JP2020007310A - Method for producing hydrogen supply material and silicon fine particles having hydrogen supply ability and/or aggregate of silicon fine particles - Google Patents

Abstract

To provide hydrogen supply materials that make it easy to take in enough hydrogen into the body to eliminate hydroxyl radicals in the body in daily life.SOLUTION: Provided is a hydrogen supply material 200 for bringing hydrogen into contact with skin and/or mucous membranes via a medium, comprising a silicon fine particles 100a with hydrogen generation ability or an aggregate thereof, an impermeable membrane 70 covering the layers comprising them, and a medium 90b containing at least one selected from the group consisting of potassium carbonate, sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, and potassium hydroxide, in contact with the silicon fine particles or the aggregate thereof through the film, when removing at least a part of the film or dissolving at least a part of the film, the medium contacting the silicon fine particles or the aggregate.SELECTED DRAWING: Figure 3A

Description

  The present invention relates to a hydrogen supply material, a method for producing the same, and a hydrogen supply method.

  In the body of animals, including humans, there is active oxygen derived from oxygen produced in the body and taken up from the lungs. While active oxygen is necessary for maintaining life, it is known that cells constituting the living body are oxidized and damaged. For example, active oxygen, especially the most oxidative hydroxyloxyl radical among active oxygen, can cause various diseases such as cancer, stroke, myocardial infarction, diabetes and other lifestyle-related diseases, and skin disorders such as skin aging and dermatitis. It is considered. In addition, it is said that the hydroxyl radical has a bad effect (including spots, dullness, or hair loss) on skin whitening or hair growth. Therefore, it is desirable that surplus active oxygen, particularly hydroxyl radical, which has not been used for a reaction beneficial to the living body, be minimized in the body as much as possible.

  The hydroxyl radical generated in the body disappears by reacting with some substances. Hydrogen is known as an example of a substance that annihilates a hydroxyl radical. Hydrogen reacts with hydroxyl radicals to produce water, which does not produce any harmful substances to living organisms. In view of the above, there has been proposed a hydrogen water generating apparatus containing hydrogen for eliminating hydroxyl radicals in the body (for example, Patent Document 1).

  However, the hydrogen concentration in the hydrogen water is as low as 1.6 ppm (saturated hydrogen concentration) at the maximum, and the hydrogen concentration in the hydrogen water is remarkably reduced with the passage of time because the hydrogen in the water easily diffuses into the air. Therefore, it is not easy to take in a sufficient amount of hydrogen into the body by the method of ingesting hydrogen water to react with hydroxyl radicals in the body. Therefore, a hydrogen-containing composition containing hydrogen and a surfactant has been proposed to facilitate the incorporation of hydrogen into the body (Patent Document 2).

  The present inventors have studied water decomposition and hydrogen generation by silicon nanoparticles, and described the results (Non-Patent Document 1, Patent Document 3, and Patent Document 4).

Japanese Patent No. 5514140 JP-A-2013-113331 JP 2016-155118 A JP 2017-104848 A

Shinsuke Matsuda et al., Water decomposition and hydrogen concentration by silicon nanoparticles, Proceedings of the 62nd JSAP Spring Meeting, 2015, 11a-A27-6

  However, even if high-concentration hydrogen water is ingested, the amount of hydrogen contained in 1 liter of hydrogen water is only up to 18 ml (milliliter) in gaseous terms, and moreover, hydrogen in the gastrointestinal tract contains a large amount of hydrogen. It will be gasified. Therefore, there is a problem that a sufficient amount of hydrogen is not necessarily taken into the body, causing a drunk symptom (so-called "burp"). On the other hand, when ingesting a hydrogen-containing composition containing hydrogen by a surfactant, it is necessary to ingest a large amount of the hydrogen-containing composition in order to take in a sufficient amount of hydrogen into the body. In addition, the above-mentioned problem that hydrogen is released in the stomach may occur.

  Therefore, the inventors of the present application have limited the means for taking hydrogen into the body to the conventional "drinking water" because the amount of hydrogen necessary for sufficiently reducing active oxygen can be introduced into the body. I focused on making it difficult to capture. If it is possible to increase the chances of bringing skin and / or mucous membranes into contact with hydrogen in a more natural manner in the behavioral scenes of human daily life (hereinafter collectively referred to as “living scenes”), Even though the amount of hydrogen that can be taken into the body in a living situation is limited, the total amount of hydrogen that can be taken through the whole is considerably large. The inventors of the present application have thought that it is possible to reach or approach an amount sufficient for reacting with hydroxyl radicals in the body by applying such a device, and worked diligently on research and development.

  The present invention solves at least one of the above technical problems, and greatly contributes to facilitating the incorporation of a sufficient amount of hydrogen into the body in a daily life scene to eliminate hydroxyl radicals in the body.

  As a result of intensive studies and analysis conducted by the inventors of the present invention based on the above viewpoints, a very interesting finding was obtained. Specifically, silicon fine particles having certain characteristics or aggregates thereof generate almost hydrogen even when brought into contact with a water-containing liquid having a pH value in a certain numerical range or a medium capable of containing the water-containing liquid. However, when it comes into contact with a water-containing liquid having a pH value in another numerical range or a medium capable of containing the water-containing liquid (hereinafter, also collectively referred to as a “medium”), hydrogen is remarkably increased. Can be generated by the present inventors. In addition, it has been found that the amount of generated hydrogen greatly increases as the pH value increases. The “water-containing liquid” in the present application includes water itself, human sweat, and human body fluid.

  On the other hand, when a means different from oral ingestion is adopted, in other words, when it is desired to take into the body (including the skin itself or the mucous membrane itself) by contacting the skin and / or the mucous membrane, the skin and / or the mucous membrane itself The present inventors have found that, in addition to the presence of hydrogen, the presence of "sweat" which cannot be avoided in daily life can also hinder the generation of hydrogen. “Skin” and “sweat” may be acidic (weakly acidic) to basic (weakly basic) in some cases. Trimming can also be a useful tool to ensure that hydrogen is more easily taken up into the body.

  The hydrogen generation mechanism by the reaction between the silicon fine particles or the aggregate thereof and water molecules is shown in the following formula (1). However, as described above, the inventors of the present application have limited reaction when the reaction represented by the formula (1) is in contact with a medium having a low pH value (typically, a pH value of less than 5). However, it has been found that the treatment proceeds when the medium comes into contact with a medium having a pH value of 6 or more. Therefore, it is very interesting that even a weakly acidic water-containing liquid having a pH value of 6 (or a medium capable of containing the water-containing liquid) can effectively generate hydrogen. It became clear. By further investigation, in order to promote the generation of hydrogen, the pH value is more preferably 7 or more (or more than 7), and even more preferably the pH value is more than 7.4. Preferably, contact with a medium having a basicity of more than 8 (hereinafter referred to as "alkaline") is effective.

(Formula 1) Si + 2H ₂ O → SiO ₂ + 2H ₂

  Based on the above findings, the present inventors have solved at least a part of the above technical problems by utilizing the silicon fine particles or aggregates thereof and appropriately adjusting or setting the use environment thereof. I found that I could do it. The present invention has been created based on the above viewpoint.

  One hydrogen supply material of the present invention includes silicon fine particles capable of generating hydrogen or an aggregate thereof, and a physiologically acceptable medium in contact with the silicon fine particles or the aggregate thereof. Further, this hydrogen supply material is a hydrogen supply material for bringing the above-mentioned hydrogen into contact with skin and / or mucous membrane via the above-mentioned medium.

  According to this hydrogen supply, the above-mentioned physiologically acceptable medium is brought into contact with the skin and / or mucous membrane by hydrogen generated by contact with silicon fine particles or agglomerates thereof, thereby providing a means different from oral ingestion. It can be used to achieve ingestion into the body (including the skin itself or the mucous membrane itself).

  In the invention of the hydrogen supply material described above, for example, the solid agent / solid material (hereinafter, referred to as a “solid agent”) of the silicon fine particles or the aggregate thereof or the silicon fine particles or the aggregate thereof Further comprising a water-impermeable film covering the layer containing, when at least a part of the film is removed or at least a part of the film is dissolved, the medium comes into contact with the silicon fine particles by hydrogen. This is a preferred aspect from the viewpoint that it is possible to select a scene that requires the occurrence of a high degree of freedom.

  In addition, one method for producing a hydrogen supply material of the present invention is to convert the above-mentioned hydrogen into the skin and / or mucous membrane via a physiologically acceptable medium using silicon fine particles or an aggregate thereof capable of generating hydrogen. Contacting with the above-mentioned medium in order to contact the medium.

  In this method for producing a hydrogen supply material, hydrogen generated by the contacting step of bringing the above physiologically acceptable medium into contact with silicon fine particles or aggregates thereof is brought into contact with skin and / or mucous membrane via the medium. Give the opportunity. As a result, according to this method for producing a hydrogen supply material, it is possible to produce a hydrogen supply material that can be taken into the body (including the skin itself or the mucous membrane itself) by using means different from oral ingestion.

  Further, in one hydrogen supply method of the present invention, the above-mentioned hydrogen is brought into contact with skin and / or mucous membrane via a physiologically acceptable medium with silicon fine particles or an aggregate thereof capable of generating hydrogen. For this purpose, the method includes a contact step of bringing the medium into contact with the aforementioned medium.

  According to this hydrogen supply method, there is an opportunity to contact the skin and / or mucous membrane with hydrogen generated by the contacting step of bringing the above physiologically acceptable medium into contact with the silicon fine particles or the aggregates thereof through the medium. give. As a result, according to this hydrogen supply method, it is possible to realize the incorporation into the body (including the skin itself or the mucous membrane itself) by using means different from oral ingestion.

  In the invention of the above-described method for producing a hydrogen supply material or the invention of the above-described hydrogen supply method, for example, the solid agent of the above-mentioned silicon fine particles or the aggregate thereof or the layer containing the above-mentioned silicon fine particles or the aggregate thereof When at least a part of the water-impermeable membrane covering the membrane is removed or at least a part of the membrane is dissolved, contacting the silicon microparticles with the above-described medium can reduce a situation where generation of hydrogen is necessary. This is a preferred embodiment from the viewpoint of enabling selection with a high degree of freedom.

  Further, in the present application, when the size of the diameter of a crystal is “nm order”, the expression “crystallite” is used instead of the expression “crystal grain (or crystal particle)”. On the other hand, when the size of the diameter of the crystal is “μm order”, the expression “crystal grain (or crystal particle)” is adopted.

  Here, “silicon fine particles” in the present application include “silicon nanoparticles” having an average crystallite diameter on the order of nm, specifically, a crystallite diameter of 1 nm or more and 100 nm or less. In a narrower sense, the “silicon fine particles” in the present application are mainly silicon nanoparticles having an average crystallite diameter of a nano-level, specifically, a crystallite diameter of 1 nm or more and 50 nm or less. Here, according to the inventor of the present application, silicon nanoparticles having a main crystallite diameter of 1 nm or more and less than 10 nm are “silicon fine particles” that have achieved the most miniaturization as one aspect that can be employed. Further, in the present application, the silicon fine particles include not only a state in which each silicon nanoparticle is dispersed, but also a plurality of silicon nanoparticles naturally gathering and having a size of about μm (about 0.1 μm or more and 1 μm or less). In a state in which an aggregate is formed.

  As described above, the “silicon fine particles” in the present application can form aggregates having a diameter of a μm level (for example, about 1 μm) by aggregating in a natural state. In order to distinguish this "aggregate", in the present application, by adding or compressing a binder, artificially assembling silicon fine particles, a solid solid of a size that can be pinched by a human finger is used. The preparation may be referred to as a “solid preparation”. Representative examples of "solids" are tablets, granules or powders which do not take the form of a mass but take the form of a powder. In addition, the “silicon fine particles” or “aggregates of silicon fine particles” of the present application can be in a layered or film-like form (hereinafter, collectively referred to as “layered form”).

  The “physiologically acceptable substance or material” in the present application is a substance or material that is substantially non-toxic and does not substantially cause side effects or adverse reactions even when it comes into contact with skin or mucous membranes. The term "physiological" includes the meaning of "medical".

  According to one hydrogen supply of the present invention, the above-mentioned physiologically acceptable medium is brought into contact with the skin and / or mucous membrane by the hydrogen generated by contacting the silicon microparticles or agglomerates thereof, thereby improving oral uptake. Can be taken into the body (including the skin itself or the mucous membrane itself) using different means.

  Further, according to one method for producing a hydrogen supply material of the present invention, it is possible to produce a hydrogen supply material that can be taken into the body (including the skin itself or the mucous membrane itself) by a means different from oral ingestion. it can.

  Further, according to one hydrogen supply method of the present invention, it is possible to realize incorporation into the body (including the skin itself or the mucous membrane itself) by using means different from oral ingestion.

It is a photograph ((a) perspective view, (b) side view) of the solid agent of 1st Embodiment. It is a mimetic diagram explaining the situation where hydrogen generated by the contact process of a 1st embodiment has contacted human skin and / or mucous membrane which bathes via a medium (bathing water). (A) A side view showing a layered structure of a layered solid agent and a medium before generating hydrogen in a modified example (2) of the first embodiment, and (b) Hydrogen in a modified example (2) of the first embodiment. FIG. 5 is a side view showing a layered structure of a layered solid agent and a medium when generating a solid. It is a side view which shows the structure of the layered solid agent in the modification (3) of 1st Embodiment. 4 is a graph showing the amount of hydrogen generated in Examples 1 and 2. It is a photograph which shows the state of the solid agent immediately after the solid agent and pure water contacted according to 1st Embodiment. It is a photograph which shows the state of the solid agent about 60 seconds after the solid agent and pure water contacted according to 1st Embodiment. It is a photograph which shows the state of the solid agent immediately after the solid agent and pure water which followed the modification (6) of 1st Embodiment contacted. 9 is a graph showing hydrogen generation amounts of Examples 3 to 7. (A) a graph showing the change over time of the amount of dissolved hydrogen generated by bringing each silicon fine particle of the second embodiment into contact with an aqueous solution in which sodium hydrogen carbonate is dissolved in pure water; 5 is a graph showing a change over time in the amount of hydrogen generated per g of the silicon fine particles according to the embodiment.

Reference Signs List 20 base 70 membrane 90a bathing water 90b medium 100 solid agent 100a layered solid agent 200 laminated structure

  Embodiments of the present invention will be described in detail with reference to the accompanying drawings.

<First embodiment>
The hydrogen supply material of the present embodiment includes silicon fine particles (or aggregates thereof) capable of generating hydrogen and a medium in contact with the silicon fine particles (or aggregates thereof). Hereinafter, as an example of the hydrogen supply material of the present embodiment, a silicon fine particle (or an aggregate thereof) and a solid agent including the silicon fine particle (or an aggregate thereof) will be described in detail. In addition, the method for producing a hydrogen supply material and the method for supplying hydrogen according to the present embodiment will be described in detail.

[1] Silicon fine particles (or an aggregate thereof) or a solid agent, and a method for producing the same The solid agent of the present embodiment is a commercially available high-purity silicon particle powder as a silicon particle (typically, a high-purity chemical research). Silicon fine particles with silicon nanoparticles as the main particles obtained by making the particle size distribution <φ5 μm (however, silicon particles having a crystal particle diameter of more than 1 μm, purity 99.9%, i-type silicon) by bead milling. (Hereinafter, also referred to as “silicon nanoparticles” for convenience) In the present embodiment, the silicon fine particles or the coagulation of the silicon fine particles are obtained by grinding the silicon particles in an ethanol solution. A step of forming an aggregate is employed.

  Specifically, 200 g of high-purity silicon powder was dispersed in 4 L (liter) of a 99.5 wt% ethanol solution using a bead mill (manufactured by Imex Co., Ltd., horizontal continuous ready mill (model: RHM-08)). Then, zirconia beads (capacity: 750 ml) having a diameter of 0.5 μm are added, and the mixture is pulverized (single-step pulverization) at 2500 rpm for 4 hours to be fined.

  In the present embodiment, the beads and the ethanol solution containing silicon nanoparticles are separated by a separation slit provided inside the grinding chamber of the bead mill device. The ethanol solution containing the silicon nanoparticles separated from the beads is heated to 30C to 35C using a reduced-pressure evaporator. As a result, by evaporating the ethanol solution, silicon nanoparticles and / or aggregates thereof are obtained.

  The silicon fine particles obtained by the above method mainly include silicon nanoparticles having a crystallite diameter of 1 nm or more and 100 nm or less. More specifically, as a result of measuring silicon nanoparticles with an X-ray diffractometer (Smart Lab made by Rigaku Denki), the following values were obtained as an example. In the volume distribution, the mode diameter was 6.6 nm, the median diameter was 14.0 nm, and the average crystallite diameter was 20.3 nm.

  Observation of the silicon nanoparticles using a scanning electron microscope (SEM) revealed that the silicon nanoparticles were partially aggregated to form somewhat large, irregular aggregates of about 0.5 μm or less. When individual silicon nanoparticles were observed using a transmission electron microscope (TEM), the main silicon nanoparticles had a crystallite diameter of about 2 nm or more and 20 nm or less.

In the present embodiment, thereafter, in a glass container, a first mixing step of mixing the hydrogen peroxide solution and the silicon nanoparticles (hereinafter, also referred to as “H ₂ O ₂ treatment” or “hydrogen peroxide solution treatment step”) Is performed). In the present embodiment, the temperature of the hydrogen peroxide solution (3.5 wt% in the present embodiment) in the mixing step is 75 ° C. The mixing time is 30 minutes. In addition, it is preferable that the stirring process is sufficiently performed in the first mixing step (hydrogen peroxide solution treatment step) because the chance of contact between the silicon nanoparticles and the hydrogen peroxide solution is increased. Further, even if the temperature of the hydrogen peroxide solution in the first mixing step (hydrogen peroxide solution treatment step) is, for example, about room temperature, at least a part of the effects of the present embodiment can be obtained.

  The silicon nanoparticles mixed with the hydrogen peroxide solution are removed by a solid-liquid separation process using a known centrifugal separator to obtain silicon nanoparticles. As a result, silicon nanoparticles whose surface has been treated with hydrogen peroxide can be obtained. Here, by treating the surface with a hydrogen peroxide solution, an alkyl group (for example, a methyl group) present on the surface of the silicon nanoparticle can be removed. As a result, the silicon nanoparticles (and silicon fine particles having the silicon nanoparticles as main particles) and the aggregate thereof are directly connected to a medium capable of containing a water-containing liquid while maintaining the hydrophilicity of the surface as a whole. A state can be formed that also has a surface that can touch. By performing such a special surface treatment, the generation of hydrogen can be more reliably promoted.

  In the present embodiment, after that, a second mixing step of mixing the silicon nanoparticles and the ethanol solution is further performed. In addition, it is preferable that the stirring process is sufficiently performed in the mixing step because the chance of contact between the silicon nanoparticles and the ethanol solution (99.5 wt% in the present embodiment) increases. The silicon nanoparticles mixed with the ethanol solution are sufficiently dried after removing the highly volatile ethanol solution by a solid-liquid separation treatment using a known centrifugal separation treatment apparatus, thereby obtaining one final product of the present embodiment. Silicon nanoparticles are produced.

  In the present embodiment, as another final silicon nanoparticle, a silicon nanoparticle in which the mixing time of the hydrogen peroxide solution and the silicon nanoparticle in the first mixing step was 60 minutes in each of the above-described steps was used. Particles were also made. In addition, another aspect of the present embodiment is to appropriately control shape or structure of silicon fine particles and aggregates thereof.

  By the way, in the present embodiment, since an isopropyl alcohol is not used and an ethanol solution and a hydrogen peroxide solution are used as in a second embodiment described later, a hydrogen supply material that is safer and more secure for a living body is used. It is noteworthy that a method for producing a hydrogen supply material and a method for supplying hydrogen can be provided.

  Thereafter, 2 g of the produced silicon nanoparticles are mixed with 38 g of sodium hydrogencarbonate powder (purity 99.5%, manufactured by Wako Pure Chemical Industries, Ltd.). This mixture is kneaded, and the solid agent 100 shown in FIG. 1 can be obtained as a substantially cylindrical mass having a diameter of about 50 mm and a height of about 8 mm using a tableting method. FIG. 1A is a perspective view of a solid agent 100 as an example, and FIG. 1B is a side view of the solid agent 100 as an example. In addition, an aspect in which silicon fine particles or agglomerates thereof, which are not a solid agent, are included in, for example, a known material constituting a known bath agent is also one mode that can be adopted.

[2] Medium and Method for Producing the Medium Next, a “medium” for contacting the above-described silicon nanoparticles (or an aggregate thereof) or the solid agent 100 is prepared.

  In the present embodiment, the “medium” does not particularly limit a material or a product. A physiologically acceptable medium capable of transcutaneously or transmucosally taking hydrogen into the body (including the skin itself or the mucous membrane itself), and at least part of the effects of the present embodiment is achieved. Can be done.

  In addition, from the viewpoint of increasing the chance that a human site comes into contact with water (or a water-containing liquid) or a medium containing the water (or a water-containing liquid) (hereinafter, also collectively referred to as a “medium”) in daily life. In other words, examples of suitable media are at least one selected from the group consisting of liquid, gel, cream, paste, emulsion, and mousse. Also, examples of other suitable media are bath water (preferably alkaline bath water). Therefore, in one example of the present embodiment, producing the bathing water is a method for producing a medium.

Therefore, in the present embodiment, as shown in FIG. 2, tap water is typically placed in a general bathtub (including a public bathtub, a public bathtub, and an indoor or outdoor bathtub installed by an inn). Store as bathing water. Before and after storing the bath water, the above-mentioned solid agent 100 is placed or charged in the bath, and the solid agent 100 is brought into contact with the bath water 90a as a medium to generate hydrogen (H ₂ ). Therefore, the solid agent 100 of the present embodiment can be used as a bathing agent.

Representative bath water that is the medium of the present embodiment is tap water such as tap water. When using the bathing water 90a of hot spring water or the like (including hot spring water to which water is added) other than the tap water, the pH value of the bath water 90a such as the hot spring water is weakly acidic (for example, pH value). Is larger than 6), as described later, a high pH value is caused by the presence of sodium hydrogencarbonate contained in the solid agent 100 of the present embodiment, and the condition as a medium that easily generates hydrogen (H ₂ ) is obtained. Can be satisfied. In other words, when the hot spring water or the like is acidic, a large amount of the solid agent 100 may be introduced or introduced into the bathing water 90a in order to satisfy the condition as a medium that easily generates hydrogen (H ₂ ). Required.

The solid preparation 100 of the present embodiment contains sodium bicarbonate. Therefore, even if the bath water 90a is neutral or weakly acidic, the silicon fine particles of the present embodiment or the agglomerates thereof are introduced by introducing or introducing the solid agent 100 into the bath water as a medium. A contact step of contacting the medium is performed. As a result, the pH of the bath water 90a can be changed to a weakly acidic medium having a pH value of 6 or more, more preferably a basic medium having a pH value of more than 7, so that the generation of hydrogen (H ₂ ) can be promoted. .

Therefore, as shown in FIG. 2, hydrogen (H ₂ ) generated by the above-described contacting step can be brought into contact with human skin and / or mucous membrane to be bathed via bathing water 90a as a medium. . As a result, according to the present embodiment, it is possible to realize the incorporation of hydrogen (H ₂ ) into the human body (including the skin itself or the mucous membrane itself) by using means different from oral ingestion.

As described above, in the present embodiment, the bathing water 90a can include a water-containing liquid having a pH value of 7 or more, and can serve as a physiologically acceptable medium. As a result, hydrogen (H ₂ ) can be brought into contact with the skin and / or mucous membrane via the medium (bathing water 90a).

Even if the solid agent of the present embodiment does not contain sodium bicarbonate, the pH value of the bathing water is 6 or more (more preferably, the pH value is 7 or more (or more than 7). If the pH value is preferably more than 7.4, and most preferably more than 8), the condition as a medium that easily generates hydrogen (H ₂ ) can be satisfied.

<Modification (1) of First Embodiment>
In the method for producing a hydrogen supply material and the hydrogen supply method according to the first embodiment, the pH value of the bath water 90a in the first embodiment is adjusted so as to satisfy the condition in which hydrogen is more easily generated, in other words, the hydrogen is reduced. It is a preferable embodiment that the method further includes an introduction step of introducing a “pH adjuster” into the medium, which adjusts the pH value so as to fall within a numerical range of a pH value that easily occurs.

  Although sodium hydrogen carbonate in the first embodiment is an example of a “pH adjuster”, the “pH adjuster” is not limited to sodium hydrogen carbonate. Therefore, a material that can be adjusted to a weakly acidic pH value of 6 or more (hereinafter, also referred to as “weakly acidic agent”), or more preferably a pH value of 7 or more (or more than 7) (more preferably, 7 or more) The material of the "pH adjuster" is not limited as long as it is a material (hereinafter, also referred to as "alkali agent") that can be adjusted to an alkalinity of more than 0.4 (more preferably more than 8). A representative example of the weakly acidic agent is at least one selected from the group consisting of citric acid, gluconic acid, phthalic acid, fumaric acid, and lactic acid, or a salt thereof. A typical example of the alkali agent is at least one selected from the group consisting of potassium carbonate, sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, and potassium hydroxide. In addition, from a physiological point of view, the most preferred alkaline agent is sodium hydrogen carbonate. Sodium bicarbonate is widely used as a food additive, and has a plurality of advantages such as a pH value adjusting function required in the present embodiment and excellent safety and versatility.

<Modification (2) of First Embodiment>
As another modified example of the first embodiment, the laminated structure 200 of the layered solid agent and the medium can be formed by forming the solid agent of the first embodiment into a layer. FIG. 3A (a) is a side view showing a layered structure 200 of a layered solid agent and a medium before generating hydrogen, and FIG. 3A (b) is a diagram showing the relationship between the layered solid agent and the medium when hydrogen is generated. FIG. 2 is a side view showing a laminated structure 200.

  As shown in FIGS. 3A (a) and 3A (b), the above-described laminated structure 200 is placed on or above the base 20 (eg, fiber, natural resin, synthetic resin, metal, semiconductor, ceramics, or glass). , At least a layered solid agent 100a and a medium 90b. Here, preferred examples of the medium 90b are physiologically acceptable and at least selected from the group of liquid, gel, cream, paste, emulsion, and mousse as described above. One type of material. It is a preferable aspect that the base 20 has elasticity. In addition, when the laminated structure 200 of the layered solid agent and the medium can be held without the base 20, the base 20 is not necessarily provided.

  As shown in FIG. 3A (a), before the generation of hydrogen, the water-impermeable membrane 70 is placed between the layered solid agent 100a and the medium 90b so that the layered solid agent 100a and the medium 90b are not in contact with each other. Is provided. Note that a film formed from a known water-impermeable material can be used as the film 70. For example, an example of the material of the water-impermeable membrane 70 is a known polymer such as polyethylene. As another example, use of a sheet having water disintegrability and water impermeability, which is disclosed in International Publication No. WO2011 / 036992, is also one embodiment.

  On the other hand, as shown in FIG. 3A (b), when the film 70 is pulled out in the direction of the arrow, at least a part of the layered solid agent 100a and the medium 90b come into direct contact. As a result, in cooperation with a pH adjuster represented by sodium bicarbonate, hydrogen can be generated when the layered solid agent 100a comes into contact with the medium 90b that can contain a water-containing liquid having a pH value of 7 or more.

  In the present embodiment, the layered solid agent 100a and the medium 90b are formed so as to be in direct contact with each other by pulling out the film 70 in the direction of the arrow (leftward on the paper), but the method of removing the film 70 is not particularly limited. . For example, when at least a part of the film 70 is removed or at least a part of the film is dissolved, the medium 90b is brought into contact with the silicon fine particles (the layered solid agent 100a in the present embodiment) or an aggregate thereof. Forming is one aspect that can be employed. In addition, about the example of the material for melt | dissolving at least one part of the film | membrane 70, employ | adopting the sheet | seat which has a water-dissolvable property and a water impermeability disclosed in International Publication WO2011 / 036992, for example can also be adopted. This is one embodiment. Further, as another aspect, in a stage before generating hydrogen, the solid agent 100 of the first embodiment may be covered with a water-impermeable membrane 70 instead of the layered solid agent 100a. By removing or dissolving the film 70, if at least a part of the solid agent 100 and the medium 90b come into direct contact, the same effect as in the case of the layered solid agent 100a can be obtained.

  Further, for example, when the medium is at least one selected from the group consisting of a liquid, a gel, a cream, a paste, an emulsion, and a mousse, two layers (layers) as shown in FIG. It is also conceivable that the solid preparation 100a and the medium 90b) do not maintain a clearly separated state. Rather, such a case is preferable from the viewpoint of promoting hydrogen generation more accurately because the contact area between the layered solid agent 100a and the medium 90b increases. It is an aspect that the medium may contain a physiologically acceptable adhesive, for example, to adhere to a human site.

<Modification (3) of First Embodiment>
As another modified example of the first embodiment, a layered solid agent produced by forming the solid agent of the first embodiment into a layer is another aspect that can be adopted. The structure 200a as an example illustrated in FIG. 3B includes a layered solid agent 100a on the base 20. In particular, when the shape of the layered solid agent can be maintained without providing the base 20, the base 20 is not necessarily provided. In addition, from the viewpoint of avoiding the contact with the moisture in the air with high accuracy, an impermeable film 70 is provided so as to cover the layered solid agent 100a as shown in a modified example (2) of the first embodiment. You may.

  As shown in FIG. 3B, for example, after the layered solid preparation 100a comes into contact with human skin or mucous membrane, hydrogen is generated by contact of sweat or body fluid containing water from the skin or mucous membrane with the layered solid preparation 100a. This is a preferable aspect of the present embodiment. According to such an embodiment, as in the modification (2) of the first embodiment, it is possible to realize that humans take in hydrogen into the body. In addition, instead of sweat or body fluid, water (tap water, etc.) can be supplied by spraying or the like before (for example, immediately before) using the layered solid agent 100a.

It is worth noting that the structure or the laminated structure of each of the above embodiments is a structure that can be adopted in various “life situations”. For example, representative examples of products that can adopt (or include) the medium are the following (1) to (4).
(1) One type of detergent selected from the group of facial cleansers, hair shampoos, body shampoos, liquid hand soaps, and liquid body soaps.
(2) Lotion (for example, containing hyaluronic acid), serum, emulsion, lotion, cosmetic cream (for example, containing collagen), foundation, skin pack (skin having gel (or gel)) One type of cosmetic material selected from the group of shaving creams, hair rinses, hair treatments, hair conditioners, hair cosmetics, antiperspirants, and UV protection cosmetics.
(3) One kind of therapeutic material selected from the group of ointments and poultices.
(4) One kind of sanitary material selected from the group of water-absorbent resin, water-absorbent nonwoven fabric, water-absorbent fiber, water-absorbent felt, and water-absorbent gel (or gel-like agent).

  Here, the above-mentioned “hair cosmetic” includes hair styling, hair oil, camellia oil, styling (material), set (material), blow (material), brushing (material), tic, hair stick, hair wax, hair foam, Including hair gel, pomade, hair cream, hair solid, hair lacquer, hair liquid, hair spray and hair water. In addition, the above-mentioned “sanitary materials” include sanitary gloves, head covers, headbands, bed pads, bed sheets, adult incontinence articles, menstrual articles, clothing, wound dressings (including wound dressings, tapes and bandages), Includes disposable diapers, including adult diapers and pediatric diapers, gauze, gowns, sanitary tissues (including towels, washcloths, patches, wet tissues, and napkins), absorbent cotton, cotton swabs, plasters, and surgical tape.

<Modification (4) of First Embodiment>
As another modified example of the first embodiment, citric acid (purity 99, manufactured by Wako Pure Chemical Industries, Ltd.) is further added to 2 g of the silicon nanoparticles and 34 g of sodium hydrogencarbonate powder used in the first embodiment. 0.5%) by adding and kneading 4 g to form a substantially cylindrical mass having a diameter of about 50 mm and a height of about 8 mm, thereby obtaining a solid agent similar to the solid agent 100 shown in FIG. Obtainable.

<Modification (5) of First Embodiment>
As another modification of the first embodiment, the same processing as the modification (4) of the first embodiment is performed except that the amount of the sodium hydrogen carbonate powder is 19 g and the amount of the citric acid is 19 g. Thus, a solid preparation is obtained. This solid agent is a substantially columnar solid agent similar to the solid agent 100 shown in FIG. 1, and has a diameter of about 50 mm and a height of about 8 mm. The mixing ratio of citric acid, sodium hydrogen carbonate, and silicon nanoparticles can be appropriately changed.

<Modification (6) of First Embodiment>
In this embodiment, the same high-purity silicon particle powder (typically, silicon particles having a crystal grain size of more than 1 μm) used in the first embodiment is subjected to the procedure described in the first embodiment. One stage grinding. In the present embodiment, zirconia beads (capacity: 750 ml) having a diameter of 0.5 μm used for one-stage pulverization are automatically separated from the solution containing silicon nanoparticles inside the bead mill pulverization chamber. Further, zirconia beads (capacity: 300 ml) of 0.3 μm are added to the solution containing the silicon nanoparticles from which the beads are separated, and the solution is pulverized (two-step pulverization) at 2500 rpm for 4 hours to be fined.

  The silicon nanoparticles containing the beads are separated from the solution containing the silicon nanoparticles as described above. The ethanol solution containing the silicon nanoparticles separated from the beads is heated to 40 ° C. using a reduced-pressure evaporator as in the first embodiment, thereby evaporating the ethanol solution to obtain silicon nanoparticles.

<Modification (7) of First Embodiment>
Incidentally, a physiologically acceptable coating layer for coating the solid preparation 100 of the first embodiment or the solid preparation described in the modified examples (4) and (5) of the first embodiment may be further provided. This is another mode that can be adopted. For example, a known gastric sparingly soluble enteric material which is a coating agent covering the outermost layer of the solid preparation 100 can be employed. An example of a physiologically acceptable coating layer that can be applied as a capsule is a capsule containing a silicon fine particle or an agglomerate thereof and manufactured from a known gastric poorly soluble enteric material. When the solid agent 100 is employed, a disintegrant may be further included. As the disintegrant, a known material can be employed. In addition, a preferred example of a more preferred disintegrant is an organic acid, and a most preferred example is citric acid. Here, the organic acid can also function as a binder that aggregates the silicon nanoparticles.

  In addition, the temperature condition of the water-containing liquid for hydrogen generation or the medium that can contain the water-containing liquid in each of the above embodiments is not limited. However, the temperature of the medium capable of generating hydrogen is higher than 0 ° C. and 50 ° C. or lower. Preferably, when the temperature of the water-containing liquid or medium is 20 ° C. (more preferably 25 ° C.) or more and 50 ° C. or less, the hydrogen generation reaction is promoted. When the temperature of the water-containing liquid or medium is 35 ° C. or more and 50 ° C. or less, the generation of hydrogen is promoted with higher accuracy. The upper limit of the temperature of the water-containing liquid or medium is not limited as long as it does not cause injury such as burns to humans.

<Example>
Hereinafter, in order to explain each of the above-described embodiments in more detail, examples will be described. However, the above-described embodiments are not limited to these examples.

(Example 1)
In order to evaluate the silicon nanoparticles themselves, the inventors of the present application examined the state of generation of hydrogen without performing a tableting step by a tableting method. Specifically, as Example 1, an experiment was performed using silicon nanoparticles processed by one-step pulverization in the first embodiment.

  10 mg of the silicon nanoparticles described in the first embodiment in the form of a powder (ie, without mixing and kneading sodium bicarbonate powder) and having a capacity of 100 ml in a glass bottle (about 1 mm borosilicate glass thickness) , Labone screw tube bottle manufactured by Asone Inc.). 30 ml of tap water having a pH value of 7.1 was put into the glass bottle, the solution was sealed under a temperature condition of 25 ° C., the hydrogen concentration in the solution in the glass bottle was measured, and the amount of hydrogen generated was determined using this. Was. For the measurement of the hydrogen concentration, a portable dissolved hydrogen meter (model DH-35A, manufactured by Toa DKK Co., Ltd.) was used.

(Example 2)
Example 2 is the same as Example 1 except that 30 ml of tap water was added and the liquid temperature was adjusted to a temperature of 37 ° C.

  FIG. 4 shows the results of Examples 1 and 2. The horizontal axis of FIG. 4 shows the time (minutes) during which the solid agent is brought into contact with the water-containing liquid, and the vertical axis of the graph shows the amount of hydrogen generated.

  As shown in FIG. 4, generation of hydrogen was confirmed even when substantially neutral water was brought into contact with the silicon nanoparticles described in the first embodiment. It was also found that the higher the liquid temperature, the greater the amount of hydrogen generated. In particular, when the liquid temperature is 37 ° C., which is close to the human body temperature, it is possible to realize the generation of hydrogen in a shorter time, and thereafter, the generation of a large amount (1.5 ml / g or more) of hydrogen is continued. It was confirmed that.

  In addition to the results of Examples 1 and 2 described above, the inventors of the present application processed various solid agents described in the first embodiment and modifications thereof processed using the tableting method. Each evaluation shown after 3 was performed.

(Example 3)
First, as Example 3, the diameter and height of each solid agent 100 manufactured by the process described in the first embodiment were reduced to 1/5 (φ10 × 1.6 mm, 16 mg of silicon nanoparticles). , Sodium bicarbonate 304 mg) was used as a sample in this example.

  The above sample was placed in a 60 ml stainless steel container. 60 ml of pure water (pH value 7.0), which is an example of a water-containing liquid, was placed in the stainless steel container and the solid agent was immersed in the stainless steel container, and the liquid temperature was maintained at 25 ° C. Under these conditions, the glass bottle was sealed, and the hydrogen concentration of the hydrogen water generated in the glass bottle was measured using the apparatus described in Example 1 to determine the amount of generated hydrogen.

  In addition, the shape of the solid agent gradually collapsed with the passage of time in pure water. With the passage of time since the solid agent came into contact with the pure water, sodium hydrogen carbonate was dissolved in the liquid, and silicon nanoparticles were almost uniformly diffused into the liquid, while partly settling on the bottom of the container. The remaining. As a result, the solid preparation exhibited a powdery form (or a fine powder form, hereinafter, collectively referred to as "powder form") that hardly stays in its original form. The dissolution of the capsule of the capsule containing the powder is also the disintegration of the dosage form, and the exposure of the powder due to the dissolution of the capsule is also included in "disintegration"). In this example, the pH value of the water-containing liquid in the vial rose to 8.3 because the sodium bicarbonate released with the disintegration of the solid agent dissolved in the water.

(Example 4)
In Example 4, the diameter and the height were each 1/5 (φ10 × 1.6 mm, 16 mg of silicon nanoparticles) with respect to the solid agent produced by the treatment described in the modification (4) of the first embodiment. 272 mg of sodium bicarbonate and 32 mg of citric acid) were used as samples. About 5 minutes after the solid agent was brought into contact with pure water at a liquid temperature of 25 ° C., almost all of the solid agent collapsed and exhibited a powdery state. In the process of disintegration of the solid agent (that is, up to 90 minutes after the contact of the solid agent with pure water), sodium bicarbonate and citric acid are released with the disintegration of the solid agent, so that the pH of the water-containing liquid is reduced. The value showed 7.6.

(Example 5)
In Example 5, the diameter and the height of each of the solid agent prepared by the procedure described as the modified example (5) of the first embodiment were 1/5 (φ10 × 1.6 mm, silicon). A solid agent that was a nanoparticle (16 mg, sodium bicarbonate 152 mg, citric acid 152 mg) was used as a sample. About 5 minutes after the solid agent was brought into contact with pure water at a liquid temperature of 25 ° C., almost all of the solid agent collapsed and exhibited a powdery state. In the process of disintegration of the solid agent (that is, up to 90 minutes after the contact of the solid agent with pure water), sodium bicarbonate and citric acid are released with the disintegration of the solid agent, so that the pH of the water-containing liquid is reduced. The value showed 6.0.

(Example 6)
In Example 6, the diameter and the height were each 1/5 (φ10 × 1.6 mm, silicon) with respect to the solid agent prepared by the procedure described as the modified example (6) of the first embodiment. A solid preparation of nanoparticles (16 mg, sodium hydrogen carbonate 272 mg, citric acid 32 mg) was used as a sample. The liquid temperature was maintained at 37 ° C. by holding the stainless steel container in a thermostat. Pure water having a pH value of 7.0 was used as the water-containing liquid. Approximately 5 minutes after the solid agent came into contact with pure water, almost all of the solid agent disintegrated and became powdery. Due to the release of sodium bicarbonate and citric acid with the disintegration of the solid agent, the pH value of the water-containing liquid was 7.6.

(Example 7)
In Example 7, the diameter and the height were each 1/5 (φ10 × 1.6 mm, 16 mg of silicon nanoparticles) with respect to the solid agent produced by the treatment described in the modification (7) of the first embodiment. , Sodium bicarbonate 152 mg, citric acid 152 mg) was used as a sample. The liquid temperature was maintained at 37 ° C. by holding the stainless steel container in a thermostat. Pure water having a pH value of 7.0 was used as the water-containing liquid. Approximately 5 minutes after the solid agent came into contact with pure water, almost all of the solid agent disintegrated and became powdery. As the sodium bicarbonate and citric acid were released along with the disintegration of the solid agent, the pH value of the water-containing liquid was 6.0.

  By the way, in each of the above-described embodiments, it is possible to visually recognize that the shape of the solid agent gradually collapses with the passage of time in pure water. FIGS. 5A and 5B show an example of the disintegration state of the solid agent. FIG. 5A and FIG. 5B show a solid agent formed using 2 g of silicon nanoparticles and 38 g of sodium hydrogen carbonate (an example according to the first embodiment) in pure water. It is a photograph which shows a state of a solid agent with the passage of time when throwing in 500 ml. FIG. 5A shows the state of the solid agent immediately after the contact between the solid agent and pure water. FIG. 5B shows the state of the solid agent about 60 seconds after the solid agent comes into contact with pure water.

  On the other hand, FIG. 5C shows that a solid agent formed using 2 g of silicon nanoparticles, 19 g of sodium bicarbonate, and 19 g of citric acid (an example according to the modified example (6) of the first embodiment) is in contact with pure water. 4 is a photograph showing a state of a solid preparation immediately after the solid preparation.

  As shown in FIG. 5A to FIG. 5C, when the solid agent comes into contact with pure water, sodium hydrogen carbonate is dissolved in the liquid over time, and silicon nanoparticles are almost uniformly diffused in the liquid. It was confirmed that some parts were sinking and remained on the bottom.

  FIG. 6 shows the results of Examples 3 to 7. The horizontal axis of FIG. 6 shows the time (minutes) during which the solid agent is brought into contact with the water-containing liquid, and the vertical axis of the graph shows the amount of hydrogen generated.

  For Example 3, as shown in FIGS. 5A and 5B, the solid formulation disintegrated its dosage form and released sodium bicarbonate. In addition, as shown in FIG. 6, the amount of generated hydrogen increased with the elapse of the contact time between the solid agent and the water-containing liquid.

  In addition, comparing Example 3 with Example 5, and Example 4 with Example 6, the amount of hydrogen generation increased under the temperature condition of 37 ° C. close to the human body temperature. Specifically, it is noteworthy that in Examples 3 and 6, it was confirmed that hydrogen of 20 ml / g or more could be generated in 240 minutes (4 hours).

  Furthermore, the results of Examples 1 and 2 and Example 6 in which the silicon nanoparticles were brought into contact with the water-containing liquid in a powder state, and the results of Examples 3 to 5 and Example 7 using the silicon nanoparticles as a solid agent In particular, it is more likely that the silicon nanoparticles are kept in a powdery state and are in contact with the water-containing liquid for a certain period of time (for example, one and a half hours) after the contact between the silicon nanoparticles and the water-containing liquid. It has become clear that hydrogen can be generated.

<Experiment for measuring the amount of hydrogen generated by contact between silicon nanoparticles and medium>
In addition, the inventors of the present application examined the time change of the amount of hydrogen generated by bringing each silicon fine particle (not a solid agent) of the present embodiment into contact with an aqueous solution in which sodium hydrogen carbonate was dissolved in pure water. Was.

  Specifically, in a glass container, 11 mg of silicon nanoparticles (30 minutes in the first mixing step) or 5 mg of silicon nanoparticles (60 minutes in the first mixing step) and sodium hydrogencarbonate (1.88 wt%) are dissolved. The mixed aqueous solution is mixed. The pH of the aqueous solution is about 8.3. Thereafter, the aqueous solution was filled up to the opening of the glass container, and the container was completely sealed with a lid so that air did not enter.

  Although the lid is made of polypropylene, the inner lid is made of a multilayer filter made of polyethylene and polypropylene, so that permeation and leakage of generated hydrogen can be sufficiently suppressed. After a while, it is visually recognized from the appearance that the silicon fine particles of the present embodiment have been uniformly mixed in the entire aqueous solution.

  FIG. 7A shows a time change of the dissolved hydrogen concentration of hydrogen generated by bringing each silicon fine particle (not a solid agent) of the present embodiment into contact with an aqueous solution in which sodium hydrogen carbonate is dissolved in pure water. FIG. FIG. 7B is a graph showing the time change of the hydrogen generation amount per 1 g of each silicon fine particle. For reference, the results in the case of using silicon fine particles for which the above-described first mixing step was not performed are also shown in each graph. In addition, the above-described dissolved hydrogen amounts were measured using a portable dissolved hydrogen concentration meter (manufactured by Toa DKK, model DH-35A) manufactured by Toa DKK.

  As shown in FIGS. 7A and 7B, it was found that the generation of hydrogen was promoted by performing the first mixing step. In particular, as shown in FIG. 7 (b), by performing the first mixing step, a hydrogen generation amount of 40 ml or more in 2 hours is continuously obtained after 2 hours from the start of hydrogen generation. Deserves special mention.

  The reason why the amount of hydrogen generated by the silicon microparticles during the mixing time of the first mixing step of 60 minutes is smaller than the amount of hydrogen generated by the silicon microparticles during the mixing time of 30 minutes is due to the oxidation on the surface of the silicon microparticles. It is considered that this influences the difference in the film thickness. That is, since the silicon fine particles having a mixing time of 60 minutes in the first mixing step have a thicker oxide film, it is difficult for the medium (aqueous solution) and the silicon fine particles to directly contact each other, so that hydrogen is generated. It is considered suppressed.

  According to further research and analysis by the present inventors, the mixing time of the first mixing step is more than 2 minutes and 50 minutes or less (more preferably 3 minutes or more and 40 minutes or less, more preferably 4 minutes or more and 30 minutes or less). Minutes, most preferably 5 minutes or more and 20 minutes or less), it is possible to realize a state having a sufficient surface area capable of directly contacting the medium while maintaining the hydrophilicity of the surface of the silicon fine particles at an appropriate level. As a result, generation of hydrogen can be more reliably promoted within the above-described mixing time.

<Second embodiment>
Similar to the first embodiment, the hydrogen supply material of the present embodiment includes silicon fine particles (or aggregates thereof) having a hydrogen generating ability and a medium in contact with the silicon fine particles (or aggregates thereof). . In the present embodiment, the hydrogen supply material of the first embodiment, and the manufacture of the hydrogen supply material, except that an isopropyl alcohol (IPA) solution is employed instead of the ethanol solution employed in the first embodiment. Since the method and the hydrogen supply method are substantially the same, the overlapping description may be omitted.

[1] Silicon fine particles (or an aggregate thereof), a solid agent, and a production method thereof The silicon fine particles of the present embodiment have an ability to generate hydrogen. In addition, the solid agent of the present embodiment is a solid agent containing the silicon fine particles and having an ability to generate hydrogen. In the solid agent of the present embodiment, commercially available high-purity silicon particle powder (typically, a particle size distribution <φ5 μm, purity 99.9%, i-type silicon, manufactured by Kojundo Chemical Laboratory Co., Ltd.) as silicon particles is used as a bead mill. Silicon fine particles (hereinafter also referred to as “silicon nanoparticles” for convenience) that are finely divided by a method and mainly include silicon nanoparticles are used. Note that an aggregate of silicon fine particles may also have a hydrogen generating ability.

  Specifically, 15 g of high-purity Si powder was dispersed in 300 ml of 99% or more isopropyl alcohol (IPA) using a bead mill device (manufactured by Imex Co., Ltd .: RMB-type badge-type ready mill), and was made of zirconia φ0.5 μm. Beads (capacity: 300 ml) are added and pulverized (single-step pulverization) for 4 hours at a rotation speed of 2500 rpm to make finer.

  The silicon nanoparticles containing the beads are separated from the silicon nanoparticles by suction filtration using a stainless steel filter (mesh 0.35 mm) attached to a bead separation container (manufactured by Imex Co., Ltd.). Thereafter, the isopropyl alcohol (IPA) solution containing the silicon nanoparticles separated from the beads is heated to 30 ° C. to 35 ° C. using a reduced-pressure evaporator to evaporate the isopropyl alcohol (IPA) to remove the silicon nanoparticles and And / or obtain an aggregate thereof.

  The silicon nanoparticles obtained by the above method mainly include silicon nanoparticles having a crystallite diameter of 1 nm or more and 100 nm or less, as in the first embodiment. Further, as in the first embodiment, the main silicon nanoparticles have a crystallite diameter of about 2 nm or more and 20 nm or less.

  Specifically, 15 g of high-purity Si powder was dispersed in 300 ml of 99% or more isopropyl alcohol (IPA) using a bead mill device (manufactured by Imex Co., Ltd .: RMB-type badge-type ready mill), and was made of zirconia φ0.5 μm. Beads (capacity: 300 ml) are added and pulverized (single-step pulverization) for 4 hours at a rotation speed of 2500 rpm to make finer.

  The silicon nanoparticles containing the beads are separated from the silicon nanoparticles by suction filtration using a stainless steel filter (mesh 0.35 mm) attached to a bead separation container (manufactured by Imex Co., Ltd.). The IPA solution containing the silicon nanoparticles separated from the beads is heated to 40 ° C. using a vacuum evaporator to evaporate the IPA to obtain silicon nanoparticles and / or aggregates thereof.

  As in the first embodiment, the silicon nanoparticles obtained by the above method mainly include silicon nanoparticles having a crystallite size of 1 nm or more and 100 nm or less. Further, as in the first embodiment, the main silicon nanoparticles have a crystallite diameter of about 2 nm or more and 20 nm or less.

  Also in the present embodiment, similarly to the first embodiment, a first mixing step of mixing the hydrogen peroxide solution and the silicon nanoparticles in a glass container is then performed. By treating the surface with the hydrogen peroxide solution, silicon nanoparticles having a relatively thin and inhomogeneous / incomplete oxide film on the surface can be formed. As a result, the silicon nanoparticles (and silicon fine particles having the silicon nanoparticles as main particles) and / or aggregates thereof can contain a water-containing liquid while maintaining hydrophilicity of the surface as a whole. A state may be formed that also has a surface that can directly contact the surface. By performing such a special surface treatment, the generation of hydrogen can be more reliably promoted.

  Then, the isopropyl alcohol (IPA) may be partially adhered to the silicon nanoparticles, and the isopropyl alcohol (IPA) is accurately removed by solid-liquid separation using a known centrifugal separator. Thorough drying produces one final silicon nanoparticle of the present embodiment.

  In the present embodiment, as another final silicon nanoparticle, a silicon nanoparticle in which the mixing time of the hydrogen peroxide solution and the silicon nanoparticle in the first mixing step was 60 minutes in each of the above-described steps was used. Particles were also made.

  Further, after kneading a mixture obtained by mixing the above silicon nanoparticles with sodium hydrogencarbonate powder in the same manner as in the first embodiment, a solid agent can be obtained by using a tableting method. it can.

  After that, the amount of hydrogen generated by the contact between the silicon nanoparticles and the medium was examined, and the result was the same as the result shown in FIG. 4 in the first embodiment.

<Other embodiments>
One embodiment of the method for producing silicon fine particles in the above-described hydrogen supply material is that silicon particles having a crystal grain size of more than 1 μm are refined by a physical pulverization method, and silicon fine particles having a crystallite size of 1 nm or more and 100 nm or less are mainly produced. Including a step of forming particles. Preferable examples of the physical pulverization method include a pulverization method using a bead mill pulverization method, a planetary ball mill pulverization method, a shock wave pulverization method, a jet mill pulverization method, or a pulverization method combining two or more of these. However, from the viewpoint of the production cost or the ease of production control, a particularly preferred example is a bead mill pulverization method alone or a pulverization method including at least a bead mill pulverization method. In addition, the example of the solid agent in each of the above-described embodiments is not only a role as a hydrogen supply material, but also a biological hydrogen generating material (biological hydrogen supply material) capable of safely generating hydrogen in vivo or in vitro. Material).

  Further, in each of the above embodiments, as the starting material, silicon particles that are commercially available high-purity silicon particle powders are employed, but the starting material is not limited to such silicon particles. From the viewpoint of realizing lower costs and / or obtaining finer silicon nanoparticles, as a starting material, for example, in the cutting of silicon in the production process of a silicon wafer used for semiconductor products such as solar cells, etc. It is also a preferred embodiment to employ silicon chips or silicon chips or polishing chips (hereinafter also referred to as “silicon chips or the like” or “chips or the like”) which is usually waste. . The target of the “silicon fine particles” is not limited to crystalline silicon. For example, silicon particles obtained by miniaturizing an amorphous silicon layer formed by a CVD method on a known substrate can be used as a starting material in each of the above embodiments. Further, amorphous or crystalline silicon particles, which are directly produced by a CVD method, a laser method, an arc discharge method or the like, so to speak, may be used as a starting material of each of the above-described embodiments, or silicon as a final form. It can also be fine particles.

  The disclosure of the above-described embodiments or examples has been described for describing the embodiments, but not for limiting the present invention. In addition, modifications that fall within the scope of the present invention, including other combinations of the above-described embodiments and examples, are also included in the claims.

  INDUSTRIAL APPLICABILITY The hydrogen supply material and the method for producing the same and the hydrogen supply method of the present invention increase the chance of bringing skin and / or mucous membranes into contact with hydrogen in various living situations in a more natural manner. , Can be used in a variety of industries, including the health industry.

Claims (15)

Silicon fine particles capable of generating hydrogen or an aggregate thereof,
A physiologically acceptable medium in contact with the silicon microparticles or the aggregate.
For contacting the hydrogen with the skin and / or mucous membrane via the medium,
Hydrogen supply. The solid agent of the silicon fine particles or the aggregate, or further comprising a water-impermeable membrane covering a layer containing the silicon fine particles or the aggregate,
When removing at least a part of the film or dissolving at least a part of the film, the medium contacts the silicon fine particles,
The hydrogen supply material according to claim 1. The medium includes at least one selected from the group consisting of potassium carbonate, sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, and potassium hydroxide,
The hydrogen supply material according to claim 1. The pH of the medium is 6 or more;
The hydrogen supply material according to any one of claims 1 to 3. The medium is at least one selected from the group consisting of liquid, gel, cream, paste, emulsion, and mousse.
The hydrogen supply material according to any one of claims 1 to 4. It contains the hydrogen supply material according to any one of claims 1 to 4,
Cleaning agents, cosmetic materials, therapeutic materials, or sanitary materials. Contacting the silicon microparticles or agglomerates thereof capable of generating hydrogen with the medium in order to bring the hydrogen into contact with skin and / or mucous membranes via a physiologically acceptable medium,
Manufacturing method of hydrogen supply material. A hydrogen peroxide solution treatment step of bringing the silicon fine particles or the aggregate into contact with a hydrogen peroxide solution,
A method for producing a hydrogen supply material according to claim 7. In the contacting step, when at least a part of the solid agent of the silicon fine particles or the aggregate or the water-impermeable film covering the layer including the silicon fine particles or the aggregate is removed or at least a part of the film When dissolved, contact the silicon fine particles or the aggregates with the medium,
The method for producing a hydrogen supply material according to claim 7. The temperature of the medium is more than 0 ° C and 50 ° C or less;
The method for producing a hydrogen supply material according to any one of claims 7 to 9. The pH of the medium is 6 or more;
The method for producing a hydrogen supply material according to any one of claims 7 to 10. The medium is at least one selected from the group consisting of liquid, gel, cream, paste, emulsion, and mousse.
The method for producing a hydrogen supply material according to any one of claims 7 to 11. The hydrogen supply material is included in a cleaning agent, a cosmetic material, a therapeutic material, or a sanitary material,
The method for producing a hydrogen supply material according to any one of claims 7 to 12. Contacting the silicon microparticles or agglomerates thereof capable of generating hydrogen with the medium in order to bring the hydrogen into contact with skin and / or mucous membranes via a physiologically acceptable medium,
Hydrogen supply method. In the contacting step, when at least a part of the solid agent of the silicon fine particles or the aggregate or the water-impermeable film covering the layer including the silicon fine particles or the aggregate is removed or at least a part of the film When dissolved, contact the silicon fine particles or the aggregates with the medium,
The hydrogen supply method according to claim 14.