WO2013031964A1 - 銀イオン抗菌液の生成方法、その方法で生成される銀イオン抗菌液、又は銀イオン抗菌粉末の生成方法、その方法で生成される銀イオン抗菌粉末 - Google Patents
銀イオン抗菌液の生成方法、その方法で生成される銀イオン抗菌液、又は銀イオン抗菌粉末の生成方法、その方法で生成される銀イオン抗菌粉末 Download PDFInfo
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- WO2013031964A1 WO2013031964A1 PCT/JP2012/072208 JP2012072208W WO2013031964A1 WO 2013031964 A1 WO2013031964 A1 WO 2013031964A1 JP 2012072208 W JP2012072208 W JP 2012072208W WO 2013031964 A1 WO2013031964 A1 WO 2013031964A1
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- zeolite
- ion antibacterial
- silver ion
- citric acid
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/12—Powders or granules
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/26—Aluminium; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q15/00—Anti-perspirants or body deodorants
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/56—Compounds, absorbed onto or entrapped into a solid carrier, e.g. encapsulated perfumes, inclusion compounds, sustained release forms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
Definitions
- the present invention is a method for producing a silver ion antibacterial solution produced by elution of silver ions contained in a crystal structure, using silver zeolite having a high safety and a low raw material cost.
- the present invention relates to a method for producing a silver ion antibacterial liquid or a silver ion antibacterial powder, and a silver ion antibacterial powder produced by the method.
- Bacteria are said to produce odors by breaking down human secretions.
- the odor of the stink is caused by sweat secreted from the apocrine sweat glands of the skin, but when the sweat is secreted on the skin, it is mixed with fat secreted from the sebaceous glands and sweat secreted from the eccrine sweat glands , It is decomposed by skin resident bacteria on the skin and armpit hair, producing a substance that emits a stink odor.
- the above-mentioned skin resident bacteria include Staphylococcus aureus and acne bacteria, and odor components include butyric acid and valeric acid. Odors include odor, sweat odor and hair odor.
- fatty acid body odor, sweat, etc.
- nitrogen compound septic urine, etc.
- sulfur compound fumeces, etc.
- Means for preventing these odors include (1) masking with fragrance, (2) adsorption with activated carbon, zeolite, etc., (3) neutralization with acid and alkali, and (4) sterilizing bacteria with antibacterial agents.
- the adsorption method (2) has a problem in slow-release performance due to its limited adsorption capacity.
- the neutralization method (3) can be applied only to specific malodors.
- the method of sterilizing bacteria with the antibacterial agent (4) is not preferable because there are allergies and other stimuli depending on the type of antibacterial agent, but silver-based inorganic antibacterial agent (silver zeolite) has high safety, antibacterial spectrum, It is evaluated for its sustainability and is used in products such as antibacterial liquids, deodorant liquids, cosmetics, and sanitary products.
- an antibacterial zeolite in which part or all of ions capable of ion exchange are ion-exchanged with metal ions of zinc ion, ammonium ion, and silver ion, and a deodorant cosmetic containing silicone have been proposed.
- antibacterial zeolite Zeomic AJ10N manufactured by Sinanen Zeomic Co., Ltd., average particle diameter of about 2.5 ⁇ m
- weight supporting silver ions of silver zeolite is described as an aerosol type. (See Patent Document 1).
- Patent Document 3 that points out that the above-mentioned silver zeolite has no immediate effect is known.
- zeolite antibacterial agents containing heavy metal ions such as zinc, silver and copper are generally used as antibacterial agents that have long-lasting antibacterial effects against bacteria and fungi.
- heavy metal ion silver ion has been widely used in recent years because it is particularly excellent in terms of safety. It is described that silver ions have insufficient bactericidal performance as compared with oxidizers such as chlorine-based bactericides regarding the bactericidal power and deodorizing power immediately after processing.
- an antibacterial agent containing a silver chloro complex salt and an oxidizing agent has been proposed in place of the zeolite antibacterial agent (see Patent Document 3).
- silver zeolites described above are inventions that utilize the elution of silver ions of silver zeolite, and are three-dimensional framework structures based on aluminosilicates, ie, silicon (Si) and aluminum (Al) via oxygen (O). It has a three-dimensional framework structure of bonded Si-O-Al-O-Si, and aluminum (+ trivalent) and silicon (+ tetravalent) share oxygen (-2 valence) with each other. It becomes electrically neutral, and the area around aluminum becomes ⁇ 1 valence (Al ⁇ ). In order to compensate for this negative charge, sodium ions (Na + ) are usually retained.
- the silver zeolite is obtained by replacing part of sodium ions in the skeleton with silver ions (Ag + ) having antibacterial properties.
- the silver ions have a structure in which the skeleton is electrostatically bonded to the skeleton, and because of the structure, the silver ions are eluted by ion exchange action to sterilize bacteria and provide excellent sustained release. It is said that it has performance (performance that exhibits antibacterial action for a long time).
- the silver zeolite utilizes elution of silver ions by ion exchange with cations existing in water, it takes a long time because the gradually eluted silver ions kill bacteria. That is, it has been pointed out as a problem that there is no immediate effect of sterilizing bacteria in a short time (see Non-Patent Document 1).
- Patent Document 4 proposes an aqueous disinfectant having an immediate effect of disinfection using an electrolysis apparatus. It is disclosed that the aqueous disinfectant can generate a silver citrate complex from silver ions generated by an electrolysis apparatus equipped with a silver electrode in an aqueous citric acid solution and the citric acid.
- the electrolyzer is an apparatus composed of a flow rate control injector 40, a citric acid tank 50, an ion chamber 70, a DC power source 80, a precipitation tank 90, a purge tank 100, and a particle filter 110.
- An anode 71 and a cathode 72 are installed in the ion chamber 70, and the anode 71 and the cathode 72 are separated from each other, and a diluted solution 62 of citric acid can pass between the anode 71 and the cathode 72.
- Each of the anode 71 and the cathode 72 is made of silver having a purity of 99.9999%.
- Patent Document 4 discloses that a silver citrate complex can be generated by an electrolysis apparatus including a silver electrode in a citric acid aqueous solution.
- Ciba Specialty Chemicals sells a solution containing the above-described silver citrate complex as TINOSAN® SDC (trade name), and this INCI (“International Nomenclature of Cosmetic Ingredients”) Is published as Citric Acid and Silver Citrate.
- TINOSAN SDC is antibacterial silver for skin care, and is reported to be a silver complex produced by unique electrical treatment using silver and citric acid (see Non-Patent Document 2).
- the silver citrate complex described in Patent Document 4 is an electrolysis apparatus composed of a flow control injector 40, a citric acid tank 50, an ion chamber 70, a DC power supply 80, a precipitation tank 90, a purge tank 100, and a particle filter 110.
- the ion chamber 70 is produced in a container filled with a diluted solution of citric acid between an anode and a cathode formed of high-purity silver. Therefore, the equipment costs for providing an electrolyzer, the maintenance costs for replacing silver as a consumable for anodes and cathodes made of high-purity silver, etc. are high, and the cost for producing a silver citrate complex. Is expensive and it is difficult to reduce the cost. Since TINASAN SDC (trade name) has been reported to be a silver complex produced by a unique electrical process, a silver citrate complex using an electrolysis apparatus similar to Patent Document 4 and a silver electrode. It is presumed that it is produced by the method of generating
- the commercially available TINOSAN SDC (trade name) is a paraben-free that does not use the preservative paraben as an antibacterial agent for skin care, and an alcohol-free that does not use alcohol. It is evaluated. However, it is difficult for general consumers to use it on a daily basis, and it is not widely used. Therefore, there is a demand for a method that can be produced inexpensively to produce a silver ion antibacterial solution containing a silver citrate complex.
- the object of the present invention is to use silver zeolite having low raw material costs and high safety characteristics, and has an immediate effect of sterilization of bacteria, and a commercially available TINOSAN A method for producing a silver ion antibacterial solution, a silver ion antibacterial solution produced by the method, or a silver ion antibacterial powder capable of inexpensively producing a silver ion antibacterial solution containing a silver citrate complex similar to SDC (trade name) A production method and a silver ion antibacterial powder produced by the method.
- Conventional silver zeolite has a structure in which Al in the three-dimensional skeleton of Si-O-Al-O-Si is electrically bonded to a cation, and is therefore evaluated to have sustained release performance by ion exchange action. .
- it is used in antibacterial liquids, deodorant liquids, cosmetics, sanitary products and the like.
- the present inventor conducted extensive studies on a method for producing silver ions that can sterilize bacteria in a short time using the above-mentioned silver zeolite as a raw material.
- the blending ratio of citric acid to the blending amount (% by weight) of silver zeolite was 1 If it is 2 or more, the present invention is completed by finding that citric acid breaks down the crystal structure forming the ion exchange site of silver zeolite and elutes all silver ions contained in silver zeolite. It came to. That is, the method for producing the silver ion antibacterial solution of the present invention is as follows.
- the method for producing a silver ion antibacterial liquid of the invention according to claim 1 is a method for producing a silver ion antibacterial liquid containing silver ions eluted from silver zeolite, wherein the silver zeolite is an A-type or X-type silver zeolite.
- a blending amount of 0.1 to 20.0% by weight of the silver zeolite is weighed, and a blending ratio of citric acid with respect to the silver zeolite of 1.2 or more is weighed and blended into purified water.
- the mixture is prepared by mixing the silver zeolite and citric acid mixed in the purified water with stirring to prepare a mixed solution containing at least a silver citrate complex and silica hydrate. And a treatment for removing silica hydrate.
- the method for producing a silver ion antibacterial solution of the invention according to claim 2 is characterized in that the silver supported amount of the silver zeolite is 0.5 to 5.0% by weight.
- the silver ion antibacterial liquid of the invention according to claim 3 is produced by the method for producing a silver ion antibacterial liquid according to claim 1 or 2.
- the silver ion antibacterial solution of the invention according to claim 4 is characterized in that the silver ion concentration of the silver ion antibacterial solution can be arbitrarily adjusted by the amount of silver zeolite and the amount of silver supported.
- the method for producing a silver ion antibacterial powder of the invention according to claim 5 is a method in which the silica hydrate is removed after the treatment for removing the silica hydrate of the silver ion antibacterial solution production method of claim 1. The liquid is freeze-dried or spray-dried to produce a silver ion antibacterial powder.
- the method for producing a silver ion antibacterial powder of the invention according to claim 6 is characterized in that the silver supported amount of the silver zeolite is 0.5 to 5.0% by weight.
- the silver ion antibacterial powder of the invention according to claim 7 is produced by the method for producing a silver ion antibacterial powder according to claim 5 or 6.
- the method for producing a silver ion antibacterial solution of the present invention uses a cheap A-type or X-type silver zeolite and citric acid as raw materials without using the electrolysis apparatus and silver electrode, and contains a silver citrate complex. Since silver ion antibacterial liquid can be produced, the manufacturing cost can be greatly reduced. In addition, the method for producing the silver ion antibacterial liquid of the present invention can be easily determined by setting the amount of citric acid to be a blending ratio of 1.2 or more if the amount of silver zeolite is determined.
- the treatment to be generated is a simple treatment operation because it comprises weighing, blending, stirring and mixing, and removing the silica hydrate to recover the silver ion antibacterial solution.
- the silver ion antibacterial liquid of the present invention can be prepared by arbitrarily adjusting the silver ion concentration in accordance with the amount of silver zeolite added and the amount of silver supported depending on the use, and since it is inexpensive, it is generally used as a popular product. In addition, for example, as an antibacterial agent for skin care, it is paraben-free and alcohol-free and anyone can use it with peace of mind. Moreover, the silver ion antibacterial liquid of the present invention exhibits an immediate effect of sterilizing bacteria in a short time, which was impossible by the ion exchange action of conventional silver-supported zeolite.
- the production method of the silver ion antibacterial powder of the present invention requires a small amount of storage space by making the silver ion antibacterial liquid into a powder form, and can be transported in large quantities by weight reduction.
- the silver zeolite used in the present invention is A-type or X-type silver zeolite (hereinafter, these silver zeolites are simply referred to as “silver zeolite”). Since X-type silver zeolite is expensive, it is preferable to use A-type silver zeolite. Since this A-type or X-type silver zeolite is dissolved by an acid, the present invention is the reason for using both zeolites. However, Y-type silver zeolite and mordenite-type silver zeolite cannot be used because they do not dissolve in acid.
- the structural formula of silver zeolite is as follows.
- the crystal structure that forms the ion exchange site of the above-mentioned silver zeolite is a structure in which silver ions are electrostatically bonded to the Al portion in the crystal structure in which the structure of Si-O-Al-O-Si is three-dimensionally bonded. It is said that silver ions in the crystal structure are eluted by the ion exchange action to kill bacteria.
- a method for producing three types of silver zeolite having a silver loading of 0.5, 2.5, and 5.0% by weight will be described.
- A-type zeolite will be described, but as a material, X-type zeolite is the same as the procedure for producing A-type zeolite.
- the manufacturing method of the silver zeolite demonstrated below is a manufacturing method used normally. 1.
- Silver zeolite with a silver loading of 0.5% by weight (1) Material Type A zeolite (dried at 110 ° C.): 1000 g Silver nitrate (AgNO 3 ): 7.9 g
- a powdery A-type silver zeolite having an average particle diameter of 2 to 2.5 ⁇ m can be obtained.
- Silver zeolite with a weight of 2.5% by weight (1) Material Type A zeolite (110 ° C. dried product): 1000 g Silver nitrate (AgNO 3 ): 39.7 g (2) The manufacturing procedure is the same as the above procedure. 3. Silver zeolite with 5.0% by weight of silver supported (1) Material Type A zeolite (110 ° C. dried product): 1000 g Silver nitrate (AgNO 3 ): 79.5 g (2) The manufacturing procedure is the same as the above procedure.
- Method of producing silver ion antibacterial solution of the present invention first, a blending amount of 0.1 to 20.0% by weight of silver zeolite is weighed, and the blending ratio of citric acid to the silver zeolite is 1.2 or more. Weighing and blending the blended amount in purified water, and then stirring and mixing the silver zeolite and citric acid blended in the purified water to mix at least the silver citrate complex and silica hydrate A silver ion antibacterial solution containing at least the above-mentioned silver citrate complex by the removal treatment comprising a treatment for preparing the solution and finally a treatment for removing the silica hydrate produced in the mixed solution. Can do.
- the citric acid is a commercially available citric acid monohydrate.
- the above-mentioned blending ratio means the ratio of the blending amount (wt%) of citric acid to the blending amount (wt%) of silver zeolite, that is, the ratio of “wt% citric acid / wt% silver zeolite”.
- the ratio is defined as “mixing ratio” and used below.
- a method for producing a silver ion antibacterial solution will be described with a specific example.
- each compounding amount of A-type or X-type silver zeolite (hereinafter referred to as “silver zeolite”), citric acid and purified water is determined.
- silver zeolite A-type or X-type silver zeolite
- citric acid and purified water is determined.
- the blended liquid is prepared by blending both materials in the purified water whose blending amount is determined in step (b).
- the appearance of the liquid mixture containing both materials is cloudy. Stir and mix until the white turbidity becomes clear to produce a mixture. The mixture becomes clear when stirred and mixed for at least 2 minutes.
- a silver ion antibacterial liquid can be produced
- y is 1 and / or 2, and when y is 3, it is hardly soluble and cannot be dissolved in water. Since most silver citrate complexes produced by the reaction of silver ions and citric acid are those of 1 silver citrate, y is 1 and x is 2.
- the subject of this invention is produced
- Silica hydrate, aluminum citrate complex, and the like are generated in addition to the silver citrate complex as the product generated in the treatment for preparing the mixed solution.
- Aluminum citrate powdered from the aluminum citrate complex is used for cosmetics as an antiperspirant, but the silica hydrate adsorbs silver hydroxide on its surface to produce silica hydrate silver hydroxide.
- silver oxide black brown
- the precipitated aggregated silica hydrate silver hydroxide is treated by decantation, (2) the precipitated aggregated silica hydrate silver hydroxide is treated with a filter, (3 ) Treated with a filter before flocculation of silica hydrate.
- divalent metal salt eg zinc citrate
- Silica hydrate can be removed by treatment by binding and precipitating metal ions to silica hydrate.
- the decantation is not limited to 24 hours. If the temperature is increased from room temperature to 70 ° C., for example, the silica hydrate silver hydroxide aggregates and precipitates in the mixed solution in 7 hours. By changing the temperature arbitrarily, the silver ion antibacterial solution can be collected by decantation in a short time.
- Treatment to bind zinc citrate or calcium citrate ions to silica hydrate, precipitate and remove them When adding silver zeolite or citric acid to purified water, add zinc citrate or calcium citrate Then, zinc ions or calcium ions are bound to silica hydrate and precipitated, and the silica hydrate to which zinc ions or calcium ions are bound is separated by a filter to recover the silver ion antibacterial solution. Alternatively, the silver hydrate antibacterial solution may be recovered by separating silica hydrate bonded with zinc ions or calcium ions by decantation.
- the treatment for removing silica hydrate is not limited to the above treatments (1) to (4), and the above treatments (1) to (4) may be used in appropriate combination.
- the silver ion antibacterial solution recovered by the treatment (3) contains a very small amount of silica hydrate.
- the mixed solution from which the silica hydrate has been removed is freeze-dried with a vacuum freeze dryer or spray-dried with a vacuum spray dryer.
- the mixed solution can be powdered.
- the mixture from which the silica hydrate has been removed is freeze-dried under reduced pressure.
- 18 g of silver ion antibacterial powder can be produced by processing with a machine.
- 1.0 g of the obtained silver ion antibacterial powder was dissolved in 1000 g of water, it was completely dissolved, and the silver ion concentration at that time was 15.2 ppm.
- silver zeolite and citric acid are mixed in a weight ratio of 0.1 to 20.0% by weight of the silver zeolite, and the mixing ratio of citric acid to the silver zeolite is 1.2. It was described that the above blending amounts were weighed and blended with purified water.
- the above-mentioned blending amount of silver zeolite and the above-mentioned blending amount of citric acid are derived from the results of the first experiment described below. In the first experiment, as described above, by mixing silver zeolite and citric acid, the proton (H + ) of citric acid is converted to the Al—O portion in the structure of Si—O—Al—O—Si of silver zeolite.
- the silver zeolite dispersion is cloudy, but the mixture is transparent due to the collapse of the skeleton structure.
- first First experiment an experiment for examining how much citric acid is added to the amount (% by weight) of silver zeolite to be transparent (hereinafter referred to as “first” First experiment)).
- second experiment an experiment for examining how much citric acid is added to the amount (% by weight) of silver zeolite to be transparent.
- A-type silver zeolite produced by the above-mentioned method for producing silver zeolite and commercially available Zeomic AJ10N (manufactured by Sinanen Zeomic Co., Ltd., silver loading amount of 2.2% by weight) were used as samples.
- Zeomic AJ10N was also weighed two types with different blending amounts to prepare a total of 12 samples. For each of the six samples having the same blending amount of 0.1 wt% or 0.5 wt%, as shown in the blending ratio column of Table 1, Sample No.
- the weighed silver zeolite and citric acid powder were mixed with purified water to prepare 200 g of a mixed solution, and the pH of the mixed solution was measured with a pH meter after 2, 10 and 30 minutes. The appearance of the mixed solution was visually determined in three stages: white turbidity, translucent and transparent.
- Table 1 shows the results of the first experiment on a total of 12 samples of the A-type silver zeolite.
- the results of the first experiment of a total of 12 samples of 0.1% by weight and 0.5% by weight of Zeomic AJ10N take into account the measurement error and the results of the first experiment of type A silver zeolite in Table 1. Then, it is omitted because it shows that it matches.
- the result of the first experiment is that the manufactured product and the commercial silver zeolite are mixed even if 30 minutes have passed since the mixing ratio of the silver zeolite is 1.1 or less.
- the liquid was translucent.
- the mixing ratio was 1.2 or more
- it was found that the mixed liquid was transparent when 2 minutes passed after mixing.
- the pH of the transparent liquid mixture showed the value of 4.0 or more. From the results of the first experiment, it was found that the mixed solution became transparent when the mixing ratio of citric acid with respect to the weight percent of silver zeolite was 1.2 or more.
- the mixing ratio of citric acid is 1.2 or more with respect to the mixing amount (% by weight) of the above-mentioned silver zeolite, so that the mixed solution becomes transparent after 2 minutes. It is presumed that the crystal structure forming the ion exchange site of the zeolite is destroyed and all the silver ions contained in the silver zeolite are eluted.
- Silver zeolite and citric acid are blended with purified water in the above blending amounts to prepare 200 g of a blended solution, which is stirred and mixed to form a mixed solution. Since the chemical reaction is normally in an equilibrium state in 24 hours, the silver ion concentration of the mixed solution was measured 24 hours after the mixed solution was formed. A semitransparent precipitate is formed in the mixed solution after 24 hours, and the precipitate is filtered to separate the precipitate, and the silver ion concentration in the obtained solution is analyzed by high frequency inductively coupled plasma (ICP) emission spectrometry. It was measured with an apparatus (ICP S-8100, manufactured by Shimadzu Corporation). On the other hand, no. No.
- ICP S-8100 high frequency inductively coupled plasma
- No. 16 is a condition in which silver zeolite (silver loading amount: 2.2% by weight) of aerosol type deodorant cosmetic described in Patent Document 1 is sprayed on the body in a state of sweating (sodium chloride 0.9% by weight). The silver ion concentration was measured assuming the same case.
- Purified water was put into a 200 g beaker at room temperature (28 ° C.), and then five kinds of blending amounts of citric acid shown in Table 2 were added to completely dissolve them. Next, A type silver zeolite (silver supported amount 2.5% by weight, dried at 110 ° C.) having five blending amounts shown in Table 2 was added while stirring. 100 g of this mixed solution was stored in a 100 g screw tube, and the properties of the mixed solution after 1 hour, 3 hours, and 24 hours were observed. The observation results are shown in Table 2.
- FIG. 5 is a photograph showing the properties of each sample at observation times of 1, 3, and 24 hours.
- the silver zeolite and citric acid were mixed at a mixing ratio of 1.2 or more, so that the silver zeolite was completely dissolved, and the liquid mixture was liquid and transparent. 5 cannot be completely dissolved because a part of silver zeolite is precipitated.
- the properties of the mixed solution are liquid and transparent until 3 hours after mixing, but after 24 hours, the sample No. In Nos. 1 and 2, the silica hydrate is agglomerated and the entire system is gelled. In this state, the silica hydrate cannot be removed by decantation or filtering. However, since the properties are liquid and transparent up to 3 hours after mixing, the silica hydrate can be removed with a filter. Accordingly, the maximum amount of silver zeolite blended is preferably 20.0% by weight.
- the comparative example of 16 shows a value of 0.45 to 0.59 ppm, and it is clear that this value has an antibacterial effect.
- the experimental examples 1 to 15 have a silver ion concentration of 2.0 ppm as a minimum, and the concentration is about 4 times that of the comparative example.
- Tables 3-1 to 3-3 which are the second experimental results of three types of silver zeolite having different silver loadings, the horizontal axis indicates three values (0. 1, 0.5, 1.0% by weight), and on the vertical axis, three values of silver ion concentration for that value are drawn, and five types of elution silver ion concentration graphs with different blending ratios are created.
- FIG. 1 is an approximate straight line graph showing the correlation between the blending amount of silver zeolite having a silver loading of 0.5 wt% and the silver ion concentration.
- FIG. 2 is a graph of an approximate line showing the correlation between the blending amount of silver zeolite having a silver loading of 2.5% by weight and the silver ion concentration.
- FIG. 3 is a graph of an approximate line showing the correlation between the blending amount of silver zeolite having a silver loading of 5.0% by weight and the silver ion concentration.
- ⁇ No. No. 13 to 15 are approximate straight lines, and the ⁇ mark is No. Approximate straight lines of samples 10 to 12, and ⁇ marks are No. It is an approximate straight line of samples 7 to 9, and the circles are No. Approximate straight lines for samples 4-6.
- 3 is a graph of approximate lines of samples 1 to 3.
- Table 4 was prepared by extracting only the data on the amount of silver zeolite 13-15 and the silver ion concentration. And based on the data of Table 4, FIG. 4 which shows the relationship between a silver zeolite compounding quantity and silver ion concentration was created.
- FIG. 4 is a graph showing the relationship between the amount of silver zeolite blended and the silver ion concentration.
- the values of the three types of silver zeolite blended amounts (0.1, 0.5, 1.0 g) are drawn on the horizontal axis. The graph was drawn by drawing the value of the silver ion concentration with respect to that value on the axis.
- Samples 11 and 14 have a silver loading of 2.5% by weight.
- Samples 12 and 15 have a silver loading of 5.0% by weight.
- FIG. 1 The approximate straight lines of both the samples of 10 and 13 (silver loading amount 0.5% by weight) are the same straight lines when taking the error into consideration.
- the approximate straight lines of both samples 11 and 14 (silver loading is 2.5% by weight) are the same straight line.
- the approximate straight lines of both the samples of 12 and 15 are the same straight line. This means that even if the silver loading is different from 0.5 wt%, 2.5 wt% or 5.0 wt%, the blending ratio is 1.2% with respect to the blending amount (wt%) of the silver zeolite. It shows that all the silver ions supported by the silver zeolite can be eluted by adding citric acid in the above blending amount (% by weight) to purified water.
- the problem of the present invention is to produce a silver ion antibacterial solution that can produce a silver ion antibacterial solution containing a silver citrate complex at low cost by using silver zeolite having low raw material costs and high safety characteristics.
- Commercially available TINOSAN SDC (trade name) is evaluated as an excellent antibacterial agent because it contains a silver citrate complex and can be used safely and without parabens and alcohol as an antibacterial agent for skin care.
- TINASAN SDC (trade name) is not used as a popular product because it is very expensive for ordinary consumers to use on a daily basis. Therefore, if a silver ion antibacterial solution containing a silver citrate complex is produced from silver zeolite, a cosmetic solution or the like in a popular price range can be produced.
- Example 1 In Example 1, 1 g of A-type silver zeolite supporting 2.5% by weight of silver and 1.2 g of citric acid having a blending ratio of 1.2 were mixed with purified water to make a 100 g aqueous solution and mixed at room temperature for 2 hours. After stirring, the silica component is agglomerated by treating at 80 ° C. for 1 hour, allowed to stand for 2 days to precipitate, and the filtrate is made into powder (silver 18.8 mg / 1.2 g) with a vacuum freeze dryer. It was.
- Comparative Example 1 In Comparative Example 1, TINOSAN SDC was powdered with a freeze dryer and used as a sample. In Comparative Example 2, the reagent citric acid was used as a sample. 10 mg of each sample was dissolved in 0.8 g of heavy water and subjected to spectral analysis by 600 MHz H NMR (nuclear magnetic resonance spectrum). The signal of the silver citrate complex could not be identified from the signals of Example, Comparative Example 1 and Comparative Example 2.
- the crystal structure that forms the ion exchange site of the above-mentioned silver zeolite is a structure in which silver ions are electrostatically bonded to the Al portion in the crystal structure in which the structure of Si-O-Al-O-Si is three-dimensionally bonded.
- Proton citric acid is type A silver zeolite (AlO 4) - (for selectivity coefficient of sodium ions is smaller than that of the silver ions) tetrahedral negative sodium ions and ion exchange existing charge site.
- Protons act on the Al—O bond part in the skeleton to break the bond.
- Disintegration of the skeletal structure due to the cleavage of the Al-O bond part releases silver ions, sodium ions, etc. adsorbed on the silver zeolite into the solution. 4).
- the released silver ions react with citric acid to form a silver citrate complex. 5.
- Aluminum also reacts with citric acid C 6 H 5 O 7 3- to form an aluminum citrate complex.
- the silver citrate complex is partially dissociated in water, and a very small amount of silver ions are also present.
- Sodium exists in water in the form of ions.
- Silicon is suspended or precipitated in the form of silica gel. At this time, a small amount of silver ions is adsorbed on the surface.
- the product contained in the mixed solution is considered to contain silver citrate complex, silica hydrate, aluminum citrate complex, and silver ions. Accordingly, the silica hydrate is naturally removed from the silver ion antibacterial solution produced by the method for producing a silver ion antibacterial solution of the present invention.
- the mixing ratio of citric acid to silver zeolite is 1.2 or more.
- citric acid having a mixing ratio of 1.2 or more it is possible to obtain optimum production conditions and economic efficiency by adding citric acid having a mixing ratio of 1.2 or more to silver zeolite. I mean.
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Abstract
Description
上記皮膚常在菌には黄色ブドウ球菌、アクネ菌等があり、臭気の成分には、酪酸、吉草酸等がある。臭いとしては、腋臭、汗臭、毛髪臭等がある。
(1)のマスキングは香料の揮発により一時的に臭気を感じさせないが、悪臭が再現されて根本的な臭気防止の効果はない。(2)の吸着法は吸着能力に限界があるために徐効性能に問題がある。(3)の中和法は特定の悪臭にしか適用できない、との問題がある。(4)の抗菌剤で細菌を殺菌する方法は、抗菌剤の種類によりアレルギー等の刺激があり好ましくないものがあるが、銀系無機抗菌剤(銀ゼオライト)は、高い安全性、抗菌スペクトル、持続性等を有することが評価され、例えば、抗菌液、消臭液、化粧品、サニタリー製品等の製品に使用されている。
例えば、イオン交換可能なイオンの一部又は全部を亜鉛イオン、アンモニウムイオン及び銀イオンの金属イオンでイオン交換した抗菌性ゼオライトと、シリコーンを含有した防臭化粧料が提案されており、該防臭化粧料の抗菌性ゼオライト((株)シナネンゼオミック製ゼオミックAJ10N、平均粒径約2.5μm)(銀ゼオライトの銀イオンを担持する重量;2.2重量%)をエアゾールタイプとして用いることが記載されている(特許文献1参照)。また、上記銀イオンの抗菌作用の喪失を抑制する試みとして、例えば、ゼオライトをアンモニウムイオン及び銀イオンで置換した銀ゼオライトに、シリコーンを配合することで耐変色性に優れた防臭化粧料が提案されている(特許文献2参照)。
しかしながら、上記銀ゼオライトは、水中に存在するカチオンとのイオン交換による銀イオンの溶出を利用しているために、徐々に溶出した銀イオンが細菌を殺菌するので長い時間がかかる。即ち細菌を短時間に殺菌する即効性能がないことが問題として指摘されている(非特許文献1参照)。
以上のように、特許文献4には、クエン酸水溶液中に銀電極を備える電気分解装置によってクエン酸銀錯体が生成できることが開示されている。
即ち本発明の銀イオン抗菌液の生成方法は、以下の通りのものである。
請求項1に係る発明の銀イオン抗菌液の生成方法は、銀ゼオライトから溶出する銀イオンを含有する銀イオン抗菌液の生成方法であって、前記銀ゼオライトがA型又はX型の銀ゼオライトであり、該銀ゼオライトの0.1~20.0重量%の範囲の配合量を秤量し、該銀ゼオライトに対するクエン酸の配合比率が1.2以上の配合量を秤量して精製水に配合する処理と、上記精製水に配合した上記銀ゼオライト及びクエン酸を撹拌し混合して、少なくともクエン酸銀錯体及びシリカ水和物を含む混合液を調製する処理と、前記混合液中に生成されるシリカ水和物を除去する処理とからなることを特徴とする。
請求項2に係る発明の銀イオン抗菌液の生成方法は、前記銀ゼオライトの銀担持量が0.5~5.0重量%であることを特徴とする。
請求項3に係る発明の銀イオン抗菌液は、請求項1又は2に記載の銀イオン抗菌液の生成方法で生成されることを特徴とする。
請求項4に係る発明の銀イオン抗菌液は、前記銀イオン抗菌液の銀イオン濃度が銀ゼオライトの配合量と銀担持量で任意に調製することができることを特徴とする。
請求項5に係る発明の銀イオン抗菌粉末の生成方法は、請求項1に記載の銀イオン抗菌液の生成方法のシリカ水和物を除去する処理の後に、上記シリカ水和物を除去した混合液を、凍結乾燥又は噴霧乾燥して銀イオン抗菌粉末を生成する処理とからなることを特徴とする。
請求項6に係る発明の銀イオン抗菌粉末の生成方法は、前記銀ゼオライトの銀担持量が0.5~5.0重量%であることを特徴とする。
請求項7に係る発明の銀イオン抗菌粉末は、請求項5又は6に記載の銀イオン抗菌粉末の生成方法で生成されることを特徴とする。
また、本発明の銀イオン抗菌液の生成方法は、銀ゼオライトの配合量が決まれば、クエン酸の配合量を配合比率1.2以上の量として簡単に決められ、また、銀イオン抗菌液を生成する処理は秤量、配合、撹拌混合、シリカ水和物を除去して銀イオン抗菌液を回収する処理からなるので、簡単な処理操作である。
本発明の銀イオン抗菌液は、その用途に応じて、その銀イオン濃度を銀ゼオライトの配合量と銀担持量で任意に調製することができ、また、安価であるから普及品として一般の人が利用でき、更に、例えばスキンケア用の抗菌剤としてパラベンフリー、アルコールフリーで誰もが安心して使用できる。
また、本発明の銀イオン抗菌液は、従来の銀担持ゼオライトのイオン交換作用では不可能であった、細菌を短時間に殺菌する即効性を発揮する。
本発明の銀イオン抗菌粉末の生成方法は、銀イオン抗菌液を粉末状にすることで、貯蔵空間が少なくてすみ、軽量化により大量に運搬することができる。
本発明に用いる銀ゼオライトは、A型又はX型銀ゼオライトである(以下、これらの銀ゼオライトを単に「銀ゼオライト」という。)。X型銀ゼオライトは高価なのでA型銀ゼオライトを用いることが好ましい。このA型又はX型銀ゼオライトは酸により溶解されるので、本発明がこの両ゼオライトを用いる理由である。しかし、Y型銀ゼオライトやモルデナイト型銀ゼオライトは酸に溶解しないので使用できない。銀ゼオライトの構造式は下記の通りである。
(αNa2 βAg2)O・Al2O3‐2SiO2nH2O (α+β=1 n=5:110℃乾燥品)
上記銀ゼオライトのイオン交換サイトを形成する結晶構造は、Si-O-Al-O-Siの構造を三次元的に結合した結晶構造中のAl部分に、銀イオンが静電気的に結合した構造を有しており、イオン交換作用により上記結晶構造中の銀イオンが溶出して細菌を殺菌するといわれている。
銀担持量0.5、2.5、5.0重量%の3種類の銀ゼオライトの製造方法を説明する。
一例としてA型ゼオライトで説明するが、材料としてX型ゼオライトもA型ゼオライトの製造の手順と同じである。なお、以下に説明する銀ゼオライトの製造方法は、普通に用いられている製造方法である。
1.銀担持量0.5重量%の銀ゼオライト
(1)材料
A型ゼオライト(110℃乾燥品):1000g
硝酸銀(AgNO3):7.9g
10Lポリ容器に水4.0Lを入れ、撹拌する。そこへ少しずつA型ゼオライト(Na型)を入れて懸濁液を作る。3時間ほど連続して撹拌し、固体内の空気を出す。
所定時間経過後pHを確認する。pH5~7になるよう、希硝酸(6倍希釈)を少量ずつ添加し、pH試験紙にて大まかなpH変化を確認する。
別途、硝酸銀を水3.0Lに混合しておき、それをA型ゼオライトスラリーに撹拌下少しずつ投入する。その後一晩撹拌放置する。
ヌッチェに磁性ロートを設置し、標準濾紙を敷き、そこへ前記銀ゼオライトスラリーを静かに注ぐ。
吸引工程の液切れ前に5L水量で洗浄する。
その後110℃で一晩乾燥し、冷却後乳鉢で粉砕する。平均粒径が2~2.5μmの粉末状のA型銀ゼオライトができる。
(1)材料
A型ゼオライト(110℃乾燥品):1000g
硝酸銀(AgNO3):39.7g
(2)製造の手順は上記手順と同様である。
3.銀担持量5.0重量%の銀ゼオライト
(1)材料
A型ゼオライト(110℃乾燥品):1000g
硝酸銀(AgNO3):79.5g
(2)製造の手順は上記手順と同様である。
本発明の銀イオン抗菌液の生成方法は、最初に、銀ゼオライトの0.1~20.0重量%の範囲の配合量を秤量し、その銀ゼオライトに対するクエン酸の配合比率が1.2以上の配合量を秤量して精製水に配合する処理と、次に、その精製水に配合した上記銀ゼオライト及びクエン酸を撹拌し混合して、少なくともクエン酸銀錯体及びシリカ水和物を含む混合液を調製する処理と、最後に、その混合液中に生成されるシリカ水和物を除去する処理とからなり、その除去処理により少なくとも上記クエン酸銀錯体を含有する銀イオン抗菌液を得ることができる。上記クエン酸は、市販品のクエン酸一水和物である。上記配合比率は、銀ゼオライトの配合量(重量%)に対するクエン酸の配合量(重量%)の割合、即ち「クエン酸の重量%/銀ゼオライトの重量%」の比率を意味しており、その比率を「配合比率」と定義して以下に用いる。
(精製水に配合する処理)
生成する銀イオン抗菌液の所望量に基づいて、A型又はX型の銀ゼオライト(以下、「銀ゼオライト」という)、クエン酸及び精製水の各配合量を決めておく。銀ゼオライトの0.1~20.0重量%の範囲の配合量を秤量し、その秤量した上記銀ゼオライトに対するクエン酸の配合比率が1.2以上の配合量を秤量し、常温(28℃)で上記配合量が決められた精製水に両材料を配合して配合液を調製する。その両材料を配合した配合液の外観は、白濁である。その白濁から透明になるまで撹拌し混合して混合液を生成する。混合液は少なくとも2分間撹拌し混合すると透明になる。又は、常温で精製水に銀ゼオライトを配合して配合液を調製し、同様に常温で精製水にクエン酸を配合して配合液を調製した後に、両液を混合し撹拌して混合液を生成する。混合液は少なくとも2分間撹拌し混合すると透明になる。何れの生成方法であっても良い。
一方、市販品の銀担持量2.2重量%のゼオミックAJ10N((株)シナネンゼオミック製)を用いて、上記生成方法と同様の方法で銀イオン抗菌液を生成できる。
次に、混合液を調製する処理において生成される生成物を説明する。
精製水に配合した銀ゼオライト((αNa2 βAg2)O・Al2O3‐2SiO2nH2O(α+β=1 n=5:110℃乾燥品))とクエン酸(C6H8O7)を撹拌し混合した混合液は、両者の化学式からみて、クエン酸銀錯体、クエン酸アルミニウム錯体、ナトリウムイオン(Na+)、シリカ水和物を含んでいる。
銀ゼオライトとクエン酸の混合により、最初に、クエン酸のプロトン(H+)が銀ゼオライトのSi-O-Al-O-Siの構造中のAl-O部分をアタックして切断し、その結果ゼオライト骨格を崩壊し、イオン交換吸着サイトが失われるので銀イオンが混合液中に溶出する。
その銀イオンはクエン酸と反応して多くの銀イオンがクエン酸銀錯体を生成し、同時にごく僅かな銀イオンを生成する。一方、アルミニウムはクエン酸と反応してクエン酸アルミニウム錯体を生成し、その他には、シリカ水和物及びナトリウムイオンを生成すると推測される。
上記クエン酸銀錯体の構造式を以下に示す。
yは1及び/又は2であり、yが3であると難溶性で水に溶けなくなる。銀イオンとクエン酸の反応で生成されるクエン酸銀錯体は、殆どがクエン酸1銀のものであるから、yが1でxが2の錯体である。
ところで、本発明の課題は、市販品のTINOSAN SDC(商品名)と同様のクエン酸銀錯体を含有する銀イオン抗菌液を安価に生成できる、銀イオン抗菌液の生成方法、その方法で生成される銀イオン抗菌液等を提供することにある。上記混合液を調製する処理において生成される生成物には、クエン酸銀錯体以外にシリカ水和物、クエン酸アルミニウム錯体等が生成される。そのクエン酸アルミニウム錯体を粉末化したクエン酸アルミニウムは制汗剤として化粧用に利用されるが、上記シリカ水和物はその表面に水酸化銀が吸着してシリカ水和物水酸化銀を生成して凝集し、その凝集生成物に光が照射されると酸化銀(黒褐色)となる恐れがあるので、混合液中から少なくともシリカ水和物は除去する必要がある。
(1)デカンテーションで除去する処理
化学反応は常温で通常24時間で平衡状態になるので、上記混合液を生成してから平衡状態になる24時間後の混合液は、シリカ水和物の表面に水酸化銀が吸着したシリカ水和物水酸化銀が凝集されて沈殿物が生成されるので、デカンテーションで銀イオン抗菌液を回収する。
上記デカンテーションは24時間に限定されるものではなく、常温から温度を高く、例えば70℃にすれば7時間で上記混合液中に上記シリカ水和物水酸化銀が凝集して沈殿するので、温度を任意に変えることで短時間にデカンテーションで銀イオン抗菌液を回収できる。
常温の28℃では、24時間で上記混合液中に凝集シリカ水和物水酸化銀が沈殿するので、濾過はWatman CF/C 濾紙でこの凝集シリカ水和物水酸化銀を分離して銀イオン抗菌液を回収することで、(1)の処理より銀イオン抗菌液の収率を向上できる。
上記したように、温度を高く、例えば70℃にすれば7時間で上記混合液中に凝集シリカ水和物水酸化銀が沈殿するので、上記濾紙で凝集シリカ水和物水酸化銀を分離して銀イオン抗菌液を、(1)の処理より収率よく回収できる。
(3)シリカ水和物の凝集前にフィルタで除去する処理
常温の28℃では10分間で上記混合液中にシリカ水和物が生成されるので、フィルタで上記シリカ水和物を分離して銀イオン抗菌液を回収する。
精製水に銀ゼオライト、クエン酸を配合する際に、クエン酸亜鉛又はクエン酸カルシウムを添加して亜鉛イオン又はカルシウムイオンをシリカ水和物に結合させ沈殿させて、フィルタで亜鉛イオン又はカルシウムイオンが結合したシリカ水和物を分離して銀イオン抗菌液を回収する。又は、亜鉛イオン又はカルシウムイオンが結合したシリカ水和物を、デカンテーションで分離して銀イオン抗菌液を回収しても良い。
シリカ水和物を除去する処理は、上記(1)~(4)の処理に限定されるものではなく、上記(1)~(4)の処理を適宜組み合わせて用いても良い。例えば、本発明の銀イオン抗菌液の用途に応じて、(3)の処理で回収した銀イオン抗菌液中に、シリカ水和物が極わずかながらでも含まれていると問題を生じる恐れがあれば、(3)の処理の後に(4)の処理を加えてシリカ水和物を除去することが好ましく、その(3)と(4)の処理の組合せで銀イオン抗菌液を回収しても良い。
次に、回収された銀イオン抗菌液を粉末状にする銀イオン抗菌粉末の生成方法を説明する。上記銀イオン抗菌液の生成方法のシリカ水和物を除去する処理の後に、そのシリカ水和物を除去した混合液を減圧凍結乾燥機で凍結乾燥、又は減圧噴霧乾燥機で噴霧乾燥することでその混合液を粉末状にすることができる。例えば、銀ゼオライト(銀担持量2.5重量%、110℃乾燥品)11.0gとクエン酸一水和物13.2gを使用すると、上記シリカ水和物を除去した混合液を減圧凍結乾燥機で処理することにより18gの銀イオン抗菌粉末が生成できる。
このようにして得られた銀イオン抗菌粉末1.0gを水1000gに溶解させると完全に溶解し、その時の銀イオン濃度は15.2ppmであった。
銀ゼオライトの一例として、上記銀ゼオライトの製造方法で製造したA型銀ゼオライトと市販品であるゼオミックAJ10N((株)シナネンゼオミック製、銀担持量2.2重量%)を試料として用いた。
A型銀ゼオライトは、0.1重量%又は0.5重量%の配合量の異なる2種類を秤量し、合計12個の試料を調製した。また、ゼオミックAJ10Nも上記の配合量の異なる2種類を秤量し、合計12個の試料を調製した。
上記0.1重量%又は0.5重量%の配合量が同じである各6個の試料に対して、表1の配合比率の欄に示すように、試料No.1及び7に対して0.9、試料No.2及び8に対して1.1、試料No.3及び9に対して1.2、試料No.4及び10に対して1.3、試料No.5及び11に対して1.5、試料No.6及び12に対して1.7を秤量した。この秤量した銀ゼオライトとクエン酸の粉末を精製水に配合して200gの配合液を調製し、2分後、10分後、30分後にその混合液のpHをpHメーターにより測定した。上記混合液の外観観察は目視により、白濁、半透明、透明の3段階で判定した。
なお、表1に示すNo.1~12のpHの値は、試料数をN=3としてその算術平均で求めた。また、以下の表に示す値は、表1に示す試料数と同様に試料数をN=3としてその算術平均で求めたものである。
以上のことから、クエン酸の配合比率を、上記銀ゼオライトの配合量(重量%)に対して1.2以上とすることで、混合液が2分後に透明になることから、クエン酸が銀ゼオライトのイオン交換サイトを形成する結晶構造を崩壊して、銀ゼオライトが含有していた全ての銀イオンを溶出するものと推測される。
続いて、第2の実験の実験例について説明する。
第2の実験は、上記銀ゼオライトの製造方法で製造した、銀担持量の異なる3種類(0.5、2.5及び5.0重量%)と、市販品であるゼオミックAJ10N((株)シナネンゼオミック製、銀担持量2.2重量%、平均粒径約2.5μm)を試料として用いた。
そして、上記銀ゼオライトの配合量に対して、クエン酸は、配合比率を試料No.1~3に対して0.6、試料No.4~6に対して0.9、試料No.7~9に対して1.1、試料No.10~12に対して1.2、試料No.13~15に対して1.4の配合量を秤量した。そして、精製水に秤量した銀ゼオライトを配合して調製した配合液100gと、精製水に秤量したクエン酸を配合して調製した配合液100gとを、混合して混合液を生成した。
一方、比較例のNo.16として、精製水に銀ゼオライトを配合した配合液100gと生理食塩液(塩化ナトリウム0.8重量%)100gを混合した混合液200gを調製して、溶出する銀イオン濃度の測定を行った。その濃度は450~590ppbであった。なお、この比較例のNo.16は、発汗(塩化ナトリウム0.9重量%)した状態の体に、特許文献1に記載のエアゾールタイプの防臭化粧料の銀ゼオライト(銀担持量が2.2重量%)を噴霧した条件と同じ場合を想定して、銀イオン濃度を測定したものである。
表2及び図5から、試料No.1~4は、銀ゼオライトとクエン酸の配合比率が1.2以上であれば銀ゼオライトは完全に溶解して、混合液の性状が液状で透明であるが、試料No.5は銀ゼオライトの一部が沈殿するために完全に溶解できない。また、混合した後3時間までは、混合液の性状が液状で透明であるが、24時間後には、試料No.1及び2はシリカ水和物の凝集が進み系全体がゲル化してしまい、この状態ではデカンテーション又はフィルタで上記シリカ水和物を除去することができない。しかしながら、混合した後3時間まではその性状が液状で透明であるので、フィルタで上記シリカ水和物を除去することができる。従って、銀ゼオライトの配合量は最大で20.0重量%が望ましい。
次に、銀担持量の異なる3種類の銀ゼオライトの第2の実験結果である表3-1~表3-3に基づいて、横軸に銀ゼオライトの配合量の3種類の値(0.1、0.5、1.0重量%)を描画し、縦軸にその値に対する銀イオン濃度の3種類の値を描画して、配合比率の異なる5種類の溶出銀イオン濃度のグラフを作成した。図1は銀担持量0.5重量%の銀ゼオライトの配合量と銀イオン濃度の相関を示す近似直線のグラフである。図2は銀担持量2.5重量%の銀ゼオライトの配合量と銀イオン濃度の相関を示す近似直線のグラフである。図3は銀担持量5.0重量%の銀ゼオライトの配合量と銀イオン濃度の相関を示す近似直線のグラフである。●印はNo.13~15の試料の近似直線であり、▲印はNo.10~12の試料の近似直線であり、△印はNo.7~9の試料の近似直線であり、○印はNo.4~6の試料の近似直線であり、◇印はNo.1~3の試料の近似直線のグラフである。
そこで、表3-1~表3-3のNo.10~12及びNo.13~15の銀ゼオライト配合量と銀イオン濃度のデータだけを摘出して表4を作成した。そして、その表4のデータに基づいて銀ゼオライト配合量と銀イオン濃度の関係を示す図4を作成した。
そこで、生成された銀イオン抗菌液を粉末にして、NMR(核磁気共鳴スペクトル)によるスペクトル分析を行った。
(実施例)
実施例1は、2.5重量%銀担持のA型銀ゼオライト1gと、その配合比率1.2のクエン酸1.2gを精製水に配合し100gの水溶液にして混合して常温で2時間撹拌した後に、80℃で1時間処理してシリカ成分を凝集させて、2日静置して沈澱させて濾過液を減圧凍結乾燥機により粉末(銀18.8mg/1.2g)にして試料とした。
(比較例)
比較例1は、TINOSAN SDCを凍結乾燥機により粉末にして試料とした。
比較例2は、試薬のクエン酸を試料とした。
各試料10mgを0.8gの重水に溶かして、600MHzH NMR(核磁気共鳴スペクトル)によるスペクトル分析を行った。
実施例、比較例1及び比較例2のシグナルからクエン酸銀錯体のシグナルを同定することはできなかった。
(混合液に含有の生成物)
上記したように、銀ゼオライトの構造式は下記の通りである。
(αNa2 βAg2)O・Al2O3‐2SiO2nH2O (α+β=1 n=5:110℃乾燥品)
上記銀ゼオライトのイオン交換サイトを形成する結晶構造は、Si-O-Al-O-Siの構造を三次元的に結合した結晶構造中のAl部分に、銀イオンが静電気的に結合した構造を有しており、イオン交換作用により上記結晶構造中の銀イオンが溶出して細菌を殺菌するといわれている。換言すれば、A型銀ゼオライトは、シリカ(SiO2)とアルミナ(Al2O3)からなるアルミノケイ酸塩で、その骨格が(AlO4)- 四面体及び(SiO4)- 四面体が三次元的に結合した結晶構造中のAl部分に、静電気的に銀イオンが吸着された構造を有している。
1.クエン酸のプロトン(陽子)がA型銀ゼオライトの(AlO4)- 四面体の負の電荷部位に存在するナトリウムイオンとイオン交換する(銀イオンに比べてナトリウムイオンの選択係数が小さいため)。
2.過剰のプロトンが骨格中のAl-O結合部分に作用してその結合を切断する。
3.Al-O結合部分の切断による骨格構造の崩壊で、銀ゼオライトに吸着していた銀イオン、ナトリウムイオン等が溶液中に放出される。
4.放出された銀イオンはクエン酸と反応してクエン酸銀錯体となる。
5.アルミニウムもクエン酸のC6H5O7 3-と反応し、クエン酸アルミニウム錯体となる。
6.クエン酸銀錯体は水中で一部解離し、極少量の銀イオンも存在する。
7.ナトリウムはイオンの形態で水中に存在する。
8.ケイ素はシリカゲルの形態で懸濁あるいは沈殿する。この時表面には少量の銀イオンが吸着されている。
従って、本発明の銀イオン抗菌液の生成方法で生成された銀イオン抗菌液は、シリカ水和物が当然ながら除去されている。
本発明の銀イオン抗菌液の生成方法で、銀ゼオライトに対するクエン酸の配合比率が1.2以上であることが解明された意義は大きい。今後、クエン酸銀錯体を含有する銀イオン抗菌液を調製する時に、銀ゼオライトに対して上記配合比率が1.2以上のクエン酸を配合すれば、製造最適条件及び経済性が得られることを意味している。
Claims (7)
- 銀ゼオライトから溶出する銀イオンを含有する銀イオン抗菌液の生成方法であって、
前記銀ゼオライトがA型又はX型の銀ゼオライトであり、該銀ゼオライトの0.1~20.0重量%の範囲の配合量を秤量し、該銀ゼオライトに対するクエン酸の配合比率が1.2以上の配合量を秤量して精製水に配合する処理と、
上記精製水に配合した上記銀ゼオライト及びクエン酸を撹拌し混合して、少なくともクエン酸銀錯体及びシリカ水和物を含む混合液を調製する処理と、
上記混合液中に生成されるシリカ水和物を除去する処理とからなることを特徴とする銀イオン抗菌液の生成方法。 - 前記銀ゼオライトの銀担持量が0.5~5.0重量%であることを特徴とする請求項1に記載の銀イオン抗菌液の生成方法。
- 請求項1又は2に記載の銀イオン抗菌液の生成方法で生成される銀イオン抗菌液。
- 前記銀イオン抗菌液の銀イオン濃度が銀ゼオライトの配合量と銀担持量で任意に調製することができることを特徴とする請求項3に記載の銀イオン抗菌液。
- 請求項1に記載の銀イオン抗菌液の生成方法のシリカ水和物を除去する処理の後に、上記シリカ水和物を除去した混合液を、凍結乾燥又は噴霧乾燥して銀イオン抗菌粉末を生成する処理とからなることを特徴とする銀イオン抗菌粉末の生成方法。
- 前記銀ゼオライトの銀担持量が0.5~5.0重量%であることを特徴とする請求項5に記載の銀イオン抗菌粉末の生成方法。
- 請求項5又は6に記載の銀イオン抗菌粉末の生成方法で生成される銀イオン抗菌粉末。
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WO2014133149A1 (ja) * | 2013-02-28 | 2014-09-04 | 株式会社タイキ | 銀イオン抗菌液の生成方法、その方法で生成される銀イオン抗菌液及びその抗菌液を含有した銀イオン含有製品 |
WO2015051020A1 (en) * | 2013-10-03 | 2015-04-09 | Polyone Corporation | Antimicrobial polymer concentrates and compounds |
JP2022003018A (ja) * | 2020-06-23 | 2022-01-11 | 佐々木化学工業株式会社 | クエン酸水素二銀及び/又はクエン酸二水素銀の製造方法並びにこれを用いた抗菌又は抗ウイルス溶液の製造方法 |
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WO2021261467A1 (ja) | 2020-06-23 | 2021-12-30 | 佐々木化学工業株式会社 | クエン酸水素二銀含有組成物及びその製造方法、並びにこれを用いた抗菌剤又は抗ウイルス剤及びその製造方法 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2014133149A1 (ja) * | 2013-02-28 | 2014-09-04 | 株式会社タイキ | 銀イオン抗菌液の生成方法、その方法で生成される銀イオン抗菌液及びその抗菌液を含有した銀イオン含有製品 |
EP2962561A4 (en) * | 2013-02-28 | 2016-01-27 | Taiki Corp Ltd | METHOD FOR PRODUCING AN ANTIBACTERIAL SILVER-ION LIQUID, AN ANTIBACTERIAL SILVER-ION LIQUID PRODUCED BY THIS METHOD, AND SILVER-ION-SUBSTANT PRODUCT COMPRISING THIS ANTIBACTERIAL LIQUID |
WO2015051020A1 (en) * | 2013-10-03 | 2015-04-09 | Polyone Corporation | Antimicrobial polymer concentrates and compounds |
JP2022003018A (ja) * | 2020-06-23 | 2022-01-11 | 佐々木化学工業株式会社 | クエン酸水素二銀及び/又はクエン酸二水素銀の製造方法並びにこれを用いた抗菌又は抗ウイルス溶液の製造方法 |
Also Published As
Publication number | Publication date |
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US10806149B2 (en) | 2020-10-20 |
KR20140086957A (ko) | 2014-07-08 |
CN103945690A (zh) | 2014-07-23 |
EP2752115A4 (en) | 2015-03-11 |
EP2752115A1 (en) | 2014-07-09 |
US20140329899A1 (en) | 2014-11-06 |
CN103945690B (zh) | 2018-05-25 |
JP2013053085A (ja) | 2013-03-21 |
CA2847562A1 (en) | 2013-03-07 |
JP5822296B2 (ja) | 2015-11-24 |
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