JP2023064370A - Hydrogen generating material and manufacturing method thereof - Google Patents

Abstract

To provide a hydrogen generating material capable of supplying more hydrogen even in applications where the usage time is short.SOLUTION: A hydrogen generating material is characterized by containing a hydrogen generator that generates molecular hydrogen by reacting with water and containing a water-absorbing resin.SELECTED DRAWING: None

Description

The present invention relates to novel hydrogen generating materials. More specifically, it relates to materials that generate hydrogen when in contact with water or liquids containing water.

In recent years, it has become clear that various beneficial effects can be obtained on the human body when hydrogen gas or water or liquid containing hydrogen is applied to the human body. For this reason, various proposals have been made for materials that generate hydrogen, products in which hydrogen is sealed, and the like.

For example, a material that generates hydrogen upon contact with water, comprising: (1) a) hydrogen-generating particles capable of reacting with water to generate hydrogen, b) a coating resin, and c) a matrix resin, (2) A hydrogen generating material is known in which at least the surfaces of hydrogen generating particles protruding from the surface of the material are covered with a coating layer containing a coating resin (Patent Document 1).

JP 2019-182699 A

However, with hydrogen generating materials such as those of the prior art, the rate of hydrogen generation is slow, and it is difficult to supply a sufficient amount of hydrogen in a short period of time. Therefore, such hydrogen generating materials are not suitable for short duration applications, for example.

SUMMARY OF THE INVENTION Accordingly, it is a primary object of the present invention to provide a hydrogen generating material capable of supplying a large amount of hydrogen even when used for a short period of time.

As a result of intensive research in view of the problems of the prior art, the inventors have found that a material having a specific structure can achieve the above objects, and have completed the present invention.

That is, the present invention relates to the following hydrogen generating material.
1. A hydrogen generating material comprising: a hydrogen generating agent that reacts with water to generate molecular hydrogen; and a water absorbent resin.
2. 2. The hydrogen generating material according to item 1, wherein the hydrogen generating agent is at least one of metal and metal hydride.
3. 3. The hydrogen generating material according to item 1 or 2, wherein the hydrogen generating agent is particulate, and the particles have a volume average particle diameter of 1 to 100 μm.
4. 4. The hydrogen generating material according to any one of items 1 to 3, wherein the water-absorbent resin contains a polyalkylene oxide resin.
5. 5. The hydrogen generating material according to any one of items 1 to 4, wherein the water absorbent resin further contains at least one of polyolefin resin and styrene resin.

ADVANTAGE OF THE INVENTION According to this invention, the hydrogen-producing material which can supply more hydrogen can be provided even in the use for a short time. In particular, in the present invention, since the water-absorbing resin is used as a so-called support for the hydrogen generating agent, the opportunity (frequency) for the hydrogen generating agent to come into contact with water in the material of the present invention increases, thereby effectively releasing hydrogen. can be generated.

The hydrogen generating material of the present invention (the material of the present invention) is characterized by containing a hydrogen generating agent that reacts with water to generate molecular hydrogen, and a water absorbent resin. Therefore, the material of the present invention is basically composed of a hydrogen generating agent and a water-absorbent resin, but may contain other components (resin components, additives, etc.) within a range that does not interfere with the effects of the present invention. Also good.

The hydrogen generating agent is not limited as long as it is a substance that reacts with water to supply molecular hydrogen, and in particular at least one of metals and metal hydrides (metal hydrides) can be preferably used. Here, the above water includes water (H ₂ O) (pure water, tap water, etc.) as a single liquid, water contained in a composition containing water (aqueous solution or water dispersion), water vapor, etc. Either one may be used.

Examples of the metal include at least one selected from the group consisting of elemental metals such as magnesium and aluminum and alloys containing them.

Examples of metal hydrides include magnesium hydride, calcium hydride, barium hydride, beryllium hydride, strontium hydride, lithium hydride, sodium hydride, sodium borohydride, sodium lithium hydride, silicon hydride, hydrogen aluminum chloride and the like. These can be used singly or in combination of two or more.

Although the form of the hydrogen generating agent is not particularly limited, it is usually preferably in the form of powder. The average particle diameter of the particles constituting the powder in this case is not particularly limited, but, for example, a volume average particle diameter of 1 to 100 μm is preferable. Therefore, particles having a volume average particle diameter of 10 to 50 μm, for example, can also be preferably used. When the volume average particle size is less than 1 μm, the particles tend to agglomerate, and the dispersibility in the water-absorbing resin may deteriorate. Moreover, when the average particle diameter exceeds 100 μm, the weight of the particles may affect the deterioration of the dispersibility in the resin. Here, the volume average particle size is a value obtained by calculating the average particle size D50 (50% particle size) from the results of the volume cumulative particle size distribution of the particle group measured by the laser diffraction method.

In addition, the particles may be composed of only the above metal or metal hydride, but as long as the effects of the present invention are not hindered, for example, the particles may be in the form of granules kneaded with a resin, or the surfaces of the particles may be It may be in the form of composite particles coated with resin or the like.

The content of the hydrogen generating agent in the material of the present invention can be appropriately set according to the desired hydrogen generation amount and the like, and can be, for example, about 0.1 to 10% by weight in the material of the present invention. Not limited. By setting it within this range, the dispersibility of the hydrogen generating agent becomes higher, and a higher hydrogen generation rate can be obtained.

The water-absorbent resin functions particularly as a support for the hydrogen generating agent and has a function of promoting contact with water. Therefore, the water-absorbent resin can function as a support or the like by encapsulating the hydrogen-generating agent or by dispersing the hydrogen-generating agent in the water-absorbent resin.

The water-absorbing resin is not particularly limited as long as it is a resin material that claims water-absorbing properties. For example, acrylic acid-vinyl alcohol copolymer, polyalkylene oxide resin, polyethylene oxide resin, polyvinyl alcohol resin, etc. Seeds can be suitably used as the water absorbent resin (the water absorbent resin of the present invention). Among these, polyalkylene oxide-based resins (eg, modified polyalkylene oxide) are more preferable because they are easy to handle during compounding and can impart water absorption performance to the base resin with a relatively small amount.

In the present invention, the water-absorbent resin means that the absorbent resin (granular or sheet-like) sufficiently dried in a desiccator is immersed in a sufficient amount of pure water (23 ° C.) and taken out after 24 hours. The weight (water absorption) when wiped off is defined as an increase of 0.2% or more from the weight of the original absorbent resin.

The content of the water-absorbing resin in the material of the present invention can be appropriately set according to, for example, the type of hydrogen generating agent used, the desired amount of hydrogen generation, and the like. Therefore, it can be set within a range of, for example, about 20 to 99.9% by weight (furthermore, about 30 to 95% by weight), but is not limited to this.

In the material of the present invention, for the purpose of mainly controlling the water absorption rate, strength, and improving workability, for example, styrene resin, polyester resin (polyethylene terephthalate, etc.) , polyolefin resins (polyethylene, polypropylene, etc.), and at least one resin such as polyethylene glycol may be used in combination as appropriate. The blending amount of these resins can be, for example, about 30 to 80% by weight in the material of the present invention, but is not limited to this.

Moreover, in the present invention, a water-absorbing agent such as starch or cellulose can be used in combination, if necessary. For example, it is also possible to use a resin composition whose water absorbency is increased by adding it to a resin having relatively low water absorbency (for example, polyolefin resin such as polyethylene and polypropylene, styrene resin, etc.). The amount of the water-absorbing agent added in this case is not particularly limited, but it can usually be about 5 to 50 parts by weight per 100 parts by weight of the resin.

The form of the material of the present invention is not particularly limited as long as the effects of the present invention are not impaired, and may be, for example, a powder (granule), a compact, or the like.

The method for producing the material of the present invention is not particularly limited, and can be appropriately selected according to, for example, the desired form, the type of raw material to be used, and the like.

In general, a method including a step of adding a hydrogen generating agent to a resin component containing a water absorbent resin may be employed. As for the method of addition, various devices such as known or commercially available mixers and kneaders may be used.

The method of adding the hydrogen generating agent is not particularly limited. etc.) dissolved in a solvent or a method of dispersing the hydrogen generating agent in a dispersion liquid dispersed in a solvent.

After mixing, it can be molded into a desired shape, if necessary. For example, known molding methods such as press molding and extrusion molding can be employed.

For example, the material of the present invention can be provided as a sheet-like molding. When the material of the present invention is in the form of a sheet, its thickness is not limited, but if it is in the range of 0.1 to 10 mm, for example, hydrogen can be efficiently supplied to the hydrogen supply destination without excess or deficiency.

In the present invention material, generally, the larger the amount of the hydrogen generating agent contained, the more the amount of the hydrogen generating agent exposed to the surface, and the easier it is to react with water. From this point of view, as described above, the content of the hydrogen generating agent can be, for example, about 0.1 to 10% by weight.

In addition, on one or both sides of this sheet-like molded body, for example, one or more selected from the group consisting of paper, metal cans, metal plates, metal foils, metal deposition films, nonwoven fabrics, cloths, and resins It is also possible to adopt a form of a laminate in which layers are laminated.

Further, the material of the present invention may be used in the form of a flat sheet as it is, but may be formed into an embossed shape or a container shape. Moreover, it is good also as a foam by foaming.

The material of the present invention can also take the form of particles (granules). Although the size of the granules in this case is not particularly limited, for example, the volume average particle diameter is preferably about 0.1 to 10 mm. If the volume-average particle size is less than 0.1 mm, the granules tend to float and workability may deteriorate. On the other hand, if it exceeds 10 mm, the surface area per unit weight is so small that the hydrogen generation rate may decrease. When the material of the present invention has the above structure, the rate of hydrogen generation increases, that is, the amount of hydrogen generated in a short period of time increases.

In the material of the present invention, the object to which the generated hydrogen is used (hydrogen supply destination) may be any object to which hydrogen is supplied through direct or indirect contact with the material of the present invention. In particular, those that can maintain or improve physical properties by the action of hydrogen (for example, reduction action) are preferred.

Moreover, the hydrogen supply destination may be water or a liquid containing water, or may be a solid or gas containing water. Therefore, for example, a) foodstuffs such as beverages, meats, seafood, vegetables, fruits, etc., b) processed foods made from the above foodstuffs as raw materials, as well as fresh flowers, fungi, bacteria, plant seeds, blood for transfusion, and infusion solutions. , bath water, washing water, detergents, air, wound dressings, cosmetics, diapers, pet beverages, aquarium water, microorganisms, soil, food, indoor spaces, human bodies, animals, plants, etc. These can serve as both a hydrogen supply destination and a water supply source to the hydrogen generating material at the same time, but the water supply source and the hydrogen supply destination may be different. In particular, the hydrogen supply destination is preferably a moisture supply source for the hydrogen generating material.

EXAMPLES Examples and comparative examples are shown below to describe the features of the present invention more specifically. However, the scope of the present invention is not limited to the examples.

Example 1
Commercially available magnesium hydride powder (Wako Pure Chemical Industries, Ltd. volume average particle size D50: 15 μm) is kneaded into a modified polyalkylene oxide water absorbent resin (Sumitomo Seika Co., Ltd. "Aquacork TWB"), magnesium hydride A containing compound was made. The ratio was 6% by weight of the magnesium hydride powder with respect to the total amount of the water absorbent resin.
A magnesium hydride-containing compound was freeze-pulverized to obtain a water-absorbing hydrogen generating material having a particle size of 10 mm or less. The water absorption capacity (moisture content when water is included) of the raw material resin was 2000%.

Example 2
Commercially available magnesium hydride powder (Wako Pure Chemical Industries, Ltd., volume average particle diameter D50: 15 μm) is mixed in advance with 68% by weight of a commercially available polyethylene resin (Prime Polymer Co., Ltd. “SP2020”) and a modified polyalkylene oxide-based water absorbent resin ( Sumitomo Seika Co., Ltd. "Aquacoke TWB", water absorption: about 3100% by weight) 32% by weight mixed resin was melted and kneaded to prepare a compound containing magnesium hydride. The ratio was 5% by weight of the magnesium hydride powder with respect to the total amount of the mixed resin.
The magnesium hydride-containing compound was sufficiently dried and then formed into a film (thickness: about 1 mm) by a melt extrusion method to obtain a water-absorbing hydrogen generating material. At this time, the content of the magnesium hydride powder relative to the water-absorbing hydrogen generating material was set at 5% by weight, and the content of the water-absorbing resin relative to the water-absorbing hydrogen generating material was set at approximately 30% by weight. The water absorption capacity of the mixed resin as the raw material was 700%.

Comparative example 1
Commercially available magnesium hydride powder (Wako Pure Chemical Industries, Ltd. volume average particle size D50: 15 μm) was kneaded into a commercially available polyethylene resin to prepare a compound containing magnesium hydride. The ratio was 6% by weight of the magnesium hydride powder with respect to the total weight of the polyethylene resin. The particle size of the obtained hydrogen generating material was 10 mm or less. The water absorption capacity of the raw material resin was 0.05%.

Comparative example 2
Commercially available magnesium hydride powder (Wako Pure Chemical Industries, Ltd. volume average particle size D50: 15 μm) was kneaded into a commercially available polyethylene resin to prepare a compound containing magnesium hydride. The ratio was 5% by weight of the magnesium hydride powder with respect to the total weight of the polyethylene resin. A compound containing magnesium hydride was formed into a film (about 1 mm thick) by a melt extrusion method to obtain a hydrogen generating material.

Test example 1
The hydrogen generating ability of the samples obtained in each example and comparative example was evaluated by the following procedure. First, after putting 1 g of a sample into a 500 mL conical flask with a pickpocket, pure water was filled up to the mouth of the conical flask. Then, it was covered with a specially made lid with a hole that penetrates the glass tube. As a result, when the lid was put on, the pure water in the Erlenmeyer flask overflowed and the air layer in the Erlenmeyer flask was removed. After that, the internal pressure increased due to hydrogen generation, and pure water was discharged through the glass tube. It was stored in a room where the temperature was controlled at about 20°C, and after 4 hours, the concentration of dissolved hydrogen and the amount of hydrogen gas not dissolved in water were measured. The dissolved hydrogen concentration was measured using a dissolved hydrogen sensor (product name "H2-500sensor" manufactured by UNISENSE, a dissolved hydrogen concentration measuring device using a diaphragm electrode method). Values obtained by dividing the dissolved hydrogen concentration and the amount of hydrogen gas not dissolved in water by the magnesium hydride concentration (% by weight) of each sample, ie, the hydrogen generation amount per unit amount of magnesium hydride, were compared. Table 1 shows the results.

As is clear from the results in Table 1, the hydrogen generating material of the present invention can supply more hydrogen in a relatively short time of 4 hours by including a hydrogen generating agent in the water absorbent resin. .

Claims (5)

A hydrogen generating material comprising: a hydrogen generating agent that reacts with water to generate molecular hydrogen; and a water absorbent resin. 2. The hydrogen generating material according to claim 1, wherein the hydrogen generating agent is at least one of a metal and a metal hydride. 3. The hydrogen generating material according to claim 1, wherein the hydrogen generating agent is particulate, and the particles have a volume average particle diameter of 1 to 100 μm. The hydrogen generating material according to any one of claims 1 to 3, comprising a polyalkylene oxide resin as the water absorbent resin. The hydrogen generating material according to any one of claims 1 to 4, further comprising at least one of polyolefin resin and styrene resin.