterial count of 1.0 × 10⁶. 5 ~5.0×10 5 The bacterial solution was prepared to have a concentration of 10 ppm / mL for inoculum use. During the shaking process, an antibacterial / antiviral aqueous solution was added to the target solution at a concentration of 10 ppm as a metal, and the antibacterial activity value was determined using the following formula.

[0070] Q B =U Bt -A Bt (However, Q B This is the antibacterial activity value, U Bt A is the mean of the logarithm of the number of viable bacteria in the blank test. Bt This value represents the logarithm of the number of viable bacteria after adding an antibacterial / antiviral aqueous solution and shaking for one hour.

[0071] An antibacterial activity value of 2.0 or higher was considered to indicate an antibacterial effect. The higher the antibacterial activity value, the better the composition is considered to have antibacterial properties.

[0072] (7) Antiviral evaluation Antimicrobial activity was evaluated according to the antiviral activity test method for antiviral processing agents established by the Society of International Antimicrobial Agents. Influenza A virus (H3N2) was used as the virus strain. 0.1 mL of the test virus suspension was added to 0.9 mL of the control sample (sterile purified water) or the test sample and thoroughly mixed. After standing at 25°C for 24 hours, this was used as the test solution. A 10-fold serial dilution series of the test solution was prepared using Eagle medium. Similarly, a 10-fold serial dilution series was prepared for the control sample and used as the "immediately after inoculation" sample for the control sample. The viral infectivity titer per 0.1 mL of the test solution and the 10-fold serial dilution series of the test solution was measured by plaque assay, and the viral infectivity titer per 1 mL of test solution was calculated. A 10-fold serial dilution series of the test solution was prepared, and the dilution ratio that met the criteria for the control test was determined. The same procedure was performed in the antiviral activity test using the dilution ratio determined in the control test. The method for measuring viral infectivity was the plaque assay method described in ISO 21702:2019, section 7.5. The antiviral activity value was calculated as follows: Antiviral activity value = "mean of the common logarithmic values ​​of the viral infectivity titer of the control sample after 24 hours" - "mean of the common logarithmic values ​​of the viral infectivity titer of the test sample after 24 hours". An antiviral effect was determined if this "antiviral activity value" was 2.0 or higher.

[0073] (8)NaOH resistance 50 g of an antibacterial / antiviral aqueous solution was weighed into a 100 mL screw-cap tube, and then a 0.1% by mass sodium hydroxide aqueous solution was added to adjust the pH to 7.0. The solution was left standing, and changes were observed to determine how many hours it took for the solution to change (discoloration or precipitate formation). A longer time before a change occurred indicated higher stability of the aqueous solution.

[0074] (9) Reactivity with acetylacetone (coloring) 1.0 g of acetylacetone (special grade, manufactured by Kanto Chemical Co., Ltd.) was mixed with 99.0 g of ethanol to obtain a 1.0% by mass acetylacetone-ethanol solution. Next, 1.0 g of this acetylacetone-ethanol solution was added to 10 g of an antibacterial / antiviral aqueous solution and stirred for 1 minute. After that, the solution was allowed to stand and the change in color was observed. The evaluation was performed according to the following criteria: The longer the time until color change, the higher the stability of the aqueous solution was considered to be. Evaluation criteria; Change in less than 6 hours: 1 Changes between 6 hours and less than 12 hours: 2 Changes between 12 and 18 hours: 3 Changes between 18 and 24 hours: 4 Change over 24 hours to less than 36 hours: 5 Changes between 36 hours and less than 48 hours: 6 No change for over 48 hours: 7

[0075] [Example 2] <Preparation of metal compound aqueous solution> In a constant temperature bath set to 20°C, 98.11 g of pure water and 2.17 g of copper(II) nitrate trihydrate (Merck Co., Ltd., 99.8% by mass content) were added to a 200 mL stainless steel beaker. The mixture was stirred with a magnetic stirrer for 30 minutes and then mixed to prepare an aqueous solution of copper compound with a Cu equivalent concentration of 0.5% by mass.

[0076] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was prepared in the same manner as in Example 1, except that 58.35 g of pure water, 21.65 g of the same organic aqueous solution as in Example 1, and 20.0 g of the copper compound aqueous solution prepared in this example were used as the metal compound aqueous solution.

[0077] [Example 3] <Preparation of metal compound aqueous solution> In a 200 mL stainless steel beaker set to a constant temperature bath at 20°C, 96.95 g of pure water and 2.59 g of zinc(II) nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 99.8% by mass content) were added and stirred with a magnetic stirrer for 30 minutes to prepare an aqueous zinc compound solution with a zinc equivalent concentration of 0.5% by mass.

[0078] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was prepared in the same manner as in Example 1, except that 54.10 g of pure water, 25.90 g of the same organic aqueous solution as in Example 1, and 20.0 g of the zinc compound aqueous solution prepared in this example were used as the metal compound aqueous solution.

[0079] [Example 4] <Preparation of metal compound aqueous solution> In a constant temperature bath set to 20°C, 99.23 g of pure water and 0.77 g of silver acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 99.9% by mass) were added to a 200 mL stainless steel beaker. The mixture was stirred with a magnetic stirrer for 30 minutes and then mixed to prepare an aqueous solution of silver compound with an Ag equivalent concentration of 0.5% by mass.

[0080] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was prepared in the same manner as in Example 1, except that 51.96 g of pure water, 8.81 g of the same organic aqueous solution as in Example 1, and 20.0 g of the silver compound aqueous solution prepared in this example were used as the metal compound aqueous solution.

[0081] [Example 5] <Preparation of metal compound aqueous solution> In a constant temperature bath set to 20°C, 99.28 g of pure water and 0.72 g of silver sulfate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 99.9% by mass) were added to a 200 mL stainless steel beaker. The mixture was stirred with a magnetic stirrer for 30 minutes and then mixed to prepare an aqueous solution of silver compound with an Ag equivalent concentration of 0.5% by mass.

[0082] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was prepared in the same manner as in Example 1, except that 71.77 g of pure water, 8.23 ​​g of the same organic aqueous solution as in Example 1, and 20.0 g of the silver compound aqueous solution prepared in this example were used as the metal compound aqueous solution.

[0083] [Example 6] <Preparation of metal compound aqueous solution> In a constant temperature bath set to 20°C, 99.36 g of pure water and 0.64 g of silver carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 99.9% by mass) were added to a 200 mL stainless steel beaker. The mixture was stirred with a magnetic stirrer for 30 minutes and then mixed to prepare an aqueous solution of silver compound with an Ag equivalent concentration of 0.5% by mass.

[0084] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was prepared in the same manner as in Example 1, except that 72.72 g of pure water, 7.28 g of the same organic aqueous solution as in Example 1, and 20.0 g of the silver compound aqueous solution prepared in this example were used as the metal compound aqueous solution.

[0085] [Example 7] <Preparation of organic solution> In a constant temperature bath set to 20°C, 90.00 g of pure water and 10.00 g of L+ tartaric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 99.9% by mass content) were added to a 200 mL stainless steel beaker. The mixture was stirred with a magnetic stirrer for 30 minutes and then mixed to prepare an organic aqueous solution with a solid content of 10% by mass.

[0086] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was prepared in the same manner as in Example 1, except that 72.96 g of pure water, 20.0 g of the same metal compound aqueous solution as in Example 1, and 7.28 g of the organic matter aqueous solution prepared in this example were used.

[0087] [Example 8] <Preparation of organic solution> In a constant temperature bath set to 20°C, 90.00 g of pure water and 10.00 g of oxalic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 98.0% by mass) were added to a 200 mL stainless steel beaker. The mixture was stirred with a magnetic stirrer for 30 minutes and then mixed to prepare an organic aqueous solution with a solid content of 10% by mass.

[0088] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was prepared in the same manner as in Example 1, except that 75.73 g of pure water, 20.0 g of the same metal compound aqueous solution as in Example 1, and 4.27 g of the organic matter aqueous solution prepared in this example were used.

[0089] [Example 9] <Manufacturing of antibacterial and antiviral aqueous solutions> In a constant temperature bath set to 20°C, 33.71 g of pure water was placed in a 200 mL stainless steel beaker. 46.29 g of 0.1 mol / L ethylenediaminetetraacetate disodium aqueous solution was added to this, and the mixture was stirred with a magnetic stirrer for 30 minutes. Next, 20.0 g of the same metal compound aqueous solution as in Example 1 was added over 30 minutes, and the mixture was stirred with a magnetic stirrer for 30 minutes to produce an antibacterial and antiviral aqueous solution.

[0090] [Example 10] <Preparation of organic solution> In a constant temperature bath set to 20°C, 90.00 g of pure water and 10.00 g of polyvinylpyrrolidone (K-90, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 100% by mass content, average molecular weight 36000, single molecular weight 111) were added to a 200 mL stainless steel beaker. The mixture was stirred with a magnetic stirrer for 60 minutes to prepare an organic aqueous solution with a solid content of 10% by mass.

[0091] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was prepared in the same manner as in Example 1, except that 74.85 g of pure water, 20.0 g of the same metal compound aqueous solution as in Example 1, and 5.15 g of the organic aqueous solution prepared in this example were used.

[0092] [Example 11] <Preparation of organic solution> In a constant temperature bath set to 20°C, 90.00 g of pure water and 10.00 g of polyvinyl alcohol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 100% by mass content, average molecular weight 1500-1800, one molecular weight 44) were added to a 200 mL stainless steel beaker. The mixture was stirred with a magnetic stirrer for 60 minutes to prepare an organic aqueous solution with a solid content of 10% by mass.

[0093] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was prepared in the same manner as in Example 1, except that 77.96 g of pure water, 20.0 g of the same metal compound aqueous solution as in Example 1, and 2.04 g of the organic matter aqueous solution prepared in this example were used.

[0094] [Example 12] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was prepared in the same manner as in Example 1, except that 78.21 g of pure water, 1.79 g of the same organic aqueous solution as in Example 1, and 20.0 g of the same metal compound aqueous solution as in Example 1 were used.

[0095] [Example 13] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was prepared in the same manner as in Example 1, except that 62.07 g of pure water, 17.93 g of the same organic aqueous solution as in Example 1, and 20.0 g of the same metal compound aqueous solution as in Example 1 were used.

[0096] [Example 14] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was prepared in the same manner as in Example 1, except that 79.46 g of pure water, 0.54 g of the same organic aqueous solution as in Example 1, and 20.0 g of the same metal compound aqueous solution as in Example 1 were used.

[0097] [Example 15] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was prepared in the same manner as in Example 1, except that 26.21 g of pure water, 53.79 g of the same organic aqueous solution as in Example 1, and 20.0 g of the same metal compound aqueous solution as in Example 1 were used.

[0098] [Example 16] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was prepared in the same manner as in Example 1, except that 99.86 g of pure water, 0.04 g of the same organic aqueous solution as in Example 7, and 0.1 g of the same metal compound aqueous solution as in Example 1, with the addition time of the metal compound aqueous solution being 1 minute.

[0099] [Example 17] <Preparation of metal compound aqueous solution> In a constant temperature bath set to 20°C, 92.1 g of pure water and 7.9 g of silver nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 99.8% by mass) were added to a 200 mL stainless steel beaker. The mixture was stirred with a magnetic stirrer for 30 minutes and then mixed to prepare an aqueous solution of silver compound with an Ag equivalent concentration of 5.0% by mass.

[0100] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was prepared in the same manner as in Example 1, except that 9.62 g of pure water, 70.38 g of the same organic aqueous solution as in Example 7, and 20.0 g of the silver compound aqueous solution prepared in this example were used as the metal compound aqueous solution, and the addition time of the metal compound aqueous solution was set to 1 minute.

[0101] [Example 18] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was prepared in the same manner as in Example 1, except that 98.65 g of pure water, 0.35 g of the same organic aqueous solution as in Example 7, and 1.0 g of the same metal compound aqueous solution as in Example 1, with the addition time of the metal compound aqueous solution being 1 minute.

[0102] [Example 19] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was prepared in the same manner as in Example 1, except that 86.48 g of pure water, 3.52 g of the same organic aqueous solution as in Example 7, and 10.0 g of the same metal compound aqueous solution as in Example 1, and the addition time of the metal compound aqueous solution was set to 1 minute.

[0103] [Example 20] <Manufacturing of antibacterial and antiviral aqueous solutions> In a constant temperature bath set to 20°C, 71.03 g of pure water and 8.97 g of the same organic aqueous solution as in Example 1 were added to a 200 mL stainless steel beaker. This was then stirred and mixed for 30 minutes using a magnetic stirrer while bubbling nitrogen at 0.5 L / min. Next, 20.0 g of the same metal compound aqueous solution as in Example 1 was added over 30 minutes. This was then stirred and mixed for 600 minutes using a magnetic stirrer while bubbling nitrogen in the same manner to produce an antibacterial and antiviral aqueous solution.

[0104] [Example 21] <Manufacturing of antibacterial and antiviral aqueous solutions> In a constant temperature bath set to 20°C, 71.03 g of pure water and 8.97 g of the same organic aqueous solution as in Example 1 were added to a 200 mL stainless steel beaker. This was then stirred and mixed for 30 minutes using a magnetic stirrer while bubbling nitrogen at 0.5 L / min. Next, 20.0 g of the same metal compound aqueous solution as in Example 1 was added over 30 minutes. This was then stirred and mixed for 300 minutes using a magnetic stirrer while bubbling nitrogen in the same manner to produce an antibacterial and antiviral aqueous solution.

[0105] [Example 22] <Manufacturing of antibacterial and antiviral aqueous solutions> In a constant temperature bath set to 20°C, 71.03 g of pure water and 8.97 g of the same organic aqueous solution as in Example 1 were added to a 200 mL stainless steel beaker. This was then stirred and mixed for 30 minutes using a magnetic stirrer while bubbling nitrogen at 0.5 L / min. Next, 20.0 g of the same metal compound aqueous solution as in Example 1 was added over 30 minutes. This was then stirred and mixed for 30 minutes using a magnetic stirrer while bubbling nitrogen in the same manner to produce an antibacterial and antiviral aqueous solution.

[0106] [Example 23] <Preparation of pure water containing microbubbles> A swirling flow type bubble generator (HYK-20-SD, manufactured by Ligaric Co., Ltd.) is used to bring ultrapure water and N2 into contact, producing pure water containing minute N2 bubbles (average bubble diameter 60 nm, number of bubbles 5.0 × 10⁶). 5 A solution containing 1 / mL was prepared.

[0107] <Preparation of metal compound aqueous solution> An aqueous solution of the metal compound was prepared in the same manner as in Example 1, except that pure water containing microbubbles prepared in this example was used.

[0108] <Preparation of organic solution> An organic aqueous solution was prepared in the same manner as in Example 1, except that pure water containing microbubbles prepared in this example was used.

[0109] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was produced in the same manner as in Example 1, except that the pure water containing microbubbles prepared in this example was used and the organic aqueous solution prepared in this example was used.

[0110] [Example 24] <Preparation of pure water containing microbubbles> A swirling flow type bubble generator (HYK-20-SD, manufactured by Ligaric Co., Ltd.) is used to bring ultrapure water and N2 into contact, producing pure water containing minute N2 bubbles (average bubble diameter 40 nm, number of bubbles 8.0 × 10⁶). 10 A solution containing 1 / mL was prepared.

[0111] <Preparation of metal compound aqueous solution> An aqueous solution of the metal compound was prepared in the same manner as in Example 1, except that pure water containing microbubbles prepared in this example was used.

[0112] <Preparation of organic solution> An organic aqueous solution was prepared in the same manner as in Example 1, except that pure water containing microbubbles prepared in this example was used.

[0113] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was produced in the same manner as in Example 1, except that the pure water containing microbubbles prepared in this example was used and the organic aqueous solution prepared in this example was used.

[0114] [Example 25] <Preparation of pure water containing microbubbles> A swirling flow type bubble generator (HYK-20-SD, manufactured by Ligaric Co., Ltd.) is used to bring ultrapure water and N2 into contact, resulting in pure water containing minute N2 bubbles (average bubble diameter 80 nm, number of bubbles 1.0 × 10⁶). 12 A solution containing 1 / mL was prepared.

[0115] <Preparation of metal compound aqueous solution> An aqueous solution of the metal compound was prepared in the same manner as in Example 1, except that pure water containing microbubbles prepared in this example was used.

[0116] <Preparation of organic solution> An organic aqueous solution was prepared in the same manner as in Example 1, except that pure water containing microbubbles prepared in this example was used.

[0117] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was produced in the same manner as in Example 1, except that the pure water containing microbubbles prepared in this example was used and the organic aqueous solution prepared in this example was used.

[0118] [Example 26] <Preparation of pure water containing microbubbles> A swirling flow type bubble generator (HYK-20-SD, manufactured by Ligaric Co., Ltd.) is used to bring ultrapure water and N2 into contact, producing pure water containing minute N2 bubbles (average bubble diameter 60 nm, number of bubbles 5.0 × 10⁶). 4 A solution containing 1 / mL was prepared.

[0119] <Preparation of metal compound aqueous solution> An aqueous solution of the metal compound was prepared in the same manner as in Example 1, except that pure water containing microbubbles prepared in this example was used.

[0120] <Preparation of organic solution> An organic aqueous solution was prepared in the same manner as in Example 1, except that pure water containing microbubbles prepared in this example was used.

[0121] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was produced in the same manner as in Example 1, except that the pure water containing microbubbles prepared in this example was used and the organic aqueous solution prepared in this example was used.

[0122] [Example 27] <Preparation of pure water containing microbubbles> A swirling flow type bubble generator (HYK-20-SD, manufactured by Ligaric Co., Ltd.) brings ultrapure water into contact with Ar to produce pure water containing minute Ar bubbles (average bubble diameter 60 nm, number of bubbles 5.0 × 10⁶). 11 A solution containing 1 / mL was prepared.

[0123] <Preparation of metal compound aqueous solution> An aqueous solution of the metal compound was prepared in the same manner as in Example 1, except that pure water containing microbubbles prepared in this example was used.

[0124] <Preparation of organic solution> An organic aqueous solution was prepared in the same manner as in Example 1, except that pure water containing microbubbles prepared in this example was used.

[0125] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was produced in the same manner as in Example 1, except that the pure water containing microbubbles prepared in this example was used and the organic aqueous solution prepared in this example was used.

[0126] [Example 28] <Manufacturing of antibacterial and antiviral aqueous solutions> In a constant temperature bath set to 20°C, 20.0 g of the same metal compound aqueous solution as in Example 1 was added to a 200 mL stainless steel beaker and stirred with a magnetic stirrer for 30 minutes. Next, 71.03 g of pure water and 8.97 g of the same organic aqueous solution as in Example 1 were added and stirred with a magnetic stirrer for 30 minutes to mix and produce an antibacterial and antiviral aqueous solution.

[0127] [Example 29] <Manufacturing of antibacterial and antiviral aqueous solutions> In the preparation of the metal compound aqueous solution, the preparation of the organic aqueous solution, and the production of the antibacterial and antiviral aqueous solution, an antibacterial and antiviral aqueous solution was produced in the same manner as in Example 1, except that a two-bladed stirring impeller (50 mm stirring blade manufactured by AS ONE Corporation) and a stirrer (Shinto Kagaku Co., Ltd. Three-One Motor BL300) were used as stirring and mixing equipment.

[0128] [Example 30] <Manufacturing of antibacterial and antiviral aqueous solutions> Except for the use of a two-bladed stirring impeller (50mm stirring blade, manufactured by AS ONE Corporation) and a stirrer (BL300 Three-One Motor, manufactured by Shinto Kagaku Co., Ltd.) as stirring and mixing devices in the preparation of the metal compound aqueous solution and the organic substance aqueous solution, an antibacterial and antiviral aqueous solution was produced in the same manner as in Example 1, except that a static mixer (model 1-N10-3311, manufactured by Noritake Co., Ltd.) was used as stirring and mixing device in the production of the antibacterial and antiviral aqueous solution.

[0129] [Example 31] <Manufacturing of antibacterial and antiviral aqueous solutions> Except for the use of a two-bladed stirring impeller (50mm stirring blade, manufactured by AS ONE Corporation) and a stirrer (BL300 Three-One Motor, manufactured by Shinto Kagaku Co., Ltd.) as stirring and mixing devices in the preparation of the metal compound aqueous solution and the organic substance aqueous solution, an antibacterial and antiviral aqueous solution was produced in the same manner as in Example 1, except that a micro-mixing server (manufactured by Hitachi Plant Technologies, Ltd.) was used as stirring and mixing device in the production of the antibacterial and antiviral aqueous solution.

[0130] [Example 32] <Preparation of metal compound aqueous solution> An aqueous solution of silver compound was prepared in the same manner as in Example 1, except that the temperature of the constant temperature bath was set to 10°C.

[0131] <Preparation of organic solution> An organic aqueous solution was prepared in the same manner as in Example 1, except that the temperature of the constant temperature bath was set to 5°C.

[0132] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was produced in the same manner as in Example 1, except that the temperature of the constant temperature bath was set to 10°C and the silver compound aqueous solution and the organic matter aqueous solution prepared in this example were used.

[0133] [Example 33] <Preparation of metal compound aqueous solution> An aqueous solution of silver compound was prepared in the same manner as in Example 1, except that the temperature of the constant temperature bath was set to 50°C.

[0134] <Preparation of organic solution> An organic aqueous solution was prepared in the same manner as in Example 1, except that the temperature of the constant temperature bath was set to 70°C.

[0135] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was produced in the same manner as in Example 1, except that the temperature of the constant temperature bath was set to 50°C and the silver compound aqueous solution and the organic matter aqueous solution prepared in this example were used.

[0136] [Example 34] <Manufacturing of antibacterial and antiviral aqueous solutions> In a constant temperature bath set to 20°C, 100g of the antibacterial and antiviral aqueous solution produced in Example 1 was taken into a 200mL stainless steel beaker. The pH was then adjusted to 9.5 using 29% by mass ammonia water (special grade, manufactured by Kanto Chemical Co., Ltd.) to produce an antibacterial and antiviral aqueous solution.

[0137] [Comparative Example 1] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was prepared in the same manner as in Example 1, except that 80.0 g of pure water and 20.0 g of the silver compound aqueous solution prepared in Example 1 were used, and no organic aqueous solution was used.

[0138] [Comparative Example 2] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was prepared in the same manner as in Example 1, except that 80.0 g of pure water and 20.0 g of the silver compound aqueous solution prepared in Example 5 were used, and no organic aqueous solution was used.

[0139] [Comparative Example 3] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was prepared in the same manner as in Example 1, except that 91.03 g of pure water and 8.97 g of the organic aqueous solution prepared in Example 1 were used, and the metal compound aqueous solution was not used.

[0140] [Comparative Example 4] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was prepared in the same manner as in Example 1, except that 91.03 g of pure water and 8.97 g of the organic aqueous solution prepared in Example 7 were used, and no aqueous solution of a metal compound was used.

[0141] [Comparative Example 5] <Manufacturing of antibacterial and antiviral aqueous solutions> In a constant temperature bath set to 20°C, 100g of the antibacterial and antiviral aqueous solution produced in Example 1 was taken into a 200mL glass beaker. The pH was then adjusted to 1.5 using 61% by mass nitric acid (special grade, manufactured by Kanto Chemical Co., Ltd.) to produce an antibacterial and antiviral aqueous solution.

[0142] [Comparative Example 6] <Manufacturing of antibacterial and antiviral aqueous solutions> In a constant temperature bath set to 20°C, 100g of the antibacterial and antiviral aqueous solution produced in Example 1 was taken into a 200mL stainless steel beaker. The pH was then adjusted to 10.0 using 29% by mass ammonia water (special grade, manufactured by Kanto Chemical Co., Ltd.) to produce an antibacterial and antiviral aqueous solution.

[0143] [Comparative Example 7] <Preparation of metal compound aqueous solution> An aqueous solution of silver compound was prepared in the same manner as in Example 1, except that the temperature of the constant temperature bath was set to 10°C.

[0144] <Preparation of organic solution> An organic aqueous solution was prepared in the same manner as in Example 1, except that the temperature of the constant temperature bath was set to 5°C.

[0145] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was produced in the same manner as in Example 1, except that the temperature of the constant temperature bath was set to 5°C and the silver compound aqueous solution and the organic substance aqueous solution prepared in this comparative example were used.

[0146] [Comparative Example 8] <Preparation of metal compound aqueous solution> An aqueous solution of silver compound was prepared in the same manner as in Example 1, except that the temperature of the constant temperature bath was set to 50°C.

[0147] <Preparation of organic solution> An organic aqueous solution was prepared in the same manner as in Example 1, except that the temperature of the constant temperature bath was set to 70°C.

[0148] <Manufacturing of antibacterial and antiviral aqueous solutions> An antibacterial and antiviral aqueous solution was prepared in the same manner as in Example 1, except that the temperature of the constant temperature bath was set to 70°C and the silver compound aqueous solution and the organic substance aqueous solution prepared in this comparative example were used.

[0149] [Table 1]

[0150] [Table 2] [Industrial applicability]

[0151] The aqueous solution according to the present invention can be used as a coating solution when manufacturing products, or as an additive during mixing and molding.

Claims

1. An aqueous solution containing a metallic element belonging to groups 11 to 15 of the periodic table and a water-soluble organic substance, having at least one of antibacterial and antiviral properties, wherein the pH of the aqueous solution is 2.0 to 9.

0.

2. The aqueous solution according to claim 1, characterized in that the metal equivalent concentration of the aforementioned metal element is 0.0001 to 1.2% by mass.

3. The aqueous solution according to claim 1, characterized in that the ratio (L / M) of the molar concentration (L) of the organic substance to the molar concentration (M) of the metal element contained in the aqueous solution is 0.1 to 30.

4. The aqueous solution according to claim 1, characterized in that the organic substance contains at least one of a hydroxyl group and a carboxyl group.

5. The aqueous solution according to claim 1, characterized in that the amount of dissolved oxygen in the aqueous solution is 3.0 mg / L or less.

6. The aqueous solution according to claim 1, characterized in that the aqueous solution contains non-oxidizing bubbles with an average bubble diameter of 40 nm to 10 μm.

7. The aqueous solution according to claim 1, characterized in that the aqueous solution contains at least one of Cu, Ag, Zn, Sn, and Bi as the metal element.

8. The amount of bubbles in the aqueous solution is 1.0 × 10 ３ ~1.0 x 10 １１ The aqueous solution according to claim 7, characterized in that it contains particles / mL.

9. A method for producing an antibacterial and antiviral aqueous solution, characterized by mixing an aqueous solution of a metal compound containing metal elements belonging to groups 11 to 15 of the periodic table with an aqueous solution of a water-soluble organic substance at 10 to 50°C.

10. The method for producing an aqueous solution according to claim 9, characterized in that at least one of the water used in the aqueous solution of the metal compound and the water used in the aqueous solution of the organic substance is bubbled with a non-oxidizing gas to reduce the amount of dissolved oxygen in the water to 3.0 mg / L or less.

11. The method for producing an aqueous solution according to claim 9, characterized in that the average bubble diameter of the bubbles contained in at least one of the water used for the aqueous solution of the metal compound and the water used for the aqueous solution of the organic substance is 40 nm to 10 μm.

12. The amount of bubbles in at least one of the water used in the aqueous solution of the metal compound and the water used in the aqueous solution of the organic substance is 1.0 × 10 ３ ~1.0 x 10 １１ A method for producing an aqueous solution according to claim 9, characterized in that the concentration is 1 / mL.

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