JPWO2015093184A1 - Hydrogen generating agent and hydrogen generating method - Google Patents

Abstract

When a predetermined moisture adjustment layer is formed on the surface of the hydrogen generating agent, when it is added to the liquid in the container, a predetermined amount of hydrogen is rapidly generated and alkaline components such as magnesium and calcium are eluted. The present invention provides a hydrogen generating agent capable of effectively suppressing the above and a hydrogenation method using such a hydrogen generating agent. A hydrogen generator for hydrogenation and a hydrogen generation method using the same with respect to a liquid contained in a container, wherein 1 to 40% by weight of a hydrogen generation component with respect to the total amount While containing magnesium, the average particle diameter of the hydrogen generating agent is set to a value within the range of 1 μm to 20 mm, and the amount of moisture permeating from the outside to all or part of the surface of the core material of the hydrogen generating agent is A moisture adjustment layer for controlling is provided.

Description

  The present invention relates to a hydrogen generating agent and a hydrogen generating method. In particular, the present invention relates to a hydrogen generating agent with little alkali component elution and a hydrogen generating method using such a hydrogen generating agent.

In recent years, attention has been paid to the effect based on imparting reducibility when hydrogen is added to water or the like, and various hydrogenation agents, hydrogenation methods, and the like have been proposed.
For example, there is disclosed a selective hydrogen addition device for a biological application liquid including a hydrogen generation system containing a hydrogen generating agent as an essential component and a hydrogen bubble forming body having a gas-liquid separation unit including an open / close valve. The hydrogen bubble forming body is installed inside a sealed container that stores the biological application liquid, and hydrogen gas is fed into the sealed container that stores the biological application liquid via the gas-liquid separation unit, thereby providing a hydrogen-containing biological application liquid. Has been proposed (see Patent Document 1).
More specifically, it contains metallic magnesium or the like as a hydrogen generator, and the open / close valve is controlled by the gas pressure of the hydrogen gas generated inside the hydrogen bubble forming body by the reaction of the hydrogen generation system and water for generation. By being pushed open, the hydrogen gas is exhausted to a sealed container that is outside the hydrogen bubble forming body, and the selective hydrogenation device uses the biological application liquid as hydrogen water.

Also composed of an upper tank into which water can be introduced, a number of filters provided in the upper tank, a stick for generating hydrogen water provided below the filter, and a lower tank provided below the upper tank In addition, a hydrogen water generator configured to store the hydrogen water generated in the upper tank in the lower tank has also been proposed (see Patent Document 2).
More specifically, the hydrogen generating component contained in the stick for generating hydrogen water is composed of magnesium 15% by weight, obsidian 15% by weight, tourmaline 15% by weight, antibacterial sand 30% by weight, and weathered coral 25% by weight. ing.

Furthermore, a reduced water generating agent that includes a chemical substance powder that is slightly soluble in water and a hydrogen generating metal and that can continuously generate hydrogen for a long time has been proposed (see Patent Document 3). .
More specifically, a mixed powder of calcium sulfite powder and metal magnesium powder (compounding ratio: 80:20 to 50:50) as a chemical substance powder slightly soluble in water is blended with the core ball. And it is the reduced water production | generation agent formed by granulating to the magnitude | size about 5 mm from them, and baking at the temperature of about 280 degreeC.

Japanese Patent No. 4652479 (claims, etc.) JP 2004-160386 A (Claims etc.) JP 2011-255360 A (Claims etc.)

  However, the hydrogen generating agents disclosed in Patent Documents 1 to 3 contain a considerable amount of alkali components such as magnesium metal and calcium as hydrogen generating components and hydrogen generating assistants, respectively, and they are eluted in water. As a result, there are problems in that they adhere to the inner wall of the container and whiten the inner surface of the container or greatly change the hydrogen ion concentration (pH value) of the water to the alkali side.

Therefore, as a result of diligent efforts, the inventor of the present invention forms a moisture adjustment layer on the surface of the hydrogen generating agent for adjusting the amount of moisture (including water vapor) that permeates from the outside. The inventors have found that when added to a liquid material, a predetermined amount of hydrogen can be rapidly generated and the elution of alkali components and the like can be effectively suppressed, and the present invention has been completed.
That is, the present invention has an object to provide a hydrogen generating agent with less elution of alkali components and the like while maintaining good hydrogen generating characteristics, and an efficient method for generating hydrogen using such a hydrogen generating agent. And

According to the present invention, a hydrogen generating agent for adding hydrogen to a liquid or moisture-containing material contained in a container, wherein the hydrogen generating component is 1 to 40% by weight based on the total amount. In addition to containing magnesium, the average particle size of the hydrogen generator is set to a value in the range of 1 μm to 20 mm, and the amount of moisture that permeates all or part of the surface of the core material of the hydrogen generator is controlled. Therefore, a hydrogen generating agent characterized in that a moisture adjusting layer is provided to solve the above-described problems.
That is, according to the present invention, by providing a moisture adjusting layer around the core of the hydrogen generating agent in whole or in part, it reacts quickly with moisture permeating from the outside, and has good hydrogen generation characteristics. It can be set as a hydrogen generating agent with little elution, such as an alkaline component, with keeping.
Therefore, it is possible to quickly hydrogenate the liquid or water-containing material contained in the container, and as a result, the hydrogen dissolves and the long-term storage stability of the liquid or water-containing material is obtained. A reduced hydrogen-containing liquid material or hydrogen-containing water-containing material that exhibits predetermined functionality can be easily produced.

In constituting the hydrogen generating agent of the present invention, it is preferable that the main component of the moisture adjusting layer is at least one of a fluororesin, a silicone resin, an olefin resin, a styrene resin, an epoxy resin, or a ceramic material.
By configuring the moisture adjustment layer with such a coating material as a main component, a predetermined water repellency can be obtained, the amount of permeated moisture can be controlled more accurately, and good hydrogen generation characteristics can be maintained. As it is, it can be set as the hydrogen generating agent with little elution of an alkali component.

Moreover, when comprising the hydrogen generating agent of this invention, it is preferable to make thickness (t) of a moisture adjustment layer into the value within the range of 0.1 micrometer-2 mm.
By using the moisture adjustment layer having such a thickness, it is possible to further improve the balance between the control of the amount of transmitted moisture, which is a reciprocal characteristic, and the elution of the alkali component.

Further, in constituting the hydrogen generating agent of the present invention, the core material of the hydrogen generating agent is preferably heat-treated at a temperature of 180 ° C. or higher.
By using the core material of the hydrogen generating agent that has been subjected to such heat treatment, each component constituting the hydrogen generating agent is more uniformly mixed and dispersed, and more excellent hydrogen generation characteristics can be exhibited. The adhesion of the moisture adjustment layer to the surface of the core material can be improved.

In constituting the hydrogen generating agent of the present invention, it is preferable that the hydrogen generating agent is fixedly disposed on the substrate.
In this way, hydrogen generator is fixed on the surface of PET film, glass rod, etc. as a base material, and hydrogen is generated without directly touching the hydrogen generator using a part of these base materials. The agent can be sufficiently and reliably brought into contact with the liquid substance or moisture-containing substance contained in the container.

Further, according to another aspect of the present invention, a packaged hydrogen generator comprising a hydrogen generator and a coating material, the coating material being a mesh material, a resin film, a metal film, A packaged hydrogen generator characterized by being at least one of a film with a gas barrier layer, a paper material, and a fiber material.
That is, in the case of the packaged hydrogen generating agent, not only the handling becomes easy, but also water (including water vapor) contained in the liquid material or water-containing material contained in the container, and the covering material. And can be rapidly hydrogenated.
As a result, hydrogen dissolves inside the liquid or moisture-containing material, effectively preventing decay and the like, and can easily produce a reduced liquid that can exhibit the specified functionality while providing long-term stability. can do.

Moreover, according to another aspect of the present invention, there is provided a hydrogen generation method using a hydrogen generating agent for hydrogenating a liquid or moisture-containing material contained in a container. ) And (2). A hydrogen generation method is provided.
(1) The surface of the core material of the hydrogen generating agent, containing 1 to 40% by weight of magnesium as a hydrogen generating component with respect to the total amount, and having an average particle size within a range of 1 μm to 20 mm Step (2) of preparing a hydrogen generating agent provided with a moisture adjusting layer for controlling the amount of moisture that permeates the whole or a part of the liquid generating agent (2) The liquid generating agent or moisture contained in the container The step of bringing into contact with the contained material By carrying out in this way, a hydrogen generating agent that reacts quickly with moisture permeating from the outside and maintains good hydrogen generation characteristics and has little elution of alkali components and the like. It can be used to generate hydrogen stably and economically.

Further, in carrying out the hydrogen generation method of the present invention, in the step (1), at the time of providing the moisture adjusting layer, at least one resin of fluororesin, silicone resin, olefin resin, styrene resin, and epoxy resin is dissolved. It is preferable to use a non-aqueous solution.
By providing a moisture adjustment layer using a non-aqueous solution in this way, a moisture adjustment layer having a uniform thickness can be accurately and reliably applied to the surface of the hydrogen generating agent without generating hydrogen during production. Can be formed.
Therefore, it can be used as a hydrogen generating agent that reacts rapidly with moisture permeating from the outside and maintains good hydrogen generation characteristics, and has less elution of alkali components, etc., and as a result, is more stable and economical. Hydrogen can be generated.

FIGS. 1A to 1B are diagrams provided to explain each aspect of the hydrogen generating agent. FIGS. 2A to 2B are views for explaining the appearance and the cross section of the pouch-type container each containing a hydrogen generating agent. FIGS. 3A to 3B are views provided to explain various bottleneck containers each containing a hydrogen generating agent. FIGS. 4A to 4B are views for explaining a spray-type container provided with a nozzle containing a hydrogen generating agent. FIGS. 5A to 5B are diagrams for explaining the embodiment of the hydrogen generator with a substrate, and FIGS. 5C to 5D are diagrams for explaining the embodiment of the hydrogenated agent that has been packaged. is there. FIG. 6 is a diagram for explaining the influence of the presence or absence of a moisture adjustment layer in the hydrogen generating agent on the relationship between elapsed time (Hrs) and oxidation-reduction potential (mV). FIG. 7 is a diagram for explaining the influence of the presence or absence of a moisture adjustment layer in the hydrogen generating agent on the relationship between the elapsed time (Hrs) and the pH value. FIG. 8 is a diagram for explaining the influence of the presence or absence of a moisture adjustment layer in the hydrogen generating agent on the relationship between the elapsed time (Hrs) and the dissolved hydrogen concentration (ppb).

[First Embodiment]
In the first embodiment, as shown in FIGS. 1A to 1B, hydrogen generating agents 20 and 20 ′ for adding hydrogen to a liquid or moisture-containing material contained in a container. In addition, 1 to 40% by weight of magnesium is contained as a hydrogen generating component with respect to the total amount of the hydrogen generating agent 20 and 20 ′, and the average particle size of the hydrogen generating agent 20 and 20 ′ is 1 μm to 20 mm. And a moisture adjusting layer 12, 12 'for controlling the amount of moisture permeating from the outside is provided on all or part of the surface of the core material 10, 10' of the hydrogen generator. It is a hydrogen generating agent characterized by being.
In the first embodiment, a container that is a container before containing a liquid substance or moisture-containing substance inside the container and that contains a hydrogen generator is also broadly defined as a hydrogen generator. May be included.

1. Container (1) Basic configuration The basic configuration of the container 100 for storing the liquid or moisture-containing substance 116 or the hydrogen generating agent 20 is particularly limited as long as the liquid can be held for a predetermined time. However, for example, a pouch-type container, a bottleneck-type container, a spray-type container having a nozzle inside, a bag-shaped container, a pack-shaped container, a purse-shaped container, a cardboard box, and the like are also preferable.
More specifically, in the case of a pouch-type container 100 having a predetermined space 116 ′ as shown in FIGS. 2A to 2B, a liquid material (not shown) is subjected to hydrogen reduction in the predetermined space 116 ′. In addition, the hydrogen reduction effect can be exhibited quickly with respect to the liquid material, and good light weight and transportability can be obtained.
Therefore, with such a pouch-type container 100, hydrogen for a liquid material that is used in a relatively small amount at one time, for example, lotion, lotion, drinking water, eye wash water, pharmaceutical drinking water, medical water, etc. It can be said that the addition is more suitable.

In addition, a bottleneck-type container (including PET bottles, cylindrical canned containers, and various three-dimensional containers) 150 and 152 as shown in FIGS. The liquid substance 116 can be economically maintained for a considerably long period under hydrogen reduction.
More specifically, such bottleneck containers 150 and 152 are usually composed mainly of PET resin, metal material (aluminum, copper, iron, alloy), glass material, etc. Alternatively, it can be said that it is suitable for long-term storage of the water-containing material 116 and prevention of scattering of hydrogen, and further, an advantage that the container itself is excellent in reusability can be obtained.
Accordingly, as exemplified by the liquid or water-containing material 116 described later, not only water but also liquid including a predetermined solid, such as boiled vegetables, vegetables and fruits, etc. are also suitable objects. It becomes.

Furthermore, as shown to Fig.4 (a)-(b), the spray type type | mold containers 160 and 170 which have the nozzles 163 and 173 inside a container are mentioned.
More specifically, nozzles 163 and 173 for taking out the hydrogenated and reduced liquid substance 116 and spraying the liquid substance 116 are connected to the ejection parts 161 and 171 via the joint caps 164 and 174. Spray type containers 160 and 170 provided.
In the case of the spray type containers 160 and 170 having such nozzles 163 and 173, the operation of the levers 162 and 172 causes the liquid material 116 in a reduced state to be ejected from the ejection holes 161 and 171 provided at the upper end of the container. According to the above, it can be sprayed in a mist, mist, foam or the like and widely used as a reduced liquid material.

Further, the liquid or moisture-containing substance 116, the inner and outer surfaces of the containers 150, 160, and 170 containing the hydrogen generating agent, or the surface of the pouch-type container 100, for example, as shown in FIG. A predetermined gas barrier layer 122 is preferably provided on a surface that does not come into contact with a substance or a moisture-containing substance.
More specifically, as a measure of gas barrier properties, the water vapor transmission rate measured according to JIS K 7129 is preferably 10 g / (m ² · 24 Hrs) or less, and the water vapor transmission rate is 0.05 to 1 g / It is more preferable to form a gas barrier layer having a value within the range of (m ² · 24 Hrs).
This is because, by forming such a gas barrier layer, it is possible to effectively prevent hydrogen generated inside the predetermined container from being excessively scattered to the outside.
Therefore, the effect of the hydrogen generating agent can be maintained for a long time.
In addition, as an aspect of a gas barrier layer, the gas barrier film etc. which consist of various organic materials and an inorganic material are mentioned, For example, from the polysilazane-type material (perhydropolysilazane etc.) whose thickness is the value within the range of 50 nm-1 mm. It is more preferable to form an inorganic gas barrier layer.

(2) Liquid substance or moisture-containing substance The liquid substance or moisture-containing substance 116 contained in the container 100, 150, 152, 160, 170 contains moisture and serves as a hydrogen generating component contained in the hydrogen generating agent 20. There is no particular limitation as long as it generates hydrogen upon contact with metallic magnesium or the like.
Moreover, the water | moisture content contained in a liquid substance or a water | moisture content may evaporate, and it may generate | occur | produce in contact with the metal magnesium etc. as a hydrogen generating component contained in the hydrogen generating agent 20 as water vapor | steam.
Therefore, for example, water (tap water), purified water, washing water, alkaline ionized water, mineral-containing water, carbonated water, seawater, saline, lotion, cosmetic milk, hair restorer, hair nourishing agent, perfume, health drink, honey , Carbonated beverages, acetic acid (vinegar), juices, soups, syrups, soy sauce, vinegar, potatoes, coffee, teas, green tea, oolong tea, milk, alcohols, tofu, boiled food, sauce boiled food It is preferable that it is at least one of soy sauce boiled food, miso, instant product, rice, vegetable, fruit, meat, fish, seafood, confectionery and the like.
In particular, in the case of cosmetic liquids such as skin lotions, skin lotions, hair growth agents, hair nourishing agents, perfumes, etc., even if the amount of UV absorber or antioxidant is reduced as much as possible, contact with the hydrogen generator of the present invention In a reduced state, long-term storability can be obtained, so that it is a suitable liquid material.
Furthermore, rice, vegetables, fruits, meats, fish, marine products, and confectionery containing reduced moisture by being hydrogenated if they are water-containing products such as rice, vegetables, fruits, and confectionery Thus, it can also be provided as functional food or health promotion food.

The liquid material is preferably a thixotropic material having a so-called thixotropic property, which is a gel in a state where no shear force is applied, but becomes a liquid material having a predetermined viscosity when a predetermined shear force is applied.
This is because such a thixotropic material has extremely excellent hydrogen retention when hydrogenated.
For example, an oxidation-reduction potential (ORP) immediately after hydrogen addition has a value of about −800 mV, and the ORP retains a value of about −200 mV even after one week with the container opened. It has been confirmed.
Therefore, it can be said that it is preferable to use a thixotropic liquid material as the liquid material in applications requiring a considerably long-term hydrogen retention.
In order to impart thixotropy to a liquid material, usually about 0.05 to 10 parts by weight of a known thixotropic material or a thickener such as silica fine particles (Aerosil etc.) with respect to 100 parts by weight of the liquid material. ), At least one compound such as aloe extract, alginic acid, alginate and the like.

2. Hydrogen generator (1) type and blending amount Further, the type of hydrogen generating component in the hydrogen generator is not particularly limited. For example, metal magnesium and magnesium oxide, or any one of them as a main component, The blending amount of magnesium is set to a value in the range of 1 to 40% by weight with respect to the total amount of the hydrogen generating agent.
The reason for this is that by using such a compounded amount of a magnesium-based hydrogen generator, a predetermined amount of hydrogen can be generated quickly and over a predetermined period in contact with a liquid or water-containing material containing moisture. This is because it can.
More specifically, when the amount of magnesium is less than 1% by weight, it is difficult to generate hydrogen rapidly and continuously over a long period of time.
On the other hand, if the amount of magnesium exceeds 40% by weight, the hydrogen generating agent may be imaged in a predetermined shape, or the presence of magnesium may be uneven and hydrogen may be stably generated. This is because it becomes difficult.
Therefore, the blending amount of magnesium is more preferably set to a value within the range of 5 to 30% by weight, and further preferably set to a value within the range of 10 to 20% by weight with respect to the total amount of the hydrogen generating agent. preferable.

Then, at least one compound such as calcium, calcium sulfite, titanium oxide, zinc oxide, metal aluminum, alumina (aluminum oxide), or a hydrogen storage alloy is added to a part of the components of the hydrogen generator, It is also preferable to adjust the amount of hydrogen generated, the hydrogen generation time, and the like.
In particular, among these, metal aluminum and alumina are suitable combinations because they themselves can react with moisture and generate hydrogen under predetermined conditions.
In addition, when using together metal aluminum and alumina, it is preferable to set it as the value within the range of 1-800 weight part with respect to 100 weight part of hydrogen generating agents containing metal magnesium etc., and within the range of 10-400 weight part More preferably, the value is more preferably in the range of 30 to 100 parts by weight.

(2) Average particle diameter Moreover, it is preferable to make the average particle diameter of a hydrogen generating agent into the value within the range of 1 micrometer-20 mm.
The reason for this is that by controlling the average particle size of the hydrogen generating agent in this way, the handling and production of the hydrogen generating agent is facilitated, and the hydrogen generation amount per unit time, the hydrogen generating time, etc. are in the desired range. This is because the control can be performed with higher accuracy.
More specifically, when the average particle size of the hydrogen generating agent is less than 1 μm, the hydrogen generating agent tends to aggregate, and it may be difficult to handle and manufacture the hydrogen generating agent, or the hydrogen generation amount per unit time is excessive. This is because the hydrogen generation time may become excessively short.
On the other hand, when the average particle size of the hydrogen generating agent exceeds 20 mm, on the contrary, the handling and production of the hydrogen generating agent may be difficult, and further, the amount of hydrogen generated per unit time may be excessively reduced. Alternatively, the hydrogen generation time may become unnecessarily long.
Therefore, the average particle size of the hydrogen generating agent is more preferably set to a value within the range of 500 μm to 8 mm, and further preferably set to a value within the range of 1 mm to 5 mm.
The average particle size of the hydrogen generator can be measured with an optical microscope, an image processing system, or a caliper according to JIS Z8901.

Further, as shown in FIG. 3 (b), the hydrogen generating agent 20, 20 ″ is brought into contact with the liquid or moisture-containing substance 116 to initially generate a relatively large amount of hydrogen for a predetermined time. After the lapse of time, it is also preferable to use a mixture of hydrogen generating agents 20, 20 ″ having different average particle diameters so that hydrogen generation can be maintained for a longer time even with a relatively small amount.
More specifically, in the long term, the first hydrogen generating agent 20 having an average particle diameter of 1 to 20 mm for maintaining a predetermined amount of dissolved hydrogen in the liquid or water-containing material, and initially It is preferable to mix and use a second hydrogen generator 20 ″ having an average particle size of 1 μm to less than 1 mm for generating a relatively large amount of hydrogen.
Furthermore, depending on the intended use of the hydrogen generator, a third hydrogen generator having an average particle diameter of more than 20 mm and a fourth hydrogen generator having an average particle diameter of less than 1 μm, or either one may be further blended. preferable.
And when mixing and using the 1st hydrogen generating agent 20 mentioned above and the 2nd hydrogen generating agent 20 '', although it depends on the use application of a hydrogen generating agent, the 1st hydrogen generating agent 100 is usually used. The mixing ratio of the second hydrogen generating agent with respect to parts by weight is preferably a value within the range of 10 to 900 parts by weight, more preferably a value within the range of 30 to 500 parts by weight, More preferably, the mixing ratio of the second hydrogen generating agent is set to a value within the range of 50 to 200 parts by weight.

(3) Moisture adjustment layer (3) -1 type In the case of the hydrogen generating agent 20 in the first embodiment, as shown in FIGS. 1A to 1B, the surface of the core material 10 of the hydrogen generating agent. A moisture adjustment layer is provided in part or all of the above.
That is, the moisture adjustment layer is formed entirely or partially on the surface of the hydrogen generating agent core material, thereby adjusting the amount of moisture permeating from the outside and bringing it into contact with the liquid in the container. In this case, it reacts quickly, generates a predetermined amount of hydrogen, and effectively suppresses elution of alkali components such as magnesium and calcium into liquid or water-containing materials.

Here, the type of the coating material constituting the moisture adjustment layer is not particularly limited, but for example, at least one of a fluororesin, a silicone resin, an olefin resin, a styrene resin, an epoxy resin, or a ceramic material. Preferably there is.
The reason for this is that by using such a type of coating material, the moisture adjusting layer can be firmly laminated on the surface of the core material of the hydrogen generating agent, and while maintaining a predetermined hydrogen permeability, This is because the outflow of the alkali component can be effectively controlled.
In addition, by adding an inorganic material composed of a silazane compound, silica material, nitride, etc. in the moisture adjustment layer, the surface protection of the hydrogen generator can be improved and the UV resistance can be improved. In addition, the amount of hydrogen generated per unit time, the hydrogen generation time, and the like can be easily adjusted to a desired range, and such hydrogen generation can be sustained for a long period of time.

More specifically, if the coating material is a silicone resin or a ceramic material (polysilazane compound), the hydrogen permeability and water vapor permeability are good, and the curing characteristics and film-forming properties are excellent. , A preferred coating material.
In addition, if the coating material is a fluororesin, an olefin resin, or a styrene resin, the hydrogen permeability and water vapor permeability are good as it is, and especially the printing characteristics and durability, or the adhesion to various substrates. Since it is excellent, it is a suitable coating material (resin).
In addition, if it is a resin contained in these coating materials, it can be easily dissolved in a non-aqueous solvent such as limonene, a fluorocarbon compound, a halogen compound, toluene, an ester compound, etc., to form a uniform solution and easy to handle. Thus, the moisture adjusting layer can be easily formed by uniformly applying or laminating the surface of the core material of the hydrogen generating agent, or immersing the core material of the hydrogen generating agent.

(3) -2 Type 2
Furthermore, it is preferable to add a colorant (inorganic colorant and organic colorant) to the moisture adjusting layer 12 as shown in FIG.
This is because the core material itself of the hydrogen generating agent is usually rich in whiteness (whiteness (WL) measured in accordance with JIS L 0803: a value of 90 or more), which is preferable as a color sensation. However, by adding such a colorant, the appearance and distinguishability of the hydrogen generator can be enhanced.
For example, as a colorant (inorganic colorant), when cobalt oxide or the like is blended in the range of 0.01 to 10% by weight with respect to the total amount of the moisture adjustment layer, for example, a blue moisture adjustment layer is provided. A hydrogen generator can be obtained.
Then, since the hydrogen generating agent itself is conspicuous, the distinguishability is improved, the hydrogen generating agent is present at a predetermined position, and the state of the hydrogen generating agent can be easily recognized.
In addition, over time, the surface of the hydrogen generating agent including the moisture adjusting layer may be covered with an insoluble material. In such a case, since the coloring property of the hydrogen generating agent decreases, replacement time and cleaning The time can be easily recognized.

(3) -3 Type 3
Moreover, in the material (resin) which comprises the moisture adjustment layer 12 as shown to Fig.1 (a), a crosslinking agent is mix | blended or the self-crosslinking property which predetermined resin has is utilized, and a moisture adjustment layer is used. It is also preferable to introduce a crosslinked structure.
The reason for this is that a moisture adjustment layer having a stronger and better adhesion can be obtained by crosslinking the resin with a crosslinking agent, so that the hydrogen generation amount can be controlled within a predetermined range, This is because it can be easily formed firmly.
In addition, when mix | blending a crosslinking agent, it is preferable to mix | blend, for example in 0.01-10 weight% with respect to the whole quantity of resin which comprises a water | moisture-content adjustment layer.

(3) -4 Thickness As shown in FIG. 1A, the thickness (t) of the moisture adjustment layer 12 is preferably set to a value within the range of 0.1 μm to 2 mm.
This is because the amount of hydrogen generation per unit time, the hydrogen generation time, and the like can be more easily controlled within a desired range by controlling the thickness of the moisture adjustment layer in this way.
More specifically, when the thickness of the moisture adjustment layer is less than 1 μm, the amount of hydrogen generated per unit time may be excessively decreased, or the hydrogen generation time may be excessively shortened.
On the other hand, if the thickness of the moisture adjustment layer exceeds 2 mm, it may be difficult to form a uniform thickness or it may be difficult to adjust the hydrogen generation amount.
Therefore, the thickness of the moisture adjusting layer is more preferably set to a value within the range of 5 to 500 μm, and further preferably set to a value within the range of 10 to 200 μm.
The thickness of the moisture adjusting layer can be calculated from the difference from the diameter of the core material before forming the moisture adjusting layer by measuring with a caliper or the like, or a cross-sectional photograph (micrograph) of the hydrogen generating agent. ) Can also be actually measured.

(3) -5 Form In addition, the form of the moisture adjustment layer is preferably a complete coating layer, but is preferably a partial coating layer, a perforated layer, or a mesh layer.
For example, as shown in FIG. 1 (a), the thickness and type of the moisture adjusting layer 12 can be obtained by using the moisture adjusting layer 12 as a complete coating layer and having no exposed portion of the core material 10 of the hydrogen generator. By only changing the above, it is possible to easily adjust the hydrogen generation amount per unit time, the hydrogen generation time, and the like to a desired range.
Moreover, as shown in FIG.1 (b), by making moisture adjustment layer 12 'into the partial coating layer which a part of core material 10 of the hydrogen generating agent exposed, thickness and kind of moisture adjustment layer 12', Alternatively, by controlling the formation area, the hydrogen generation amount per unit time, the hydrogen generation time, and the like can be adjusted to values within a desired range.
In addition, although not shown, the exposed area of the core material of the hydrogen generating agent can be easily controlled by forming a perforated layer in which a plurality of holes are formed in a part of the complete coating layer as a form of the moisture adjustment layer. As a result, the hydrogen generation amount per unit time, the hydrogen generation time, etc. can be accurately adjusted to values within a desired range.
Furthermore, although not shown in the drawing, the moisture adjustment layer is formed as a mesh layer, thereby reducing the adhesion of the moisture adjustment layer even when the exposed area of the core material of the hydrogen generating agent is relatively large. As a result, the hydrogen generation amount per unit time, the hydrogen generation time, and the like can be accurately adjusted to values within a desired range.

(4) Additive In addition, in the moisture adjusting layer 12 of the hydrogen generator 20 or the core 10 of the hydrogen generator, as a water-soluble material or a hydrophobic material, phosphate glass, borosilicate glass, carbonate compound And at least one of sulfite compounds is preferably further blended.
The reason for this is that when a water-soluble material is blended, it gradually dissolves by contact with water, so that voids are generated inside the hydrogen generating agent and moisture easily permeates, and as a result, over a long period of time. This is because the hydrogen generation amount per unit time, the hydrogen generation time, and the like can be more easily controlled within a desired range.
On the other hand, when a hydrophobic material is blended, although the time until water contacts with magnesium is relatively long, as a result, hydrogen can be generated as a hydrogen generator over a long period of time. This is because it can.

Moreover, when mix | blending such a water-soluble material or hydrophobic material, it is preferable to make the compounding quantity into the value within the range of 1-100 weight part with respect to 100 weight part of constituent materials of a moisture adjustment layer. .
This is because the amount of hydrogen generation per unit time, hydrogen generation time, etc. can be more easily controlled within a desired range by using such water-soluble materials or hydrophobic materials. is there.
More specifically, when the blending amount of the water-soluble material or hydrophobic material is less than 1 part by weight, the amount of hydrogen generated per unit time may be excessively reduced or the hydrogen generation time may be excessively shortened. It is because there is a case to do.
On the other hand, when the blending amount of the water-soluble material or the hydrophobic material exceeds 100 parts by weight, it is difficult to uniformly disperse in the hydrogen generator or it is difficult to form the hydrogen generator to a uniform thickness. This is because the hydrogen generating agent may be easily peeled off from the container surface.
Therefore, the blending amount of the water-soluble material or the hydrophobic material is more preferably set to a value within the range of 10 to 80 parts by weight with respect to 100 parts by weight of the constituent material of the moisture adjusting layer. More preferably, the value is within the range.

Other additives other than water-soluble materials in the moisture adjusting layer of the hydrogen generator or the core of the hydrogen generator include binder components, colorants (inorganic colorants and organic colorants), fluorescent agents In addition, it is preferable that at least one of a brightening agent, an ultraviolet absorber, an antioxidant, an antistatic agent, an oxygen scavenger (iron oxide or ascorbic acid) is further blended.
The reason for this is that by adding such an additive, further functionality can be added to or improved with respect to the hydrogen generator.

(5) Fixing position and fixing method In addition, the hydrogen generating agent 20 is preferably unfixed so that it can move freely inside the container 100 and generate hydrogen uniformly. Is preferably fixed at a predetermined position in the container.
Here, the fixing position and fixing method of the hydrogen generating agent are not particularly limited, but the adhesive is usually applied to the inside of various containers, the inner wall of the container, or the surface of the nozzle disposed in the container. It is preferable to fix so that it cannot move freely using a fixing tool.
In other words, by fixing the hydrogen generating agent in such a place, in the case of a small container or the like, on the contrary, the opportunity to come into contact with the liquid or moisture content increases, while the fixing position is determined. This is because the hydrogen generating agent can be easily exchanged when the amount of hydrogen generation or the like decreases.

(6) Hydrogen generating agent with base material Further, the hydrogen generating agent 20 is fixed to various base materials 24 and 28, and as shown in FIGS. It is also preferable to adopt an embodiment.
The reason for this is that in the case of the hydrogen generator with a base material in which the hydrogen generator is fixedly arranged on the surface as the base material, the hydrogen generator is directly touched using a part of these base materials. This is because the hydrogen generating agent can be sufficiently and reliably brought into contact with the liquid or moisture-containing material contained in the container.
That is, if it is a hydrogen generator with a base material, the hydrogen generator can be disposed at an arbitrary position, and handling such as replacement becomes easy.

Here, as the substrate, a film substrate such as PET film or paper, a metal plate such as an aluminum plate or a copper plate, a glass rod such as a glass rod or a ceramic rod, a fiber member such as a woven fabric or a non-woven fabric, a rope or a thread, etc. And at least one stirring member such as a spoon or a spatula.
In particular, as shown in FIG. 5 (a), if the substrate 24 is a resin film such as a PET film, the hydrogen generating agent 20 can be uniformly embedded through the adhesive layer 22, etc. Furthermore, since the handle portion 24a can be easily formed, it is a suitable base material.
Further, as shown in FIG. 5B, if the base material 28 is a glass rod, the hydrogen generating agent 20 can be directly fixed and arranged on the surface using the adhesive 26. In addition, the one end 28a of the glass rod as the base material 28 can be grasped and a stirring contact with the liquid or moisture-containing material 116 can be attempted.

(7) Packaged hydrogen generator It is also preferable that the packaged hydrogen generator comprises a hydrogen generator and a coating material. The covering material includes at least one of a mesh material, a resin film, a metal film, a film with a gas barrier layer, a paper material, and a fiber material (including woven fabric and nonwoven fabric).
That is, even in the case of the packaged hydrogen generating agent, the moisture or water vapor of the liquid contained in the container, the moisture or water vapor of the moisture-containing material, and a covering material such as a mesh material or a resin film are used. And can be quickly hydrogenated.
As a result, the generated hydrogen dissolves in the liquid or water-containing material, and not only the long-term storage stability of the liquid or water-containing material is obtained, but also the reduced liquid material or A reduced water-containing material can be easily produced.

Here, a specific example of the packaged hydrogen generating agent will be described with reference to FIGS. 5 (c) to 5 (d).
The packaged hydrogen generating agent 20c shown in FIG. 5C is configured such that the periphery of the hydrogen generating agent 20 is covered with a bag-like mesh material 30 and can be handled as a unit. That is, this is a mode that takes into account the convenience of replacing the hydrogen generating agent 20.
FIG. 5D shows the usage state of the packaged hydrogen generating agent, and shows a pouch bag (polypropylene bag) 20d containing the packaged hydrogen generating agent. More specifically, the packaged hydrogen generating agent accommodated in the inside of the pouch bag 20d is surrounded by an olefin resin film around the hydrogen generating agent, and further, the periphery of the olefin resin film is embossed and laminated. It is formed in a stick shape as a whole.
In addition, as a suitable olefin resin film, a transparent film made of LLDPE, LDPE, HDPE, PP, TPX or the like having a thickness of 10 μm to 200 μm can be given.
That is, with such a hydrogen generating agent in use, hydrogen can be generated quickly and over a predetermined period by contacting moisture (water vapor) generated from a plurality of fruits through the covering material. As a result, the generated hydrogen is scattered through the covering material, and this time, the hydrogen is dissolved into the fruit and can be reduced.
Therefore, the hydrogen generator thus packaged in a predetermined container, for example, a pouch bag, can be used in combination with a water-containing material to obtain a reduced water content suitable as a functional food or a health food. Can be easily obtained.

(8) Heat treatment Further, in constituting the hydrogen generating agent, the core material of the hydrogen generating agent is preferably heat-treated (including a baking treatment) at a temperature of 180 ° C or higher.
As described above, the heat treatment at a predetermined temperature or higher is performed, so that the components constituting the hydrogen generating agent are more uniformly mixed and dispersed, and the hydrogen generating agent core material is maintained while maintaining good hydrogen generating characteristics. This is because the adhesion of the moisture adjustment layer to the surface of the film can be improved.
Conversely, when the heat treatment temperature is less than 180 ° C., the uniformity of each component constituting the hydrogen generating agent is insufficient, or the whole is not granular, or there are many low molecular weight substances. This is because it may remain and hydrogen generation may be significantly reduced.
Therefore, the heat treatment temperature is preferably set to a value within the range of 220 to 300 ° C, more preferably set to a value within the range of 230 to 290 ° C, and a value within the range of 250 to 280 ° C. Further preferred.
The heat treatment time depends on the heat treatment temperature, but is usually preferably a value within a range of 5 to 600 minutes, more preferably a value within a range of 10 to 300 minutes, More preferably, the value is within a range of ˜60 minutes.

3. Characteristic (1) Redox potential Next, with reference to FIG. 6, the change with time of the redox potential (mV) of the liquid material (water) contained in the container when contacted with the hydrogen generator will be described. .
That is, in FIG. 6, the elapsed time (Hrs) is logarithmically plotted on the horizontal axis, and the value (mV) of the oxidation-reduction potential (ORP) of the liquid material (water) is plotted on the vertical axis. The contact conditions such as the concentration of the hydrogen generating agent are in accordance with Example 6 described later.
Line A is a characteristic curve when the moisture adjusting layer is not provided on the surface of the hydrogen generating agent, that is, when only the core material of the hydrogen generating agent of the present invention is used as the hydrogen generating agent. Line B is a characteristic curve in the case where a moisture adjusting layer is provided on the surface of the hydrogen generating agent, that is, when a predetermined moisture adjusting layer is formed on the core material of the hydrogen generating agent of the present invention. is there.

As indicated by the line A in FIG. 6 (without the moisture adjustment layer), in the liquid material (water) that initially had an oxidation-reduction potential of about 580 mV, the hydrogen generator was replaced with hydrogen over time. Since a considerable amount of is generated, the value of the oxidation-reduction potential rapidly decreases, and after about 6 hours, a value of about -110 mV is obtained as the oxidation-reduction potential.
Next, after 12 hours, the oxidation-reduction potential becomes a value of about -220 mV, and thereafter, the oxidation-reduction potential decreases until 72 hours, and a value of about -440 mV is obtained.
Furthermore, as time passes, the value of the oxidation-reduction potential gradually increases. After 96 hours, about -400 mV, after 1176 hours, about -200 mV, after 3840 hours, A tendency to increase to a value of about −100 mV was observed.
That is, although a considerable amount of hydrogen generation from the hydrogen generating agent lasts for at least about 72 hours, after that, the amount of hydrogen generated decreases while the amount of hydrogen scattered outside from the liquid (water) increases. Thus, it is estimated that such a characteristic curve was obtained.

On the other hand, as shown by the line B (with the moisture adjustment layer) in FIG. 6, the liquid material (water) that initially had an oxidation-reduction potential of about 580 mV is converted into a considerable amount of hydrogen from the hydrogen generator. As the time elapses, the value of the oxidation-reduction potential rapidly decreases with the passage of time, and after about 6 hours, a value of about −130 mV is obtained.
Subsequently, after 12 hours, the oxidation-reduction potential becomes a value of about -240 mV, and thereafter, the value of the oxidation-reduction potential decreases, and after 72 hours, a value of about -380 mV is obtained.
Furthermore, as time passes, the value of the oxidation-reduction potential gradually increases. After 96 hours, about -360 mV, after 1176 hours, about -180 mV, after 3840 hours, A tendency to increase to a value of about −100 mV was observed.
That is, in line B (with a moisture adjusting layer), a considerable amount of hydrogen generation from the hydrogen generating agent continues for at least about 72 hours, but thereafter the amount of hydrogen generation decreases, while liquid (water ) To the outside, it is estimated that the characteristic curve has a tendency to increase the oxidation-reduction potential.
Therefore, since there is almost no significant difference between the line A and the line B, that is, no significant difference regarding the redox potential in the liquid material based on the presence or absence of the moisture adjustment layer was observed. In other words, it is understood that both the hydrogen generator and the liquid or moisture-containing substance are in contact with each other and react quickly to generate hydrogen, so even if a moisture adjustment layer is provided, It can be said that the good hydrogen generating property in the hydrogen generating agent is maintained as it is.

(2) pH Value Next, with reference to FIG. 7, the change with time of the pH value of the liquid material contained in the container when the hydrogen generator is brought into contact will be described.
That is, in FIG. 7, the elapsed time (Hrs) is logarithmically plotted on the horizontal axis, and the pH value (−) of the liquid material (water) is plotted on the vertical axis. The contact conditions such as the concentration of the hydrogen generating agent are in accordance with Example 6 described later.
Line A is a characteristic curve when the moisture adjusting layer is not provided on the surface of the hydrogen generating agent, that is, when only the core material of the hydrogen generating agent of the present invention is used as the hydrogen generating agent.
Line B is a characteristic curve in the case where a moisture adjusting layer is provided on the surface of the hydrogen generating agent, that is, when a predetermined moisture adjusting layer is formed on the core material of the hydrogen generating agent of the present invention. is there.

As indicated by the line A in FIG. 7 (without the water adjustment layer), in the liquid material (water) having an initial pH of about 8, the pH value gradually increases with the passage of time, and 6 hours have passed. Later, a value of about 8.3 is obtained, and a value of about 8.6 is obtained after 12 hours.
Next, a pH value of about 8.8 is obtained after 24 hours, and a pH value of about 9.0 is obtained after 48 hours.
Furthermore, even if the time elapses, the pH value continues to increase. After 96 hours, about 9.3, after about 1176 hours, about 10.0, after about 3840 hours, about 10.5. There was a tendency to increase up to the value of.
That is, it is presumed that such a characteristic curve is obtained by increasing the elution of the alkali component from the hydrogen generating agent while corresponding to the hydrogen generation.
However, as described above, after 96 hours, the amount of hydrogen generated from the hydrogen generating agent is estimated to have decreased, but the pH value has increased as it is. It is presumed that there are parts corresponding to other phenomena.

On the other hand, as indicated by the line B (with water adjustment layer) in FIG. 7, in the liquid material (water) whose pH is about 8 initially, the pH value gradually increases with the elapsed time, and 6 hours have elapsed. Later, a value of about 8.2 is obtained, and a value of about 8.3 is obtained after 12 hours.
Then, after 24 hours, the pH value is about 8.5, and after 48 hours, the pH value is about 8.7, and after about 96 hours, the value is about 8.8.
However, even after 1176 hours, the pH value was about 9.5, and after 3840 hours, the value was about 9.8, and the degree of increase was low.
That is, in line B (with a moisture adjustment layer), the pH value increases with time, but clearly the degree of increase is lower than line A, and the increased pH value also tends to be low. It was observed.
Therefore, it can be said that by providing the moisture adjusting layer, the elution of the alkaline component from the hydrogen generating agent is effectively suppressed.

(3) Dissolved Hydrogen Concentration Next, with reference to FIG. 8, the change with time of the dissolved hydrogen concentration of the liquid contained in the container when brought into contact with the hydrogen generator will be described.
In FIG. 8, the elapsed time (Hrs) is logarithmically plotted on the horizontal axis, and the dissolved hydrogen concentration (ppb) of the liquid material (water) is plotted on the vertical axis. The contact conditions such as the concentration of the hydrogen generating agent are in accordance with Example 6 described later.
Line A is a characteristic curve when the moisture adjusting layer is not provided on the surface of the hydrogen generating agent, that is, when only the core material of the hydrogen generating agent of the present invention is used as the hydrogen generating agent. Line B is a characteristic curve in the case where a moisture adjusting layer is provided on the surface of the hydrogen generating agent, that is, when a predetermined moisture adjusting layer is formed on the core material of the hydrogen generating agent of the present invention. is there.

As indicated by the line A in FIG. 8 (without the water adjustment layer), initially, in the liquid material (water) having a dissolved hydrogen concentration of 0 ppb, hydrogen is generated from the hydrogen generating agent over time, Along with this, the value of the dissolved hydrogen concentration suddenly increases, and after about 6 hours, a value of about 50 ppb is obtained, and after about 12 hours, a value of about 230 ppb is obtained.
Next, after 24 hours, the dissolved hydrogen concentration significantly increased to a value of about 350 ppb, but after that, the dissolved hydrogen concentration gradually decreased, and after 48 hours, about 340 ppb, after 72 hours. Is about 330 ppb, and after about 96 hours, a value of about 320 ppb is obtained.
Further, as time elapses, the dissolved hydrogen concentration rapidly decreases, and after about 1176 hours, about 280 ppb and after about 3840 hours, values of about 60 ppb are obtained.
That is, the dissolved hydrogen concentration increases rapidly until a predetermined time, but thereafter, the dissolved hydrogen concentration gradually decreases, and when the predetermined time elapses, the dissolved hydrogen concentration tends to decrease rapidly. It is estimated that

On the other hand, for the line B (with water adjustment layer) in FIG. 8, the dissolved hydrogen concentration suddenly increases with the generation of hydrogen in the liquid material (water) having a dissolved hydrogen concentration of 0 ppb, A value of about 370 ppb is obtained after 24 hours.
However, after that, the dissolved hydrogen concentration gradually decreased with the lapse of time, and when the predetermined time elapsed, the dissolved hydrogen concentration tended to decrease rapidly.
Therefore, since there is almost no significant difference between the line A and the line B, that is, there is no significant difference regarding the dissolved hydrogen concentration based on the presence or absence of the moisture adjustment layer. It is understood that the liquid material comes into contact and reacts quickly to generate hydrogen.
From this, it can be said that even if the moisture adjusting layer is provided, the good hydrogen generating property of the hydrogen generating agent is maintained as it is.

[Second Embodiment]
The second embodiment is a hydrogen generation method using a hydrogen generating agent for adding hydrogen to a liquid or moisture-containing material contained in a container, and includes the following steps (1) and (2 The hydrogen generation method is characterized by comprising:
(1) The surface of the core material of the hydrogen generating agent, containing 1 to 40% by weight of magnesium as a hydrogen generating component with respect to the total amount, and having an average particle size within a range of 1 μm to 20 mm Step (2) of preparing a hydrogen generating agent provided with a moisture adjusting layer for controlling the amount of moisture that permeates the whole or a part of the liquid generating agent (2) The liquid generating agent or moisture contained in the container The process of contacting the contents

1. Hydrogen Generating Agent Preparation Step The hydrogen generating agent preparation step is a step of manufacturing the hydrogen generating agents 20, 20 ′ as shown in FIGS.
Here, since the aspect of the hydrogen generating agent can be the same as that described in the first embodiment, the description thereof will be omitted.

2. Step of contacting the hydrogen generating agent with the liquid or water-containing material Next, the step of contacting the hydrogen generating agent 20 with the liquid or water-containing material 116 places the liquid or water-containing material 116 inside the container 100. In the accommodated state, the hydrogen generating agent 20 is further accommodated and brought into contact with the liquid or moisture-containing substance 116 to generate predetermined hydrogen.
More specifically, it is usually from the surface of the hydrogen generating agent only by bringing the liquid or moisture-containing material contained in the container into contact with the hydrogen generating agent under a temperature condition of 15 to 40 ° C. A predetermined amount of hydrogen can be rapidly generated.
In that case, the liquid or moisture-containing material does not necessarily have to be stationary in the container, and the liquid or moisture-containing material is in a state of being stirred and the liquid or moisture-containing material is flowing. May be.
Then, whether or not a predetermined amount of hydrogen is generated by contact with the hydrogen generating agent can be confirmed by visual observation as the appearance of bubbles or the like, but as described later, in the liquid or moisture-containing material It can be confirmed with quantitativeness by measuring a change in oxidation-reduction potential or by measuring a change in dissolved hydrogen concentration.
In addition, if an ultrasonic vibration device or the like is provided in a part of or around the container for storing the hydrogen generating agent, the liquid or water-containing material and the hydrogen generating agent are included in the contact process with the hydrogen generating agent. This is a more preferable embodiment because it can contact more uniformly and generate a predetermined amount of hydrogen quickly and quantitatively.

3. Maintenance Step The maintenance step is a step of storing the liquid or moisture-containing material 116 and the hydrogen generating agent 20 in the container 100 as they are in contact with each other.
That is, if the dissolved hydrogen concentration or oxidation-reduction potential of the liquid or water-containing material contained in the container becomes constant, if left as it is, at least 3 as shown in FIGS. It has been found that months maintain a value equal to or higher than a predetermined value as the dissolved hydrogen concentration and redox potential.
Therefore, according to the hydrogen generating agent of the present invention, the dissolved hydrogen concentration and the oxidation-reduction potential are values within a desired range, depending on the concentration of the hydrogen generating agent and the type of liquid or moisture content, or environmental conditions. Can be maintained for several months.

[Example 1]
1. Preparation of hydrogen generator and liquid or water-containing material As a forming material of the container 100 shown in FIG. 2A, a PET layer (thickness 20 μm) in which an aluminum foil having a thickness of 9 μm is laminated via an adhesive A rectangular sheet base material 100a, 100b (vertical x horizontal: 11 cm x 6 cm) comprising an adhesive layer (thickness 50 μm) made of LLDPE and an olefin film (thickness 30 μm) as a heat seal material Two sheets were prepared by cutting out from the sheet.
On the other hand, in producing the hydrogen generating agent 20 shown in FIG. 1 (a), first, in a predetermined mixing container, a granulating core 14 and metallic magnesium 16 having an average particle diameter of 30 μm as a hydrogen generating component, 5 g (mixing amount: 5% by weight) and 20 g of calcium sulfite as a binder are stored, granulated mechanochemically with mixing and stirring, and heated at 280 ° C. for 30 minutes. (Baking) to obtain a hydrogen generating core material 10 having an average particle diameter of 5 mm.
Next, a limonene resin solution (solid content: 20% by weight) in which a styrene resin was dissolved for forming the moisture adjusting layer 12 on the surface of the core material 10 of the hydrogen generator was prepared.
Then, the limonene resin solution is spray-applied to the entire surface of the core material 10 of the hydrogen generator, and a moisture adjustment layer (type 1 in Table 1) 12 made of styrene resin is formed so that the thickness after drying becomes 20 μm. Then, it was heated and dried to obtain a hydrogen generator 20 having a moisture adjusting layer 12 as a complete film.

And as shown in FIG.2 (b), two sheet base materials 100a and 100b were heat-sealed, aligning so that a heat seal material might be in the facing state.
That is, in the first stage, using a heat sealing apparatus equipped with a flat plate-like heat plate, the two sheet base materials are sandwiched, and the width is 6 mm, and the two sides in the vertical direction and the horizontal direction are arranged. One side was heat-sealed to obtain a pouch-type container.
Next, the prepared pouch-shaped container contains one prepared hydrogen generator and 10 ml of water (containing no UV absorber or antioxidant) in the vertical direction as a non-sealed part. It was accommodated in the space inside the container from the one side.
Next, one side in the horizontal direction that remained without being sealed was immediately heat-sealed using a heat-sealing device equipped with a flat plate-like heat plate.
Finally, after changing the flat heat plate to an embossed heat plate, the outer periphery of the four sides was heat-sealed so as to have a width of 3 mm using a heat seal device.
In this way, a plurality of pouch-type containers (indicated in Table 1 simply as pouch-type containers) containing water and a hydrogen generating agent were prepared and subjected to a constant temperature and humidity condition of 25 ° C. and 50% RH. While keeping, it was subjected to the following evaluation.

2. Evaluation of hydrogen generator (1) Measurement of redox potential (ORP) (Evaluation 1)
The pouch-type container was opened, and hydrogen was generated from the hydrogen generator in the contained water. Then, the oxidation-reduction potential (ORP) after the lapse of 24 hours was measured using an ORP meter Lutron PH-280 (manufactured by Toa Denpa Kogyo Co., Ltd.). Evaluated.
A: −200 mV or less ○: −100 mv or less Δ: −10 mv or less ×: over −10 mv

(2) Measurement of dissolved hydrogen concentration (Evaluation 2)
The pouch-type container was opened, and hydrogen was generated from the hydrogen generator in the contained water. Then, the dissolved hydrogen concentration after the lapse of 24 hours was measured using a dissolved hydrogen meter KM210ODU (manufactured by Kyoei Denshi Co., Ltd.), and hydrogen generation was evaluated from the value according to the following criteria.
◎: 200 ppb or more ○: 150 ppb or more Δ: 50 ppb or more ×: less than 50 ppb

(3) Measurement of pH value (Evaluation 3)
The pouch-type container was opened, and hydrogen was generated from the hydrogen generator in the contained water. Then, the pH value after the lapse of 24 hours was measured using a commercially available pH meter, and then the alkaline component elution prevention property was evaluated according to the following criteria.
A: The pH is a value of 8.3 or less.
○: pH is a value of 8.5 or less.
Δ: pH is a value of 8.8 or less.
X: pH is a value exceeding 8.8.

[Example 2]
In Example 2, the average particle diameter of metallic magnesium as a hydrogen generating component in the hydrogen generating agent is 30 μm, the blending amount of the metallic magnesium is 2.5% by weight, and the average particle diameter of the hydrogen generating agent is 8 mm. A hydrogen generator was produced in the same manner as in Example 1, and the oxidation-reduction potential and the like were evaluated. The obtained results are shown in Table 1.

[Example 3]
In Example 3, the average particle diameter of metallic magnesium as a hydrogen generating component in the hydrogen generating agent is 30 μm, the blending amount of the metallic magnesium is 7.5% by weight, and the average particle diameter of the hydrogen generating agent is 0.1%. A hydrogen generator was produced in the same manner as in Example 1 except that the thickness was 5 mm, and its oxidation-reduction potential and the like were evaluated. The obtained results are shown in Table 1.

[Example 4]
In Example 4, the average particle diameter of metallic magnesium as a hydrogen generating component in the hydrogen generating agent was 15 μm, the blending amount of the metallic magnesium was 10% by weight, and the average particle diameter of the hydrogen generating agent was 1 mm. Produced a hydrogen generating agent in the same manner as in Example 1 and evaluated its oxidation-reduction potential and the like. The obtained results are shown in Table 1.

[Example 5]
In Example 5, the average particle diameter of metallic magnesium as a hydrogen generating component in the hydrogen generating agent was 25 μm, the blending amount of the metallic magnesium was 20% by weight, and the average particle diameter of the hydrogen generating agent was 3 mm. Produced a hydrogen generating agent in the same manner as in Example 1 and evaluated its oxidation-reduction potential and the like. The obtained results are shown in Table 1.

[Examples 6 to 8]
In Examples 6 to 8, a predetermined container is a PET bottle (capacity is a bottleneck type from a pouch-type container, and an inorganic gas barrier film (thickness 1 μm) made of a polysilazane material is formed on the outer surface. : 500 ml, liquid (water): 500 ml), and the compounding amount of metal magnesium as a hydrogen generating component in the hydrogen generating agent is 5.0 wt%, 2.5 wt%, 20.0 wt%, respectively. A hydrogen generator (average particle size: 5 mm, 10) was produced in the same manner as in Example 1, and the oxidation-reduction potential of the liquid material was evaluated using the hydrogen generator. The obtained results are shown in Table 1.

[Comparative Example 1]
In Comparative Example 1, the oxidation-reduction potential in the liquid material was evaluated in the same manner as in Example 1 except that the blending amount of the hydrogen generator was 0% by weight, that is, no hydrogen generator was blended. The obtained results are shown in Table 1.

[Comparative Example 2]
In Comparative Example 2, the predetermined container is a PET bottle (capacity: 500 ml) that is a pouch-type container, is a bottleneck type, and has an inorganic gas barrier film (thickness 1 μm) made of a polysilazane material on the outer surface. Liquid substance (water): 500 ml), and only the hydrogen generating agent core material of Example 1 (average particle size: 5 mm, 10) was used as the hydrogen generating agent having no moisture adjusting layer. In the same manner as in Example 1, the redox property of the liquid material was evaluated. The obtained results are shown in Table 1.
In addition, since the hydrogen generating agent which does not have a water | moisture-content adjustment layer was used, the phenomenon that a white thing adheres to the inner surface of a PET bottle and the whole PET bottle turns white after 24 hours etc. was seen.

[Comparative Example 3]
In Comparative Example 3, as the hydrogen generator having no moisture adjusting layer, only the core material of the hydrogen generator of Example 2 (average particle size: 5 mm, 1 piece) was used. The oxidation-reduction potential of the liquid material was evaluated. The obtained results are shown in Table 1.

[Examples 9 to 16]
In Examples 9 to 13, the resin that constitutes the moisture adjustment layer of the hydrogen generator is changed from styrene resin to fluororesin, and in Examples 14 to 16, the resin that constitutes the moisture adjustment layer of the hydrogen generator is changed to While changing from styrene resin to fluororesin, the thickness of the moisture adjustment layer (types 2 and 3 in Table 1) made of each resin is 50 μm, and the hydrogen generator (average particle diameter) has a moisture adjustment layer consisting of a complete coating. : 0.5-8 mm).
And in Examples 9-16, the oxidation-reduction property of a liquid substance (water) was evaluated using the hydrogen generating agent which has a water | moisture-content adjustment layer similarly to Examples 1-8. The obtained results are shown in Table 2.

[Examples 17 to 18]
In Examples 17 to 18, the PET bottle has thixotropic properties obtained by blending an aloe extract (concentration of 5% by weight) with respect to the total amount of liquid (100% by weight). A hydrogen generator having a moisture adjusting layer, as in Examples 15 and 16, except that water and thixotropic water (Aerosil 200 concentration: 0.1% by weight) formed by blending dry silica were accommodated. Was used to evaluate the redox property of the thickened liquid. The obtained results are shown in Table 2.

According to the hydrogen generating agent of the present invention and the hydrogenation method using the same, by providing a predetermined moisture adjusting layer or the like on the surface of the core material of the hydrogen generating agent, the liquid material or the water-containing material in the container is provided. In the case of contact, a predetermined amount of hydrogen can be rapidly generated, and elution of alkali components such as magnesium and calcium can be effectively suppressed.
Therefore, even if the amount of UV absorbers and antioxidants is reduced as much as possible in liquids such as lotions, etc., due to the action of dissolved hydrogen in the liquids, a good antioxidant effect It was confirmed that can be demonstrated.
On the other hand, as a liquid substance, even when foods boiled in water or soy sauce are stored, since it is maintained in a reducing atmosphere for a long period of time, it does not rot but stays fresh for a long period of time, for example, It was confirmed that it could be retained for at least 3 months.
Furthermore, in a given container, for example, a cardboard box with a plastic bag, it can be stored in a fresh state for a long period of time just by coexisting a packaged hydrogen generator and fruits and vegetables for a long time, and in a reduced state. It has been found that fruits and vegetables can be easily obtained and can be provided as new functional foods and health foods.

10: hydrogen generator core material, 12: moisture adjusting layer, 14: granulation core, 16: magnesium (magnesium magnesium or magnesium oxide), 20, 20a, 20b: hydrogen generator, 20c: packaged hydrogen Generator: 20d: Pouch bag containing packaged hydrogen generator, 22: Adhesive layer, 24: Substrate (PET film), 24a: Handle, 26: Adhesive, 28: Substrate (glass rod), 28a: handle, 30: mesh, 100, 150, 152, 160, 170: container 100a, 100b: raw material sheet, 112: heat seal part (first heat seal part), 112 ': boundary line (first boundary) Line), 114: heat seal part (second heat seal part), 114 ′: boundary line (second boundary line), 116: liquid substance or moisture-containing substance, 116 ′: predetermined space, 12 : Gas barrier layer, 161, 171: injection holes, 162 and 172: Lever, 163 and 173: nozzle, 164, 174: joint cap, 165, 175: bottle container main body, 175: gas barrier layer

Claims (8)

A hydrogen generator for hydrogenating liquid or moisture contained in a container,
While containing 1 to 40% by weight of magnesium as a hydrogen generating component with respect to the total amount,
The average particle size of the hydrogen generator is a value in the range of 1 μm to 20 mm,
In addition, a moisture adjustment layer for controlling the amount of moisture that permeates is provided on all or part of the surface of the core material of the hydrogen generator,
A hydrogen generator characterized by   2. The hydrogen generator according to claim 1, wherein a main component of the moisture adjustment layer is at least one of a fluororesin, a silicone resin, an olefin resin, a styrene resin, an epoxy resin, or a ceramic material.   The hydrogen generating agent according to claim 1 or 2, wherein the thickness of the moisture adjusting layer is set to a value within a range of 0.1 µm to 2 mm.   The hydrogen generating agent according to any one of claims 1 to 3, wherein the core material of the hydrogen generating agent is heat-treated at a temperature of 180 ° C or higher.   The hydrogen generator according to any one of claims 1 to 4, wherein the hydrogen generator is fixedly disposed on a substrate. A packaged hydrogen generator comprising the hydrogen generator and a coating material,
A packaged hydrogen generator, wherein the covering material is at least one of a mesh material, a resin film, a metal film, a film with a gas barrier layer, a paper material, and a fiber material. A hydrogen generation method using a hydrogen generating agent for adding hydrogen to a liquid or water-containing material contained in a container, comprising the following steps (1) and (2): Hydrogen generation method.
(1) The surface of the core material of the hydrogen generating agent, containing 1 to 40% by weight of magnesium as a hydrogen generating component with respect to the total amount, and having an average particle size within a range of 1 μm to 20 mm Step (2) of preparing a hydrogen generating agent provided with a moisture adjusting layer for controlling the amount of permeated moisture on all or a part of the liquid (2) A liquid material containing the hydrogen generating agent in the container Or the step of contacting with moisture   In the step (1), when the moisture adjustment layer is provided, a non-aqueous solution in which at least one of a fluororesin, a silicone resin, an olefin resin, a styrene resin, and an epoxy resin is dissolved is used. Item 8. The method for generating hydrogen according to Item 7.

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