JP6656823B2 - Raw material for producing electrolytic water, electrolytic solution using the same, electrolytic water produced from the electrolytic solution, and method for producing the electrolytic solution and electrolytic water - Google Patents

Description

  The present invention is a raw material for producing electrolyzed water having antioxidant properties such as anti-aging of the skin, in addition to antibacterial properties such as washing and disinfecting, antiviral properties, antifungal properties, etc., and an electrolytic solution using the same. The present invention relates to electrolytic water produced from an electrolytic solution and a method for producing the electrolytic solution. In particular, the raw material for producing the electrolyzed water relates to a chloride powder supporting noble metal nanoparticles.

  Defined as "aqueous solutions that have obtained useful and reproducible functions through artificial processing, for which the scientific basis for processing and function has been or will be elucidated" In recent years, "functional water" has been attracting attention and used in various industrial fields such as electronics, food processing, service, agriculture, forestry and fisheries, health and hygiene, and water treatment (Non-Patent Document 1).

  In "functional water", dissolved chemical control water dissolved nitrogen, hydrogen, or carbon dioxide, etc., and ozone with strong oxidizing power were dissolved. Ultrasonic excitation water used by injecting external energy into ozone water and dissolved gas control water, exhibits completely different behavior from liquid water and gaseous water vapor, and has super oxidizing water with high oxidative decomposition power, pure water or Electrolyzed water having an oxidizing / reducing power, which is obtained by electrolyzing water to which a drug is added, and the like (Non-Patent Document 2).

  Among them, electrolyzed water has been attracting attention as a disinfectant to replace sodium hypochlorite (NaClO), which is the most consumed disinfectant in the world. This is because the following problems are inherent in sodium hypochlorite. First, when NaClO is mixed with organic matter, it produces a harmful substance called trihalomethane. Second, when NaClO is decomposed, harmful chloric acid is generated, and harmful bromic acid generated from a bromine compound contained in the raw material salt is contained. Third, foods and dishes have a chlorine odor and require a large amount of water for rinsing. In addition, there are a number of other problems, such as rough skin and mixing with acids to cause chlorine generation. In that regard, electrolyzed water has a clear generation principle, generation equipment, and standards for generated water, and has a public and scientific basis for its effectiveness and safety. It is characterized by being water, and has come to be widely used as a disinfectant / disinfectant mainly for sanitary management. For example, in the food processing industry, sterilization of food ingredients, container sterilization, cooling water, disinfection of work clothes, etc., in the service industry, disinfection of foodstuffs, tableware, prevention of fresh food drying, bath hot water, sterilization of guest rooms, etc., agriculture, forestry and fisheries In the sanitation industry, such as seed disinfection, fruit tree disinfection, disinfection of fish and shellfish, disinfection of fish farms, etc. It is applied to water sterilization, discharge wastewater sterilization, building air sterilization and deodorization, and the like.

  Such electrolyzed water is roughly classified into acidic electrolyzed water having a pH of 6.5 or less and alkaline electrolyzed water having a pH of 7.5 or more. Acidic electrolyzed water is a general term for aqueous solutions obtained by electrolysis of tap water and aqueous solutions containing chloride ions, and has strong bactericidal activity against various pathogenic bacteria, food poisoning bacteria, viruses, etc., and the bactericidal factor is generated by electrolysis. Hypochlorous acid (HClO). All acidic electrolyzed water has high safety and has passed the acute toxicity test, skin irritation test, mutagenicity test, and mucous membrane irritation test, so it is designated as a food additive because it has no risk of harm to health. , And hypochlorous acid water. On the other hand, alkaline electrolyzed water is a general term for an aqueous solution generated by electrolysis of a sodium chloride (NaCl) aqueous solution.

  Further, the acidic electrolyzed water may be strongly acidic electrolyzed water (strongly acidic hypochlorous acid aqueous solution), weakly acidic electrolyzed water (weakly acidic hypochlorous acid aqueous solution), slightly acidic electrolyzed water, depending on the composition of the electrolytic solution, electrolysis apparatus, electrolysis conditions and the like. It is classified into water (slightly acidic hypochlorous acid water) and neutral electrolyzed water.

  Strongly acidic electrolyzed water electrolyzes a 0.2% or less aqueous NaCl solution in a two-chamber or three-chamber electrolytic cell in which an anode and a cathode are separated by a diaphragm, and the effective chlorine concentration generated on the anode side is reduced. It is electrolyzed water having a pH of 2.7 or less and containing 20 to 60 ppm of HClO as a main component. Strongly acidic electrolyzed water having an effective chlorine concentration of 40 ppm exhibits antibacterial and antiviral activities comparable to sodium hypochlorite having a high concentration of 1,000 ppm. Weakly acidic electrolyzed water is obtained by electrolyzing a 0.2% or less aqueous NaCl solution in a two-chamber or three-chamber electrolytic cell in which an anode and a cathode are separated by a diaphragm. Is an electrolyzed water having a pH of 2.7 to 5.0 and containing HClO having an effective chlorine concentration of 10 to 60 ppm as a main component. Antibacterial and antiviral activities and safety similar to strongly acidic electrolyzed water have been confirmed. Slightly acidic electrolyzed water is produced by electrolyzing a 2 to 6% hydrochloric acid aqueous solution or a mixture of hydrochloric acid and an aqueous solution of sodium chloride in a single-chamber electrolytic cell in which an anode and a cathode are not separated by a diaphragm. Is electrolyzed water having a pH of 5 to 6.5 and containing HClO of 10 to 80 ppm as a main component. This slightly acidic electrolyzed water is characterized in that all the generated water is sterilized water, and the same antibacterial and antiviral activities and safety as those of the strongly acidic electrolyzed water have been confirmed. Although not intended for drinking, the pH is 5.8. Hydrochloric acid electrolyzed slightly acidic electrolyzed water having a water quality of about 6.5 is suitable for drinking. Neutral electrolyzed water can be produced by electrolyzing tap water containing chloride ions, particularly Cl −, in a single-chamber non-diaphragm electrolytic cell, has several ppm of available chlorine, and has a pH of 6.5 to 6.5. 7.5 is shown. This electrolyzed water also has bactericidal activity, but has not been approved for food additives and the like, and is therefore treated as sterilized water.

Similarly, the alkaline electrolyzed water is also classified into a strongly alkaline electrolyzed water and an electrolyzed hypochlorite. Strongly alkaline electrolyzed water is obtained by electrolyzing a 0.2% or less aqueous NaCl solution in a two-chamber or three-chamber electrolytic cell in which an anode and a cathode are separated by a diaphragm, and is formed on the cathode side. 0.5 to 11.5 of alkaline electrolyzed water today. It, like dilute sodium hydroxide, can damage mucous membranes and is not approved as a food additive. Electrolyzed hypochlorite is alkaline electrolyzed water having a pH of 7.5 or more, which is generated when an aqueous solution of 0.2% or less NaCl is electrolyzed by a single-chamber electrolysis apparatus in which an anode and a cathode are not separated by a diaphragm. In this electrolyzed water, most of HClO generated by the anodic reaction becomes hypochlorite ion (ClO ⁻ ) due to alkalinity, and has a weaker bactericidal activity than HClO. -200 ppm), and has excellent bactericidal activity. This electrolytic hypochlorite is recognized to be equivalent to a dilute solution of sodium hypochlorite, and can be used similarly to food additives.

  On the other hand, in recent years, similar to electrolyzed water, the effects of nanoparticles of noble metals such as platinum (Pt) and gold (Au) such as antioxidant, antibacterial, bacteria-free, mold-proof, freshness-maintaining, and odor-proof have attracted attention. This is because Pt and Au are also highly safe materials approved as food additives, and can now produce nanoparticles having an extremely large surface area. In particular, a dispersion of Pt and Au nanoparticles decomposes reactive oxygen species (superoxide anion, hydrogen peroxide, hydroxy radical, etc.) involved in cancer, diabetes, atopic dermatitis, Alzheimer, retinitis pigmentosa, etc. It is highly useful as an antioxidant (Patent Documents 1 to 3). Furthermore, utilizing this antioxidant ability, it has been applied to cosmetics for preventing skin aging, external preparations for skin, and the like (Patent Documents 4 to 7). Furthermore, noble metal nanoparticles are known to have antiviral and antibacterial properties, and are replaced with NaClO, antiviral agents such as Norofilus and influenza (Non-patent Document 3), and medical antibacterial with excellent washing durability. It has been applied to linens, antibacterial linens for accommodation facilities, antibacterial agents for daily antibacterial clothing (Patent Document 8), and the like.

  As described above, the electrolyzed water and the noble metal nanoparticle dispersion are both highly safe materials having antibacterial properties, antiviral properties, antioxidant properties, and the like, but each has its own problems.

  Electrolyzed water decomposes when HClO, its efficacy factor, comes in contact with light or air, so its effect is short, it is inactivated by mixing with those containing proteins and amino acids, and the surface tension of electrolyzed water is high, Poor wettability and permeability and uneven effect. As a method for improving the wettability and permeability of electrolyzed water to solve these problems, addition of a surfactant and microbubble treatment have been reported (Patent Documents 9 to 11). No specific countermeasure has been found for inactivation by mixing with a substance containing amino acids or amino acids.

  On the other hand, the problem of the noble metal nanoparticle dispersion liquid is that a method for producing nanoparticles that do not contain impurities such as a dispersant and have a small particle diameter and a narrow distribution has not been found. The presence of dispersants and other impurities will cover the surface of the noble metal nanoparticles, and the presence of large particles will reduce the surface area of the noble metal nanoparticles, both of which have the antioxidant, antiviral, It causes a reduction in antibacterial, sterilization, antifungal, freshness preserving, and deodorizing abilities (Patent Document 7 and Non-Patent Document 4).

  Conventionally, nanoparticles have been produced by a gas phase method, a liquid phase method, and a solid phase method, but in the present technical field, since they are used as a dispersion of noble metal nanoparticles, one of the liquid phase methods (Patent Documents 1 to 6 and 8). This reduction method is often used at a laboratory level because noble metal nanoparticles can be easily generated by reducing a noble metal ion dissolved in an aqueous solution of a noble metal chloride with a reducing agent. However, in this reduction method, a noble metal nanoparticle is required to have a dispersant having a surfactant activity for being present as a stable dispersion, and this causes a reduction in various effects of the noble metal nanoparticle. There are problems (Patent Document 7 and Non-Patent Document 4). Other liquid phase methods include hydrothermal synthesis using a supercritical liquid, sol-gel method using a chemical reaction called hydrolysis and polycondensation, and changing from a soluble metal salt to a sparingly soluble metal salt, and firing the precipitate. Precipitation method, reverse micelles, submerged dispersion method using micelles as a field for chemical reaction, etc., but the process of nucleation, growth, and termination makes it difficult to control the particle size, and a few nm There is a common problem that it is difficult to produce the following fine nanoparticles, a dispersant is required, and contamination of impurities cannot be avoided.

  Unlike the liquid phase method, as a method for producing nanoparticles that do not require a dispersant, there are a solid phase method and a gas phase method. Although the solid phase method is used as a mass production technique for particles of various substances, the particle size limit is about 1 μm, it is difficult to produce fine and high-purity nanoparticles, and the operation of classification is also required. And it is difficult to use as nanoparticles in the technical field. The vapor phase method includes a chemical vapor deposition (CVD) method, a vapor phase synthesis method, an evaporation / aggregation method, and the like. In the CVD method, a reactive monomer activated by plasma or the like chemically reacts in a heating furnace to form nanoparticles through nucleation, condensation, and aggregation, but the production efficiency is low and the energy efficiency is low. Therefore, there is a problem that the production cost is high and the particle diameter becomes non-uniform due to the processes of nucleation, condensation, and aggregation. The gas phase synthesis method is a method of producing nanoparticles by oxidizing, reducing, and nitriding in a reaction gas of metal chloride, but does not use a dispersant, but has the problem of mixing impurities based on raw materials. is there. The evaporation / aggregation method is a method of producing nanoparticles by once evaporating a metal in an inert gas by a method such as laser ablation, sputtering, or vacuum evaporation, and then cooling the same, and has the same problems as the CVD method. There is. In any case, when used as a dispersion in the present technical field, the fundamental problem of requiring a dispersant cannot be solved because the nanoparticles are uniformly dispersed in a harmless liquid.

  Under these circumstances, in recent years, a method for producing nanoparticles that does not require a dispersant by using plasma-induced cathodic electrolysis of molten salt or liquid-phase laser ablation has been developed (Patent Documents 12 to 15). However, the plasma-induced cathodic electrolysis method has been attempted to improve the productivity and energy loss because of poor productivity, but the problem of requiring a washing step with distilled water or the like and a filtration step using a filter has not been solved. (Patent Document 12). The liquid phase laser ablation method is a simple method of irradiating a laser to a precious metal plate in a liquid and simultaneously irradiating an ultrasonic wave, and a cosmetic of Pt nanoparticles using this method has been reported (Patent Document 7). . However, similarly to the gas-phase laser ablation in the preceding paragraph, there is a problem that the particle diameter becomes non-uniform, and a method of irradiating the laser (Patent Document 13), selection of a solvent such as hexane, triethylamine, silicon oil, and heavy water (Patent) Literatures 14 and 15) and the addition of a plasma generator (Patent Literature 15) have been studied, but the apparatus becomes complicated, the productivity is low, the solvent is expensive, and the safety of the noble metal nanoparticles is poor. It becomes liquid. Therefore, the problem of a manufacturing method that can exert the effects of the noble metal nanoparticles more effectively and must be overcome in order to make the antioxidant, antiviral agent, antibacterial agent, etc. using the noble metal nanoparticles highly safe. There is.

  Further, a physical vapor deposition (PVD) method has been developed in which metal vapor emitted by vacuum deposition or sputtering is deposited as metal nanoparticles on a substrate or a carrier. This method is a method of controlling a film formation process by a vacuum evaporation method or a sputtering method, that is, a method of generating metal nanoparticles by stopping growth at island-shaped metal particles formed at an early stage of film formation, and forming a particle diameter and It is easy to control its distribution and attracts attention as a method for producing metal nanoparticles containing no impurities, and is expected in various fields such as household goods requiring antibacterial and sterilization, catalysts for exhaust gas and wastewater treatment, and electronic components such as solar cells. (Patent Documents 16 to 18).

WO 2005/023467 pamphlet WO 2006/101106 pamphlet JP 2007-176944 A JP 2005-139102 A JP 2005-179500 A JP 2008-063295 A JP-A-2005-067556 Japanese Patent Application Laid-Open No. 2008-056552 JP 2006-176475 A JP 2006-176489 A JP 2013-010758 A JP 2008-106309 A JP 2009-299112 A JP 2010-077458 A JP 2010-144201 A JP 2009-511754 A WO 2012/150804 pamphlet JP 2009-246025 A

Functional water research promotion foundation homepage, http: // www. fwf. or. jp / index. html, "What is functional water?" Supervised by Masayuki Tsuda, edited by the Japan Industrial Cleaning Council, “Functional Water Learned from the Beginning”, published by the Industrial Research Institute, August 15, 2002 Nikkan Kogyo Shimbun Business Line, http: // www. nikkan. co. jp / news / nkx1020140206ccas. html, "Eu-BS launches antiviral spray to destroy norovirus with platinum nano" Everyware homepage, http: // www. pt-nano. net / index. html, “Nano-platinum particle solution” Yasunori Taga, "Research on Thin Film Process Technology", Integrated Engineering, Vol. 22, (2010) 53-64.

  The present invention has been developed to solve the problems of electrolyzed water (the effect factor is that HClO is decomposed by light or air to have a short effect, is inactivated by mixing with protein or amino acid-containing water, Poor permeability and non-uniform effect) and the problems of the noble metal nanoparticle dispersion (large particle size and wide particle size distribution, the noble metal nanoparticle dispersion contains impurities such as dispersants) Therefore, the antioxidant, antiviral, antibacterial, antifungal, antifungal, freshness, deodorant, etc. that can solve the effects of noble metal nanoparticles can be effectively exhibited for a long period of time. It is to provide a raw material capable of producing electrolyzed water having a high water content. Another object of the present invention is to provide an electrolytic solution using the raw material, electrolytic water obtained by electrolyzing the electrolytic solution, and a method for producing the electrolytic solution and the electrolytic water.

  The present inventors have prepared chloride powders supporting noble metal nanoparticles by a PVD method, and after dissolving these powders in water, obtained by electrolysis. It is an electrolyzed water that can effectively demonstrate the antioxidant, antiviral, antibacterial, antifungal, antifungal, freshness, deodorant, and other effects of water and noble metal nanoparticles for a long period of time, and has high safety. Heading, the present invention has been completed. In particular, the chloride powder supporting the noble metal nanoparticles of the present invention uses sodium chloride (NaCl) or potassium chloride (KCl) as a noble metal, and includes platinum (Pt), gold (Au), silver (Ag), and iridium (Ir). ) Or those produced using these alloys have been found to be preferable.

  That is, the present invention provides a chloride powder in which noble metal nanoparticles, which are raw materials for producing electrolyzed water containing noble metal nanoparticles, are supported by a PVD method. Further, the present invention provides an electrolytic solution obtained by dissolving a chloride supporting the noble metal nanoparticles in water, electrolytic water produced by electrolysis of the electrolytic solution, and a method for producing the electrolytic solution and electrolytic water.

  Electrolyzed water obtained by electrolyzing an electrolytic solution obtained by dissolving chloride powder carrying noble metal nanoparticles of the present invention in water is used for sanitary control such as washing, disinfection, deodorization, etc. of electrolytic water and noble metal nanoparticles, and for fresh foods. In addition to antibacterial properties, antiviral properties, antifungal properties, etc. required for maintaining freshness, etc., it also has antioxidant properties required for health preservation such as skin aging prevention and beautiful skin effect of precious metal nanoparticles, and the efficacy factor of electrolyzed water Even if HClO is decomposed, the effect of the noble metal nanoparticles can be maintained semipermanently. In addition, conventional electrolyzed water is inactivated by mixing with those containing proteins and amino acids, or the effect is poor due to poor wettability and permeability of electrolyzed water, but due to the presence of noble metal nanoparticles, , Can solve these problems. Furthermore, noble metal nanoparticles are supported on chloride powder by the PVD method, so they do not contain a dispersant, have a small particle size, have a narrow particle size distribution, and when dissolved in water, noble metal nanoparticles become uniform. Since the electrolyte solution is dispersed in the metal nanoparticles, the effect of the conventional metal nanoparticles can be surpassed. However, it is not clear why the dispersant is not required and the dispersion is uniform, but it is considered that the process involves dissolving and dispersing the noble metal nanoparticles in water with the chloride powder supported. Can be

  Therefore, an electrolytic solution in which the noble metal nanoparticles are uniformly dispersed can be obtained only by dissolving the chloride supporting the noble metal nanoparticles in the aqueous solution. Furthermore, by electrolyzing this electrolytic solution as it is, in addition to the antibacterial properties, antiviral properties, antifungal properties, etc. required for sanitary control such as washing, disinfection, deodorization, etc. and maintaining freshness of fresh foods, it also prevents skin aging. Electrolyzed water in which noble metal nanoparticles having antioxidant properties required for health preservation such as skin care and skin effect are uniformly dispersed can be easily obtained. In the early stage of application of the electrolyzed water to the human body or clothing, the effects of the electrolyzed water and the noble metal nanoparticles act synergistically, and after the HClO of the electrolyzed water is decomposed, the effect of the noble metal nanoparticles is increased. It will last semipermanently.

  Further, in the field of agriculture, particularly in the sterilization and disinfection of soil and fruit trees, spray cooling, and the like, the use of electrolytic water produced using an electrolytic solution in which KCl powder carrying noble metal nanoparticles is dissolved can be used to fertilize soil. The component K is supplied, and in addition to effects such as sterilization, bacteria elimination, cooling, and the like, it is possible to bring about excellent growth effects on agricultural crops.

1 is a schematic view of a typical apparatus for producing noble metal nanoparticles supported on chloride powder. It is a principle diagram of a two-chamber type electrolytic cell. It is a principle figure of a three-chamber type electrolytic cell. It is a principle diagram of a single-chamber type electrolytic cell.

  Noble metals do not have a clear scientific definition, but are generally characterized by being not easily subject to chemical changes, always having a metallic luster, being produced in small quantities, and being expensive. Specifically, it refers to gold (Au), silver (Ag), and the platinum group (platinum (Pt), palladium (Pd), rhodium (Rh), iridium (Ir), ruthenium (Ru), osmium (Os)). Things. Although the above-mentioned noble metals are suitable for the noble metals forming the nanoparticles of the present invention, alloys thereof may be used. In particular, Pt, Au, Ag, Ir, and alloys thereof are preferable. Among them, Pt, Au and Ag, which are recognized as safe as food additives, are even more preferable.

  The chloride supporting the noble metal nanoparticles is sodium chloride (NaCl) or potassium chloride (KCl), and is used as a powder having a small amount of impurities and an average particle diameter of 1 μm to 3 mm. In particular, considering the solubility in water, the average particle diameter is more preferably 1 μm to 1 mm, and still more preferably 1 μm to 500 μm. Further, the chloride powder is preferably spherical in which noble metal nanoparticles are easily deposited.

  The PVD method is suitable for supporting the noble metal nanoparticles on the chloride powder, and a vacuum evaporation method, an ion beam evaporation method, an ion plating method, and various sputtering methods can be used. FIG. 1 shows a schematic diagram of a production apparatus of metal nanoparticles using an ion beam sputtering method as a representative example. In this manufacturing apparatus, a physical vapor deposition tank 1 having at least an ion source 2, a vapor deposition source 3 of a noble metal or an alloy thereof, an inert gas introduction system 8, and a vacuum exhaust system 9 is provided below the vapor deposition source 3 and the vapor deposition source 3. By installing a shutter 4 provided with a slit 5 that is precisely rotated by a motor 6 between the deposited powder 7 and a chloride powder 10 that is a substance to be deposited on which the deposition substance 7 is deposited, The deposition material 7 beaten out from the substrate is intermittently deposited on the surface of the chloride powder 10. Moreover, a screw 11 is provided at the bottom of the manufacturing apparatus so that the chloride powder 10 is evenly exposed to the deposition material 7. The chloride powder 10-1 at the bottom of the manufacturing apparatus is lifted up by the screw 11 like the chloride powder 10-2, and is intermittently vapor-deposited with the chloride powder 10-3 to attach the noble metal nanoparticles. Then, it reaches the chloride powder 10-4 which is not exposed to the deposition source for a certain period of time. Although a shutter mechanism is provided in FIG. 1, the shutter mechanism is not necessarily required, and the chloride powder 10 is deposited on the chloride material 10 so that the noble metal nanoparticles are accurately deposited on the chloride powder 10. Any method can be adopted as long as the mechanism can control the time of exposure to the compound. For example, there is a method of controlling an ion beam emitted from the ion source 2.

  In the above method of supporting the noble metal nanoparticles on the chloride powder, the mechanism of generation of the noble metal nanoparticles on the surface of the chloride powder serving as the base material is not clear, but is presumed as follows. It is said that there are three general film formation mechanisms such as vapor deposition and sputtering, such as Volmer-Weber (VW) growth, Frank-van der Merwe (FM) growth, and Transki-Krastanov (SK) growth (non-film formation). Patent Document 5). Among them, the VW growth mode, that is, a three-dimensional island-like nucleus is formed from the initial stage of growth, grows with an increase in the deposition amount, coalesces, and eventually forms a continuous film “Island growth (Island growth)”. Focusing on the (Growth) mode, there are differences in the film formation mechanism due to various parameters such as the surface energy and temperature of the physical vapor deposition material and the substrate. While performing physical vapor deposition, a new deposition surface is always pointed at the deposition material, so that a three-dimensional sea-island structure, that is, one in which noble metal nanoparticles are successively generated on the surface of the chloride powder. It is possible (Patent Document 18).

  Here, the average particle diameter of the noble metal nanoparticles with respect to the chloride powder in the production of the chloride powder supported by the noble metal nanoparticles exhibits various effects of the noble metal nanoparticles if it is 100 nm or less, but the surface area is large. Since the higher the activity, the more preferably it is 50 nm or less, more preferably 10 nm or less. The deposition amount of the noble metal nanoparticles is set according to the composition of the electrolytic solution obtained by dissolving the chloride powder supported by the noble metal nanoparticles in water or dilute hydrochloric acid. The concentration of the noble metal nanoparticles required to solve the problem of the electrolyzed water in the manufactured electrolyzed water is not particularly limited as long as the noble metal nanoparticles are present. However, effectively and economically, regardless of the type of the electrolyzed water, the concentration of the noble metal nanoparticles present in the electrolyzed water is preferably 0.1 to 100 μM, and preferably 0.1 to 5 μM. More preferably, the concentration is more preferably 0.1 to 1 μM, and noble metal nanoparticles are deposited on the chloride powder so as to have such a concentration.

Therefore, the aqueous chloride solution for producing general strongly acidic electrolyzed water, weakly acidic electrolyzed water, slightly acidic electrolyzed water, electrolyzed hypochlorite, and strongly alkaline electrolyzed water is used at a concentration of 0.2% or less. For example, in order to have noble metal nanoparticles at a concentration of 0.1 to 100 μM in electrolytic water produced from 100 L of a 0.2% NaCl aqueous solution, for example, Pt nanoparticles deposited on 200 g of NaCl powder must be , About 1.95 × 10 ^{−4 to} 1.95 g. This corresponds to a weight ratio of Pt / NaCl of about 1 × 10 ⁻⁶ to 1 × 10 ⁻³ . In this way, the amount of each noble metal nanoparticle deposited on each chloride powder can be appropriately determined. By the way, tap water is usually used as a chloride aqueous solution for producing neutral electrolyzed water, and an electrolytic solution having a chloride concentration of about 2 to 6% and a hydrochloric acid concentration of about 0.2 to 0.6% is electrolyzed. Therefore, the chloride alone is added to a chloride aqueous solution in which the noble metal nanoparticles are dissolved to adjust the concentration and used.

Specifically, spherical chloride powder having an average particle diameter of 1 μm to 3 mm is charged into the physical vapor deposition tank 1 shown in FIG. 1, and the vapor deposition source 3 is provided with a noble metal or an alloy thereof. Next, the inert gas Ar is introduced into the physical vapor deposition tank 1 from the inert gas introduction system 8 while evacuating from the vacuum evacuation system 9 so that the degree of vacuum of the physical vapor deposition tank 1 is 1 × 10 ⁻⁴ to 1 torr. . When the degree of vacuum is stabilized, the precious metal or its alloy of the evaporation source 3 is evaporated on the fixed flat substrate at a rate of 1 分 の to 10 μm / min per unit area while rotating the screw 11 and the rotary motor 6, and the predetermined amount is Nanoparticles are formed up to the weight of the noble metal nanoparticles. The evaporation rate is set in advance in a preliminary experiment by a general gravimetric method.

  The noble metal nanoparticles produced in this way are used as an electrolytic solution for electrolysis, and in the case of strongly acidic electrolyzed water, weakly acidic electrolyzed water, electrolytic hypochlorite, or strongly alkaline electrolyzed water, it is added to water. It is dissolved to a chloride concentration of 0.2% or less, that is, a NaCl or KCl concentration. In the case of slightly acidic electrolyzed water, it is dissolved in about 2 to 6% of dilute hydrochloric acid or about 2 to 6% of dilute hydrochloric acid so as to have a chloride concentration of about 0.2% or less, that is, a NaCl or KCl concentration. Is done. In any case, the water used is limited as long as it does not contain any artificially added chlorides, such as tap water, groundwater, pure water (distilled water, deionized water, RO water, etc.). However, pure water that is less affected by impurities is preferable.

  The electrolytic solution adjusted in this way is a two-chamber electrolytic cell and a three-chamber electrolytic cell shown in FIGS. 2 and 3 when producing strongly electrolytic electrolyzed water, weakly acidic electrolyzed water, or strongly alkaline electrolyzed water. In the case of using slightly acidic electrolyzed water, neutral electrolyzed water, or electrolyzed hypochlorite, each is manufactured under general manufacturing conditions using a single-chamber electrolysis tank shown in FIG. Here, as the electrode, carbon (C), Pt, Au, titanium (Ti) coated with Pt or Au, or the like used in an existing electrolytic cell can be used. However, electrodes of various materials such as Ti can be used for the cathode, but it is preferable to use insoluble electrodes such as C, Pt, and Au. This is because the polarity can be reversed by switching the anode and the cathode, so that the life of the electrode can be extended. 2 to 4 are principle diagrams of the electrolytic cell, and do not require a special electrolytic cell. Generally, an electrolytic cell commercially available from Toshiba Corporation, Hoshizaki Electric Co., Ltd. or the like can be used.

  Hereinafter, the present invention will be described by using a raw material for producing slightly acidic electrolyzed water containing Pt nanoparticles, an electrolytic solution produced using the raw material, and electrolytic water produced by electrolysis of the electrolytic solution as examples. Although described more specifically, the technical idea of the present invention is not limited by the embodiments.

  For the NaCl powder, a powder obtained by sieving NaCl powder (manufactured by Nippon Seisho) having an average particle diameter of 180 to 500 μm of 85% or more with a fine mesh of 80 mesh (wire diameter 0.14 mm) to remove fine powder of 180 μm or less is used. Was.

Next, Pt nanoparticles were deposited on the NaCl powder using the physical vapor deposition tank 1 shown in FIG. After charging the NaCl powder into the physical vapor deposition tank 1 and fixing Pt to the vapor deposition source 3, the physical vapor deposition tank 1 is sealed, and the vacuum evacuation system 9 is set to a degree of vacuum of about 1 × 10 ⁻⁴ torr. While evacuating, inert gas Ar was introduced into the physical vapor deposition tank 1 from the inert gas introduction system 8. After the degree of vacuum is stabilized, Pt of the vapor deposition source 3 is evaporated at a rate of 1000 ° / min per unit area while rotating the screw 11 and the rotating motor 6, and the weight ratio of Pt / NaCl is about 1 × 10 ^−4. Nanoparticles were formed until It was confirmed by a transmission electron microscope that the particle size of the formed Pt nanoparticles was 1 to 5 nm.

(Example 1) Slightly acidic electrolyzed water in which Pt nanoparticles are dispersed The thus prepared NaCl powder supporting Pt nanoparticles is diluted with 5% diluted hydrochloric acid obtained by diluting 35% hydrochloric acid (produced by Asahi Glass) with tap water. When dissolved and adjusted to have a NaCl concentration of 0.1%, an electrolyte solution (1) for slightly acidic electrolyzed water in which Pt nanoparticles were uniformly dispersed was obtained.

  The electrolytic solution (1) was electrolyzed with a DC power supply of about 3 to 4 V × 4 A using a one-chamber electrolytic cell shown in FIG. 4, then diluted with tap water, pH was about 6, and effective chlorine concentration was about 10 ppm. The slightly acidic electrolyzed water containing Pt nanoparticles was obtained. The slightly acidic electrolyzed water in which the Pt nanoparticles are dispersed has antioxidant properties, antibacterial properties, antiviral properties, antifungal properties, etc., immediately after application, and shows a synergistic effect between the Pt nanoparticles and the slightly acidic electrolyzed water. These effects were semipermanently retained by the Pt nanoparticles.

(Example 2) Electrolytic hypochlorite in which Pt nanoparticles were dispersed The NaCl powder carrying the Pt nanoparticles of Example 1 was dissolved in tap water so as to be a 0.1% NaCl aqueous solution. Dispersed uniformly. The same amount of a 5% aqueous NaCl solution was added to the aqueous NaCl solution in which the Pt nanoparticles were dispersed, and an electrolytic solution (2) for electrolytic hypochlorite in which the Pt nanoparticles were dispersed was obtained.

  The electrolytic solution (2) was electrolyzed with a DC power supply of about 3 to 4 V × 4 A using a one-chamber electrolytic cell shown in FIG. 4, then diluted with tap water, pH was about 8, and effective chlorine concentration was about 10 ppm. Of the electrolysis hypothermia containing Pt nanoparticles was obtained. This Pt nanoparticle-dispersed electrolytic hypochlorite also has a synergistic effect between the Pt nanoparticle and the electrolytic hypochlorite in antioxidant properties, antibacterial properties, antiviral properties, antifungal properties, etc. immediately after application, and These effects were semipermanently retained by the Pt nanoparticles.

(Example 3) Neutral electrolyzed water in which Pt nanoparticles were dispersed The NaCl powder supporting the Pt nanoparticles of Example 1 was dissolved in tap water so as to be a 0.1% NaCl aqueous solution. Dispersed uniformly. In a NaCl aqueous solution in which the Pt nanoparticles are dispersed, a NaCl carrier is dissolved to form a 4% NaCl aqueous solution, and 35% hydrochloric acid (manufactured by Asahi Glass) is added to adjust the hydrochloric acid concentration to 0.4%. A dispersed electrolyte solution (3) for neutral electrolyzed water was obtained.

  Using the one-chamber electrolytic cell shown in FIG. 4, the above-mentioned electrolytic solution (2) was electrolyzed with a DC power supply of about 3 to 4 V × 4 A, then diluted with tap water, pH was about 7, and effective chlorine concentration was about 10 ppm. Neutral water containing Pt nanoparticles was obtained. The neutral electrolyzed water in which the Pt nanoparticles are dispersed also exhibits antioxidant properties, antibacterial properties, antiviral properties, antifungal properties, etc., immediately after application, exhibiting a synergistic effect between the Pt nanoparticles and the neutral electrolyzed water, and These effects were semipermanently retained by the Pt nanoparticles.

  INDUSTRIAL APPLICABILITY The present invention can be used in various industries such as food processing, agriculture, fisheries, service, medical care and nursing, water and sewage treatment, and air treatment. And in all industries, various foods, work clothes, containers and utensils, processing and transport equipment, fingers, toilets, workplaces and facilities, sterilization, sanitization, washing, cleaning of cooling water, water supply, clean water, drainage, etc. Not only can it be used for a wide range of applications, such as deodorization, deodorization, and mold control. In particular, when used in the agricultural field, fertilizer components are supplied in addition to the effects of sterilization, sterilization, washing, and the like, so that they exhibit excellent effects in growing crops.

DESCRIPTION OF SYMBOLS 1 Physical vapor deposition tank 2 Ion source 3 Deposition source 4 Shutter 5 Slit 6 Rotary motor 7 Deposition substance 8 Inert gas introduction system 9 Vacuum exhaust system 10 Chloride powder (substance to be vapor-deposited / base material)
DESCRIPTION OF SYMBOLS 11 Screw 12 Stirring motor 13 Moving path of chloride powder 14 Electrolyzer 15 Anode 16 Cathode 17 Power supply 18 Cation exchange membrane 18 'Anion exchange membrane 19 Electrolyte inlet 20 Acidic electrolyzed water outlet 21 Alkaline electrolyzed water outlet 22 Electrolyte Exit 23 Water inlet

Claims (2)

A first step of depositing noble metal or noble metal alloy nanoparticles on the chloride powder by using a physical vapor deposition method, and a step of depositing the noble metal or noble metal alloy nanoparticles produced in the first step on the chloride powder with water. Or a second step of dissolving in dilute hydrochloric acid. A first step of depositing noble metal or noble metal alloy nanoparticles on the chloride powder by using a physical vapor deposition method, and a step of depositing the noble metal or noble metal alloy nanoparticles produced in the first step on the chloride powder with water. Alternatively, a method for producing electrolyzed water, comprising: a second step of dissolving in dilute hydrochloric acid; and a step of electrolyzing the electrolytic solution produced in the second step.

Images