Oral composite composition

Abstract

To provide an oral composite composition having a silicon suboxide that can draw out a stronger hydrogen generation capability of silicon fine particles.SOLUTION: One composite composition of the present invention comprises a silicon fine particle having hydrogen generation capability, and a silicon suboxide (SiOX, where x is 1 / 2, 1, or 3 / 2) and / or a mixed composition of the silicon suboxide and silicon dioxide, at least partially covering the surface of the silicon fine particle.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a composite composition, more specifically to a composite composition containing silicon particles and / or aggregates thereof capable of generating hydrogen, as well as to pharmaceuticals, hydrogen suppliers, feeds, supplements, food additives, health foods, and formulations containing the composite composition. [Background technology]

[0002] Hydrogen applications are widespread, with many promising applications. For example, there are reports on its involvement in the development and treatment of oxidative stress. For example, within the bodies of animals, including humans, reactive oxygen species are produced in the mitochondria of cells through metabolism, subcutaneously under ultraviolet light, and derived from oxygen taken up through the lungs. While reactive oxygen species are necessary for life, they are known to oxidize and damage the cells that make up living organisms. In particular, the hydroxyl radical, which has the most oxidizing power of all reactive oxygen species, is thought to cause various diseases, including cancer, stroke, myocardial infarction, diabetes, and other lifestyle-related diseases, as well as skin disorders such as skin aging and dermatitis. Therefore, it is desirable to minimize the presence of excess reactive oxygen species, especially the hydroxyl radical, that are not used in beneficial reactions.

[0003] Considering oxidative stress in the body, hydroxyl radicals generated in the body are eliminated by reacting with several substances. Antioxidants found in the body, such as polyphenols, vitamin C, α-tocopherol, and glutathione, are generally considered to be examples of substances that can eliminate hydroxyl radicals. However, these substances not only eliminate hydroxyl radicals but also reactive oxygen species that function in the body, such as hydrogen peroxide, potentially resulting in adverse side effects such as a weakened immune system. Hydrogen is also known to be able to eliminate hydroxyl radicals. However, hydrogen only reacts with hydroxyl radicals among reactive oxygen species, and therefore does not cause the adverse side effects described above. Therefore, a hydrogen water generator containing hydrogen that eliminates hydroxyl radicals in the body has been proposed (e.g., Patent Document 1).

[0004] However, the solubility of hydrogen in water at 25°C is extremely low, with a saturated solubility of 1.6 ppm, and hydrogen in hydrogen water easily diffuses into the air. Therefore, in order to absorb the amount of hydrogen needed to eliminate hydroxyl radicals, it is necessary to maintain a high concentration of dissolved hydrogen in hydrogen water. Therefore, ingesting hydrogen water alone is not enough to absorb enough hydrogen to react with hydroxyl radicals in the body. Therefore, a hydrogen-containing composition containing hydrogen and a surfactant has been proposed to facilitate the absorption of hydrogen into the body (Patent Document 2), but it is not possible to maintain a high hydrogen concentration in the body for a long period of time. Hydroxy radicals are short-lived and constantly generated in the body, so a constant supply of high concentrations of hydrogen is required to eliminate them.

[0005] In light of the above background, the present inventors have disclosed an oral solid preparation that contains silicon microparticles as a main component and has high hydrogen generating capacity (Patent Document 3). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 5514140 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-113331 [Patent Document 3] International Publication No. WO2017 / 130709 [Patent Document 4] International Publication No. WO2018 / 037752 [Patent Document 5] International Publication No. WO2018 / 037818 [Patent Document 6] International Publication No. WO2018 / 037819 [Non-patent literature]

[0007] [Non-Patent Document 1] Matsuda et al., "Water decomposition and hydrogen concentration by silicon nanoparticles," Proceedings of the 62nd Spring Meeting of the Japan Society of Applied Physics, 2015, 12-031 Summary of the Invention [Problem to be solved by the invention]

[0008] However, even if one ingests hydrogen water, the amount of hydrogen contained in 1 liter of hydrogen water at 25°C is only 18 ml in gaseous form. Furthermore, because hydrogen is the smallest molecule, light, and highly diffusive, it is impossible to completely preserve hydrogen water in a container. To give an example of in vivo use, much of the hydrogen in hydrogen water gasifies in the stomach. This results in insufficient hydrogen being absorbed into the body, leading to the problem of aerophagia (commonly known as "burping"). Therefore, according to publicly known information, it is impossible to maintain a high hydrogen concentration in the stomach for a long period of time by ingesting hydrogen water, or to ingest it intermittently many times over a long period of time. On the other hand, when ingesting a hydrogen-containing composition in which hydrogen is encapsulated using a surfactant, it is impossible to absorb a sufficient amount of hydrogen into the body through ingestion of the hydrogen-containing composition for a long period of time. In addition, the aforementioned problem of hydrogen being released in the stomach may also occur. Furthermore, in known methods, if hydrogen is applied to the skin, it will be used in the atmosphere, and the hydrogen will diffuse and scatter into the atmosphere in a short time due to a diffusion rate that is much higher than that inside the body, making absorption through the skin extremely difficult or impossible. Note that although the situation inside the body has been described here, various problems remain for practical use in industry, plants, or for energy purposes.

[0009] The present invention can solve at least one of the above-mentioned technical problems and greatly contribute to strengthening the hydrogen generation ability of silicon microparticles containing silicon suboxide, i.e., generating a large amount of hydrogen in the body or in space for a long period of time, or extracting it more reliably. Note that the amount of hydrogen generated can be adjusted as desired depending on the application by adjusting the amount of composite composition used, the size of the microparticles, etc. [Means for solving the problem]

[0010] Through previous research and development, the inventors have discovered a technology for generating hydrogen at the required location, rather than dissolving hydrogen gas in water or other liquids beforehand. They have also conducted extensive analysis and research to significantly increase the amount of hydrogen generated from silicon microparticles, by extracting hydrogen for a longer period of time, more strongly, or more reliably. Previous efforts have focused on optimizing the environment in which silicon microparticles exist (e.g., in vivo, a pH value for hydrogen generation that does not adversely affect the human body, such as the pH value of intestinal fluid). For example, when used on the skin, similar hydrogen generation can be achieved by using an appropriate pH adjuster. Furthermore, for the various fields mentioned above, such as industrial, plant, or energy applications, hydrogen generation methods, hydrogen storage methods, and hydrogen usage methods suited to each application and situation can be considered. Therefore, providing a composite composition that realizes a novel, safe, and effective hydrogen generation method and a method for using the same would be extremely valuable industrially.

[0011] However, through further research and development, the inventors have focused on the microscopic physical properties or characteristics of the silicon fine particles themselves, more specifically, the surface of the silicon fine particles, the oxidation state and composition of the silicon oxide film covering the surface, the physical and chemical surface configuration of the silicon oxide film surface, and the interface between the surface and the silicon oxide film, and have discovered that by actively utilizing these physical properties or characteristics, it is possible to significantly increase the amount of hydrogen generated from the silicon fine particles and to bring out stronger or more reliable hydrogen generation ability for a longer period of time.The inventors have also discovered that the amount of hydrogen generated required depending on the application can be freely adjusted by the method for preparing the composite composition, the amount used, the size of the fine particles, the pH value, etc.

[0012] The present inventors have analyzed and investigated from various viewpoints the surfaces of silicon microparticles produced by a unique chemical process, the silicon oxide film covering the surfaces, and / or the interface between the surfaces and the silicon oxide film. As a result, it has become clear that a silicon oxide film in a special state is formed on the silicon microparticles when they are first produced. After further analysis, the present inventors have ascertained the following points. (1) The silicon oxide film contains a large amount of so-called "silicon suboxides," which are multiple types of oxides that are stoichiometrically different from SiO2. (2) The presence of a composite composition comprising silicon particles and the silicon oxide film (including silicon suboxide and silicon dioxide). (3) The presence of a composite composition formed by covering at least a portion of the surface of a silicon fine particle constituting the silicon particle with various silicon oxide films (including silicon suboxide and silicon dioxide) using the silicon fine particle as a nucleus. (4) The surfaces of the silicon fine particles are hydrophilic, the concentration of hydrogen bonded to the surfaces of the silicon fine particles (concentration of SiH groups) is low, and the surface of the silicon oxide film has many OH groups (i.e., SiOH groups).

[0013] The present inventors have discovered a technology that uses safe silicon and allows for the appropriate selection of any hydrogen generation rate, any gas generation amount, and any hydrogen generation time with water (e.g., pH value of 7 or higher), as well as a composite composition for this purpose. In addition, as will be shown below, by elucidating in detail the chemical structure and molecular structure of silicon microparticles containing silicon suboxide, as well as the changes in molecular structure in response to reactions, the detailed atomic-level conditions of the composite composition have been clarified for the first time, which is of great technical significance.

[0014] First, silicon suboxide contains many silicon dangling bonds. The silicon dangling bonds have an energy level within the band gap of the silicon oxide film, and it is thought that chemical species move in a hopping manner via the energy level. Therefore, the silicon dangling bonds are chemical species (hydroxide ions (OH)) that oxidize silicon microparticles. - It is believed that the diffusion or migration of ions) in the silicon oxide film is promoted. Also, the silicon dangling bonds present at the interface between silicon and the silicon oxide film reduce the activation energy of the hydrogen generation reaction.

[0015] Here, the present inventors have discovered that suboxides present in silicon oxide films act as active intermediates that mediate chain reactions.

[0016] Research conducted by the present inventors to date has revealed that the generation of hydrogen by the reaction of silicon with water can be explained by the following chemical reaction formula. In chemical reaction equation (1), silicon and hydroxide ions (OH - ) react to produce SiO2 and hydrogen, as well as electrons (e). This reaction is thought to occur at the interface between silicon and the silicon oxide film. The generated electrons move to the surface of the silicon oxide film, where water molecules receive the electrons, producing hydroxide ions and hydrogen, as shown in chemical reaction equation (2). Therefore, after the overall reaction (chemical reaction equation (1) + chemical reaction equation (2) = chemical reaction equation (3)), the concentration of hydroxide ions does not change. However, because the chemical reaction shown in chemical reaction equation (1) is the rate-determining reaction, the reaction rate increases significantly as the concentration of hydroxide ions increases.

[0017] [ka]

[0018] Here, chemical reaction formula (1) is not a one-step reaction, but consists of the following multi-step reactions (4) to (7).

[0019] [ka]

[0020] During hydrogen generation, the amount of silicon suboxide hardly changed. This is thought to be due to the parallel progression of the reactions represented by chemical equations (4) to (7). Silicon suboxides, SiO, SiO, and SiO, are present at the interface between the silicon oxide film and silicon and / or within the silicon oxide film. As each reaction proceeds, silicon suboxide is formed and further oxidized, increasing the amount of silicon dioxide (SiO). Therefore, the "silicon oxide" in the "broad sense" above can be said to be a mixed composition of silicon suboxide and silicon dioxide. In accordance with the definition of chemical terminology, a substance in which at least silicon suboxide is present on the surface of silicon microparticles can be called a "composite." Note that the "composite composition" in this application does not necessarily have to coincide with the aforementioned "composite." For example, the "composite composition" in this application includes a case in which "silicon microparticles and a mixed composition of silicon suboxide and silicon dioxide" are included.

[0021] The above-mentioned chemical reactions (5) to (7) occur, and hydrogen is generated when silicon suboxide is oxidized and silicon dioxide (SiO2) is formed. In addition, in order to cause the reactions of the above-mentioned chemical reactions (4) to (7), OH - The ions penetrate into the silicon oxide film.

[0022] Therefore, by forming a silicon oxide film containing a large amount of silicon suboxide and / or the interface between the silicon oxide film and a silicon crystal layer, the present inventors have obtained the following findings (X) and (Y). (X) Silicon fine particles and water (especially hydroxide ions (OH - This promotes the reaction with silicon ions, making the hydrogen generation ability of silicon microparticles stronger, i.e., leading to the continuous generation of large amounts of hydrogen gas for a long period of time, or to the extraction of hydrogen gas with higher accuracy. (Y) As shown in the above reaction formulas (1) to (7), OH - By utilizing the reaction of ions, the rate of hydrogen generation can be controlled by adjusting the pH value.

[0023] As a result, the present inventors have realized silicon microparticles containing a large amount of silicon suboxide by manufacturing silicon microparticles with the above-mentioned ingenuity.

[0024] As described above, it has become clear that conditions suitable for generating hydrogen are formed, which enhances the hydrogen generating ability of silicon microparticles, i.e., large amounts of hydrogen gas are generated continuously for a long period of time or are extracted more reliably.

[0025] Furthermore, by applying additional processing to the silicon microparticles described above, the inventors not only succeeded in producing silicon microparticles containing a large amount of silicon suboxide, but also in converting the silicon microparticles containing silicon suboxide into hydrophilic particles when viewed macroscopically. Specifically, the inventors removed hydrogen atoms resulting from reactions with silicon atoms that were bonded to the surface of the silicon oxide film containing the silicon suboxide contained in the silicon microparticles, thereby realizing the bonding of many hydroxyl groups (OH groups) to the surface of the silicon oxide film. In other words, by realizing the formation of many SiOH groups, the silicon microparticles containing the silicon oxide film containing silicon suboxide became hydrophilic when viewed macroscopically. As a result, the silicon microparticles, which are more likely to come into contact with or react with water, have stronger hydrogen generating ability, i.e., they are able to generate large amounts of hydrogen gas continuously for a long period of time or with greater certainty.

[0026] As described above, the present inventors have discovered that by modifying the surface of silicon microparticles containing silicon suboxide, the silicon oxide film covering the surface, and at least a portion of the interface between the surface and the silicon oxide film, microscopic physical properties or characteristics can be formed, which leads to stronger hydrogen generation ability of the silicon microparticles, i.e., the continuous generation of large amounts of hydrogen gas over long periods of time, or the more reliable extraction of this hydrogen gas. Furthermore, as a result of further research and development, the present inventors have also discovered that composite compositions containing silicon microparticles at least partially comprising such a silicon oxide film containing silicon suboxide can be used as composite compositions for oral and topical use. Furthermore, the present inventors have also discovered that the amount of hydrogen generated, the method for preparing the composite composition, the amount of the composite composition used, the size of the microparticles constituting the composite composition, the pH value, and other factors required depending on the application can be adjusted as desired. The present invention was first created by incorporating the above-mentioned unique perspectives and innovations.

[0027] One composite composition of the present invention comprises silicon fine particles and silicon suboxide (SiO ) covering at least a portion of the surface of the silicon fine particles. X , where x is ½, 1, and ¾) and / or mixed compositions of the silicon suboxide and silicon dioxide.

[0028] According to the above-mentioned composite composition, the silicon oxide film covering at least a portion of the surface of the silicon microparticles contains the above-mentioned silicon suboxide, thereby making it possible to enhance the hydrogen generation ability of the silicon microparticles, i.e., to generate large amounts of hydrogen gas continuously for a long period of time, or to extract it more reliably.

[0029] In the present application, regardless of the size of the diameter of the crystal (not including the silicon oxide film), the basic unit to be measured for "diameter" is expressed as "crystallite."

[0030] Furthermore, the term "silicon microparticles" as used herein refers to particles primarily made up of silicon particles having an average crystallite diameter on the micron level or less, specifically, a crystallite diameter of 1 nm to 500 μm. In a narrower sense, the term "silicon microparticles" as used herein refers to particles primarily made up of silicon nanoparticles having an average crystallite diameter on the nano level, specifically, a crystallite diameter of 1 nm to 50 nm (or, more broadly, 1 nm to 500 nm). Furthermore, the term "silicon microparticles" as used herein refers not only to silicon microparticles in a dispersed state, but also to silicon microparticles in a state in which multiple silicon microparticles aggregate to form aggregates on the order of μm (generally, 0.1 μm to 500 μm). The above-mentioned numerical ranges for "silicon microparticles" are merely examples, and are not limited to these numerical ranges. The crystallite diameter is appropriately selected depending on the application, usage, required functions, etc. of the "silicon microparticles." Furthermore, the "fine silicon particles" may be used in a state where they are mixed with other substances, as long as the "fine silicon particles" are not in a state where they do not exhibit their hydrogen generating ability. Furthermore, the "silicon oxide" in this application is a mixed composition of the silicon suboxide and silicon dioxide.

[0031] Furthermore, the term "water-containing liquid" in this application refers to water or an aqueous solution, including, for example, gastrointestinal fluid of animals (including humans). The term "gastrointestinal fluid" refers to fluid in the small intestine and the large intestine. It goes without saying that examples of "water-containing liquid" are not limited to the above examples. The "pH adjuster" in this application is not particularly limited to any particular material, as long as it is an agent (hereinafter referred to as "alkaline agent") that can adjust the pH value to an alkaline range of greater than 7 (typically greater than 7.4). It also includes application on the skin of animals (including humans). When using the composite composition as a drug for neutralizing reactive oxygen species in the body, it is preferable to use an alkaline agent approved as a pharmaceutical (official product), quasi-drug, or food additive. As mentioned above, the composite composition is not limited to use in animals (including humans). Examples of alkaline agents include sodium bicarbonate, sodium carbonate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium bicarbonate, potassium carbonate, and other pH adjusters for pharmaceuticals, quasi-drugs, foods, or cosmetics. Among these, sodium bicarbonate, the most commonly used product, is widely used as a pharmaceutical, quasi-drug, or food additive, and combines the pH value adjusting function required by the present invention with several advantages, such as excellent safety and versatility. Meanwhile, in industrial applications, pH adjusters are not limited to the aforementioned pH adjusters, and a wide range of pH adjusters can be used. A preferred embodiment of any pH adjuster is that it is in a form that is not decomposed by acid. In particular, when the composite composition of the present application is orally ingested, it is preferable that it be in a form that is not decomposed or is difficult to decompose by gastric acid. [Effects of the Invention]

[0032] According to one composite composition of the present invention, the silicon oxide film covering at least a portion of the surface of the silicon microparticles contains the above-mentioned silicon suboxide, making it possible to more strongly or more reliably utilize the hydrogen generation ability of the silicon microparticles. [Brief explanation of the drawings]

[0033] [Figure 1]1 shows XPS spectra of the Si2p region when the surface states of silicon fine particles of the first embodiment and the silicon fine particles of modified example (1) of the first embodiment are measured using an X-ray photoelectron spectroscopy analyzer (XPS analyzer), and the XPS spectrum of the Si2p region when the silicon fine particles of modified example (1) of the first embodiment are brought into contact with water at approximately 37°C to generate hydrogen and the surface state is measured after a predetermined time (reaction time). The dotted lines indicate the results of peak separation of the spectrum into Si0, Si+, Si2+, Si3+, and Si4+. [Figure 2] 1 is a graph showing the change in the film thickness of a silicon oxide film, the change in the film thickness of silicon dioxide (SiO2) contained therein, and the change in the film thickness of silicon suboxide ("suboxide" in the figure), calculated based on the measurement results of FIG. 1, over a predetermined time (reaction time) when silicon fine particles of the modified example (1) of the first embodiment are brought into contact with water to generate hydrogen. [Figure 3] FT-IR spectrum (top) of silicon microparticles having silicon suboxide after the pulverization process of the first embodiment, and FT-IR spectrum (bottom) of silicon microparticles having silicon suboxide after the modification process of the first embodiment. [Figure 4] FIG. 1 is a conceptual diagram showing a structural model of the surface of a silicon microparticle that constitutes at least a part of the composite composition of the first embodiment, a silicon oxide film containing silicon suboxide that covers the surface, and / or the interface between the surface and the silicon oxide film. [Figure 5] 1 is a graph showing the relationship between the amount of hydrogen generated and the reaction time when silicon microparticles in an example of variant (1) of the first embodiment are reacted with an aqueous solution adjusted to pH 10 using sodium bicarbonate and sodium carbonate and water at approximately 36°C. [Figure 6] 10 is a graph showing the relationship between the amount of hydrogen generated and reaction time when an aqueous solution of modified silicon particles according to the third embodiment, adjusted to pH 8.2 using sodium bicarbonate, reacts with water at approximately 36°C. [Figure 7]10 is a graph showing the relationship between the amount of hydrogen generated and reaction time when an aqueous solution of modified silicon particles in variant (1) of the third embodiment, adjusted to pH 8.2 using sodium bicarbonate, reacts with water at approximately 36°C. [Figure 8] (a) A side view showing the laminated structure of the layered body and the medium before hydrogen generation in another embodiment (3), and (b) a side view showing the laminated structure of the layered body and the medium when hydrogen is generated in another embodiment (3). [Figure 9] FIG. 10 is a side view showing a layer structure in a modified example of the other embodiment (3). [Explanation of symbols]

[0034] 10a Layered body 20 base 70 Impermeable membrane 90b Medium 100 laminated structure 200 structures DETAILED DESCRIPTION OF THE INVENTION

[0035] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will now be described in detail with reference to the accompanying drawings.

[0036] [1] Composite composition and its manufacturing method First Embodiment The composite composition of this embodiment is a composite composition containing silicon fine particles having hydrogen generating ability. In addition, the composite composition of this embodiment contains silicon dioxide (SiO2) and silicon suboxide (SiO2) in a silicon oxide film that covers at least a part of the surface of the silicon fine particles. X , where x is 1 / 2, 1, and 3 / 2).

[0037] Furthermore, the film thickness of the silicon oxide film can vary by generating hydrogen, as described below, but the range is 0.5 nm to 20 nm. Additionally, the amount of silicon suboxide contained in the silicon oxide film can also vary by generating hydrogen, but a suitable example of a silicon suboxide composition ratio (silicon atomic ratio) in the silicon oxide film before the hydrogen generation reaction described below is 10% or more. While there is no particular need to set an upper limit, if one is to be mentioned, the upper limit is 80% (i.e., 80% or less).

[0038] Next, the method for producing the composite composition of this embodiment will be described, along with the state of the surfaces of silicon microparticles, the silicon oxide film covering the surfaces, and / or the interface between the surfaces and the silicon oxide film, as measured or observed by various analyses in several steps of the process.

[0039] The composite composition of this embodiment uses, as silicon particles, silicon fine particles obtained by pulverizing, for example, commercially available high-purity silicon particle powder (manufactured by Kojundo Chemical Laboratory Co., Ltd., particle size distribution <φ5 μm (however, typically, silicon particles with a crystal particle size of more than 1 μm, purity 99.9%, i-type 5658 silicon) using a bead mill in a liquid such as ethanol. The silicon fine particles contain, for example, silicon nanoparticles and / or aggregates of silicon nanoparticles. Note that this embodiment is not limited to the size, purity, pulverization method, or dispersion solvent of the silicon particle powder used as the raw material for the composite composition described above. Furthermore, the examples employed in embodiments or variants other than this embodiment are merely examples, and are not limited to the aspects of those embodiments or variants.

[0040] As a specific example, a bead mill device (RMH-type horizontal continuous ready mill manufactured by Imex Co., Ltd.) is used to disperse 200 g of high-purity silicon particle powder (manufactured by Kojundo Chemical Laboratory Co., Ltd., particle size distribution <φ5 μm, purity 99.9% or higher) as silicon particles in a mixed solution of 4000 ml of 99% or higher alcohol such as ethanol, isopropyl alcohol (IPA), or methanol (however, in this embodiment, ethanol) and a small amount of water (for example, 0.1 wt% or more and 10 wt% or less, more preferably more than 1 wt% and 2 wt% or less), and φ0.5 μm zirconia beads (volume 2900 ml) are added. The mixture is then pulverized in air at room temperature for 4 hours at a rotation speed of 2500 rpm to reduce the particle size. In addition, the use of ethanol (e.g., 99.5 wt%) as the alcohol contained in the mixed solution is a preferred embodiment from the viewpoint of increasing the certainty of the safety (e.g., safety to the human body) of the silicon microparticles and the composite composition containing the silicon microparticles that are finally produced.

[0041] As another example of the above-mentioned grinding process, it has been confirmed that when the grinding time using a bead mill device is 1 hour, silicon nanoparticles having an average particle size of 100 nm or less, silicon fine particles having a size of 40 nm to 0.5 μm and containing the silicon nanoparticles, and / or silicon particles whose main particles are aggregates of the silicon nanoparticles and silicon fine particles containing the silicon nanoparticles can be obtained.

[0042] Further research by the present inventors has revealed that using a solvent containing a small amount of water in addition to the above-mentioned solvents results in the formation of a silicon oxide film containing more suboxides during or after the milling process. This finding can significantly contribute to further improving the hydrogen generation ability of silicon microparticles. The present inventors have also discovered that the milling process of this embodiment results in silicon microparticles with a more approximately spherical or discoid shape. The milling method is not limited to bead milling. For example, other milling methods, such as high-pressure collision, can also be used as appropriate. Furthermore, the primary solvent is not limited to ethanol. For example, other alcohols, such as isopropanol, and / or solvents other than alcohols, such as acetone, acetonitrile, THF, and acetate esters, can be used instead of or in addition to the ethanol.

[0043] Additionally, as will be described in detail later, the present inventors have made an interesting finding by analyzing silicon microparticles (including silicon nanoparticles) using FT-IR analysis. Specifically, during the process of producing silicon microparticles (the above-mentioned grinding process), it is believed that a slight hydrogen generation reaction occurs as a result of the silicon microparticles reacting with water contained in alcohol (typically ethanol) and / or water vapor in the air. It is known that in the initial reaction between silicon and water, water molecules partially decompose and adsorb to H and OH. It is believed that as a result of the slight reaction with water during the grinding process, hydrogen atoms bond to silicon atoms at the interface between the silicon microparticles and the silicon oxide film, which is why Si-H3, Si-H2, and Si-H were identified in the FT-IR analysis. Therefore, while H-SiO3, H-SiO2, and H-SiO present on the surface of the silicon oxide film are responsible for the hydrophobicity, Si-H3, Si-H2, and Si-H present at the interface between the silicon microparticles and the silicon oxide film containing silicon suboxide are not involved in the hydrophobicity. Furthermore, as described above, hydrogen atoms bonded to silicon atoms are easily removed by surface treatment using hydrogen peroxide.

[0044] Thereafter, the mixed solution containing silicon microparticles (including silicon nanoparticles) separated from the beads in the bead mill grinding device is heated to 40°C using a vacuum evaporator to evaporate the mixed solution, thereby obtaining dried silicon microparticles (including silicon nanoparticles). The dried silicon microparticles can be stored in a vacuum container or a nitrogen-substituted container. Note that the separation and drying methods for the silicon nanoparticles obtained by grinding are not limited to the methods disclosed in this embodiment. For example, known separation and / or drying methods used in the production of other particles can also be used.

[0045] An example of silicon microparticles (including silicon nanoparticles) obtained by the above method is mainly composed of silicon nanoparticles with a crystallite diameter of 1 nm to 500 nm. More specifically, when the silicon nanoparticles were measured using an X-ray diffractometer (Rigaku Corporation, Smart Lab), the following values ​​were obtained, for example: In the volume distribution, the mode diameter of the silicon crystallites was 6.6 nm, the median diameter was 14.0 nm, and the average crystallite diameter was 20.3 nm. Note that the above results are merely examples of results from a pulverization process, and therefore the present embodiment is not limited to the above values.

[0046] When an example of the silicon microparticles was observed using an SEM (scanning electron microscope), some of the silicon microparticles were aggregated, resulting in a slightly larger, irregular shape of about 0.1 μm or more. Furthermore, when the aggregated individual silicon microparticles were observed using a TEM (transmission electron microscope), most of the crystallites contained in the observation field had a crystallite diameter of about 2 nm to 40 nm. Note that the above results are merely examples of results from a pulverization process, etc., and therefore the present embodiment is not limited to the above numerical values.

[0047] As will be described later, the silicon oxide film covering at least a portion of the surface of the silicon fine particles produced by the above-mentioned pulverization process contains a large amount of silicon suboxide, which makes it possible to more effectively or reliably utilize the hydrogen generation ability of the silicon fine particles. More specifically, by using the silicon fine particles, a high hydrogen generation rate can be achieved for a long period of time, for example, 20 hours or more from the start of generation.

[0048] <Modification (1) of the First Embodiment> In one preferred embodiment, the surfaces of the silicon microparticles produced in the first embodiment described above may be further modified by contacting them with aqueous hydrogen peroxide. This modification process allows the silicon microparticles, including silicon nanoparticles, to be hydrophilic when viewed macroscopically. The method for contacting the surfaces of the silicon microparticles with aqueous hydrogen peroxide is not limited. For example, the modification process can be performed by immersing the silicon microparticles in 3 wt % aqueous hydrogen peroxide (e.g., about 10°C to about 80°C, or about 20°C to about 50°C from the viewpoint of achieving lower costs) contained in a known container. Similar modification can also be achieved by immersing the silicon microparticles in ozone water and / or sodium percarbonate instead of aqueous hydrogen peroxide. Alternatively, similar modification can also be achieved by contacting the silicon microparticles with at least one selected from the group consisting of aqueous hydrogen peroxide, aqueous ozone, and sodium percarbonate.

[0049] Specifically, by performing the above-described modification process, hydrogen atoms adsorbed on the surface of the silicon oxide film containing silicon suboxide contained in the silicon fine particles can be removed, and many hydroxyl groups (OH groups) (i.e., SiOH groups) can be present on the surface of the silicon oxide film. As a result, the silicon fine particles containing silicon suboxide can be made hydrophilic from a macroscopic perspective, and the silicon fine particles containing silicon suboxide, which more reliably promote contact or reaction with water, can exhibit stronger or more reliable hydrogen generation ability. Therefore, the silicon fine particles containing silicon suboxide (i.e., an example of a composite composition) can function as a hydrogen supply material. As described above, performing the modification process using hydrogen peroxide solution at approximately room temperature is also preferable from the perspective of achieving low-cost and safe processing. In addition, using hydrogen peroxide solution in the modification process of this embodiment is a preferable embodiment from the perspective of generating hydrogen using a material that is safer and more reliable (e.g., less harmful to the human body) than ethanol.

[0050] When an example of silicon microparticles containing silicon suboxide of this modification was observed using a scanning electron microscope (SEM), some of the silicon microparticles were aggregated to form slightly larger, irregular shapes of about 0.1 μm or more. Furthermore, when the aggregates of the individual silicon microparticles were observed using a transmission electron microscope (TEM), most of the crystallites in the observed field had crystallite diameters of about 2 nm to 40 nm.

[0051] A detailed investigation of the rate at which hydrogen is generated when silicon microparticles having silicon suboxide of this modified example are brought into contact with water revealed that the rate at which hydrogen is generated is approximately 10 times faster than the rate at which silicon microparticles having silicon suboxide of the first embodiment are brought into contact with water, as described below.

[0052] In the modification step of this embodiment, hydrogen peroxide is used to modify the surface of the silicon microparticles. However, as described above, the material for realizing the modification step of the first embodiment is not limited to hydrogen peroxide. Another example is to use sodium percarbonate instead of hydrogen peroxide. Sodium percarbonate reacts with water to produce hydrogen peroxide, which can provide the same effect as the first embodiment.

[0053] <Comparative analysis between the first embodiment and the modified example (1) of the first embodiment> Below are shown the results of measurements and considerations using various analytical methods of the state of the surface (including silicon oxide on the surface; the same applies below) of silicon microparticles having silicon suboxide of the first embodiment and the state of the surface (including silicon oxide on the surface; the same applies below) of silicon microparticles having silicon suboxide of variant (1) of the first embodiment.

[0054] [XPS analysis results] The present inventors analyzed the surfaces of the silicon fine particles (an example of a composite composition) of the above-mentioned two embodiments using an X-ray photoelectron spectrometer (XPS analyzer) (manufactured by Shimadzu Corporation, model: KRATOS AXIS 165).

[0055] FIG. 1 shows XPS spectra of the Si2p region obtained by measuring the surface state of each silicon microparticle during continuous reaction of silicon microparticles having silicon suboxide according to the first embodiment and the modified example (1) of the first embodiment with water at a pH of 7 and a temperature of 36° C. using an XPS analyzer with an Mg Kα radiation source, as well as XPS spectra of the Si2p region obtained by measuring the surface state after a predetermined time (reaction time) has elapsed since the silicon microparticles according to the modified example (1) of the first embodiment were brought into contact with water to generate hydrogen.

[0056] The dotted line in Fig. 1 indicates the spectrum of Si 0 , Si + , Si2+ , Si 3+ , Si 4+ The peak separation results are shown in Fig. 1. All Si2p peaks are separated by 0.61 eV and have an intensity ratio of 2:1. 3 / 2 Peak and Si2p 1 / 2 In Figure 1, of the two types of peaks mentioned above, Si2p 3 / 2 Only the area is shown by a dotted line.

[0057] In addition, the objects of measurement in this analysis are immediately after the crushing process (after the crushing process in the figure), immediately after the modification process with hydrogen peroxide solution (after the modification process in the figure), 1 hour after the silicon microparticles that have been modified have been in contact with ultrapure water, 2 hours after the silicon microparticles that have been modified have been in contact with ultrapure water, 4 hours after the silicon microparticles that have been modified have been in contact with ultrapure water, 6 hours after the silicon microparticles that have been modified have been in contact with ultrapure water, and 24 hours after the silicon microparticles that have been modified have been in contact with ultrapure water. Note that the data immediately after the crushing process in Figure 1 (after the crushing process in the figure) is also used as the result for the silicon microparticles having silicon suboxide of the first embodiment described above.

[0058] 2 shows the change in the film thickness of silicon dioxide (SiO2) (shown by the open circle in FIG. 2) and the change in the film thickness of silicon suboxide (SiO2) calculated based on the measurement results of FIG. 1 over a predetermined time (reaction time) when silicon fine particles having silicon suboxide of the modified example (1) of the first embodiment are continuously brought into contact with water at pH 7 and 36°C to generate hydrogen. X, where x is 1 / 2, 1, and 3 / 2) (triangles in FIG. 2), and the film thickness of the mixed composition of the silicon suboxide and silicon dioxide (i.e., silicon oxide) (black circles in FIG. 2). Note that the reaction time in these analyses refers to the contact time when the silicon microparticles are continuously contacted with pure water at pH 7. The above-mentioned film thicknesses can be calculated based on the integrated intensity ratio of the peaks in the Si 2p region. Note that the film thickness of the above-mentioned silicon oxide film is the thickness obtained by adding together the film thicknesses of the silicon dioxide and silicon suboxide components.

[0059] Here, the above-mentioned film thicknesses are calculated using the following method based on the integrated intensity ratio of the peaks in the Si2p region as shown below.

[0060] <How to calculate film thickness> The XPS spectrum of the Si2p region is + , Si 2+ , Si 3+ , and Si 4+ Here, the peaks are separated into Si 0 , Si + , Si 2+ , Si 3+ , and Si 4+ indicates that the number of oxygen atoms bonded to one silicon atom is 0, 1, 2, 3, or 4. All Si2p peaks are separated by 0.61 eV and have an intensity ratio of 2:1. 3 / 2 (high energy side) and Si2p 1 / 2 (low energy side). If the area intensity of the peak due to the silicon oxide film is I(oxide), the following equation is given:

[0061]

number

[0062] Here, I(Si 4+ ), I(Si 3+ ), I(Si 2+ ), and I(Si +) is the area intensity of the peaks due to SiO2, Si2O3, SiO, and Si2O. The thickness of the silicon oxide film (t oxide ) is the area intensity of the Si2p peak of I(oxide) and silicon fine particles, and I(Si 0 ), it is given by the following equation. This equation assumes that the shape of the silicon microparticle is a cylinder with radius R and height equal. (O. Renault, R. Marlier, N.T. Barrett, E. Martinez, T. Baron, M. Gely, and B. De Salvo, Modeling the XPS Si 2p core-level intensities of silicon nanocrystals for determination of oxide shell thickness, Surf. Interface Anal. 38, 486-488 (2006))

[0063]

number

[0064] Here, N is the number density of silicon atoms, σ is the photoionization cross section, λ is the mean free path of photoelectrons, and the subscripts oxide and Si indicate the values ​​for silicon oxide film and silicon microparticles. (σ oxide / σ Si ), λ oxide , and λ SiThe values ​​used for the thicknesses were 1.1, 2.9 nm, and 2.5 nm, which are the values ​​reported in the literature (M.F. Hochelia, Jr. and A.H. Carim, Surf. Sci. Lett. 197, L260 (1988). and H. Kobayashi, Asuha, O. Maida, M. Takahashi, and H. Iwasa, Nitiric acid oxidation of Si to form ultrathin silicon dioxide layers with a low leakage current density, J. Appl. Phys. 94(11) 7328-7335 (2003)).

[0065] The number density of silicon atoms in the silicon oxide film, N oxide is given by the following formula:

[0066]

number

[0067] Here, N(SiO), N(SiO), N(SiO), and N(SiO) represent the atomic densities of silicon atoms in SiO, SiO, SiO, and SiO, respectively.

[0068] In addition, the thickness of the silicon dioxide film (t SiO2 ), and the thickness of the suboxide (t suboxide ) are the thicknesses of the silicon oxide films (t oxide ) can be calculated using the following formula:

[0069]

number

[0070] where N suboxide is given by the following equation (6).

[0071]

number

[0072] <Analysis of each analysis result> As shown in Figure 1, the Si 0 The peak of the Si and the broad Si peak due to the silicon dioxide (SiO2) film 4+ As shown in the area surrounded by the dashed line in the figure, the Si suboxide + , Si 2+ , Si 3+ A peak was observed.

[0073] In FIG. 1, when comparing the results immediately after the pulverization process (corresponding to silicon fine particles having silicon suboxide in the first embodiment) with the results immediately after the modification process using hydrogen peroxide water in the modified example (1) of the first embodiment (after the modification process in FIG. 1), it is clear that the silicon dioxide (SiO2) film is a barrier against the silicon dioxide (SiO2) film. 4+ Almost no change in peak intensity was observed. Furthermore, as shown in Figure 2, it was confirmed that there was almost no change in the silicon dioxide (SiO2) film thickness between the results immediately after the pulverization process (after the pulverization process in Figure 2, corresponding to the silicon microparticles having silicon suboxide in the first embodiment) and the results immediately after the modification process using hydrogen peroxide water in Modification (1) of the first embodiment (after the modification process in Figure 1). Additionally, the silicon oxide film thickness shown in Figure 2 closely matched the oxide film thickness determined from the observation of cross-sectional electron microscope photographs.

[0074] Furthermore, as shown in Figure 1, the longer the reaction time for generating hydrogen, the greater the intensity of the peaks due to silicon dioxide, confirming that the thickness of the silicon dioxide film increased with the reaction time. In this analysis, the thickness of the silicon dioxide film measured after the hydrogen generation reaction was completed was 10.5 nm. It is noteworthy that a silicon oxide film as thick as 10.5 nm was formed under the extremely low temperature condition of 36°C. As described above, the realization of this thick film can be said to be one of the representative effects resulting from the fact that the silicon fine particles of the first embodiment, particularly the modified example (1) of the first embodiment, contain abundant silicon suboxide, the presence of abundant OH groups (i.e., SiOH groups) on the silicon oxide film, and / or the hydrophilicity due to the absence of almost any hydrogen atoms on the surface.

[0075] The inventors also determined the thickness of the silicon dioxide film and the silicon suboxide film in the silicon oxide film immediately after the modification process using hydrogen peroxide water in the modified example (1) of the first embodiment (after the modification process in FIG. 1) from the XPS spectrum in FIG. 1. As a result, the thickness of the silicon dioxide film formed on the surface of the silicon microparticles was 1.7 nm, and the thickness of the silicon suboxide was 1.0 nm.

[0076] Therefore, the above calculation results prove that the silicon oxide film of about 2.7 nm formed on the surface of the silicon microparticles contains many suboxides. The silicon suboxides contain many silicon dangling bonds. The silicon dangling bonds have an energy level within the band gap, and chemical species (hydroxide ions (OH)) that oxidize the silicon microparticles via this energy level are generated. - It is believed that the hopping conduction of atoms (ions, etc.) promotes the diffusion (or migration) of chemical species. Therefore, as mentioned above, silicon suboxide can be said to function as an active intermediate.

[0077] The inventors' research and analysis have revealed that the hydrogen generation ability of the silicon fine particles can be enhanced or more reliably achieved when the relationship between the first silicon atom number (A1) of the silicon dioxide and the second silicon atom number (A2) of the silicon suboxide in the silicon oxide film satisfies the following formula (7). Therefore, by setting the silicon suboxide composition ratio (silicon atomic ratio) in the silicon oxide film to 10% or more, it is possible to enhance or more reliably achieve a longer-lasting, continuous hydrogen generation ability. The silicon suboxide composition ratio (silicon atomic ratio) in the silicon oxide film immediately after the pulverization process (corresponding to the silicon fine particles in the first embodiment) in FIG. 1 was approximately 38% according to the results of one experiment using a sample. Furthermore, the silicon suboxide composition ratio (silicon atomic ratio) in the silicon oxide film immediately after the modification process using hydrogen peroxide water in Modification Example (1) of the first embodiment was approximately 28% according to the results of one experiment using a sample. The amount of hydrogen generated by the composite composition in the above-described embodiment or modification can be adjusted as needed depending on the application by changing the method for preparing the composite composition, the amount of the composite composition used, the size of the fine particles constituting the composite composition, the pH value, or the like.

[0078]

number

[0079] In addition, from the viewpoint of enhancing or more reliably deriving hydrogen generation ability, the composition ratio (silicon atomic ratio) of the silicon suboxide in the silicon oxide film is 10% or more, regardless of whether the product is a pulverized product or a pulverized product surface-treated with hydrogen peroxide or the like. While there is no particular upper limit to the composition ratio, if one were to be specified, the upper limit would be 80% (i.e., 80% or less). A more preferred embodiment is one in which the aforementioned numerical range is 20% or more and 70% or less.

[0080] As described above, both the silicon fine particles of the first embodiment and the silicon fine particles of the modified example (1) of the first embodiment form a silicon oxide film containing a large amount of silicon suboxide and / or an interface between the silicon oxide film containing a large amount of silicon suboxide and a silicon crystal layer, thereby forming hydroxide ions (OH - As a result, by employing the silicon microparticles having silicon suboxide of the first embodiment and the silicon microparticles having silicon suboxide of the modification (1) of the first embodiment, the hydrogen generating ability of the silicon microparticles can be strengthened, that is, a large amount of hydrogen can be generated in the body for a long period of time or extracted with a high degree of accuracy.

[0081] On the other hand, as shown in Figure 2, the thickness of the silicon suboxide film observed during the hydrogen evolution reaction remained almost constant, while only the silicon dioxide film thickness increased. This proves that the chemical reactions represented by the aforementioned chemical reaction formulas (4) to (7) proceeded essentially simultaneously. This result also indicates that the silicon suboxide acts as an active intermediate in the chain reaction.

[0082] [FT-IR analysis results] The inventors further analyzed the surfaces of silicon suboxide-containing silicon fine particles immediately after the milling process of the first embodiment and the surfaces of silicon suboxide-containing silicon fine particles immediately after the modification process with hydrogen peroxide solution of Modification (1) of the first embodiment using a Fourier transform infrared spectrometer (FT-IR device) (manufactured by JASCO Corporation, model: FT / IR-6200). Figure 3 shows the FT-IR spectrum of the silicon suboxide-containing silicon fine particles after the milling process and the FT-IR spectrum of the silicon suboxide-containing silicon fine particles after the modification process. Note that the intensity of the lower spectrum is four times that of the upper spectrum for ease of viewing.

[0083] By this FT-IR analysis, using the following method, it was found that the surface concentration of OH groups (i.e., SiOH groups) on the surfaces of the silicon fine particles having silicon suboxide immediately after the pulverization treatment in the first embodiment was 1.5×10 14 / cm 2 It is calculated that:

[0084] First, the thickness of the silicon oxide film is determined from the XPS spectrum of the Si2p region. The same cylindrical structural model as that used when the thickness of the silicon oxide film was determined from the XPS spectrum of the Si2p region is assumed. In this model, the volume V of silicon oxide is given by the following equation (8):

[0085]

number

[0086] On the other hand, the surface area S of the silicon oxide film is given by the following formula (9).

[0087]

number

[0088] The area intensity I(LO) of the LO peak of a silicon oxide film is proportional to the volume of the silicon oxide film, the atomic density N(oxide) of silicon atoms in the silicon oxide film, and the oscillator strength σ(LO) of the O-Si-O antisymmetric stretching vibration (LO phonon). On the other hand, the area intensity I(OH) of the OH stretching vibration peak of OH groups present on the surface is proportional to the surface area of ​​the silicon oxide film, the surface concentration c(OH) of OH groups, and the oscillator strength σ(OH) of the OH stretching vibration. Therefore, the ratio of the LO phonon peak intensity to the OH stretching vibration peak intensity (I(OF) / I(LO)) can be calculated using the following equation (10):

[0089]

number

[0090] The surface concentration of OH groups on the surface of the silicon suboxide-containing silicon fine particles immediately after the pulverization treatment in the first embodiment, calculated using equation (9), was 2 × 10 14 / cm 3 On the other hand, the surface concentration of OH groups on the surface of silicon microparticles containing silicon suboxide immediately after the modification process using hydrogen peroxide solution was 4.5 × 10 14 / cm 3 The surface concentration of OH groups estimated using the above method was in good agreement with the value calculated using the area intensity of the vibration peak due to calcium carbonate and its oscillator strength when a standard sample was prepared by mixing 10 wt% calcium carbonate into silicon microparticles. It is noteworthy that the value immediately after the modification process was more than twice the surface concentration of OH groups on the surface of silicon microparticles having silicon suboxide immediately after the milling process in the first embodiment.

[0091] As shown in Figure 3, the FT-IR spectrum in the Si-H stretching vibration region shows a peak at 2240 cm -1 The peak due to H-SiO3 is at 2192 cm -1 The peak due to H-SiO2 is at 2155 cm -1 The H-SiO peak at 2135 cm -1 The peak due to Si-H3 at 2110cm -1 The peak due to Si-H2 is at 2077 cm -1 The peaks are separated into six peaks, one due to Si-H, and the other due to H-SiO3, H-SiO2, and H-SiO. H-SiO3, H-SiO2, and H-SiO are due to hydrogen atoms bonded to the surface of the silicon oxide film. On the other hand, as already mentioned, Si-H3, Si-H2, and Si-H are due to hydrogen atoms bonded to silicon atoms at the interface between the silicon fine particles and the silicon oxide film as a result of a slight hydrogen generation reaction that occurs when the silicon fine particles react with the water contained in the ethanol and / or water vapor in the air during the process of producing the silicon fine particles (the above-mentioned grinding process).

[0092] As shown in Figure 3, after the milling process, at least a portion of the surface of the silicon microparticles containing silicon suboxide is covered with a thin silicon oxide film, and hydrogen atoms are bonded to the surface of the silicon oxide film. As a result, the surface of the silicon oxide film exhibits hydrophobicity from a macroscopic perspective. Therefore, H-SiO3, H-SiO2, and H-SiO present on the surface of the silicon oxide film are responsible for the hydrophobicity. However, Si-H3, Si-H2, and Si-H present at the interface are not thought to contribute to the hydrophobicity.

[0093] In the silicon microparticles having silicon suboxide immediately after the modification process using hydrogen peroxide solution in the modified example (1) of the first embodiment, the peak intensities of the stretching vibrations due to H-SiO3, H-SiO2, and H-SiO are significantly reduced, which means that the hydrogen atoms bonded to the surface of the silicon oxide film have been removed. The total concentration of H-SiO3, H-SiO2, and H-SiO on the surface of the silicon microparticles before the modification process was 1.8 × 10 14 / cm 2 However, after the modification process, the concentration was 4×10 13 / cm 2 As a result, it was found that the hydrogen atoms on the silicon oxide film were removed by the modification process using hydrogen peroxide water.

[0094] 2252 cm observed in silicon fine particles containing silicon suboxide after the grinding process. -1 The peak intensity of the Si-H stretching vibration due to H-SiO3 and 2192cm -1 The peak intensity of the Si-H stretching vibration due to H-SiO2 at 2155cm -1 It can be seen that the peak intensity of the Si-H stretching vibration due to H-SiO in the sample is significantly reduced by the modification process. It is worth noting that the aforementioned H-SiO2 and H-SiO are formed by the bonding of hydrogen atoms to suboxides.

[0095] As mentioned above, the concentration of hydroxyl groups (OH groups) present on the surface of the silicon oxide film containing silicon suboxide is 5×10 13 / cm 2 On the other hand, in the silicon microparticles having silicon suboxide after the modification process, as described above, the hydrogen atoms bonded to the surface of the silicon oxide film are removed. Therefore, the concentration of SiH groups on the surface of the silicon microparticles is 2×10 14 / cm 2 It can be said that hydrogen atoms have been removed until the surface of the silicon oxide film containing silicon suboxide is below 0.5. It was also confirmed that many hydroxyl groups (OH groups) are present on the surface of the silicon oxide film containing silicon suboxide. It can be said that the combination of the above factors has made the surface of the silicon microparticles containing silicon suboxide hydrophilic.

[0096] Based on the above-mentioned analytical results, the present inventors considered that the states of the surface of the silicon microparticle, the silicon oxide film covering the surface, and / or the interface between the surface and the silicon oxide film change according to the following structural model during the above-mentioned chemical reactions.

[0097] 4 is a conceptual diagram showing a structural model of the surface of a silicon microparticle having silicon suboxide that constitutes at least a part of the composite composition of this embodiment, the silicon oxide film containing silicon suboxide that covers the surface, and / or the interface between the surface and the silicon oxide film, where (a) to (d) respectively show the following states. (a) After the grinding process (b) After the modification process (c) When the hydrogen generation reaction is progressing after contact with water with a pH of 7 (reaction time is approximately 6 hours or more) (d) When the hydrogen generation reaction is completed

[0098] As shown in Figure 4, after the pulverization process, the silicon microparticles are covered with a silicon oxide film of about 2.5 nm. Furthermore, H-SiO3, H-SiO2, and H-SiO are present on the surface of the silicon oxide film (Figure 4(a)). As mentioned above, due to the presence of H-SiO3, H-SiO2, and H-SiO, the surface of the silicon oxide film is, macroscopically, hydrophobic, so its reactivity with water is not very high. Furthermore, as shown in Figure 4(a), the silicon oxide film and / or the interface between the silicon microparticles and the silicon oxide film contain many suboxides.

[0099] A subsequent modification process dramatically changes the surface of the silicon oxide film. Because much of the H-SiO3, H-SiO2, and H-SiO are removed by the modification process, the surface of the silicon oxide film becomes hydrophilic, so to speak, and its reactivity with water becomes significantly higher (Figure 4(b)). As shown in Figure 4(b), many hydroxyl groups (OH groups) exist on the surface of the silicon oxide film. Even at this stage, many suboxides are present in the silicon oxide and / or at the interface between the silicon particles and the silicon oxide.

[0100] Furthermore, when the hydrogen generation reaction is progressing upon contact with water (FIG. 4(c)), the reaction rate at which silicon suboxide is produced from the silicon microparticles and the reaction rate at which silicon dioxide is produced from the silicon suboxide become approximately equal. As a result, the amount of silicon suboxide remains approximately constant, while the amount of silicon dioxide (film thickness) increases. For example, the hydrogen generation reaction stops when the silicon dioxide film thickness reaches approximately 15 nm (FIG. 4(d)). Note that the thickness of 15 nm shown in FIG. 4 is merely an example, and this embodiment is not limited to this value. Furthermore, according to the inventor's analysis, the silicon microparticles containing silicon suboxide that have undergone the pulverization and modification processes of this embodiment have a silicon oxide film (including silicon dioxide and silicon suboxide) with a film thickness of 3 nm to 20 nm (typically 15 nm or less) 168 hours (7 days) after hydrogen generation upon contact with water. Therefore, if the thickness of the silicon oxide film after 168 hours (7 days) from the time of hydrogen generation is within the above-mentioned numerical range, it can be recognized with a high degree of certainty as the silicon microparticles of this embodiment. The reaction between the silicon microparticles and water is not limited to these conditions. Other conditions include, for example, the reaction conditions of pH 10 and 36°C shown in Figure 5.

[0101] As described above, by performing the pulverization and modification processes of this embodiment, it is possible to remove hydrogen atoms adsorbed on the surface of the silicon oxide film of the silicon suboxide-containing silicon particles and to create a state in which many hydroxyl groups (OH groups) are present on the surface of the silicon oxide film containing silicon suboxide. As a result, the silicon particles can be made hydrophilic from a macroscopic perspective, and the silicon particles, which more reliably promote contact and reaction with water, have stronger hydrogen generating ability, i.e., they can generate large amounts of hydrogen in the body for a long time or more reliably. Furthermore, as described above, performing the modification process using hydrogen peroxide solution at approximately room temperature is also preferable from the perspective of achieving low-cost and safe processing.

[0102] <Modification (2) of the First Embodiment> In the first embodiment and the modified example (1) of the first embodiment, the modification step is performed by immersing the silicon microparticles in hydrogen peroxide solution at about room temperature, but the means for the modification step is not limited to the means disclosed in the modified example (1) of the first embodiment. For example, instead of immersion in hydrogen peroxide solution, another possible embodiment is to use a known ball mill and bring the hydrogen peroxide solution into contact with the silicon microparticles using the ball mill.

[0103] In this modified example (2), for example, commercially available high-purity silicon particle powder (particle size distribution <φ1 mm (but typically silicon particles with a crystal grain size of more than 100 μm), purity 99.9%) is used as silicon particles, and a ball mill is used to grind the silicon particles in the atmosphere using a ball mill machine in a mixed solution of ethanol and water in the same manner as in the first embodiment, using stainless steel balls with a diameter of 5 mm. As a result, by separating the balls and the primary silicon particles in the atmosphere, primary silicon particles with an average particle diameter of 3 μm can be obtained.

[0104] Another possible embodiment is to obtain silicon microparticles having silicon suboxides similar to those of the first embodiment by further performing a grinding process in which the silicon particles obtained by this modification (2) are ground using the bead mill device of the first embodiment.

[0105] In the above-mentioned "another embodiment," the silicon fine particles are mainly composed of silicon suboxide-containing silicon particles having a crystallite diameter of 5 nm to 500 nm in volume distribution. More specifically, the silicon suboxide-containing silicon fine particles were measured using an X-ray diffractometer, and the following values ​​were obtained: In the volume distribution, the mode diameter of the silicon crystallites was 9.3 nm, the median diameter was 26.1 nm, and the average crystallite diameter was 41.5 nm. When the silicon fine particles were observed using an SEM, it was found that some of the silicon suboxide-containing silicon fine particles had aggregated to form slightly larger, amorphous aggregates measuring 0.5 to 5 μm. Furthermore, when individual silicon fine particles were observed using a TEM, it was found that most of them had a crystallite diameter of approximately 5 nm to 50 nm.

[0106] <Modification (3) of the First Embodiment> Furthermore, 5 mg of silicon microparticles according to the first embodiment, variant (1) of the first embodiment, or variant (2) of the first embodiment are mixed with approximately 500 mg of sodium bicarbonate powder (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.5%). This mixture is kneaded and compressed into tablets as cylindrical blocks with a diameter of approximately 8 mm and a height of approximately 4 mm. Tablets are an example of bulk formulations. A preferred embodiment involves separately forming silicon microparticles having stable silicon suboxide and a pH adjuster such as sodium bicarbonate into nanocapsules, microcapsules, regular capsules, or coatings that are stable under acidic conditions but dissolve under basic conditions. By adopting the above-described embodiment, it is possible to avoid reaction in the presence of water under acidic conditions and promote dissolution and reaction between the silicon microparticles and water under basic conditions.

[0107] <Modification (4) of the First Embodiment> In the first embodiment and the modified example (1) of the first embodiment, a mixed solution of ethanol and a small amount of water (0.1 wt% to 2 wt%) is used in the grinding process using a bead mill, but the first embodiment is not limited to this mixed solution. For example, even if 2-propanol is used instead of ethanol, or even if any of the various solvents already mentioned is used, the same effects as those of the first embodiment or the modified example (1) of the first embodiment can be achieved.

[0108] <Second embodiment> One of the features of the composite composition of this embodiment is that it is produced by carrying out the grinding step using an acidic solution (typically having a pH value of 3 to 6) instead of the ethanol and a small amount of water used in the grinding step of the first embodiment. Note that the description overlapping with the first embodiment may be omitted.

[0109] The raw material for the composite composition in this embodiment is, for example, a high-purity silicon particle powder (particle size 300 μm or less) obtained by pulverizing commercially available i-type polycrystalline silicon with a purity of 99.99% or more using a jet mill method and passing the pulverized silicon through a 300 μm sieve. Note that this embodiment is not limited to the size, purity, pulverization method, or dispersion solvent of the silicon particle powder used as the raw material for the composite composition.

[0110] As a specific example, a bead mill (RMH-type horizontal continuous ready mill manufactured by Imex Co., Ltd.) was used. In the bead mill, 2.1 g of the high-purity silicon particle powder described above was dispersed in 78 mL of an acidic solution (in this embodiment, hydrochloric acid (HCl aqueous solution)) adjusted to a pH value of 3 to 5. Then, 0.5 μm zirconia beads (volume 2900 mL) were added. The resulting solution was milled in air at a rotation speed of 2500 rpm for 75 minutes with the cooling water temperature of the bead mill set to approximately 6°C. The pH-adjusting solution for forming the acidic solution is not limited to hydrochloric acid. For example, a pH value of 5 or 6 is also a preferred embodiment from the viewpoint of increasing the reliability of the safety (e.g., safety to the human body) of the final silicon fine particles (including silicon nanoparticles and / or silicon nanoparticle aggregates) and the composite composition containing the silicon fine particles.

[0111] It has been confirmed that even when the method for producing a composite composition of this embodiment is adopted, at least some of the effects achieved by the composite composition and its production method of the first embodiment can be achieved.

[0112] [XPS analysis results] The present inventors analyzed the surface of an example of silicon microparticles (composite composition) of this embodiment using an X-ray photoelectron spectroscopy analyzer (XPS analyzer) (Shimadzu Corporation, Model: KRATOS AXIS 165). For the silicon microparticles analyzed, the pH value of the acidic solution used in the above-mentioned milling process was 5.0. Analysis of the observed XPS spectrum revealed that the silicon microparticles formed by milling using hydrochloric acid (HCl aqueous solution) at pH 5.0 using a bead mill had a 1.6 nm silicon dioxide film, a 1.0 nm silicon suboxide, and a 2.6 nm silicon oxide film.

[0113] <Third embodiment> The composite composition of this embodiment is characterized in that it is formed without the pulverization step of the first or second embodiment. Note that descriptions that overlap with those of the first or second embodiment or their respective modifications may be omitted.

[0114] The raw material of the composite composition in this embodiment is the high-purity silicon particle powder (particle size 300 μm or less) of the second embodiment. Note that this embodiment is not limited to the size, purity, pulverization method, or dispersion solvent of the silicon particle powder used as the raw material of the composite composition.

[0115] In this embodiment, the pulverization step is not performed, but a modification step is performed in which the surfaces of the silicon particles are brought into contact with hydrogen peroxide solution to modify the surfaces, as in the modified example (1) of the first embodiment. Specifically, the modified silicon particles (an example of a composite composition) of this embodiment are formed by bringing the silicon particles into contact with hydrogen peroxide solution having a concentration of, for example, 3 wt % for 30 minutes.

[0116] Then, 78 ml of 36°C water (aqueous solution) adjusted to pH 8.2 using sodium bicarbonate was added to prepare an aqueous solution, and the modified silicon particles were dispersed in the aqueous solution. In this embodiment, the amount of hydrogen gas generated by immersing the modified silicon particles in the aqueous solution was measured using a hydrogen concentration meter. Figure 6 is a graph showing the relationship between the amount of hydrogen gas generated and reaction time in this embodiment.

[0117] <Modification (1) of the third embodiment> Furthermore, as one of the modified examples of this embodiment, we will explain an example (modified example) in which the same process as in the third embodiment is performed, except that the 300 μm sieve used in the process of forming the modified silicon particle powder in the third embodiment is changed to a 45 μm sieve.

[0118] In this embodiment, modified silicon particles (an example of a composite composition) having a particle size of 45 μm or less are formed. Figure 7 is a graph showing the relationship between the amount of hydrogen gas generated and reaction time in this modified example.

[0119] As described above, it was confirmed that a sufficient amount of hydrogen was generated in a relatively short time in the third embodiment and its modified examples. Therefore, even if the composite composition is formed without carrying out the pulverization step in the first or second embodiment, at least some of the effects of the first or second embodiment can be achieved.

[0120] <Other embodiment (1)> The composite composition of each of the above-described embodiments or variations thereof can be used, for example, as a pharmaceutical preparation. Furthermore, its use is not limited to tablets. For example, the same effects as those described above can be achieved even when capsules in which the powdered composite composition is encapsulated are used instead of tablets. The composite composition can generate more hydrogen when it is in a powder form with a large surface area rather than in a block form. However, when it is formulated as a tablet or capsule, oral ingestion becomes easier. Furthermore, by formulating it as a tablet or capsule, the composite composition maintains a block form to some extent in the stomach, but disintegrates and becomes powdery after passing through the stomach. Therefore, the surface area of ​​the composite composition exposed to gastric juice and / or stomach contents in the stomach, where the hydrogen generation reaction is desired to be suppressed, can be reduced, and the surface area exposed to water-containing liquid in the small intestine and / or large intestine, where the hydrogen generation reaction is desired to be promoted, can be increased.

[0121] The composite composition may also be formulated as a granule. Granule formulations turn into powder sooner after oral ingestion than tablets or capsules. However, because gastric juice has a low pH value (approximately 1.5), the powder forms little hydrogen immediately after reaching the stomach, but generates hydrogen in the presence of water after passing through the stomach.

[0122] The composite composition may be in the form of a powder. Powders are easy to handle when the composite composition is used as a food additive, such as a component of a food, including a health food. When used as a food additive, the composite composition can be mixed with silicon particles having a crystallite diameter of 1 nm to 10 μm, or 1 nm to 500 nm (more narrowly, 1 nm to 100 nm). The silicon fine particles are preferably contained in an amount of 1% by mass or more. While there is no upper limit to the content of silicon fine particles, it is preferable to set it to 40% by mass or less, taking into account the taste.

[0123] An example of a coating layer that can be applied to a tablet is a known gastrointestinal-insoluble enteric material that is a coating agent that covers the outermost layer of a tablet.An example of a coating layer that can be applied to a capsule is a capsule itself that contains the composite composition and is made of a known gastrointestinal-insoluble enteric material.

[0124] As described above, examples of suitable formulations for utilizing the composite composition include tablets, which are bulk formulations that can be easily orally ingested in sufficient amounts, or capsules in which the powdered composite composition (which may be in an aggregated state) is encapsulated. When tablets are used, a disintegrant may further be included. Known materials can be used as disintegrants. A more suitable example of a disintegrant is an organic acid, and the most suitable example is citric acid. Here, the organic acid can also function as a binder to agglomerate silicon microparticles or silicon nanoparticles. The composite composition can also be used, for example, as a granular, flake-like, and / or minced food topping (typically, "furikake" or "sprinkle") for various food ingredients.

[0125] <Other embodiment (2)> Furthermore, the composite composition of each of the above-described embodiments or their variations can transdermally or transmucosally introduce hydrogen into the body (including the skin itself or the mucosa itself) by using, for example, a "medium" that is brought into contact with the composite composition. The medium of the present embodiment is not particularly limited to a material or product. Any physiologically acceptable medium can achieve the effects of the present embodiment. Therefore, anything that includes the composite composition and the medium that comes into contact with the composite composition can function as a hydrogen supply material.

[0126] As a specific example, from the viewpoint of increasing the opportunities for human parts to come into contact with water (or a water-containing liquid) or a medium containing the water (or a water-containing liquid) (hereinafter collectively referred to as "medium") in daily life situations, an example of a suitable medium is at least one selected from the group consisting of liquid, gel, cream, paste, emulsion, and mousse. Another example of a suitable medium is bath water (preferably alkaline bath water). Therefore, in one example of this embodiment, producing the bath water constitutes a method of producing the medium.

[0127] To explain bath water in more detail, tap water is typically stored as bath water in a typical bathtub (including bathtubs in public bathhouses, public baths, and indoor or outdoor bathtubs installed by hotels). Before or after storing the bath water, the composite composition described above is placed or poured into the bathtub, and a contacting step is carried out in which the composite composition is brought into contact with the bath water as a medium, thereby generating hydrogen (H2). Therefore, the composite composition of this embodiment can be used as a bath additive, so to speak.

[0128] Therefore, the hydrogen (H2) generated by the contact step can be brought into contact with the skin and / or mucous membrane of a person taking a bath via bath water as a physiologically acceptable medium. As a result, according to this embodiment, it is possible to take in hydrogen (H2) into the human body (including the skin itself or mucous membrane itself) using a means other than oral ingestion.

[0129] <Other embodiment (3)> In addition, the composite composition of each of the above-described embodiments and their modifications may also be employed in the form of a layered body in which the composite composition is formed into a layer, or a layered body in which the composite composition is contained in a layered base material, which can thus function as a hydrogen supply material.

[0130] In this embodiment, a layered body in which the composite composition is formed into a layer, or a layered body in which the composite composition is contained in a layered base material, can be used to form a layered structure 100 of the layered body and a medium. Fig. 8(a) is a side view showing the layered structure 100 of the layered body and a medium before hydrogen generation, and Fig. 8(b) is a side view showing the layered structure 100 of the layered body and a medium when hydrogen is generated.

[0131] As shown in FIGS. 8(a) and 8(b), the above-described laminated structure 100 includes at least a layered body 10a and a medium 90b on or above a base 20 (e.g., fiber, natural resin, synthetic resin, metal, semiconductor, ceramic, or glass). A suitable example of the medium 90b is at least one physiologically acceptable material selected from the group consisting of liquid, gel, cream, paste, emulsion, and mousse. The medium 90b may also contain a pH adjuster, such as sodium bicarbonate. It is a preferred embodiment that the base 20 is stretchable. In addition, if the laminated structure 100 of the layered body 10a and the medium 90b can be maintained without the base 20, the base 20 is not necessarily required.

[0132] As shown in FIG. 8(a), before hydrogen generation, an impermeable membrane 70 is provided between the layered body 10a and the medium 90b to prevent contact between the layered body 10a and the medium 90b. A membrane made of a known impermeable material can be used as the membrane 70. For example, the material of the impermeable membrane 70 is a known polymer such as polyethylene. Another example is the water-decomposable and impermeable sheet disclosed in International Publication No. WO2011 / 036992.

[0133] 8(b), when the membrane 70 is pulled out in the direction of the arrow, at least a portion of the layered body 10a and the medium 90b come into direct contact with each other. As a result, hydrogen can be generated when the layered body 10a comes into contact with the medium 90b, which can contain a water-containing liquid with a pH value of 7 or more (preferably, greater than 7, and even more preferably, greater than 7.4) in cooperation with a pH adjuster such as sodium bicarbonate.

[0134] In this embodiment, the layered body 10a and the medium 90b are formed to come into direct contact with each other by pulling out the film 70 in the direction of the arrow (to the left on the paper), but the method for removing the film 70 is not particularly limited. For example, one possible embodiment is to form the film 70 so that the medium 90b comes into contact with the composite composition (the layered body 10a in this embodiment) when at least a portion of the film 70 is removed or when at least a portion of the film is dissolved. In one possible embodiment, a water-decomposable and water-impermeable sheet, as disclosed in International Publication No. WO 2011 / 036992, can be used as a material for dissolving at least a portion of the film 70.

[0135] In another embodiment, before hydrogen generation, the composite composition of each of the above-described embodiments or their modifications may be covered with an impermeable film 70 instead of the layered body 10a. By removing or dissolving the film 70, the composite composition and the medium 90b may come into direct contact with each other, and the same effect as in the case of the layered body 10a may be achieved.

[0136] Furthermore, for example, when the medium is at least one selected from the group consisting of liquid, gel, cream, paste, emulsion, and mousse, it is possible that the two layers (layered body 10a and medium 90b) do not remain clearly separated as shown in Figure 8(b). In fact, such a case is preferable from the viewpoint of promoting hydrogen generation with a higher degree of accuracy, since the contact area between layered body 10a and medium 90b is increased. In addition, one embodiment in which the medium contains a physiologically acceptable adhesive for adhesion to a human body part is also adoptable.

[0137] <Modification of other embodiment (3)> As a modification of the above-described other embodiment (3), the layered body formed from the composite composition in a layer form can be used alone or as a laminated structure with a base 20. An example structure 200 shown in FIG. 9 includes a layered body 10a on a base 20. Note that, if the shape of the layered body can be maintained without the base 20, the base 20 does not necessarily need to be provided. Furthermore, from the viewpoint of reliably avoiding contact with moisture in the air, an impermeable film 70 may be provided to cover the layered body 10a.

[0138] 9, one preferred embodiment of this invention is that, for example, after the layered body 10a comes into contact with human skin or mucous membrane, sweat or body fluids containing moisture from the skin or mucous membrane come into contact with the layered body 10a, thereby generating hydrogen. This embodiment also allows a person to take in hydrogen, as in the other embodiment (3). Instead of sweat or body fluids, water (such as tap water) can be supplied by spraying or the like before (e.g., immediately before) using the layered body 10a.

[0139] It is worth noting that the structures or laminated structures that can be employed in other embodiment (3) and its modifications can be employed in various "life situations." For example, the following are representative examples of products that can employ (or contain) the medium: (A) to (D). (A) One cleanser selected from the group consisting of facial cleanser, hair shampoo, body shampoo, liquid hand soap, and liquid body soap. (B) One cosmetic material selected from the group consisting of lotions (e.g., containing hyaluronic acid), serums, emulsions, lotions, cosmetic creams (e.g., containing collagen), foundations, skin packs (including skin packs having gels (or gel-like agents)), shaving creams, hair rinses, hair treatments, hair conditioners, hair cosmetics, antiperspirants, and UV protection cosmetics. (C) One type of therapeutic material selected from the group consisting of ointments and poultices. (D) One sanitary material selected from the group consisting of water-absorbent resins, water-absorbent nonwoven fabrics, water-absorbent fibers, water-absorbent felts, and water-absorbent gels (or gel-like agents).

[0140] Here, the above-mentioned "hair cosmetics" includes hair styling products, hair oils, camellia oil, styling products, setting products, blow-dry products, brushing products, hair sticks, hair wax, hair foam, hair gel, pomade, hair cream, hair solid, hair lacquer, hair liquid, hair spray, and hair water. Furthermore, the above-mentioned "hygienic materials" includes hygienic gloves, head covers, headbands, bed pads, bed sheets, adult incontinence products, menstrual products, clothing, wound dressings (including wound dressings, tapes, and bandages), disposable diapers, including adult diapers and infant diapers, gauze, gowns, hygienic tissues (including wet towels, washcloths, patches, wet tissues, and napkins), absorbent cotton, cotton swabs, adhesive bandages, and surgical tape.

[0141] <Other embodiment (4)> The composite composition of each of the above-described embodiments or variations thereof can also be used as feed for, for example, animals (including dogs, cats, horses, sheep, rabbits, or chickens, but excluding fish) kept for farming (including farm animals in this application), animals for food, animals (including foxes, bears, deer, snakes, or crocodiles) whose fur or skin can be used for clothing or leather products (including pouches, various cases, or bags), animals used for medical purposes, or fish, including farmed fish. Furthermore, it can also be used as an industrial chemical or pharmaceutical.

[0142] Furthermore, the composite compositions of the above-described embodiments or their modifications can also be used as human supplements or food additives. It is noteworthy that the composite compositions of the above-described embodiments or their modifications have hydrogen generating ability and can therefore exhibit antiseptic properties for various foods or materials. For example, fresh foods, including vegetables, fruits, fresh fish, and meat, can be preserved for a longer period of time by contacting the composite composition containing water or water soaked in the composite composition. Furthermore, the preservation of various cosmetics or fragrances, including perfumes, emulsions, or lotions containing water (moisture), can be prolonged by soaking the composite composition in the cosmetics or fragrances.

[0143] <Other embodiment (5)> Furthermore, the composite compositions of the above-described embodiments and their modifications can naturally aggregate to form aggregates with diameters on the μm level (e.g., about 20 μm). By artificially assembling the composite compositions by adding a binder or compressing them, a solid preparation in the form of a mass large enough to be picked up by a human finger can be formed. The preparation can also be applied to plants (including trees).

[0144] Specifically, in this embodiment, the composition is embedded in the soil (containing moisture) in which the plant is planted or grows naturally, thereby utilizing the soil as a medium containing a water-containing liquid. Hydrogen (H2) is generated by contacting the composition with the soil as a medium. As a result, the plant in contact with the soil can absorb the hydrogen via its roots, stems, or exoskeleton. This can prevent or inhibit photosynthesis inhibition, leaf bleaching, growth promotion, and / or plant death. Furthermore, depending on the plant, sugar content can also be increased. Typical examples of moisture in this embodiment include rainwater or artificial water. The number or amount of the composition in the soil is not particularly limited.

[0145] Another aspect of this embodiment may involve introducing or pouring the formulation into a naturally occurring or artificial water reservoir (medium) to bring the formulation into contact with a water-containing liquid. Hydrogen (H) is generated by contacting the formulation with the water-containing liquid. In this aspect, the animal can take in hydrogen via the water-containing liquid by contacting or immersing the animal in the water reservoir. As a result, hydrogen taken in directly, transdermally, or transmucosally can appropriately eliminate, remove, or reduce excess reactive oxygen (particularly hydroxyl radicals) in the animal's body, thereby improving the animal's health and / or preventing disease.

[0146] Furthermore, if the pH value of the above-mentioned puddle is higher than weak acidity (for example, pH value of 5 or higher), the use of a mixture of the composition of this embodiment and sodium bicarbonate will result in a high pH value, and the condition as a medium that easily generates hydrogen (H2) can be met. In other words, if the water-containing liquid such as a puddle is acidic, it will be necessary to introduce or pour a large amount of the composition into the soil to meet the condition as a medium that easily generates hydrogen (H2).

[0147] By using the mixture of the compound of this embodiment and sodium bicarbonate, even if the soil or the water reservoir as a medium is neutral or slightly acidic, the compound can be buried, introduced, or poured into the soil or the water reservoir as a medium, thereby undergoing a contact step in which the composite composition comes into contact with the medium, thereby promoting the generation of hydrogen (H2).

[0148] Therefore, the hydrogen (H2) generated by the contact step can be brought into contact with the skin and / or mucous membranes of an animal or the leaves, stems, skin, and / or roots of a plant via the soil or puddle as a medium. As a result, according to this embodiment, it is possible to realize the uptake of hydrogen (H2) into the body of an animal or plant. For example, in animals, the hydrogen can exhibit a function of inhibiting aging. Furthermore, in plants, the hydrogen can exhibit a function of inhibiting corrosion.

[0149] Furthermore, this embodiment is not limited to cases where the composite composition or the blend is used as is. Another suitable embodiment is where the composite composition or the blend is contained in or incorporated into a "matrix" such as an animal drug, livestock or pet food, animal feed, or botanical drug, plant fertilizer, or plant compost. For example, a typical example is where the composite composition or the blend is mixed or kneaded into the matrix as an additive, for example, at 0.1 wt% to 50 wt%. Therefore, in this embodiment, not only a blend in which the composite composition is incorporated into a botanical drug, plant fertilizer, or plant compost, but also the above-mentioned "matrix" is a "compound" in the broad sense. Therefore, contact of the above-mentioned matrix with a medium can be used as a suitable means for animals or plants to take up hydrogen, for example, transdermally or transmucosally.

[0150] <Example> In the following, examples will be given to explain each of the above-described embodiments in more detail, but the above-described embodiments are not limited to these examples.

[0151] (Example 1-1) First, 200 g of silicon microparticles containing silicon suboxide according to the first embodiment (i.e., an example of the composite composition according to the first embodiment) were placed in a reaction vessel, and 500 ml of 3 wt% aqueous hydrogen peroxide solution was added. The temperature was set to 35°C while stirring, and the silicon microparticles were immersed in the hydrogen peroxide solution for 30 minutes to perform a surface modification process on the silicon microparticles. The surface-modified silicon microparticles (i.e., an example of the composite composition according to Modification (1) of the first embodiment) were then subjected to solid-liquid separation by vacuum filtration using ashless quantitative filter paper (GE Healthcare Japan, Grade 42, particle retention capacity: 2.5 μm). After washing with water, the silicon microparticles were dispersed in ethanol and then centrifuged for solid-liquid separation. The surface-modified silicon microparticles after solid-liquid separation were dried under reduced pressure at 40°C. The dried silicon microparticles were then stored in a vacuum container or a nitrogen-substituted container. The surfaces of the silicon microparticles that underwent the modification process exhibited hydrophilic properties.

[0152] (Example 1-2) First, 200 g of silicon microparticles of the first embodiment (i.e., an example of the composite composition of the first embodiment) were placed in a reaction vessel, and 250 ml of 10 wt% aqueous hydrogen peroxide solution was added. The temperature was set to 20°C while stirring, and the silicon microparticles were immersed in the hydrogen peroxide solution for 60 minutes to perform a surface modification process on the silicon microparticles. The surface-modified silicon microparticles (i.e., an example of the composite composition of Modification (1) of the first embodiment) were then subjected to solid-liquid separation by vacuum filtration using ashless quantitative filter paper (GE Healthcare Japan, Grade 42, particle retention capacity: 2.5 μm). After washing with water, the silicon microparticles were dispersed in ethanol and then centrifuged for solid-liquid separation. The surface-modified silicon microparticles after solid-liquid separation were dried under reduced pressure at 40°C. The dried silicon microparticles were then stored in a vacuum container or a nitrogen-substituted container. The surfaces of the silicon microparticles that underwent the modification process exhibited hydrophilicity.

[0153] (Examples 1-3) First, 200 g of silicon microparticles of the first embodiment (i.e., an example of the composite composition of the first embodiment) were placed in a reaction vessel, and 500 ml of 3 wt% hydrogen peroxide solution was added. The temperature was set to 60°C while stirring, and the silicon microparticles were immersed in the hydrogen peroxide solution for 30 minutes to perform a surface modification process on the silicon microparticles. The surface-modified silicon microparticles (i.e., an example of the composite composition of Modification (1) of the first embodiment) were then subjected to solid-liquid separation by vacuum filtration using ashless quantitative filter paper (GE Healthcare Japan, Grade 42, particle retention capacity: 2.5 μm). After washing with water, the silicon microparticles were dispersed in ethanol and then centrifuged for solid-liquid separation. The surface-modified silicon microparticles after solid-liquid separation were dried under reduced pressure at 40°C. The dried silicon microparticles were then stored in a vacuum container or a nitrogen-substituted container. The surfaces of the silicon microparticles that underwent the modification process exhibited hydrophilicity.

[0154] Example 2 5 mg of silicon microparticles of the first embodiment (i.e., an example of the composite composition of the first embodiment) was used as a raw material. 78 ml of water with a pH of 7 and a temperature of 36°C was added to the raw material (silicon microparticles) to disperse the raw material, and the hydrogen gas generated while stirring was measured with a hydrogen concentration meter. The amount of hydrogen gas generated over time is shown in Table 1. The amount of hydrogen gas generated was also identified and quantitatively evaluated by gas chromatography mass spectrometry (GC / MS).

[0155] After the reaction between the raw material and water was completed, the silicon fine particles after the reaction were analyzed using the XPS apparatus and FT-IR apparatus of the first embodiment. The results showed that the silicon fine particles after the reaction still retained their hydrogen generating ability.

[0156] [Table 1]

[0157] Example 3 5 mg of silicon microparticles (i.e., surface-modified silicon microparticles) of modified example (1) of the first embodiment were used as raw material. 78 ml of water at 36°C and pH 7 was added to the raw material (silicon microparticles) to disperse the raw material, and the generated hydrogen gas was measured with a hydrogen concentration meter. As shown in Table 2, the amount of hydrogen gas generated over time was more than 10 times the value of the results in Table 1. The amount of hydrogen gas generated was also identified and quantitatively evaluated by GC / MS analysis.

[0158] After the reaction between the raw material and water was completed, the silicon fine particles after the reaction were analyzed using the XPS apparatus and FT-IR apparatus of the first embodiment. The results showed that the silicon fine particles after the reaction (i.e., surface-modified silicon fine particles) still retained their hydrogen generating ability.

[0159] [Table 2]

[0160] Example 4 5 mg of silicon microparticles of the first embodiment (i.e., an example of the composite composition of the first embodiment) was used as a raw material. 78 ml of 36°C water (aqueous solution) adjusted to pH 8.3 using sodium bicarbonate was added to the raw material (silicon microparticles) to disperse the raw material, and the generated hydrogen gas was measured with a hydrogen concentration meter. The amount of hydrogen gas generated over time is shown in Table 3. The amount of hydrogen gas generated was also identified and quantitatively evaluated by GC / MS analysis.

[0161] After the reaction between the raw material and water was completed, the silicon fine particles after the reaction were analyzed using the XPS apparatus and FT-IR apparatus of the first embodiment. The results showed that the silicon fine particles after the reaction still retained their hydrogen generating ability.

[0162] [Table 3]

[0163] Example 5 Five mg of silicon microparticles (i.e., surface-modified silicon microparticles) of the modified example (1) of the first embodiment were used as raw material. 78 ml of 36°C water (aqueous solution) adjusted to pH 8.3 using sodium bicarbonate was added to the raw material (silicon microparticles) to disperse the raw material, and the hydrogen gas generated was measured with a hydrogen concentration meter. As shown in Table 4, the amount of hydrogen gas generated over time was more than 15 times the value of the results in Table 3. This increase in the amount of hydrogen generated is due to the alkaline pH. Even more notably, the amount of hydrogen gas generated, especially in the initial stage of the reaction, was significantly higher than the results in Table 3. The amount of hydrogen gas generated was also identified and quantitatively evaluated using GC / MS analysis.

[0164] After the reaction between the raw material and water was completed, the silicon fine particles after the reaction were analyzed using the XPS apparatus and FT-IR apparatus of the first embodiment. The results showed that the silicon fine particles after the reaction (i.e., surface-modified silicon fine particles) still retained their hydrogen generating ability.

[0165] [Table 4]

[0166] Example 6 200 g of silicon microparticles of the first embodiment (i.e., an example of the composite composition of the first embodiment) were used as raw material. 250 ml of 10 wt% hydrogen peroxide solution, prepared by diluting 35% hydrogen peroxide, was added to the raw material (silicon microparticles) to disperse the raw material. A surface modification process was performed by immersing the silicon microparticles in hydrogen peroxide solution at 35°C for 30 minutes to modify the silicon microparticles' surfaces. The surface-modified silicon microparticles (i.e., an example of the composite composition of Modification (1) of the first embodiment) were then subjected to solid-liquid separation by vacuum filtration using ashless quantitative filter paper (GE Healthcare Japan, Grade 42, particle retention capacity: 2.5 μm). The silicon microparticles were dispersed in ethanol and then centrifuged for solid-liquid separation. The surface-modified silicon microparticles after solid-liquid separation were then dried under reduced pressure at 40°C. The dried silicon microparticles were then stored in a vacuum container or a nitrogen-substituted container. The surfaces of the silicon microparticles that had undergone the modification process exhibited hydrophilic properties.

[0167] The surfaces of the silicon particles were then analyzed using an XPS analyzer, and the ratio of the number of silicon atoms in the silicon suboxide (i.e., the composition ratio of the silicon suboxide) to the number of silicon atoms in the silicon oxide film (i.e., the sum (100%) of the number of silicon atoms in the silicon dioxide and the number of silicon atoms in the silicon suboxide) was found to be approximately 60%.

[0168] Example 7 An example in which sodium percarbonate is used instead of the hydrogen peroxide solution of the modified example (1) of the first embodiment will be described.

[0169] 5 mg of silicon microparticles of the first embodiment (i.e., an example of the composite composition of the first embodiment) were used as raw material. 180 ml of water was added to the raw material (silicon microparticles), and 1.8 g of sodium percarbonate was further added to prepare an aqueous solution, and the raw material was dispersed in the aqueous solution. A modification process was carried out to modify the surface of the silicon microparticles by immersing the silicon microparticles in water with stirring for 30 minutes at 30°C. The surface-modified silicon microparticles (i.e., an example of the composite composition of Modification (1) of the first embodiment) were then subjected to solid-liquid separation by vacuum filtration using ashless quantitative filter paper (GE Healthcare Japan, Grade 42, particle retention capacity: 2.5 μm). After washing with water to remove sodium carbonate adhering to the silicon microparticles, the silicon microparticles were dispersed in ethanol and then centrifuged for solid-liquid separation. The surface-modified silicon microparticles after solid-liquid separation were then dried under reduced pressure at 40°C. The dried silicon microparticles were then stored in a nitrogen-substituted container. The surfaces of the silicon microparticles that had undergone the modification process exhibited hydrophilic properties.

[0170] Example 8 5 mg of silicon microparticles obtained in Example (7) (i.e., silicon microparticles surface-modified with sodium percarbonate) were used as a raw material. 78 ml of water with a pH of 7 and a temperature of 36°C was added to the raw material (silicon microparticles) to disperse the raw material in the water. In this example, the amount of hydrogen gas generated by immersion in the aqueous solution was measured using a hydrogen concentration meter.

[0171] It was confirmed that the thickness of the silicon oxide film (including silicon dioxide and silicon suboxide) 168 hours (7 days) after the hydrogen generation was approximately 13 nm. Therefore, if the thickness of the silicon oxide film 168 hours (7 days) after the hydrogen generation is in the above-mentioned range of 3 nm to 20 nm (typically 15 nm or less), it can be recognized with a high degree of certainty as the silicon microparticles of variant (1) of the first embodiment.

[0172] Example 9 5 mg of silicon microparticles of the first embodiment (i.e., an example of the composite composition of the first embodiment) was used as a raw material. 78 ml of 36°C water (aqueous solution) adjusted to pH 10 using sodium bicarbonate and sodium carbonate was added to the raw material (silicon microparticles) to prepare an aqueous solution, and the raw material was dispersed in the aqueous solution. In this example, the amount of hydrogen gas generated by immersing the raw material in the aqueous solution was measured using a hydrogen concentration meter. The amount of hydrogen generated over time was significantly increased compared to when water of pH 7 or pH 8.3 was used. The amount of hydrogen generated was also identified and quantitatively evaluated using GC / MS analysis. Figure 5 is a graph showing the relationship between the amount of hydrogen gas generated and reaction time in this example.

[0173] Example 10 5 mg of silicon microparticles of the first embodiment (i.e., an example of the composite composition of the first embodiment) was used as a raw material. 78 ml of 36°C water (aqueous solution) adjusted to pH 8.3 using caustic soda was added to the raw material (silicon microparticles) to prepare an aqueous solution, and the raw material was dispersed in the aqueous solution. In this example, the amount of hydrogen gas generated by immersing the raw material in the aqueous solution was measured using a hydrogen concentration meter. The amount of hydrogen generated over time was significantly increased compared to when water with a pH of 7 was used. The amount of hydrogen generated was also identified and quantitatively evaluated using GC / MS analysis.

[0174] Example 11 Five mg of silicon microparticles (i.e., surface-modified silicon microparticles) of the modified example (1) of the first embodiment were used as the raw material. 30 ml of water (aqueous solution) at 36.5°C, adjusted to pH 8.3 using caustic soda, was prepared, and the raw material (silicon microparticles) was added to the aqueous solution to disperse the raw material. In this example, the amount of hydrogen gas generated by immersing the raw material in the aqueous solution was measured using a hydrogen concentration meter. The amount of hydrogen generated over time was significantly greater than when water with a pH of 7 was used. The amount of hydrogen generated was also identified and quantitatively evaluated using GC-MAS analysis.

[0175] Example 12 5 mg of silicon microparticles of the first embodiment (i.e., an example of the composite composition of the first embodiment) was used as a raw material. 78 ml of water (aqueous solution) that had been adjusted to pH 8.3 using caustic soda and preheated to 60°C was added little by little to the raw material (silicon microparticles) to disperse the raw material in the aqueous solution. In this example, the amount of hydrogen gas generated by immersing the raw material in the aqueous solution was measured using a hydrogen concentration meter.

[0176] In this example, it was confirmed that hydrogen was generated much more rapidly than the results shown in Table 3. Furthermore, the rate at which hydrogen was generated over time was significantly higher than when water of pH 7 was used. The amount of hydrogen generated was also identified and quantitatively evaluated using GC / MS analysis.

[0177] Example 13 5 mg of silicon microparticles (i.e., surface-modified silicon microparticles) of the modified example (1) of the first embodiment were used as raw material. 78 ml of water (aqueous solution) that had been adjusted to pH 10 using caustic soda and preheated to 60°C was added little by little to the raw material (silicon microparticles) to disperse the raw material in the aqueous solution. In this example, the amount of hydrogen gas generated by immersing the raw material in the aqueous solution was measured using a hydrogen concentration meter.

[0178] In this example, it was confirmed that hydrogen was generated more rapidly than in Example 11. The amount of hydrogen generated was also identified and quantitatively evaluated by GC / MS analysis.

[0179] Example 14 The composite composition produced in the second embodiment was subjected to solid-liquid separation by vacuum filtration using ashless quantitative filter paper (GE Healthcare Japan, Grade 42, particle retention capacity: 2.5 μm). The surface-modified silicon microparticles after solid-liquid separation were subjected to a drying treatment under reduced pressure at 40°C. The dried silicon microparticles were then stored in a vacuum container or a container substituted with nitrogen. The surface of the composite composition produced in the second embodiment exhibited hydrophilicity.

[0180] An example of the composite composition obtained in Example 14 is mainly composed of silicon nanoparticles having a crystallite diameter of 1 nm to 500 nm. More specifically, the silicon nanoparticles were measured using an X-ray diffractometer (Rigaku Corporation, Smart Lab), and the average crystallite diameter was, for example, 28.0 nm. Note that the above-mentioned average crystallite diameter result is merely an example of the result of a pulverization process, and therefore this example is not limited to the above-mentioned numerical value.

[0181] Example 15 5 mg of silicon microparticles obtained in Example 14 (i.e., an example of the composite composition of the second embodiment) was used as a raw material. 78 ml of water at 36°C and pH 7 was added to the raw material (silicon microparticles) to disperse the raw material, and the hydrogen gas generated while stirring was measured with a hydrogen concentration meter. The amount of hydrogen gas generated over time is shown in Table 5. The amount of hydrogen gas generated was also identified and quantitatively evaluated by gas chromatography mass spectrometry (GC / MS).

[0182] [Table 5]

[0183] Incidentally, the silicon fine particles of each of the above-described embodiments can be brought into contact with a first water-containing liquid having a pH value of less than 7 in a first contact step, and then brought into contact with a second water-containing liquid having a pH value of 7 or more in a subsequent second contact step, thereby generating hydrogen in the second contact step. Therefore, the silicon fine particles of each of the above-described embodiments can have significant hydrogen generating ability when brought into contact with a water-containing liquid having a pH value of 7 or more.

[0184] Furthermore, the temperature conditions of the second water-containing liquid for generating hydrogen in each of the above-described embodiments are not limited. Although this may depend on the pH of the second water-containing liquid, if the temperature of the second water-containing liquid is 80°C or less, hydrogen generation is highly likely to be promoted. However, the upper limit of the temperature of the second water-containing liquid is not inherently limited. For example, when the composite composition of this embodiment is used as an industrial chemical, it may exceed 50°C. However, as the temperature increases, problems arise such as the need for higher heat resistance in the equipment (including the container) and the need for careful handling, so even when used as an industrial chemical, it is preferable to use it at 100°C or less. [Industrial Applicability]

[0185] The composite composition of the present invention can be widely used in various industries that utilize hydrogen, including agriculture, agriculture and livestock farming, forestry, fisheries, the pet industry, industries dealing with bonsai or fresh flowers, the pharmaceutical (including quasi-drug) and medical industry, the food industry, the veterinary industry and the arborist industry, industries dealing with industrial reducing agents, rust prevention applications and industrial chemical synthesis processes, and further, new energy industries such as fuel cells.

Claims

1. Silicon microparticles, Silicon suboxide (SiO Ｘ , where x is ½, 1, and ¾) and / or a mixed composition of the silicon suboxide and silicon dioxide; composite composition.

2. The silicon fine particles contain silicon nanoparticles. The composite composition of claim 1.

3. a composition ratio (ratio of silicon atoms) of the silicon suboxide in the silicon oxide film, which is a film of the mixed composition, is 10% or more and 80% or less; The composite composition according to claim 1 or claim 2.

4. The thickness of the silicon oxide film, which is a film of the mixed composition, is 0.5 nm or more and 15 nm or less. The composite composition according to any one of claims 1 to 3.

5. the surfaces of the silicon fine particles have SiOH groups and are hydrophilic; The composite composition according to any one of claims 1 to 4.

6. The number density of SiH groups on the surface of the silicon microparticles is 2×10 １４ / cm ２ Below is the The composite composition according to any one of claims 1 to 5.

7. The concentration of hydroxyl groups on the surface of the silicon fine particles is 5×10 １３ / cm ２ That's all. The composite composition according to any one of claims 1 to 6.

8. The average crystallite diameter of the silicon fine particles is 1 nm or more and 10 μm or less. The composite composition according to any one of claims 1 to 7.

9. The average crystallite diameter of the silicon nanoparticles is 1 nm or more and 500 nm or less. The composite composition of claim 2.

10. The surface of the silicon fine particles is in contact with at least one selected from the group consisting of hydrogen peroxide water, ozone water, and sodium percarbonate. The composite composition according to any one of claims 1 to 9.

11. The composite composition according to any one of claims 1 to 10, Pharmaceuticals.

12. The composite composition according to any one of claims 1 to 10, Quasi-drug.

13. A composite composition according to any one of claims 1 to 10; a physiologically acceptable medium in contact with the composite composition; allowing the hydrogen generated from the composite composition to contact the skin and / or mucous membrane via the medium; Hydrogen supply material.

14. further comprising a water-impermeable film covering the composite composition or a layer containing the composite composition; When at least a portion of the film is removed or when at least a portion of the film is dissolved, the medium contacts the composite composition. The hydrogen supply material according to claim 13.

15. 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 claim 13 or 14.

16. The composite composition according to any one of claims 1 to 10, feed.

17. for animals (excluding fish), 17. The feed of claim 16.

18. For fish, 17. The feed of claim 16.

19. The composite composition according to any one of claims 1 to 10, supplement.

20. The composite composition according to any one of claims 1 to 10, food additives.

21. The composite composition according to any one of claims 1 to 10, Healthy food.

22. The composite composition according to any one of claims 1 to 10 is incorporated into a plant medicine, a plant fertilizer, or a plant compost. compound.

23. The composite composition according to any one of claims 1 to 10 is in contact with water. Fresh food, cosmetics, or toiletries.

Images