Disilver hydrogen citrate-containing composition, method for producing the same, antibacterial agent or antiviral agent using the same, and method for producing the same

Abstract

To provide powder of a powdery pure disilver hydrogen citrate-containing composition having excellent solubility, a method of obtaining conveniently and efficiently the composition containing disilver hydrogen citrate, an antibacterial agent or an antiviral agent that contains the composition containing disilver hydrogen citrate, and its manufacturing method.SOLUTION: A manufacturing method of a composition containing disilver hydrogen citrate of the present invention comprises: (1) a step of adding a silver compound and citric acid in such an amount that the disilver hydrogen citrate reaches a saturation amount, to a solvent, forming a reaction liquid, (2) a step of adding a basic agent to the reaction liquid and controlling pH to 2.0 to 5.5 to precipitate a composition containing disilver hydrogen citrate, and (3) a step of recovering precipitated composition containing disilver hydrogen citrate.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a composition containing disilver hydrogen citrate, a method for producing the same, an antibacterial agent or antiviral agent using the same, and a method for producing the same.

Background Art

[0002] In recent years, there has been an increasing awareness of hygiene, particularly in the prevention of infectious diseases, and there has been a growing demand for antibacterial and antiviral properties on the surface of the human body and articles around us. As substances having antibacterial properties, organic antibacterial agents such as triclosan, zinc pyrithione, and quaternary ammonium have been conventionally known. Although organic antibacterial agents exhibit strong bactericidal properties in a short time, they may cause skin allergies in humans or hormonal disturbances in organisms in the environment, which may not be preferable. In addition, organic antibacterial agents have a high bactericidal effect but at the same time have a narrow antibacterial spectrum. Therefore, in recent years, silver compounds have attracted attention as alternative materials.

[0003] As such a silver compound, for example, silver citrate is known. Silver citrate has attracted particular attention in recent years because it combines the immediate effect like that of organic bactericides and the safety and sustainability like those of inorganic silver antibacterial agents. As a method for producing a solution containing silver citrate, for example, a method of electrolyzing in an aqueous citric acid solution using a silver electrode (Patent Document 1), a method using trisilver citrate (Patent Document 2), and a method of dissolving silver zeolite in a citric acid solution (Patent Document 3) are known.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, in the method described in Patent Document 1, it takes as long as 144 hours to obtain a silver dihydrogen citrate solution having a silver ion concentration of 2400 ppm. This results in poor production efficiency and requires an expensive high-purity silver electrode, thus increasing the production cost. In the method described in Patent Document 2, silver citrate tribasic with poor solubility (solubility at 25°C: 0.0284 g / L, silver concentration 170 ppm) is used, which not only deteriorates workability but also makes it difficult to obtain a solution having a high silver ion concentration. In the method described in Patent Document 3, there is a risk that silica or aluminum, which are skeletal components derived from zeolite, may be mixed in as impurities, making it difficult to obtain pure silver citrate. When removing impurities, the number of steps increases and the production cost becomes high.

[0006] Therefore, an object of the present invention is to provide a novel powdery pure silver dihydrogen citrate-containing composition that can be easily dissolved in water or a citric acid solution, and a method for producing the same. Further, an antibacterial agent or antiviral agent comprising the silver dihydrogen citrate-containing composition, and a method for producing the same are provided.

Means for Solving the Problems

[0007] As a result of intensive studies, the present inventors prepared an aqueous solution by adding a silver compound and citric acid in such amounts that the resulting silver hydrogen citrate-containing composition would be in an amount equal to or greater than the saturation amount, added a base agent thereto to raise the pH of the solution to a desired pH range, and precipitated a silver hydrogen citrate-containing composition in an amount equal to or greater than the saturation amount from this reaction solution, thereby finding that a pure silver hydrogen citrate-containing composition free of powdery citric acid can be easily obtained by filtration operations and light water washing operations as solid-liquid separation, and completed the present invention. As a result of further studies, it was found that the silver hydrogen citrate-containing composition is a composition composed of silver hydrogen citrate and silver dihydrogen citrate, or silver hydrogen citrate and silver citrate tribasic, and further that it can be precipitated as a crystal mixture composed of the target components in a molar ratio by only an operation of adjusting an arbitrary pH value, and obtained by filtration operations and light water washing operations as solid-liquid separation. Furthermore, since the crystal mixture can be easily dissolved in water or a citric acid solution, and the solution has a broad antibacterial spectrum, shows no cytotoxicity, and shows virus inactivating activity, it was found that it can be used as an antibacterial agent and / or an antiviral agent, and further completed the present invention.

[0008] That is, the present invention includes the following aspects. [1] (1) A step of adding a silver compound and citric acid in such amounts that silver hydrogen citrate is in an amount equal to or greater than the saturation amount in a solvent to obtain a reaction solution, (2) A step of adding a base agent to the reaction solution to adjust the pH to 2.0 to 5.5 and precipitate a silver hydrogen citrate-containing composition, and (3) A step of recovering the precipitated silver hydrogen citrate-containing composition, A method for producing a silver hydrogen citrate-containing composition, comprising the above steps. [2] The method for producing a silver hydrogen citrate-containing composition according to [1], wherein the silver hydrogen citrate-containing composition further contains silver dihydrogen citrate or silver citrate tribasic, and the silver concentration in the composition is 36.1 wt% to 63.1 wt%. [3] The method for producing a silver hydrogen citrate-containing composition according to [1] or [2], wherein the silver compound is silver nitrate. [4] After the steps (1) to (3), (4) A step of repeating the operations of the steps (1) to (3) on the reaction solution and further recovering a composition containing disilver hydrogen citrate The method for producing a composition containing disilver hydrogen citrate according to any one of [1] to [3], comprising the above steps. [5] A method for producing an antibacterial agent or an antiviral agent, comprising producing a composition containing disilver hydrogen citrate by the method for producing a composition containing disilver hydrogen citrate according to any one of [1] to [4], and then mixing the obtained composition containing disilver hydrogen citrate with water or a citric acid solution. [6] A composition comprising disilver hydrogen citrate and silver dihydrogen citrate, or disilver hydrogen citrate and trisilver citrate, and having a silver concentration of 37.2 wt% or more and 57.9 wt% or less. [7] An antibacterial agent or an antiviral agent comprising the composition according to [6]. [Advantages of the Invention]

[0009] According to the production method of the present invention, a pure composition containing disilver hydrogen citrate with excellent solubility can be obtained simply and with high efficiency. Further, even when trisilver citrate with poor workability is mixed into disilver hydrogen citrate, the composition can be obtained by a filtration operation using the production method of the present invention. The silver hydrogen citrate-containing composition of the present invention has a broad antibacterial spectrum and further has virus-inactivating activity. Therefore, as an antibacterial agent or antiviral agent, it can be used in pharmaceuticals, quasi-drugs, oral care agents, disinfectants, detergents, cosmetics, health care products, bactericides, fungicides, preservatives, deodorants, surface treatment agents, maintenance of various process hygiene, food freshness retainers, food packaging materials, fabrics including fibers, clothing, bedding, etc., freshness retention of agricultural products, sanitary members, agricultural materials, pesticide substitutes, prevention of livestock infectious diseases, the automotive industry, etc. Further, for example, if the powder of the novel silver hydrogen citrate-containing composition of the present invention is used as a deodorant, since it has an oxidizing power derived from silver, it can react with components such as sulfur-based gases, amine-based gases, aldehyde-based gases, propionic acid, and isovaleric acid that cause bad odors to make them odorless, and it is possible to exhibit the effect as a deodorant.

Brief Description of the Drawings

[0010]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0011] In the present invention, the "diammonium hydrogen citrate-containing composition" is a composition containing at least diammonium hydrogen citrate, preferably a composition composed of diammonium hydrogen citrate and silver dihydrogen citrate, or diammonium hydrogen citrate and trisilver citrate, and may also be represented as diammonium hydrogen citrate and silver dihydrogen citrate, or diammonium hydrogen citrate and trisilver citrate obtained by the production method of the present invention. It is preferable that the composition is composed of diammonium hydrogen citrate and silver dihydrogen citrate in order to redissolve the powder of the diammonium hydrogen citrate-containing composition in citric acid or the like. The silver content contained in these diammonium hydrogen citrate-containing compositions is preferably from 36.1 wt% to 63.1 wt%, more preferably from 36.1 wt% to 53.2 wt%. That is, the solubility in water or a citric acid solution is higher for silver dihydrogen citrate than for diammonium hydrogen citrate, and higher for diammonium hydrogen citrate than for trisilver citrate. Therefore, from the viewpoint of preparing an antibacterial agent or an antiviral agent, it is more desirable that silver dihydrogen citrate is contained in the diammonium hydrogen citrate-containing composition at 25% or more. The molar ratios of the above diammonium hydrogen citrate and silver dihydrogen citrate and trisilver citrate and silver dihydrogen citrate can be calculated from the weight of the silver citrate powder obtained by drying treatment and the silver concentration measured by high-frequency inductively coupled plasma (ICP) emission spectrometry after dissolving a part of it in a nitric acid solution. The diammonium hydrogen citrate-containing composition of the present invention preferably does not substantially contain citric acid, and more preferably consists essentially of only silver dihydrogen citrate, diammonium hydrogen citrate and / or trisilver citrate. In this specification, "final pH of the mother liquor" or "final pH" refers to the pH of the aqueous solution in the step of precipitating the diammonium hydrogen citrate-containing composition. In order to control the ratio of diammonium hydrogen citrate in the diammonium hydrogen citrate-containing composition, a method of adjusting the final pH of the mother liquor from pH 2.0 to pH 5.5 is preferable. According to the present invention, the silver hydrogen citrate-containing composition consists of silver hydrogen citrate and silver dihydrogen citrate, or silver hydrogen citrate and silver citrate tribasic, and it is possible to easily obtain a powder of the silver hydrogen citrate-containing composition in which the silver content contained in the silver hydrogen citrate-containing composition consisting of silver hydrogen citrate and silver dihydrogen citrate or silver hydrogen citrate and silver citrate tribasic is 36.1 wt% or more and less than 63.1 wt%.

[0012] In this specification, "silver citrate" refers to a compound selected from the group consisting of silver dihydrogen citrate, silver hydrogen citrate, and silver citrate tribasic, and combinations thereof. Silver citrate can be represented by the following structural formula. Silver dihydrogen citrate means a silver citrate compound where x = 2 and y = 1 in the formula, silver hydrogen citrate means a silver citrate compound where x = 1 and y = 2 in the formula, and silver citrate tribasic means a silver citrate compound where x = 0 and y = 3 in the formula. Structural formula of silver citrate JPEG0007710732000001.jpg2054

[0013] One aspect of the present invention is a method for producing a silver hydrogen citrate-containing composition. First, a predetermined amount of a solvent is filled into a reaction vessel. Water is preferred as the solvent, and pure water or ion-exchanged water is more preferred.

[0014] Next, a predetermined amount of citric acid and a silver compound are added. While stirring the reaction solution, it is confirmed that the added chemicals are completely dissolved. Then, the pH of the reaction solution is checked, and subsequently, a base agent is added to raise the reaction solution to a predetermined pH value. After the reaction solution reaches the predetermined pH, stirring is continued to complete the reaction. From the viewpoint of increasing the yield of the silver hydrogen citrate-containing composition and efficiently recovering the silver hydrogen citrate-containing composition, the final pH is preferably pH 2.0 to pH 5.5, and more preferably pH 3.5 to pH 4.5.

[0015] The "citric acid" of the present invention may be an anhydride or a hydrate, but from the viewpoint of solubility, it is preferably a hydrate. The silver compound is not particularly limited, and examples thereof include silver nitrate and silver sulfate. From the viewpoint of efficiently producing a composition containing disilver hydrogen citrate, silver nitrate is preferable. Since the "base" of the present invention gradually accumulates in the system for increasing the pH value of the reaction solution, in order to prevent the generated nitrate compound from precipitating and mixing into silver citrate, sodium hydroxide or potassium hydroxide with high solubility of the generated nitrate is preferable, and sodium hydroxide is more preferable. Further, at the time of charging, it is preferably added dropwise in a small amount in the form of an aqueous solution, and more preferably, an aqueous solution of sodium hydroxide is added dropwise in a small amount.

[0016] The molar ratio of the amount of the silver compound added in the first step to the amount of citric acid is preferably 1:0.8 to 1.2, and more preferably 1:0.95 to 1.05. The reason is that the reaction solution is repeatedly used to effectively use silver. Therefore, if the silver concentration remaining in the reaction mother liquor affects the equivalent ratio of silver and citric acid involved in the reaction and changes, the yield of silver citrate will vary during subsequent reactions.

[0017] In the present invention, an amount of a silver compound and citric acid such that the amount of disilver hydrogen citrate and / or silver dihydrogen citrate, disilver hydrogen citrate and / or trisilver citrate generated in the reaction mother liquor at a desired pH becomes equal to or more than the saturation amount is required. After adding these agents to the reaction solution while stirring, a base is further added to adjust the reaction solution to a desired pH value. When the base is added at this time, silver citrate precipitates in the reaction solution accordingly, and when the stirring is stopped, it precipitates at the bottom of the reaction vessel. Then, this is recovered. The recovery method is not particularly limited, and examples thereof include filtration and decantation.

[0018] The recovered disilver hydrogen citrate and silver dihydrogen citrate, or disilver hydrogen citrate and trisilver citrate are preferably washed gently with water and then dried under normal pressure or reduced pressure. By drying, powdered disilver hydrogen citrate and silver dihydrogen citrate, or disilver hydrogen citrate and trisilver citrate can be obtained. When the proportion of trisilver citrate in the precipitated disilver hydrogen citrate-containing composition increases, the precipitate becomes a sticky cake-like shape as in the case of Comparative Example 1, and it becomes a paste on the filter, causing clogging and making filtration difficult. On the other hand, as was also revealed in Example 8, if the final pH of the mother liquor is adjusted to pH 5.5 or lower in order to make the molar ratio of the trisilver citrate it contains 42% or less, although the filtration operation of the precipitate takes some time, it was newly found that the filtration operation is possible and the disilver hydrogen citrate-containing composition can be made into powder. From the viewpoint of suppressing the thermal decomposition of the disilver hydrogen citrate-containing composition obtained by solid-liquid separation, the drying temperature is preferably 60°C or lower, more preferably 50°C or lower. The above drying may be carried out by vacuum drying or freeze drying.

[0019] In one aspect of the present invention, the reaction mother liquor after recovering disilver hydrogen citrate and silver dihydrogen citrate or disilver hydrogen citrate and trisilver citrate can be reused. It is an efficient method for producing silver citrate with less silver loss. That is, after recovering the disilver hydrogen citrate-containing composition, silver compound and citric acid are added again to the reaction mother liquor, and a base agent is further added, so that the disilver hydrogen citrate-containing composition precipitates in the reaction solution. Through the same operation, a homogeneous disilver hydrogen citrate-containing composition can be recovered. In addition, when preparing the disilver hydrogen citrate-containing composition for the first time, instead of the aqueous solvent into which citric acid and an equivalent amount of silver nitrate are added in Example 1, there is also a method of adding citric acid and sodium citrate in advance to the aqueous solvent to make a buffer solution composition with a pH of about 2 to 5 as shown in Example 1-2. The reason is that when a sodium hydroxide solution is dropped into the reaction solution, the pH of the system is stabilized and the desired pH adjustment can be ensured. Such preparation is not necessary for the step of precipitating a composition containing disilver hydrogen citrate that reuses the reaction mother liquor recovered in the second and subsequent runs in the reaction solution. The inventors have also found the invention described in Japanese Patent Application No. 2020-107646 (not published as of the filing date of this application) prior to the present invention. In the invention described in Japanese Patent Application No. 2020-107646, citric acid and sodium citrate are added in advance in an aqueous solvent to form a buffer solution composition with a pH of about 2 to 5, and a silver compound and a metal citrate are added thereto at once to precipitate a supersaturated state of disilver hydrogen citrate and / or silver dihydrogen citrate. The reason is that, as a means to keep the pH substantially constant, by adjusting the molar ratio of monovalent citrate ions to divalent citrate ions to a composition ratio corresponding to the citrate equilibrium composition at that pH, the reaction system is maintained at a constant pH from the beginning to the end, so it is judged to be a gentle and stable preparation method. Although this method is a logical and ideal basic method for obtaining a composition containing disilver hydrogen citrate, it is a complicated process that requires time, effort, and cost. As a result of further intensive efforts, the present invention has been developed. Even if the composition containing disilver hydrogen citrate obtained by the method described in Japanese Patent Application No. 2020-107646 and the method of the present invention is controlled under any same final pH conditions, the ratio of the composition containing disilver hydrogen citrate will not be the same. For example, when the final pH is adjusted to pH 4.0, the molar ratio of disilver hydrogen citrate and silver dihydrogen citrate constituting the composition containing disilver hydrogen citrate is 1:4 to 6 in the former case, but it is different from the molar ratio results shown in Examples 1, 2, and 4 of the present invention. The reason why the inside of the disilver hydrogen citrate composition is greatly different due to the difference between the former preparation method and the preparation method of the present invention is that, since a high-concentration sodium hydroxide solution is dropped in the method of the present invention, the pH around the dropping solution temporarily rises to the high pH side, generating more highly charged citric acid, and accordingly, the silver citrate composition tends to be generated. When producing a disilver hydrogen citrate-containing composition according to the production method of the present invention, nitrates (for example, sodium nitrate) accumulate in the reaction mother liquor as the number of repetitions increases. However, even if nitrates are generated, their solubility in water is very high, so they do not interfere with the reaction. Therefore, the production method of the disilver hydrogen citrate-containing composition of the present invention is excellent in mass productivity. Also, as the number of preparations increases, the amount of the reaction mother liquor increases little by little, but it does not inhibit the production reaction of the disilver hydrogen citrate-containing composition.

[0020] Here, in a reaction mother liquor environment where the pH exceeds 5.5, the resulting disilver hydrogen citrate-containing composition has the drawback that its dissolution in water is small and filtration is difficult. This is because the molar ratio of trisilver citrate in the disilver hydrogen citrate-containing composition exceeds 42% compared to disilver hydrogen citrate. As a result, the precipitate becomes a sticky cake-like shape, which turns into a paste on the filter, causing clogging and making filtration impossible. Also, forced solid-liquid separation by decantation takes a long time, and it takes too much time and cost to powderize it. Furthermore, in the dilution operation with water or citric acid solution required to adjust to the final use form in the market, the poor solubility causes it to take too much time and is not practical. The reason is that when the molar ratio of trisilver citrate in the disilver hydrogen citrate-containing composition precipitated in the reaction mother liquor exceeds 42% and occupies a large proportion, the aggregation action between fine particles due to trisilver citrate is affected, and even when trying to recover the precipitated product, the fine particles become a paste on the filter during filtration, making filtration impossible. This phenomenon was confirmed from the fact that it was difficult to filter and solid-liquid separate and recover the precipitate of the disilver hydrogen citrate-containing composition obtained in Comparative Example 1.

[0021] At present, a citric acid solution containing silver dihydrogen citrate by an electrolysis method has been put into practical use. However, in this production method, it is difficult to obtain a large amount of silver dihydrogen citrate on an industrial scale. In this production method (electrolysis method), a silver plate is immersed as an electrode plate in a citric acid solution, and a direct current is passed through it. As the reaction proceeds, water is also electrolyzed on the electrode surface accordingly, and minute bubbles cover the electrode surface, making it difficult for the current to flow and reducing the production capacity of silver dihydrogen citrate. It takes a long time (for example, 144 hours) to raise the concentration of the final form of silver dihydrogen citrate to 2400 ppm. For this reason, this method is not suitable for industrial mass production, the cost is high, and the silver concentration is limited to about 2400 ppm of the silver concentration in a 6 wt% citric acid solution. Since the final form of the reactant is a citric acid solution in which silver dihydrogen citrate is dissolved, it occupies a large amount of space during storage and transportation. Further, in order to obtain a higher concentration of silver ions, a higher concentration of citric acid is required, but this has the drawback of increasing the viscosity of the citric acid solution and deteriorating the workability during production. Furthermore, although the silver dihydrogen citrate solution (silver concentration 2400 ppm) produced by the electrolysis method can be freeze-dried and powdered, the production cost thereby becomes high, and moreover, the obtained powder is a mixed powder composed of 10 wt% silver dihydrogen citrate and 90 wt% citric acid, so it is not possible to efficiently obtain only a pure silver hydrogen citrate-containing composition.

[0022] On the other hand, according to the present invention, a silver hydrogen citrate-containing composition that is easily soluble in water or a citric acid solution can be obtained by a simple method and on an industrial scale. Further, since the silver hydrogen citrate-containing composition can be obtained as a dry powder containing no impurities, the occupied volume during storage and transportation can be reduced. Furthermore, due to the solubility of the silver hydrogen citrate-containing composition, it also becomes easy to prepare a high-concentration silver citrate solution (for example, a silver ion concentration exceeding 2400 ppm) by adding the silver hydrogen citrate-containing composition to a citric acid solution. A solution obtained by dissolving the obtained powder of the silver hydrogen citrate-containing composition in water or a citric acid solution can be further diluted to obtain an antibacterial agent or an antiviral agent using these novel mixed powders containing a silver hydrogen citrate mixed powder having a desired silver concentration.

[0023] From the viewpoint of redissolving in water or a citric acid solution, the above antibacterial agent or antiviral agent is preferably produced by mixing the composition containing disilver hydrogen citrate obtained by the production method of the present invention with a 1 wt% to 10 wt% citric acid solution, preferably a 5 wt% to 7 wt% citric acid solution.

[0024] Depending on the purpose, the above antibacterial agent or antiviral agent can be appropriately blended with antibacterial agents and known additives other than the composition containing disilver hydrogen citrate, such as preservatives, stabilizers, humectants, ultraviolet absorbers, fragrances, surfactants, viscosity modifiers, pH adjusters, etc. as antibacterial and antiviral agents.

[0025] The silver concentration in the above antibacterial agent or antiviral agent is not particularly limited. However, as is clear from the test results in Table 3 of Example 10, the minimum growth inhibitory concentration of silver that exhibits antibacterial effects against Gram-negative bacteria, Gram-positive bacteria, yeast, and fungi, and the silver concentration that enables antiviral properties as revealed by the antiviral test results in Tables 4 and 6 of the same example. Furthermore, from the test results in Tables 5 and 7 of the same example, it was found that the silver concentration that has no cytotoxicity and is safe is preferably 1.0 ppm to 200 ppm, more preferably 5 ppm to 100 ppm, and even more preferably 30 ppm to 50 ppm.

[0026] The disilver hydrogen citrate-containing composition of the present invention can exhibit an antibacterial effect by silver ions derived from a silver compound, regardless of the difference in the type of bacteria and the presence or absence of acquisition of drug resistance of bacteria by antibiotics. Further, an antibacterial agent or an antiviral agent obtained by diluting the powder of the disilver hydrogen citrate-containing composition of the present invention with water or a citric acid solution to a desired silver ion concentration coats the surface of the adherend with these by a coating operation, an impregnation operation, or the like, and the disilver hydrogen citrate-containing composition of the present invention remains on the surface at the trace where the moisture has evaporated. As a result, the processed surface to which the disilver hydrogen citrate-containing composition is attached has an antibacterial or antiviral function. Further, even if it is recoated with alcohol or the like from above, the effect persists because the disilver hydrogen citrate-containing composition remains on the surface as it is when it evaporates. The effect of the antibacterial agent and the antiviral agent of the disilver hydrogen citrate-containing composition persists forever unless the surface is washed off with water or the like. Therefore, this agent has high and persistent antibacterial and antiviral properties, has a broad antibacterial spectrum, and further has a virus-inactivating ability, and thus can be used as a useful antibacterial agent or antiviral agent. For example, in List N which publishes effective disinfectant products for Covid-19 approved by the US Environmental Protection Agency (EPA), among the disinfectants in this list, the EPA-registered food contact surface disinfectant that has been safely approved and does not need to be washed off even if it directly touches food, has high safety, sufficient bactericidal power against Covid-19, and furthermore, it is reported that the residual property of its ability is ensured for more than 24 hours. It is considered to be made using Silverion2400 composed of silver dihydrogen citrate and citric acid manufactured by Pure Bioscience. PURE(R) Hard Surface disinfectant (EPA Reg. No. 72977-5-73912) was added and published in List N on June 24, 2020 after receiving approval from the US Environmental Protection Agency (EPA). Its antibacterial or antiviral functional safety is due to the silver ions in silver dihydrogen citrate, and since its silver concentration is specified as 30 ppm in the technical data, the silver concentration of the silver dihydrogen citrate-containing composition of the present invention containing silver dihydrogen citrate is from 37.2% to 57.When adjusting the amount of the antibacterial or antiviral agent to the same silver concentration of 30 ppm using 1 kg of powder with a content of 9% or less, first prepare an aqueous citric acid solution by adjusting citric acid monohydrate to a concentration of about 5 wt% with purified water treated by ion exchange resin treatment, RO membrane treatment, EDI treatment, etc., or deionized water of the same or higher quality. Then, prepare a stock solution of the silver hydrogen citrate-containing composition of the present invention with a silver concentration of 2,400 ppm by diluting and dissolving 1 kg of the composition 155 to 241 times. Store the stock solution. If necessary, further dilute it 80 times with the deionized water to prepare a solution with a silver concentration of 30 ppm. In this way, an amount of 12,400 to 19,280 liters can be easily and quickly secured. When this is directly spray-coated as an antibacterial or antiviral agent on the face, head, fingers, wrists, etc., and the liquid of the antibacterial or antiviral agent is evenly spread by hand over the entire surface of the skin, hair, etc., assuming that a sufficient amount per person per application is about 10 ml, it is possible to spray and coat these parts 1,240,000 to 1,928,000 times in total. On the traces where the moisture has evaporated, this antibacterial or antiviral agent remains on the surface of the skin, etc. in a uniform and high-concentration state, and its effect persists until it is washed off with water. Also, when evenly spray-coating the antibacterial or antiviral agent diluted to a silver concentration of 30 ppm on porous materials such as masks, clothes, living spaces, and filters, on the traces where the moisture has evaporated, this antibacterial or antiviral agent adheres to these porous surfaces and remains in a uniform and high-concentration state, and its effect persists until it is washed off with water. Furthermore, when evenly spray-coating the antibacterial or antiviral agent diluted to a silver concentration of 30 ppm on non-porous materials such as tableware, metal, glass, building materials, plastics, floors, tiles, and concrete, on the traces where the moisture has evaporated, this antibacterial or antiviral agent adheres to these non-porous surfaces and remains in a uniform and high-concentration state, and its effect persists until it is washed off with water. Therefore, for example, as a recent case, the problem of the rapid spread of infection on board the USS Theodore Roosevelt aircraft carrier, where some crew members contracted Covid-19, and ultimately about 60% of the 5,000 crew members were infected during the voyage, is still fresh in memory. At that time, even though it was difficult to store a dilution solution of silver at a concentration of 30 ppm in a volume ranging from 12,400 liters (62 drums of 200 liters each) to 19,280 liters (96 drums of 200 liters each) as a standby for unexpected emergencies, if the powder of the composition containing disilver hydrogen citrate of the present invention in this new form, which requires the least amount of occupied space, was stored in a container with a humidity-blocking and light-shielding function such as a pale can on board the aircraft carrier, with 1 kg of the powder and 12.05 kg of citric acid monohydrate, then, by means of the device for obtaining the deionized water that is considered to be installed on all ships, a 10-ml solution of an antibacterial or antiviral agent with a diluted silver concentration of 30 ppm could be provided to the crew members. This would serve as an antibacterial or antiviral agent with continuous effectiveness against 1,240,000 to 1,928,000 doses of Covid-19. Moreover, it is considered that the remaining amount, after being spray-applied to human skin, the head, etc., could also be applied by spray or other means to all objects that humans might touch, made of porous or non-porous materials. It is easily conceivable that this would enable an appropriate and sustainable response to this unexpected emergency through the antibacterial and antiviral functions.

[0027] As a usage mode of the "antibacterial agent" or "antiviral agent" in the present invention, in the medical field, as pharmaceuticals, it can be used as a medical disinfectant, a wound dressing, a burn dressing, a bedsore dressing, a gastric fistula, an intestinal fistula, PEG, etc., in all commercial forms such as catheters, indwelling needles, gauze, bandages, dressings, plaster bandages, etc. for covering the affected area, as a composition of an antibacterial agent or an antiviral agent. Also, it can be used as a composition of an antibacterial agent or an antiviral agent in all commercial forms to prevent secondary infections from medical devices that people may touch, office equipment, household appliances, lockers, all clothes, masks, protective goggles, surgical caps, gloves, preventive clothing, aprons, etc. around medical staff in the hospital, hospital beds, blankets, sheets, blanket covers, pillows, pillow covers, partition curtains, etc., and patient rooms, intensive care units, examination rooms, treatment rooms, laboratories, physical therapy rooms, corridors, doctor's offices, pharmacies, administrative offices, cafeterias, kitchens, bathrooms, toilets, waiting rooms, etc., as well as medical waste and laundry.

[0028] As a usage mode of the "antibacterial agent" or "antiviral agent" in the present invention, in the personal care field, it is related to disinfectant products for the face, head, hands, feet, whole body, hair, body hair, and skin, feminine hygiene products, intimate care products, foot care products, oral care products such as toothpaste, dental floss products, sunscreen, after-sun care products, and lipstick products. In the cosmetics field, it is related to basic cosmetics, makeup, underarm deodorants, underarm antiperspirants, shampoos, rinses, conditioners, treatments, and cleansing agents. In the medical field, it can be used as a composition of an antibacterial agent or an antiviral agent in all commercial forms related to hair growth promoters, hair removers, depigmenting agents, hair colorants, anti-acne agents, and disinfection of the oral cavity, anus, urethra, vagina, etc.

[0029] As usage modes of the "antibacterial agent" or "antiviral agent" in the present invention, it can be used in all activity areas of the military and the Self-Defense Forces, all activity areas of the police, all activity areas of the Japan Coast Guard, all activity areas of the fire department and rescue teams, and all activity areas of kindergartens, nurseries, childcare facilities, toys for play, schools, and their dormitories, cafeterias, etc., and further in families, hospitals, nursing facilities, hotels, beauty salons, barbershops, restaurants, sports gyms, offices, workplaces, factories, public facilities, etc., and all articles that people can touch inside means of transportation such as airplanes, helicopters, trains, buses, monorails, gondolas, ships, automobiles, etc., and inside air conditioners, filters, etc. For example, among these, it can be used for doors, furniture, fabric products, household appliances, switches, tableware, cooking utensils, cooking ranges, sinks, etc., floor surfaces, wall surfaces, glass windows, bathtubs, toilets, bedding, utensils and toys for infants and young children, equipment, devices, peripheral equipment, tools, desks, desk peripheral equipment, members inside automobiles, clothing, masks, protective goggles, gloves, hats, shoes, aprons, etc. It can be used as a composition of an antibacterial agent or an antiviral agent in a new functional agent product in combination with a surface cleaning composition containing a detergent, a soil suspending agent, a fluorescent brightening agent, an abrasive, etc., waxes, etc.

[0030] As usage modes of the "antibacterial agent" or "antiviral agent" in the present invention, for the maintenance and management of hygiene in the food processing factory field, such as mechanical parts, their peripheral equipment, utensils, inside air conditioners and filters, etc., and in the food contact inner surface process, inside food packaging materials, etc., for the maintenance and management of hygiene of all working environments, clean environment preservation facilities, articles, surfaces, spaces, etc., and for the maintenance and management of hygiene of all clothing, hats, masks, protective goggles, gloves, shoes, etc. worn by workers, it can be used as a composition of an antibacterial agent or an antiviral agent in any commercial form.

[0031] As a usage mode of the "antibacterial agent" or "antiviral agent" in the present invention, in the agricultural field, it can be used as an antibacterial agent or antiviral agent in the form of a product such as a disease prevention agent that replaces antibiotics and organic pesticides used to control the microbial contamination of harvested fruits, vegetables, root vegetables, rhizomes, bulbs, seafood, and meats in general, maintain freshness, and replace organic pesticides for molds, bacteria, and viruses in grains, etc., and a highly safe pesticide for molds, bacteria, and viruses in soil disease-causing fungi.

[0032] As a usage mode of the "antibacterial agent" or "antiviral agent" in the present invention, in the livestock industry, it can be used as a composition of an antibacterial agent or antiviral agent in the form of a product for maintaining and managing the hygiene of all items, surfaces, spaces, and the surface of the meat itself that come into contact with the meat during the meat processing process, mechanical parts, their peripheral equipment, the interior and filters of air conditioners, utensils, etc., and the hygiene maintenance and management of the food contact inner surface process, etc., and the hygiene maintenance and management of all working environments, clean environment preservation facilities, items, surfaces, spaces, etc., and all clothes, hats, masks, protective goggles, gloves, boots, etc. worn by workers, and further for all animal drugs, etc. in the form of a product for all livestock infectious diseases (such as bovine dermatomycosis, mastitis in dairy cows, avian influenza, swine cholera, etc.) caused by any mold, bacteria, or virus.

[0033] As a usage mode of the "antibacterial agent" or "antiviral agent" in the present invention, in the industrial field, it can be used as a composition of an antibacterial agent or antiviral agent in any form of product for various water treatment devices such as filters, cooling water, service water pools, swimming pools, hot water systems, air conditioning systems, hot springs, mineral springs, pipes, tanks, water treatment equipment, peripheral equipment, pumps, etc. for cooling towers, dryers, and compressors, and for various products such as preservatives, anti-mold agents, and antimicrobial drugs. That is, various industrial applications are possible.

[0034] As the method of use in the usage mode of the "antibacterial agent" or "antiviral agent" in the present invention, any form of product in which a film is formed on the surface of any object by methods such as spraying, coating, spraying, dipping, transfer, etc., or any liquid, solid, semi-solid, gel, sol, stick, capsule form, and the product form conforming to the usage method according to the product shape, or the product form of a composition in which the fiber itself having a sustained-release effect or an emergency treatment effect in an emergency, or a bag, container, capsule, etc. containing this, may be used in any form of product usage method.

[0035] Also, for example, if the powder of the novel composition containing disilver hydrogen citrate of the present invention is used as a deodorant, since it has an oxidizing power derived from silver, it can also react with components such as sulfur-based gases, amine-based gases, aldehyde-based gases, propionic acid, isovaleric acid, etc. that cause bad odors to make them odorless, and can exhibit the effect as a deodorant.

[0036] If this novel composition powder containing disilver hydrogen citrate obtained by the production method of the present invention is used as an antiviral agent, this agent can also inactivate mutant virus strains such as the H5N1 subtype virus, which is the cause of highly pathogenic avian influenza (HPAI) having an envelope similar to that of, for example, influenza A virus (H3N2), and can exhibit an effect as a useful antiviral agent. Also, although the severe acute respiratory syndrome coronavirus (SARS) or the pathogenic coronavirus COVID-19 has a spike protein structure different from that of influenza, if it has an envelope sensitive to silver ions, it is considered that it can be inactivated in the same way.

[0037] Composition of the precipitated composition containing disilver hydrogen citrate Shows the calculation method of the molar ratio occupied by silver dihydrogen citrate and disilver hydrogen citrate or silver dihydrogen citrate and trisilver citrate in the composition containing disilver hydrogen citrate. From the molecular formula of silver citrate, silver dihydrogen citrate is composed of C6H7O7·Ag. Its molecular weight is 298.99. Therefore, since the atomic weight of silver is 107.87, the silver concentration in silver dihydrogen citrate is 107.87 / 298.99×100 = 36.1 wt%. Similarly, that of disilver hydrogen citrate is represented by C6H6O7·2Ag and its molecular weight is 405.86. Therefore, the silver concentration in disilver hydrogen citrate is 107.87×2 / 405.86×100 = 53.2 wt%. Trisilver citrate is represented by C6H5O7·3Ag. Its molecular weight is 512.73. Therefore, the silver concentration in trisilver citrate is 107.87×3 / 512.73×100 = 63.1 wt%. That is, the fact that the silver concentration in the obtained disilver hydrogen citrate-containing composition is in the range of 36.1 wt% to 53.2 wt% indicates that this silver citrate is composed of silver dihydrogen citrate and disilver hydrogen citrate. Similarly, the fact that the silver concentration in the disilver hydrogen citrate-containing composition is in the range of 53.2 wt% to 63.1 wt% indicates that this disilver hydrogen citrate-containing composition is composed of disilver hydrogen citrate and trisilver citrate.

[0038] Method for determining the molar composition ratio of silver dihydrogen citrate and disilver hydrogen citrate For example, taking the following Example 1 as an example, the silver concentration of the obtained disilver hydrogen citrate-containing composition is 49.5 wt%. Since this means that the silver concentration in the disilver hydrogen citrate-containing composition is within the range of 36.1 wt% to 53.2 wt%, it shows that this sample is a composition composed of silver dihydrogen citrate and disilver hydrogen citrate. Here, if the abundance ratio of silver dihydrogen citrate (by weight) is X, then (0 < X < 1) The following equation holds. 36.1X + 53.2(1 - X) = 49.5 From this, X = 0.217 is obtained, and it can be seen that this disilver hydrogen citrate-containing composition is composed of 21.7 wt% of silver dihydrogen citrate and 78.3 wt% of disilver hydrogen citrate. Furthermore, if the weight ratio (wt%) of each silver citrate is divided by the molecular weight of that silver citrate, the molar ratio can be obtained. Calculated in this way, the molar ratio of silver dihydrogen citrate to silver hydrogen citrate in this silver citrate was 0.27 to 0.73.

[0039] Molar composition ratio of silver hydrogen citrate and silver citrate Similar to the above calculation example, for example, taking Example 8 below, the silver concentration of the obtained silver hydrogen citrate-containing composition is 57.9 wt%. This means that the silver concentration in the silver hydrogen citrate-containing composition is in the range of 53.2 wt% to 63.1 wt%, indicating that this sample is a composition composed of silver hydrogen citrate and silver citrate. Here, if the abundance ratio (by weight) of silver hydrogen citrate is Y, then (0 < Y < 1) The following equation holds. 53.2Y + 63.1(1 - Y) = 57.9 From this, Y = 0.527 is obtained, and it can be seen that this sample is composed of 52.7 wt% of silver hydrogen citrate and 47.3 wt% of silver citrate. Furthermore, if the respective weight ratios (wt%) are divided by the molecular weight of the silver citrate, the respective molar ratios can be obtained. Calculated in this way, the molar ratio of silver hydrogen citrate to silver citrate in this silver hydrogen citrate-containing composition was 0.58 to 0.42.

[0040] The present invention will be described in more detail below based on examples, but the present invention is not limited by these examples.

Examples

[0041] <Example 1: Production of a silver hydrogen citrate-containing composition. (When the final pH of the reaction solution is 4.0)> At room temperature (25 °C), 20.8 g (0.10 mol) of citric acid monohydrate and 17.0 g (0.1 mol) of silver nitrate were accurately weighed into 1000 mL of ion-exchanged water, and these were added to obtain a reaction solution. After confirming that the added chemicals were completely dissolved and the reaction solution became transparent, a sodium hydroxide solution (8 wt%) was added dropwise little by little to the reaction solution, and the reaction solution with a pH of 1.6 was raised to pH 4.0. The reaction solution began to become turbid 2 to 3 minutes after the start of the dropwise addition of the sodium hydroxide solution. Stirring was continued for another 3 hours after the reaction solution reached pH 4.0 to promote the reaction. In this way, a supersaturated aqueous solution in which a silver hydrogen citrate-containing composition precipitated was prepared. Thereafter, stirring was stopped, and the reaction solution was subjected to solid-liquid separation by suction filtration using a No. 5C standard filter paper (pore size: 1 μm). The filter residue was gently washed with water, placed in a sealed dryer, and dried at 50 °C under reduced pressure for 2 weeks to obtain 18.95 g of a powdery silver hydrogen citrate-containing composition. The vacuum pump used at this time was a diaphragm type vacuum pump (DA-20 type manufactured by ULVAC Kiko Co., Ltd.), and the air pressure in the dryer was constantly maintained at 0.05 atm or less.

[0042] Analysis of the silver concentration in the reaction mother liquor, which is the filtrate obtained by solid-liquid separation by suction filtration, was carried out by sampling a small amount of it, diluting it with a dilute nitric acid solution, and measuring it using an inductively coupled plasma optical emission spectrometer (ICP S 8000 manufactured by Shimadzu Corporation), and it was 2200 ppm. On the other hand, the silver concentration in the silver hydrogen citrate-containing composition obtained by pulverizing the solid-liquid separated filter residue into a powder by the above method was determined by sampling a small amount of it, accurately weighing it, and measuring the weight. It was dissolved in 100 ml of dilute nitric acid (2 M / L) to prepare a sample, and the above ICP analysis was performed to determine the silver concentration. At this time, the silver concentration of the silver hydrogen citrate-containing composition powder was 49.5 wt%. Since the silver concentration in the silver hydrogen citrate-containing composition is within the range of 36.1 wt% to 53.2 wt%, according to the above-described calculation method, it is shown that the sample of Example 1 is a composition composed of silver dihydrogen citrate and silver hydrogen citrate. The result of the molar ratio in this exemplified calculation method was that the molar ratio of silver dihydrogen citrate to silver hydrogen citrate in the silver hydrogen citrate-containing composition was 0.27 to 0.73.

[0043] <Example 1-2: Production of a composition containing disilver hydrogen citrate. When the initial deionized water in Example 1 was replaced with a citrate buffer (pH 4) only for the first time> The deionized water in Example 1 was replaced with a citrate buffer (pH 4) only for the first time, and when the sodium hydroxide solution was added dropwise to adjust the pH of the mother liquor to the desired value, it was examined whether the dropping state of the sodium hydroxide solution affected the reaction product. It was prepared according to the preparation method of Example 1 above. For the citrate buffer (pH 4), 14.0 g of citric acid monohydrate and 12.6 g of sodium citrate dihydrate were previously added to 1000 mL of deionized water to prepare a buffer solution with a pH of 4. Subsequently, 20.8 g (0.1 mol) of citric acid monohydrate and 17.0 g (0.1 mol) of silver nitrate were accurately weighed in the same manner as in Example 1 and added to the above citrate buffer (pH 4). Subsequently, in Example 1, 98 mL of a sodium hydroxide solution (8 wt%) was added dropwise to the reaction mother liquor at a rate of about 10 mL / min. to adjust the pH to 4. The dropping operation took about 15 minutes. On the other hand, in this Example 1-2, 80 mL of a sodium hydroxide solution (8.0 wt%) was added all at once, and the remaining 21 mL was carefully added dropwise to adjust the pH of the mother liquor to pH 4. The time required for this was about 3 minutes. The subsequent preparation steps were the same as those in Example 1. In this way, 19.35 g of a powdery composition containing disilver hydrogen citrate was obtained. Example 1-2 can shorten the operation time compared to Example 1. Although such a method for preparing a composition containing disilver hydrogen citrate is possible, it is necessary to add a step of preparing the citrate buffer (pH 4), and furthermore, citric acid and sodium citrate are separately required as raw materials for the citrate buffer (pH 4).

[0044] <Example 2: Production of a composition containing disilver hydrogen citrate. Reuse of the reaction mother liquor at (pH 4.0)> While stirring, 20.8 g (0.10 mol) of citric acid (monohydrate) and 17.0 g (0.1 mol) of silver nitrate were accurately weighed and added to 1.12 L of the reaction mother liquor, which was the filtrate obtained by suction filtration and solid-liquid separation from Example 1. After confirming that the added chemicals were completely dissolved and the reaction solution became completely transparent, a sodium hydroxide solution (8 wt%) was added dropwise to the reaction solution to adjust the reaction solution to pH 4.0. The reaction solution began to become turbid 2 to 3 minutes after the start of dropping the sodium hydroxide solution. Stirring was continued for another 3 hours after the reaction solution reached pH 4.0 to promote the reaction. In this way, a supersaturated aqueous solution in which the silver hydrogen citrate-containing composition precipitated was prepared. After that, stirring was stopped, and all of the reaction solution was subjected to solid-liquid separation by suction filtration using a No. 5C standard filter paper (pore size: 1 μm). The filtration residue was gently washed with water and dried at 50 °C under reduced pressure for 2 weeks to obtain 23.59 g of a powdery silver hydrogen citrate-containing composition. The analysis result of its silver concentration, which was treated in the same manner as in Example 1, was 50.4 wt% in the powder of the silver hydrogen citrate-containing composition. Since the silver concentration of this silver hydrogen citrate-containing composition was within the range of 36.1 wt% to 53.2 wt%, this sample of Example 2 was also shown to be a composition composed of silver dihydrogen citrate and silver hydrogen citrate. When calculating the molar ratio according to Example 1, the molar ratio of silver dihydrogen citrate to silver hydrogen citrate in this silver hydrogen citrate-containing composition was 0.21 to 0.79.

[0045] <Example 3: Production of silver hydrogen citrate-containing composition. (Reuse of reaction mother liquor at pH 3.6)> While stirring, 20.8 g (0.10 mol) of citric acid (monohydrate) and 16.8 g (0.1 mol) of silver nitrate were accurately weighed and added to 1.25 L of the reaction mother liquor, which was the filtrate obtained by suction filtration in Example 2 and subjected to solid-liquid separation. Thereafter, in the same manner as in Example 1, it was confirmed that the added chemicals were completely dissolved and the reaction solution became completely transparent, and then a sodium hydroxide solution (8 wt%) was added dropwise to the reaction solution to adjust the reaction solution to pH 3.6. The reaction solution began to become turbid 2 to 3 minutes after the start of the dropwise addition of the sodium hydroxide solution. Stirring was continued for another 3 hours after the reaction solution reached pH 3.6 to promote the reaction. In this way, a supersaturated aqueous solution in which a silver hydrogen citrate-containing composition precipitated was prepared. Thereafter, stirring was stopped, and all of the reaction solution was subjected to solid-liquid separation by suction filtration using a No. 5C standard filter paper (pore size: 1 μm). The filter residue was gently washed with water and dried at 50 °C under reduced pressure for 2 weeks to obtain 23.95 g of a powdery silver hydrogen citrate-containing composition. When treated in the same manner as in Example 1, the analysis result of the silver concentration showed that the silver concentration in the powder of the silver hydrogen citrate-containing composition was 46.6 wt%. Since the silver concentration was within the range of 36.1 wt% to 53.2 wt%, this sample of Example 3 was also shown to be a composition composed of silver dihydrogen citrate and silver hydrogen citrate. When calculating the molar ratio according to Example 1, the molar ratio of silver dihydrogen citrate to silver hydrogen citrate in this silver hydrogen citrate-containing composition was 0.46 to 0.54.

[0046] <Example 4: Production of a silver hydrogen citrate-containing composition. Production using a 2-fold concentration of raw materials at (pH 4.0). And reuse of the reaction mother liquor> While stirring, 42.0 g (0.20 mol) of citric acid (monohydrate) and 34.0 g (0.20 mol) of silver nitrate were accurately weighed and added to 1.41 L of the reaction mother liquor, which was the filtrate obtained by suction filtration in Example 3 and subjected to solid-liquid separation. Thereafter, in the same manner as in Example 1, it was confirmed that the added chemicals were completely dissolved and the reaction solution became completely transparent, and then a sodium hydroxide solution (8 wt%) was dropped into the reaction solution to adjust the reaction solution to pH 4.0. The reaction solution began to become turbid 2 to 3 minutes after the start of dropping the sodium hydroxide solution. Stirring was continued for another 3 hours after the reaction solution reached pH 4.0 to promote the reaction. In this way, a supersaturated aqueous solution in which a silver hydrogen citrate-containing composition precipitated was prepared. Thereafter, stirring was stopped, and all of the reaction solution was subjected to solid-liquid separation by suction filtration using a No. 5C standard filter paper (pore size: 1 μm). The filtration residue was gently washed with water and dried at 50 °C under reduced pressure for 2 weeks to obtain 45.49 g of a powdery silver hydrogen citrate-containing composition. When treated in the same manner as in Example 1, the analysis result of its silver concentration showed that the silver concentration in the powder of the silver hydrogen citrate-containing composition was 49.8 wt%. Since the silver concentration was within the range of 36.1 wt% to 53.2 wt%, this sample of Example 4 was also shown to be a composition composed of silver dihydrogen citrate and silver hydrogen citrate. When calculating the molar ratio according to Example 1, the molar ratio of silver dihydrogen citrate to silver hydrogen citrate in this silver hydrogen citrate-containing composition was 0.25 to 0.75.

[0047] <Example 5: Production of a silver hydrogen citrate-containing composition. Production using a 2-fold concentration of raw materials at (pH 4.5). And reuse of the reaction mother liquor> While stirring, 42.0 g (0.20 mol) of citric acid (monohydrate) and 34.0 g (0.20 mol) of silver nitrate were precisely weighed and added to 1.68 L of the reaction mother liquor, which was the filtrate obtained by suction filtration in Example 4 and subjected to solid-liquid separation. Thereafter, in the same manner as in Example 1, it was confirmed that the added chemicals were completely dissolved and the reaction solution became completely transparent, and then a sodium hydroxide solution (8 wt%) was dropped into the reaction solution to adjust the reaction solution to pH 4.0. The reaction solution began to become turbid 2 to 3 minutes after the start of dropping the sodium hydroxide solution. Stirring was continued for another 3 hours after the reaction solution reached pH 4.5 to promote the reaction. In this way, a supersaturated aqueous solution in which a silver hydrogen citrate-containing composition precipitated was prepared. Thereafter, stirring was stopped, and all of the reaction solution was subjected to solid-liquid separation by suction filtration using a No. 5C standard filter paper (pore size: 1 μm). The filtration residue was gently washed with water and dried at 50 °C under reduced pressure for 2 weeks to obtain 45.49 g of a powdery silver hydrogen citrate-containing composition. Treated in the same manner as in Example 1, the analysis result of the silver concentration showed that the silver concentration in the powder of the silver hydrogen citrate-containing composition was 49.8 wt%. Since the silver concentration was within the range of 36.1 wt% to 53.2 wt%, this sample of Example 5 was also shown to be a composition composed of silver dihydrogen citrate and silver hydrogen citrate. Calculating the molar ratio according to Example 1, the molar ratio of silver dihydrogen citrate to silver hydrogen citrate in this silver hydrogen citrate-containing composition was 0.25 to 0.75.

[0048] <Example 6: Production of a silver hydrogen citrate-containing composition. Production using a 2-fold concentration of raw materials at (pH 2.5). And reuse of the reaction mother liquor> While stirring, 42.0 g (0.20 mol) of citric acid (monohydrate) and 34.0 g (0.20 mol) of silver nitrate were accurately weighed and added to 1.87 L of the reaction mother liquor, which was the filtrate obtained by suction filtration in Example 5 and subjected to solid-liquid separation. Thereafter, in the same manner as in Example 1, it was confirmed that the added chemicals were completely dissolved and the reaction solution became completely transparent, and then a sodium hydroxide solution (8 wt%) was added dropwise to the reaction solution to adjust the reaction solution to pH 2.5. The reaction solution began to become turbid 2 to 3 minutes after the start of the dropwise addition of the sodium hydroxide solution. Stirring was continued for another 3 hours after the reaction solution reached pH 2.5 to promote the reaction. In this way, a supersaturated aqueous solution in which a silver hydrogen citrate-containing composition precipitated was prepared. Thereafter, stirring was stopped, and the entire reaction solution was subjected to solid-liquid separation by suction filtration using a No. 5C standard filter paper (pore size: 1 μm). The filter residue was gently washed with water and dried at 50 °C under reduced pressure for 2 weeks to obtain 44.27 g of a powdery silver hydrogen citrate-containing composition. Treated in the same manner as in Example 1, the analysis result of its silver concentration showed that the silver concentration in the powder of the silver hydrogen citrate-containing composition was 39.7 wt%. Since the silver concentration was within the range of 36.1 wt% to 53.2 wt%, this sample of Example 6 was also shown to be a composition composed of silver dihydrogen citrate and silver hydrogen citrate. Calculating the molar ratio according to Example 1, the molar ratio of silver dihydrogen citrate to silver hydrogen citrate in this silver hydrogen citrate-containing composition was 0.84 to 0.16.

[0049] <Example 7: Production of a silver hydrogen citrate-containing composition. Production using a 2-fold concentration of raw materials at (pH 2.0). And reuse of the reaction mother liquor> While stirring, 42.0 g (0.20 mol) of citric acid (monohydrate) and 34.0 g (0.20 mol) of silver nitrate were precisely weighed and added to 2.10 L of the reaction mother liquor, which was the filtrate obtained by suction filtration in Example 6 and subjected to solid-liquid separation. Thereafter, in the same manner as in Example 1, it was confirmed that the added chemicals were completely dissolved and the reaction solution became completely transparent, and then a sodium hydroxide solution (8 wt%) was added dropwise to the reaction solution to adjust the reaction solution to pH 2.0. The reaction solution began to become turbid 2 to 3 minutes after the start of the dropwise addition of the sodium hydroxide solution. Stirring was continued for another 3 hours after the reaction solution reached pH 2.0 to promote the reaction. In this way, a supersaturated aqueous solution in which a silver hydrogen citrate-containing composition precipitated was prepared. Thereafter, the stirring was stopped, and all of the reaction solution was subjected to solid-liquid separation by suction filtration using a No. 5C standard filter paper (pore size: 1 μm). The filter residue was gently washed with water and dried at 50 °C under reduced pressure for 2 weeks to obtain 26.33 g of a powdery silver hydrogen citrate-containing composition. Treated in the same manner as in Example 1, the analysis result of its silver concentration showed that the silver concentration in the powder of the silver hydrogen citrate-containing composition was 37.2 wt%. Since the silver concentration was within the range of 36.1 wt% to 53.2 wt%, this sample of Example 7 was also shown to be a composition composed of silver dihydrogen citrate and silver hydrogen citrate. Calculating the molar ratio according to Example 1, the molar ratio of silver dihydrogen citrate to silver hydrogen citrate in this silver hydrogen citrate-containing composition was 0.95 to 0.05.

[0050] <Example 8: Production of a silver hydrogen citrate-containing composition. Production using a 2-fold concentration of raw materials at (pH 5.5). And reuse of the reaction mother liquor> To 2.72 L of the reaction mother liquor, which was the filtrate obtained by solid-liquid separation by suction filtration in Comparative Example 1, 42.0 g (0.20 mol) of citric acid (monohydrate) and 34.0 g (0.20 mol) of silver nitrate were precisely weighed and added to the reaction mother liquor, which was the above-mentioned filtrate, while stirring. Thereafter, in the same manner as in Example 1, it was confirmed that the added chemicals were completely dissolved and the reaction solution became completely transparent, and then a sodium hydroxide solution (8 wt%) was added dropwise to the reaction solution to adjust the reaction solution to pH 5.5. The reaction solution began to become turbid 2 to 3 minutes after the start of the dropwise addition of the sodium hydroxide solution. Stirring was continued for another 3 hours after the reaction solution reached pH 5.5 to promote the reaction. In this way, a supersaturated aqueous solution in which a silver hydrogen citrate-containing composition precipitated was prepared. Thereafter, stirring was stopped, and all of the reaction solution was subjected to solid-liquid separation by suction filtration using a No. 5C standard filter paper (pore size: 1 μm). Solid-liquid separation could not be easily performed as in the case of the precipitate of the silver hydrogen citrate-containing composition precipitated in the low pH range. The obtained silver citrate was dried under reduced pressure at 50 °C for 2 weeks to obtain 37.59 g of a powdery silver hydrogen citrate-containing composition. Treated in the same manner as in Example 1, the analysis result of its silver concentration showed that the silver concentration in the powder of the silver hydrogen citrate-containing composition was 57.9 wt%. Since this means that the silver concentration in the silver hydrogen citrate-containing composition is within the range of 53.2 wt% to 63.1 wt%, according to the above-described calculation method, this sample of Example 8 is shown to be a composition composed of silver dihydrogen citrate and trisilver citrate. The result of the molar ratio by the exemplified calculation method was that the molar ratio of silver dihydrogen citrate to silver hydrogen citrate in this silver hydrogen citrate-containing composition was 0.58 to 0.42.

[0051] <Example 9: Production of a silver hydrogen citrate-containing composition. Production using a 2-fold concentration of raw materials at (pH 5.0). And reuse of the reaction mother liquor> While stirring, 42.0 g (0.20 mol) of citric acid (monohydrate) and 34.0 g (0.20 mol) of silver nitrate were precisely weighed and added to 3.12 L of the reaction mother liquor, which was the filtrate obtained by suction filtration in Example 8 and subjected to solid-liquid separation. Thereafter, in the same manner as in Example 1, it was confirmed that the added chemicals were completely dissolved and the reaction solution became completely transparent. Then, a sodium hydroxide solution (8 wt%) was dropped into the reaction solution to adjust the reaction solution to pH 5.0. The reaction solution began to become turbid 2 to 3 minutes after the start of dropping the sodium hydroxide solution. Stirring was continued for another 3 hours after the reaction solution reached pH 5.0 to promote the reaction. In this way, a supersaturated aqueous solution in which silver dihydrogen citrate and trisilver citrate were precipitated was prepared. Thereafter, the stirring was stopped, and all of the reaction solution was subjected to solid-liquid separation by suction filtration using a No. 5C standard filter paper (pore size: 1 μm). The obtained silver dihydrogen citrate-containing composition was dried under reduced pressure at 50 °C for 2 weeks to obtain 37.15 g of a powdery silver dihydrogen citrate-containing composition. Treated in the same manner as in Example 1, the analysis result of its silver concentration showed that the silver concentration in the silver dihydrogen citrate-containing composition powder was 57.0 wt%. Since the silver concentration was within the range of 53.2 wt% to 63.2 wt%, this sample of Example 9 was shown to be a composition composed of silver dihydrogen citrate and trisilver citrate. When calculating the molar ratio according to Example 8, the molar ratio of silver dihydrogen citrate to silver hydrogen citrate in this silver dihydrogen citrate-containing composition was 0.68 to 0.32.

[0052] The preparation results of the silver dihydrogen citrate-containing compositions from Example 1 to Example 9 are shown in Table 1. Table 1 Preparation Results of Silver Dihydrogen Citrate-Containing Compositions JPEG0007710732000002.jpg73170

[0053] <Comparative Example 1: Production of silver dihydrogen citrate-containing composition. Production at (pH 7.5).> While stirring, 42.0 g (0.20 mol) of citric acid (monohydrate) and 34.0 g (0.20 mol) of silver nitrate were accurately weighed and added to 1.20 L of the reaction mother liquor, which was the filtrate obtained by suction filtration in Example 7 and subjected to solid-liquid separation. Thereafter, in the same manner as in Example 1, it was confirmed that the added chemicals were completely dissolved and the reaction solution became completely transparent, and then a sodium hydroxide solution (8 wt%) was dropped into the reaction solution to adjust the reaction solution to pH 7.5. The reaction solution began to become cloudy 2 to 3 minutes after the start of dropping the sodium hydroxide solution. Stirring was continued for another 3 hours after the reaction solution reached pH 7.5 to promote the reaction. In this way, a supersaturated aqueous solution in which a silver hydrogen citrate-containing composition precipitates was prepared. Thereafter, stirring was stopped, and all of the reaction solution was subjected to solid-liquid separation by suction filtration using a No. 5C standard filter paper (pore size: 1 μm). However, the filter paper became clogged after a few minutes and solid-liquid separation could not be performed. Therefore, all of the reaction solution was taken back into the container again and left standing overnight. The next day, since the precipitate had completely settled to the bottom, the supernatant (mother liquor) was taken out into another container, 1.0 L of ion-exchanged water was added and stirred to redisperse the precipitate, and it was left standing overnight again. Thereafter, the silver hydrogen citrate-containing composition obtained by decantation was dried under reduced pressure at 50 °C for 2 weeks to obtain 65.83 g of a powdery silver hydrogen citrate-containing composition. Treated in the same manner as in Example 1, the analysis result of its silver concentration showed that the silver concentration in the silver hydrogen citrate-containing composition was 62.2 wt%. Since the silver concentration is within the range of 53.2 wt% to 63.2 wt%, this sample is shown to be a composition consisting of silver hydrogen citrate and trisilver citrate.

[0054] Calculating the molar ratio according to the calculation method described in, the molar ratio of silver dihydrogen citrate to trisilver citrate in this silver hydrogen citrate-containing composition was 0.13 to 0.87. The results are shown in Table 2.

[0055] <Comparative Example 2: Production of a silver hydrogen citrate-containing composition. Production at (pH 1.8).> While stirring, 42.0 g (0.20 mol) of citric acid (monohydrate) and 34.0 g (0.20 mol) of silver nitrate were precisely weighed and added to 3.52 L of the reaction mother liquor, which was the filtrate obtained by suction filtration and solid-liquid separation in Example 9. The pH of the reaction solution was pH 1.4. Next, a sodium hydroxide solution (8 wt%) was added dropwise to the reaction solution to adjust the pH of the reaction solution to pH 1.8. In this case, the reaction solution was transparent, and no precipitate of the silver hydrogen citrate-containing composition was formed. The results are shown in Table 2. Table 2 Preparation Results of Silver Citrate in Comparative Examples JPEG0007710732000003.jpg36170

[0056] Next, the pH values in Table 1 above and the molar ratio of silver dihydrogen citrate / silver hydrogen citrate were plotted in FIG. 1.

[0057] Next, the pH values in Tables 1 and 2 above and the molar ratio of silver hydrogen citrate / silver citrate were plotted in FIG. 2.

[0058] <Example 10: Production and Evaluation of Antibacterial Agent or Antiviral Agent> 〔Bactericidal Effect of Silver Hydrogen Citrate-Containing Composition〕 0.505 g of the powder of the silver hydrogen citrate-containing composition composed of silver hydrogen citrate and silver dihydrogen citrate obtained in Example 1 was added to 100 mL of a citric acid solution (6.0 wt%) and dissolved to obtain a solution used as an antibacterial agent and an antiviral agent. When the silver ion concentration in the obtained solution was measured using a high-frequency inductively coupled plasma (ICP) emission spectrometer (manufactured by Shimadzu Corporation, "ICP S-8100"), it was 2480 ppm. Using the obtained antibacterial agent or antiviral agent, the antibacterial performance was evaluated by measuring the minimum growth inhibitory concentration (MIC) of silver ions against various bacteria according to the agar plate dilution method of the standard method of the Japanese Society for Chemotherapy. Specifically, the test bacteria were cultured in Mueller-Hinton broth (MHB) medium (30.0% (w / v) meat extract, 1.75% (w / v) casamino acids, 0.15% (w / v) soluble starch, pH 7.3 ± 0.1), and the number of test bacteria was 1.0×10 4 ~5.0×10 4An inoculum solution was prepared to have a concentration of CFU / mL. Using the test solution diluted 10-fold with MHB medium (silver ion concentration: 248 ppm) as a reference, a two-fold dilution series was created up to a silver ion concentration of 0.5 ppm. Each sample was subjected to shaking culture under the conditions of 100 - 200 rpm (horizontal shaking), an amplitude of 40 - 60 mm, and a temperature of 35 - 37 °C so that each sample was uniformly mixed, and cultured for 24 hours. The results are shown in Table 3. From the results of this test, it can be seen that the antibacterial or antiviral agent using the powder of these novel silver hydrogen citrate-containing compositions of the present invention exhibits an effect as an antibacterial agent with a broad antibacterial spectrum that exerts an antibacterial effect against Gram-negative bacteria, Gram-positive bacteria, yeast, and fungi.

[0059] Table 3 Minimum inhibitory concentration of silver hydrogen citrate-containing composition JPEG0007710732000004.jpg62151

[0060] 〔Effect against virus〕 All of the following tests were conducted in an environment at 25 °C. Influenza A virus (H3N2) and feline coronavirus were used as test viruses, and MDCK cells (cells derived from canine kidneys) were used as host cells.

[0061] (1) Antiviral test for influenza A virus An antiviral test was conducted using the silver hydrogen citrate-containing composition solution (silver concentration 2480 ppm) used in Example 10. 10.0 mL of this stock solution was added to 490 mL of ion-exchanged water and diluted 50-fold to obtain an antiviral test solution (silver 50 ppm) with a silver concentration of 50 ppm. This is because a silver concentration of 50 ppm is often used at a silver concentration of 10 - 100 ppm in many products under consideration for practical use. 1.6×10 was added to 9 mL of this antiviral test solution. 81.0 mL of the virus suspension at PFU / mL was added and allowed to stand at 25 °C for 5 minutes and 10 minutes to obtain a test solution. 0.5 mL was collected from the test solution after standing and added to 4.5 mL of a chemical inactivator (0.85% physiological saline containing 0.05% Tween 80) and mixed. By doing so, the reaction between the chemical and the virus was stopped, and the viable virus was evaluated for its virus infectivity titer by the plaque method. After 5 minutes, there were 100 or less, that is, the viable virus was reduced to 1 / 100 million. The same was true after 10 minutes. As a result, it was found that this agent has practically sufficient virus inactivating performance against influenza virus. There are various types of influenza viruses such as pathogenic influenza (H1N5) and avian influenza whose spike properties are different from those of influenza A virus (H3N2). It is imagined that silver ions adsorb to these spikes and lose their function, suggesting that this agent can inactivate various types of influenza viruses including mutated influenza viruses. The results are shown in Table 4.

[0062] (2) Host cell verification test (2-1) Cytotoxicity confirmation test To confirm whether this agent having a virus inactivating function is simultaneously safe for humans. 0.5 mL of the above antiviral test solution was added to 4.5 mL of a chemical inactivator and mixed. This was stained with cells in the same manner as the plaque measurement method to confirm the presence or absence of cytotoxicity. Phosphate buffered saline was used as a control. As a result of this test, it was found that this sample is a safe agent that does not show toxicity to cells derived from canine kidneys, similar to physiological saline. This is shown in Table 5.

[0063] (2-2) Confirmation test for cell susceptibility to virus It was confirmed whether the viruses used in these tests maintained appropriate sensitivity in the specified test method. 1.0 mL of the above antiviral solution was added to 9 mL of a chemical inactivator and mixed, and 5 mL was collected from the mixture and transferred to a test tube. Here, an influenza A virus (H3N2 type) suspension (4 - 6×10 4It was prepared to be [[PFU / mL]], and 0.05 mL of this suspension was added to the above test tube. It was allowed to stand at 25 °C for 30 minutes, and the virus infectious titer was measured by the plaque method to confirm that there was no decrease in cell sensitivity to the virus. Phosphate buffered saline was used as a control. The virus used had sufficient activity, and no decrease in sensitivity was observed. From these results, it was found that this agent is highly safe again and has a sufficient inactivating effect on the virus. The results are shown in Table 5.

[0064] From the above test results, the antibacterial solution using the disilver hydrogen citrate-containing composition of the present invention has a broad antibacterial spectrum and has a strong antibacterial effect against Gram-negative bacteria such as Escherichia coli, Pseudomonas aeruginosa, and Klebsiella pneumoniae. In addition, it also had an antibacterial effect against Gram-positive bacteria such as Staphylococcus aureus and Bacillus subtilis, pathogenic yeasts such as Candida, and fungi such as Trichophyton and Cladosporium. Also, from Tables 3 to 5, the antiviral solution of the present invention has no cytotoxicity and shows a remarkable inactivating effect against viruses such as influenza virus.

[0065] Table 4 Antiviral test JPEG0007710732000005.jpg37159

[0066] Table 5 Test for the presence or absence of cytotoxicity and cell sensitivity of the virus JPEG0007710732000006.jpg27159

[0067] (2) Antiviral test against feline coronavirus (Feline infectious peritonitis virus ATCC VR-2127) The surface protein structure (envelope) of the coronavirus and the above-mentioned influenza virus is different. Among antiviral agents, there are cases where the effect is exhibited in the former but not in the latter. Generally, there are few drugs that can exert sufficient antiviral effects against the coronavirus. Here, an antiviral test was conducted using the composition solution containing disilver hydrogen citrate (silver concentration: 2480 ppm) used in Example 10. 20.2 mL of this stock solution was added to 480 mL of ion-exchanged water and diluted 24.8-fold to obtain an antiviral test solution (silver 100 ppm) with a silver concentration of 100 ppm. This is because a silver concentration of 100 ppm is often used at a silver concentration of 10 - 100 ppm in many products under consideration for practical use. 1.0 mL of a virus suspension of 1.6×10 8 PFU / mL was added to 9 mL of this antiviral test solution, and the test solution was obtained by allowing it to stand at 25°C for 30 minutes and 60 minutes. 0.5 mL was collected from the test solution after standing and added to 4.5 mL of a drug inactivator (0.85% physiological saline containing 0.05% Tween 80) and mixed. By doing so, the reaction between the drug and the virus was stopped, and the viable virus was evaluated for its virus infectivity titer by the plaque method. After 30 minutes, it decreased to 350 (PFU / mL), that is, the viable virus decreased to 350 (PFU / mL) out of 1.8 million (PFU / mL) of the control sample, which is 1 / 5000, and after 60 minutes, the virus was completely inactivated (below the detection limit). Although it cannot be tested with the pathogenic coronavirus COVID-19, it was tested with a feline coronavirus that is structurally similar to it. It was found that this agent has practically sufficient virus inactivation performance. The results are shown in Table 6.

[0068] (2) Host cell verification test (2-1) Cytotoxicity confirmation test To confirm whether this drug having virus inactivation ability is safe for humans. 0.5 mL of the above antiviral test solution was added to 4.5 mL of a drug inactivator and mixed. This was used to stain cells in the same manner as the plaque measurement method to confirm the presence or absence of cytotoxicity. Phosphate buffered saline was used as a control. As a result of this test, it was found that this sample is safe and does not show toxicity to cells derived from canine kidneys, similar to physiological saline. This is shown in Table 7.

[0069] (2-2) Cell susceptibility confirmation test for virus It was confirmed whether the viruses used in these tests maintained appropriate susceptibility in the specified test methods. 1.0 mL of the above antiviral solution was added to 9 mL of a chemical inactivator and mixed, and 5 mL was taken from the mixture and transferred to a test tube. Here, a feline coronavirus suspension (4 - 6×10 4 PFU / mL) was prepared, and 0.05 mL of this suspension was added to the above test tube. It was allowed to stand at 25 °C for 30 minutes, the virus infectious titer was measured by the plaque method, and a decrease in cell susceptibility to the virus was confirmed. Phosphate buffered saline was used as a control. The viruses used had sufficient activity, and no decrease in susceptibility was observed. As a result, it was found that this agent is highly safe and has a sufficient inactivating effect on viruses. The results are shown in Table 7.

[0070] Table 6 Antiviral test JPEG0007710732000007.jpg37159

[0071] Table 7 Confirmation test for the presence or absence of cytotoxicity and cell susceptibility of virus JPEG0007710732000008.jpg27159

[0072] From Table 3, the disilver hydrogen citrate-containing antibacterial solution using the novel disilver hydrogen citrate-containing composition of the present invention has a broad antibacterial spectrum against various bacteria, and in particular, has a strong antibacterial effect against Gram-negative bacteria such as Escherichia coli, Pseudomonas aeruginosa, and Klebsiella pneumoniae. It was also found that it has an antibacterial effect against Gram-positive bacteria such as Staphylococcus aureus and Bacillus subtilis, pathogenic yeasts such as Candida, and fungi such as Trichophyton and Aspergillus niger, and exhibits its effect as a useful antibacterial agent. Also, from Tables 4 to 7, when these novel silver hydrogen citrate-containing composition powders of the present invention are used as antiviral agents, they have no cytotoxicity and show a remarkable inactivating effect against virus species such as influenza virus and coronavirus, and it has been found that they exhibit effects as useful antiviral agents. This agent is a practical antibacterial and antiviral agent.

[0073] <Analysis of Commercially Available Aqueous Silver Dihydrogen Citrate Solution> The silver concentration of a commercially available aqueous silver dihydrogen citrate solution (manufactured by Ciba Specialty Chemicals, "TINOSAN SDC") was measured by ICP analysis. The silver concentration was 2700 ppm. Also, 50 ml of this sample was collected and dried at 40 °C under reduced pressure for 2 weeks to obtain silver citrate powder on the powder. An attempt was made to determine the molar ratio of silver dihydrogen citrate and silver hydrogen citrate in the obtained silver citrate powder, but the coexisting citric acid concentration was described as 6 wt%, and about 90 wt% in the dry powder was citric acid. Therefore, the molar ratio of silver hydrogen citrate and silver dihydrogen citrate could not be determined by the calculation method used in this patent.

Industrial Applicability

[0074] The manufacturing method of the silver hydrogen citrate-containing composition of the present invention can reuse the reaction mother liquor after recovering silver hydrogen citrate and silver dihydrogen citrate or silver hydrogen citrate and silver tricitrate, and is an efficient method for manufacturing silver citrate with less loss of expensive silver, and is excellent in mass productivity. In addition, a powdery silver hydrogen citrate-containing composition with excellent solubility can be obtained simply and with high efficiency. Furthermore, by using the manufacturing method of the present invention, even when silver tricitrate with poor workability is mixed into silver hydrogen citrate, it is possible to obtain the said-containing composition by a filtration operation, and it is extremely useful as an industrial manufacturing method.

[0075] The silver hydrogen citrate-containing composition of the present invention can exhibit an antibacterial effect due to silver ions derived from a silver compound, regardless of changes in the type of bacteria and the acquisition of bacterial resistance by antibiotics. Further, an antibacterial agent or antiviral agent prepared by diluting and adjusting the powder of the silver hydrogen citrate-containing composition of the present invention to an arbitrary silver ion concentration with water or a citric acid solution coats the surface to be adhered with these by application or the like, and on the trace where the moisture of the surface to be adhered has evaporated, the silver hydrogen citrate-containing composition of the present invention remains in a film form with a uniform silver ion concentration. Further, even if the surface to be adhered is re-coated with alcohol or the like by re-disinfection from above, as long as the alcohol or the like evaporates, it remains as it is. Therefore, the effects of the antibacterial agent and the antiviral agent continue forever unless the surface to be treated is washed off with water or the like.

[0076] The silver hydrogen citrate-containing composition of the present invention has high persistence and a broad antibacterial spectrum, and further has a virus inactivating activity. Therefore, as an antibacterial agent or antiviral agent, in the medical field, it can be used as a pharmaceutical medical disinfectant, a wound dressing, a burn dressing, a bedsore dressing, a gastric fistula, an intestinal fistula, PEG, etc., a catheter, an indwelling needle, an antibacterial agent or antiviral agent composition in any commercial form such as gauze, bandage, dressing, plaster bandage for covering the affected area. Further, it can be used as an antibacterial agent or antiviral agent composition in any commercial form for medical devices that may be touched by people, office equipment, household appliances, lockers, all clothes around medical staff in the hospital, masks, protective goggles, surgical caps, gloves, preventive clothes, aprons, etc., hospital beds, blankets, sheets, blanket covers, pillows, pillow covers, partition curtains, etc. in the hospital, and patient rooms, intensive care units, examination rooms, treatment rooms, laboratories, physical therapy rooms, corridors, medical offices, pharmacies, administrative offices, cafeterias, kitchens, bathrooms, toilets, waiting rooms, etc., and also for preventing secondary infections from medical waste and laundry.

[0077] The silver hydrogen citrate-containing composition of the present invention is related to disinfection products for the face, head, hands, feet, whole body, hair, body hair, and skin, feminine hygiene products, intimate care products, foot care products, oral care products such as toothpaste, dental floss products, sunscreen, after-sun care products, and lip stick products in the personal care field. In the cosmetics field, it is related to basic cosmetics, makeup, underarm deodorants, underarm antiperspirants, shampoos, rinses, conditioners, treatments, and cleansing agents. In the medical field, it can be used as a composition of antibacterial or antiviral agents in various product forms related to hair growth promoters, hair removal agents, depigmenting agents, hair coloring agents, anti-acne agents, and disinfection of the oral cavity, anus, urethra, vagina, etc.

[0078] The silver hydrogen citrate-containing composition of the present invention can be used in all activity areas of the military and the Self-Defense Forces, all activity areas of the police, all activity areas of the Japan Coast Guard, all activity areas of the fire department and rescue teams, and all activity areas of kindergartens, nurseries, childcare facilities, toys for play, schools, and their dormitories, cafeterias, etc. Furthermore, it can be used in all items that people can touch inside homes, hospitals, nursing facilities, hotels, beauty salons, barbershops, restaurants, sports gyms, offices, workplaces, factories, public facilities, etc., and in airplanes, helicopters, trains, buses, monorails, gondolas, ships, automobiles, etc., which are means of transportation, as well as in air conditioners, filters, etc.

[0079] More specifically, for example, it can be used for doors, furniture, fabric products, household appliances, switches, tableware, cooking utensils, cooking ranges, sinks, etc., floor surfaces, wall surfaces, glass windows, bathtubs, toilets, bedding, products, toys, equipment, devices, peripheral equipment, tools, desks, desk peripheral equipment, components inside automobiles, clothing, masks, protective goggles, gloves, hats, shoes, aprons, etc. It can be used as a composition of antibacterial or antiviral agents for new functional agent products in combination with surface cleaning compositions containing detergents, soil suspending agents, fluorescent brighteners, abrasives, etc., and waxes, etc.

[0080] The silver hydrogen citrate-containing composition of the present invention can be used as an antibacterial or antiviral agent in various product forms for maintaining and managing the hygiene of mechanical parts, their peripheral equipment, utensils, the interior of air conditioners and filters, etc., and the food contact inner surface process, the interior of food packaging materials, etc. in the food processing factory field; for maintaining and managing the hygiene of all working environments, clean environment preservation facilities, articles, surfaces, spaces, etc.; and for maintaining and managing the hygiene of all clothing, hats, masks, protective goggles, gloves, shoes, etc. worn by workers.

[0081] In the agricultural field, the silver hydrogen citrate-containing composition of the present invention can be used as an antibacterial or antiviral agent in a product form such as a disease prevention agent that replaces antibiotics and organic pesticides used to prevent microbial contamination and maintain freshness of harvested fruits, vegetables, root vegetables, rhizomes, bulbs, and seafood, meats in general, and to control molds, bacteria, and viruses in grains, etc.; and a highly safe pesticide that replaces organic pesticides for molds, bacteria, and viruses of soil disease-causing fungi. In the livestock field, it can be used as a composition of an antibacterial or antiviral agent in various product forms for maintaining and managing the hygiene of all articles, surfaces, spaces, and the surface of the meat itself in the processes where meat comes into contact during the meat butchering process, mechanical parts, their peripheral equipment, the interior of air conditioners and filters, utensils, etc., and the food contact inner surface process, etc.; for maintaining and managing the hygiene of all working environments, clean environment preservation facilities, articles, surfaces, spaces, etc.; for maintaining and managing the hygiene of all clothing, hats, masks, protective goggles, gloves, shoes, etc. worn by workers; and further for all animal drugs, etc. against livestock infectious diseases (such as bovine dermatomycosis, mastitis in dairy cows, avian influenza, swine cholera, etc.) caused by various molds, bacteria, and viruses.

[0082] In the industrial field, the silver hydrogen citrate-containing composition of the present invention can be used as a composition of an antibacterial or antiviral agent in various product forms for water treatment devices such as filters, cooling water, service water pools, swimming pools, hot water systems, air conditioning systems, hot springs, mineral springs, pipes, tanks, water treatment equipment, peripheral equipment, pumps, etc. of cooling towers, dryers, compressors, etc., and for various industrial applications such as preservatives, fungicides, antimicrobial drugs, etc.

[0083] As for the method of use of the disilver hydrogen citrate-containing composition of the present invention in the usage mode, it can be in the form of a product in which a film is formed on the surface of any object by methods such as spraying, coating, spraying, dipping, transfer, etc., or in any liquid, solid, semi-solid, gel, sol, stick, capsule form, and the product form conforming to the usage method according to the product shape, or the product form of a composition agent in which this is encapsulated in the fiber itself, bag, container, capsule, etc. having a sustained release effect or an emergency treatment effect in an emergency, etc. Any product form usage method is acceptable.

[0084] In addition, if the powder of the novel disilver hydrogen citrate-containing composition of the present invention is dissolved in a citric acid solution and used as a deodorant, since it has an oxidizing power derived from silver, it can react with components such as sulfur-based gases, amine-based gases, aldehyde-based gases, propionic acid, isovaleric acid, etc. that cause bad odors and make them odorless, and it is possible to exhibit the effect as a deodorant.

[0085] If this novel disilver hydrogen citrate-containing composition powder obtained by the production method of the present invention is used as an antiviral agent, this agent can also inactivate mutant virus strains such as the H5N1 subtype virus, which is the cause of highly pathogenic avian influenza (HPAI) having an envelope similar to, for example, the A-type influenza virus (H3N2), and can exhibit an effect as a useful antiviral agent. In addition, although the severe acute respiratory syndrome coronavirus (SARS) or the pathogenic coronavirus COVID-19 has a spike protein structure different from that of influenza, it is also considered possible to inactivate them in the same way if they have an envelope sensitive to silver ions. Therefore, the disilver hydrogen citrate-containing composition of the present invention, its production method, and the antibacterial or antiviral agent using the same and its production method are extremely useful industrially.

Claims

1. (1) A step of adding a silver compound and citric acid in an amount such that the amount of disilver hydrogen citrate becomes equal to or more than the saturation amount in a solvent to obtain a reaction solution; (2) A step of adding a base agent to the reaction solution to adjust the pH to 2.0 to 5.5 and precipitate a disilver hydrogen citrate-containing composition; and (3) A step of recovering the precipitated disilver hydrogen citrate-containing composition, A method for producing a disilver hydrogen citrate-containing composition, comprising the above steps.

2. The method for producing a disilver hydrogen citrate-containing composition according to Claim 1, wherein the disilver hydrogen citrate-containing composition further contains silver dihydrogen citrate or trisilver citrate, and the silver concentration in the composition is 36.1 wt% to 63.1 wt%.

3. The method for producing a disilver hydrogen citrate-containing composition according to Claim 1, wherein the silver compound is silver nitrate.

4. After the steps (1) to (3), (4) A step of repeating the operations of the steps (1) to (3) in the reaction solution and further recovering a disilver hydrogen citrate-containing composition The method for producing a disilver hydrogen citrate-containing composition according to Claim 1, comprising the above step.

5. A method for producing an antibacterial agent or an antiviral agent, comprising producing a disilver hydrogen citrate-containing composition by the method for producing a disilver hydrogen citrate-containing composition according to any one of Claims 1 to 4, and then mixing the obtained disilver hydrogen citrate-containing composition with water or a citric acid solution.

6. A composition comprising disilver hydrogen citrate and silver dihydrogen citrate, or disilver hydrogen citrate and trisilver citrate, wherein the silver concentration thereof is 37.2 wt% or more and 57.9 wt% or less.

7. An antibacterial agent or an antiviral agent comprising the composition according to Claim 6.

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