WO2018131505A1

WO2018131505A1 - Hydrogen gas-containing gel, and food and cosmetic containing same

Info

Publication number: WO2018131505A1
Application number: PCT/JP2017/047223
Authority: WO
Inventors: 悠柴原; 健豊永; 井上　和美; 幸人末次; 大助西尾; 宏一豊島; 武田　徹
Original assignee: 株式会社新菱
Priority date: 2017-01-11
Filing date: 2017-12-28
Publication date: 2018-07-19
Also published as: JP6569885B2; JPWO2018131505A1

Abstract

Provided are: a hydrogen gas-containing gel from which hydrogen gas does not easily escape during storage even when hydrogen gas is contained in a high concentration; and a food and a cosmetic containing the hydrogen gas-containing gel. The hydrogen gas-containing gel includes a gel, hydrogen gas dissolved in the gel, and bubble hydrogen gas contained in the gel, wherein the content of the bubble hydrogen gas in the hydrogen gas-containing gel is 0.1-70 vol% (v/w), and the gel melting temperature of the gel is 40°C or higher, or the gel does not have a gel melting temperature.

Description

Hydrogen gas-containing gel, and foods and cosmetics containing the same

The present invention relates to a hydrogen gas-containing gel, and foods and cosmetics containing the same.
This application claims priority on January 11, 2017 based on Japanese Patent Application No. 2017-002407 filed in Japan, the contents of which are incorporated herein by reference.

In recent years, hydrogen gas is expected to have various functions such as a function of removing active oxygen and a function of enhancing biological activity. Therefore, cosmetics, foods, beverages and the like containing hydrogen gas have attracted attention.

As cosmetics containing hydrogen gas, for example, a gel (Patent Document 1) is proposed in which an aqueous solution obtained by adding a carboxy polymer or the like to hydrogen water is neutralized with a neutralizing agent.
In addition, as a food containing hydrogen gas, for example, a gel (Patent Document 2) is proposed in which hydrogen gas in microbubbles is blown into an aqueous solution such as agar or gelatin and the aqueous solution is cooled to gel.

JP 2007-314496 A JP 2009-165459 A

The cosmetic of Patent Document 1 is based on hydrogen water in which hydrogen gas is dissolved in water. For this reason, the hydrogen gas content of the cosmetic of Patent Document 1 is only 1.6 ppm (2% by volume [v / w]) of the saturation solubility of hydrogen gas in water at 20 ° C. at the maximum.
On the other hand, the food of Patent Document 2 is obtained by enclosing microbubbled hydrogen gas in a gel, and is said to contain 2 to 3 times as much hydrogen gas as hydrogen gas contained in saturated hydrogen water.

In order to fully develop various functions of hydrogen gas, it is desired to further increase the content of hydrogen gas contained in the entire food and cosmetics. However, even if the gel (gel) contains a hydrogen gas having a saturation solubility higher than that of the hydrogen gas in water, the hydrogen gas easily escapes from the gel. In particular, in a high-temperature environment, the gel melts, so that hydrogen gas easily escapes from the gel.
Since the hydrogen gas that escapes from the gel may ignite, it is desirable that the hydrogen gas does not easily escape from the gel containing hydrogen gas at a high concentration during storage.

The present invention provides a hydrogen gas-containing gel in which hydrogen gas does not easily escape during storage despite containing hydrogen gas at a high concentration, and foods and cosmetics containing the same.

The present invention has the following aspects.
<1> A hydrogen gas-containing gel containing a gel, hydrogen gas dissolved in the gel, and a hydrogen gas in a bubble state contained in the gel; and the hydrogen gas in the bubble state in the hydrogen gas-containing gel A hydrogen gas-containing gel having a content of 0.1 to 70% by volume [v / w]; the gel melting temperature of the gel being 40 ° C. or higher, or the gel having no gel melting temperature.
<2> The gel includes a network structure formed from a gelling agent and a liquid medium; the gelling agent is gelatin, agar, carrageenan, pectin, guar gum, tamarind gum, glucomannan, carob bean gum, xanthan gum, pullulan , Carboxymethylcellulose, alginic acid, alginate, alginic acid derivative, carboxyvinyl polymer, carboxyvinyl polymer derivative, polyvinyl alcohol, polyvinyl alcohol derivative, polyvinyl pyrrolidone, polyvinyl pyrrolidone derivative, polyacrylic acid and silicone. The <1> hydrogen gas-containing gel.
<3> A food comprising the hydrogen gas-containing gel of <1> or <2>.
<4> A cosmetic comprising the hydrogen gas-containing gel of <1> or <2>.

Although the hydrogen gas-containing gel of the present invention contains hydrogen gas at a high concentration, it is difficult for hydrogen gas to escape from the gel during storage.
Although the food of the present invention contains hydrogen gas at a high concentration, it is difficult for hydrogen gas to escape from the food during storage.
Although the cosmetic of the present invention contains hydrogen gas at a high concentration, it is difficult for hydrogen gas to escape from the cosmetic during storage.

The following definitions of terms apply throughout this specification and the claims.
“Gel” refers to a liquid medium held in a network structure formed by physical aggregation of a gelling agent by hydrogen bonding or the like, or crosslinking of the gelling agent by covalent bonding or the like.
“Physical gel” refers to a liquid medium held in a network structure formed by physical aggregation of a gelling agent by hydrogen bonding or the like.
“Chemical gel” refers to a liquid medium held in a network structure formed by crosslinking of a gelling agent by a covalent bond or the like.
“Gelling” means that a liquid composition containing a gelling agent and a liquid medium changes to a gel containing a network structure formed from the gelling agent and a liquid medium.
“Gel melting” means that a gel containing a network structure formed from a gelling agent and a liquid medium is changed to a liquid composition containing the gelling agent and the liquid medium.
The “gelling agent” refers to a compound capable of forming a network structure capable of holding a liquid medium by physical aggregation by hydrogen bonding or the like or crosslinking by covalent bonding or the like.
“Hydrogen gas content in the hydrogen gas-containing gel (volume% [v / w])” is the volume of hydrogen gas contained in a predetermined mass (100 g) of the hydrogen gas-containing gel (cm) ³ ) The ratio.
“Saturated solubility of hydrogen gas in a liquid medium” refers to the saturated solubility of hydrogen gas in a liquid medium (water or the like) under atmospheric pressure. The “dissolution of gas” that defines the saturation solubility is a state in which Henry's law is established and the gas is dissolved in a molecular form according to the pressure.

The content rate of hydrogen gas in a bubble state in the hydrogen gas-containing gel is determined as follows. Under conditions of atmospheric pressure and 25 ° C., 0.5-1 g of hydrogen gas-containing gel is precisely weighed into a head space GC analysis sample bottle (capacity: 20 mL) used for GC analysis, and 10 mL of water is added and sealed. To do. After shaking the sample bottle well by hand, mix thoroughly with an ultrasonic cleaner. The sample bottle is heated to 70 ° C., and heating is continued at 70 ° C. until the bubbles disappear from the hydrogen gas-containing gel. After the bubbles disappear, the gas phase gas in the sample bottle is collected, the hydrogen gas is quantified by gas chromatograph (GC) analysis (TCD detector), and the hydrogen gas content in the bubble state in the hydrogen gas-containing gel (Volume% [v / w%]) is calculated. The saturation solubility of hydrogen gas in water is 1.6 ppm (2% by volume [v / w]) at 20 ° C. and 1.5 ppm (1.8% by volume [v / w]) at 70 ° C., which is almost unchanged. That is, since the amount of dissolved hydrogen gas in the gel (substantially water) that is the base material of the hydrogen gas-containing gel is almost the same before and after the measurement, the hydrogen gas content determined by the above method was included in the gel. It can be regarded as the content of hydrogen gas in a bubble state.
The gelation temperature is determined as follows. A 50 mL glass screw bottle with a standard mercury thermometer attached to the outer wall was placed in a thermostatic water bath with a liquid composition of about half the volume of the screw bottle and sealed, and heated to 75 ° C. The temperature of the water bath is gradually lowered, and the temperature at which the liquid composition stops flowing even when the screw bottle is tilted at 45 ° and 90 ° is defined as the gelation temperature.
The gel melting temperature is determined as follows. In a 50 mL glass screw bottle with a standard mercury thermometer attached to the outer wall, about half of the screw bottle's capacity gel and sealed tightly are immersed in a constant temperature water bath and cooled to 10 ° C., and then the constant temperature water bath is gradually The temperature at which the gel begins to flow when the screw bottle is tilted to 45 ° and 90 ° is defined as the gel melting temperature.
In the present specification and claims, “to” indicating a numerical range means that numerical values described before and after the numerical value are included as a lower limit value and an upper limit value.

<< Hydrogen gas-containing gel >>
The hydrogen gas-containing gel of the present invention includes a gel, hydrogen gas dissolved in the gel, and hydrogen gas in a bubble state contained in the gel.
That is, the hydrogen gas-containing gel is dissolved hydrogen corresponding to the saturation solubility of hydrogen gas in the liquid medium contained in the gel (1.6 ppm (2% by volume [v / w]) at 20 ° C. when the liquid medium is water). It contains gas and hydrogen gas in a bubble state that is excess hydrogen gas that could not be dissolved in the liquid medium contained in the gel.

<Hydrogen gas>
The hydrogen gas content in the hydrogen gas-containing gel is 0.1 to 70% by volume [v / w], preferably 2 to 60% by volume [v / w], and 6 to 50% by volume [v / w]. v / w] is more preferable, and 10 to 45% by volume [v / w] is further preferable. If the hydrogen gas content in the hydrogen gas-containing gel is equal to or higher than the lower limit of the above range, the total hydrogen gas content in the hydrogen gas-containing gel is combined with the amount of dissolved hydrogen gas in the gel. Compared to the conventional hydrogen gas-containing gel that contains only dissolved hydrogen gas (up to about 1.6 ppm (2% by volume [v / w]) of the saturation solubility of hydrogen gas in water at 20 ° C. at the maximum), hydrogen gas has Various functions can be fully expressed. As long as the hydrogen gas content in the hydrogen gas-containing gel is up to the upper limit of the above range, the hydrogen gas bubbles can be dispersed in the gel.

The hydrogen gas content in the hydrogen gas-containing gel is determined by the amount of the gelling agent, the supply amount of the hydrogen gas when the liquid composition includes the hydrogen gas in the gas state, and the liquid composition in the production method described later. It can be adjusted by appropriately selecting the stirring conditions (number of rotations, time, etc.) etc.

<Gel>
The gel is a base for dissolving hydrogen gas in the hydrogen gas-containing gel and including hydrogen gas in a bubble state, and includes a network structure formed from a gelling agent and a liquid medium.
The gel may further contain other components other than the network structure formed from the gelling agent and the liquid medium, if necessary.
Gels are roughly classified into physical gels and chemical gels.

(Physical gel)
In the physical gel, since the network structure is formed by physical aggregation of the gelling agent, the network structure is easily eliminated by heating. Therefore, the physical gel can return to the original liquid composition by heating.

A liquid composition that can form a physical gel has a gelation temperature that changes from a liquid composition to a gel upon cooling.
The gelation temperature of the liquid composition capable of forming a physical gel is preferably 0.5 to 65 ° C, more preferably 10 to 60 ° C, and still more preferably 20 to 55 ° C. When the gelation temperature of the physical gel is within the above range, the liquid composition is easily maintained in a gel state in the normal use temperature range of the hydrogen gas-containing gel. Therefore, the gel can contain a lot of gas in a bubble state. Further, since the gel can hold the gas in a bubble state for a long time, the gas can be released for a long time.

A physical gel has a gel melting temperature that changes from a gel to a liquid composition upon heating.
The gel melting temperature of the physical gel is 40 ° C. or higher, preferably 50 ° C. or higher, and more preferably 60 ° C. or higher. If the gel melting temperature of the physical gel is equal to or higher than the lower limit of the above range, the gel is difficult to melt, so that the hydrogen gas is difficult to escape from the hydrogen gas-containing gel. The higher the gel melting temperature of the physical gel, the better, and the upper limit of the gel melting temperature of the physical gel is not particularly limited.

The gel melting temperature of the physical gel can be adjusted by appropriately selecting the type of gelling agent, the concentration of the gelling agent, and the combination of gelling agents when two or more gelling agents are used in the production method described later. .

(Chemical gel)
In chemical gels, since the network structure is formed by cross-linking of a gelling agent, the network structure is difficult to be eliminated. Therefore, the chemical gel does not change to the original liquid composition by heating or the like. That is, chemical gels do not have a gel melting temperature.
A chemical gel that does not have a gel melting temperature does not melt, so that it is difficult for hydrogen gas to escape from the hydrogen gas-containing gel.

A chemical gel having no gel melting temperature is selected by appropriately selecting the type of gelling agent, the concentration of the gelling agent, and the combination of gelling agents when two or more gelling agents are used in the production method described later. Can be prepared.

(Gelling agent)
Examples of the gelling agent that can form a network structure in the physical gel include proteins or polysaccharides derived from natural products, polymers having a hydrogen bonding group, polymers having an aggregating hydrophobic group, and the like.
Examples of proteins or polysaccharides derived from natural products include gelatin, agar, carrageenan, pectin, glucomannan, pullulan, alginic acid, sodium alginate, potassium alginate, calcium alginate, alginate, propylene glycol alginate, etc. Alginate derivative, aureobasidium culture solution, succinoglycan, ama seed gum, gum arabic, arabinogalactan, welan gum, cassia gum, gati gum, curdlan, caraya gum, carob bean gum, xanthan gum, chitosan, guar gum, guar gum enzyme degradation product, yeast cell wall, Psyllium seed gum, mackerel mugwort seed gum, gellan gum, tamarind seed gum, tara gum, dextran, tragacanth gum, toro Aoi, Microfibrous cellulose, Far celerane, Fukuronori extract, Macrohomopsis gum, Ramzan gum, Levan, Okra extract, Seaweed cellulose, Brown algae extract, Konjac potato extract, Sweet potato cellulose, Soy polysaccharide, Nata de coco, Carboxymethyl cellulose, Agarose Etc.
As the gelling agent capable of forming a network structure in the physical gel, one kind may be used alone, or two or more kinds may be used in combination.

Examples of the gelling agent that can form a network structure in a chemical gel include a polymer having a crosslinkable functional group, a polyfunctional monomer, a monofunctional monomer, and a silicone-based polymer. Specifically, carboxymethyl cellulose, carboxyvinyl polymer, carboxyvinyl polymer derivative, polyvinyl alcohol, polyvinyl alcohol derivative, polyvinyl pyrrolidone and polyvinyl pyrrolidone derivative, polyhydroxyethyl methacrylate, polyacrylic acid, polystyrene sulfonic acid, silicone (dimethicone, cyclic dimethicone) And synthetic polymers such as methylphenylpolysiloxane, cross-linked dimethylpolysiloxane, methylsiloxane network polymer, polyether-modified silicone, acrylic-modified silicone, and amedicon).
As the gelling agent capable of forming a network structure in a chemical gel, one kind may be used alone, or two or more kinds may be used in combination.

A physical gel and a chemical gel are preferably used because the chemical gel does not have a gel melting temperature, so that the hydrogen gas does not easily escape from the hydrogen gas-containing gel even at high temperatures.

Gelling agents include gelatin, agar, carrageenan, pectin, glucomannan, pullulan, alginic acid, alginate, alginic acid derivative, aureobasidium culture solution, succinoglycan, amased gum, arabic gum, arabinogalactan, welan gum, cassia gum, Gati gum, curdlan, karaya gum, carob bean gum, xanthan gum, chitosan, guar gum, guar gum enzyme degradation product, yeast cell wall, psyllium seed gum, mackerel mugwort seed gum, gellan gum, tamarind seed gum, tara gum, dextran, tragacanth gum, trolley aoy, microfibrous cellulose , Fur cerelan, fukuronori extract, macrohomopsis gum, rhamzan gum, levan, okra extract, seaweed cellulose, brown algae extract, konjac Extract, sweet potato cellulose, soybean polysaccharide, nata de coco, carboxymethylcellulose, agarose, carboxyvinyl polymer, carboxyvinyl polymer derivative, polyvinyl alcohol, polyvinyl alcohol derivative, polyvinyl pyrrolidone and polyvinyl pyrrolidone derivative, polyhydroxyethyl methacrylate, polyacrylic acid, polystyrene It is preferably one or more selected from the group consisting of sulfonic acid and silicone, gelatin, agar, carrageenan, pectin, guar gum, tamarind gum, glucomannan, carob bean gum, xanthan gum, pullulan, carboxymethyl cellulose, alginic acid, alginic acid Salt, alginic acid derivative, carboxyvinyl polymer, carboxyvinyl polymer derivative, More preferably, it is one or more selected from the group consisting of livinyl alcohol, polyvinyl alcohol derivatives, polyvinyl pyrrolidone, polyvinyl pyrrolidone derivatives, polyacrylic acid and silicone, and from the group consisting of agar, carrageenan and carboxyvinyl polymer. It is further more preferable that it is 1 type, or 2 or more types.

(Liquid medium)
The liquid medium is a medium for dissolving or dispersing components other than the liquid medium.
The liquid medium is preferably at least one liquid medium selected from water capable of dissolving the gelling agent, lower alcohol having 1 to 5 carbon atoms, and glycol from the viewpoint of dissolving the gelling agent. Examples of water include purified water. Examples of the lower alcohol include ethyl alcohol and isopropyl alcohol. Examples of the glycol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, and the like.

As the liquid medium, an aqueous medium containing water is preferable. The aqueous medium may further contain a lower alcohol. The proportion of water in the aqueous medium is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 100% by mass in the aqueous medium (100% by mass).
If the ratio of water in the aqueous medium is equal to or higher than the lower limit of the above range, gelation is likely, and a large amount of hydrogen gas in a bubble state is easily retained in the substrate for a long time. Moreover, it is preferable that it is difficult to ignite.

(Other ingredients)
Examples of other components include food additives, raw materials used in cosmetics (excluding gelling agents and liquid media), and the like.

Food additives include sweeteners, coloring agents, preservatives, thickening stabilizers (excluding gelling agents), antioxidants, coloring agents, bleaching agents, fungicides, yeast foods, gum bases, and Kansui. , Bitterings, Enzymes, Brighteners, Flavors, Acidulants, Softeners, Seasonings, Tofu coagulants, Emulsifiers, Hydrogen ion concentration adjusters (pH adjusters), Swelling agents, Nutrition enhancers, Other food additives Is mentioned.

Raw materials used in cosmetics include other ingredients that are the basis of cosmetics (excluding liquid media and gelling agents); drugs that give various functions to cosmetics; satisfaction that affects vision, smell, etc. Examples include raw materials for imparting sensory characteristics for imparting a feeling; quality-maintaining raw materials for retaining cosmetic quality.
Examples of other components (excluding the liquid medium and the gelling agent) include surfactants, oily components, and powder components.
Examples of the drug include moisturizing ingredients (softeners, emollients), astringents (antiperspirants), refreshing agents, ultraviolet inhibitors, and other drugs.
Examples of the raw material for imparting sensory characteristics include fragrances and pigments.
Examples of the quality-maintaining raw material include antiseptics, antioxidants, metal sequestering agents (metal ion element sealing agents), anti-fading agents, and buffering agents.

Specific examples of other components include, for example, glycerin fatty acid ester, sucrose fatty acid ester, stearylloyl calcium lactate, sorbitan fatty acid ester, propylene glycol fatty acid ester, propoxymethyl cellulose sodium, propoxymethyl cellulose calcium, sodium starch glycolate, sodium polyacrylate , Methylcellulose, hydroxymethylcellulose, sodium chondroitin sulfate, benzoic acid and its salt, sorbic acid and its salt, paraoxybenzoic acid esters, sodium dehydroxyacetate, propionic acid and its salt, white protein, polylysine, pectin degradation product, erythorbic acid And salts thereof, isopropyl citrate, dibutylhydroxytoluene, dl-α-tocopherol, nordihydroguaya Tic acid, butyl hydroxy anisole, propyl gallate, vitamin variety, amino derivatives, nucleic acids, lipids, antioxidants, anti-glycation agents, fats and the like.
Other components may be used alone or in combination of two or more.

(Ratio of each component)
The proportion of the liquid medium is preferably 50 to 99% by mass, more preferably 55 to 97% by mass, and further preferably 65 to 95% by mass. If the ratio of the liquid medium is not more than the upper limit of the above range, the liquid composition is sufficiently gelled, and it is easy to hold a large amount of hydrogen gas in the gel state for a long time. If the ratio of the liquid medium is equal to or higher than the lower limit of the above range, the fluidity of the liquid composition is maintained, so that hydrogen gas in a bubble state can be contained in the liquid composition in a large amount for a long time.

When the hydrogen gas-containing gel contains a gelling agent, the ratio of the gelling agent is preferably 1 to 50% by mass, more preferably 3 to 45% by mass, and more preferably 5 to 35% by mass in the gel (100% by mass). Is more preferable. When the ratio of the gelling agent is at least the lower limit of the above range, the liquid composition is sufficiently gelled, and it is easy to keep a large amount of hydrogen gas in the gel state for a long time in the gel. If the ratio of the gelling agent is not more than the upper limit of the above range, the fluidity of the liquid composition is maintained, so that hydrogen gas in a bubble state can be contained in the liquid composition in a large amount for a long time.

The proportion of other components may be appropriately selected within the range of known blending proportions according to the characteristics, functions, etc. required for the hydrogen gas-containing gel.

<Method for producing hydrogen gas-containing gel>
The hydrogen gas-containing gel of the present invention can be produced, for example, by a method having the following steps (I) to (III) in sequence.
Step (I): Preparation of a liquid composition containing a gelling agent and a liquid medium.
Step (II): Inclusion of hydrogen gas in a bubble state in the liquid composition.
Step (III): A liquid composition containing hydrogen gas in a bubble state is gelled to obtain a hydrogen gas-containing gel.

(Process (I))
Step (I) is a step of preparing a liquid composition containing a gelling agent and a liquid medium.
The liquid composition can be prepared, for example, by charging a gelling agent and a liquid medium in a dissolution tank and dissolving the gelling agent in the liquid medium by stirring. Other components other than the gelling agent and the liquid medium may be further added to the liquid composition.

Examples of the apparatus used for preparing the liquid composition include a tank with a stirrer or a kettle. The material of the apparatus can be selected in consideration of the corrosion resistance to the gelling agent, the liquid medium, hydrogen gas, etc .; the heat resistance at the operating temperature; the elution into the liquid composition, etc., within the range not impairing the effects of the present invention. Examples of the material for the apparatus include stainless steel, glass lining, fluororesin lining, and plastic. In addition, since flammable hydrogen gas is used, it is also necessary to consider equipment that has safety measures that can prevent ignition or explosion.

(Process (II))
Step (II) is a step in which hydrogen gas in a bubble state is included in the liquid composition after step (I).
By supplying hydrogen gas to the liquid composition, a liquid composition containing hydrogen gas in a bubble state is obtained. Other components other than the gelling agent and the liquid medium may be further added to the liquid composition containing hydrogen gas in a bubble state.

The viscosity of the liquid composition when supplying hydrogen gas is preferably 1 to 30,000 mPa · s. 10 to 20,000 mPa · s is more preferable, and 100 to 10,000 mPa · s is more preferable. When the viscosity of the liquid composition is less than the lower limit of the above range, hydrogen gas is likely to be dispersed as bubbles in the liquid composition, but hydrogen gas is likely to float and hardly stay in the liquid composition. When the viscosity of the liquid composition exceeds the upper limit of the above range, it is difficult to disperse hydrogen gas as bubbles in the liquid composition, and it is difficult to uniformly disperse hydrogen gas.
About the temperature of the liquid composition at the time of hydrogen gas supply, what is necessary is just the temperature which can achieve the viscosity range of an above described liquid composition, and should just set it suitably.
That is, if the viscosity of the liquid composition is equal to or higher than the lower limit, it is easy to control the rising of the hydrogen gas in dispersing the hydrogen gas as bubbles in the liquid composition, and the hydrogen gas is retained in the liquid composition. Cheap. Moreover, if the viscosity of a liquid composition is below the said upper limit, it will be easy to disperse | distribute hydrogen gas uniformly as a bubble in a liquid composition.

The supply amount of the hydrogen gas is an amount such that the total amount of the hydrogen gas dissolved in the liquid composition and the hydrogen gas in the bubble state exceeds the saturation solubility of the hydrogen gas in the liquid medium (water, etc.) The hydrogen gas-containing gel obtained in this way is in such an amount that the hydrogen gas content in the bubble state is 0.1 to 70% by volume [v / w].

The charged amount of the gelling agent and the liquid medium, and the supply amount of hydrogen gas may be appropriately set according to the desired hydrogen gas content in the hydrogen gas-containing gel. Further, the temperature and viscosity of the liquid composition may be appropriately set according to the types of the gelling agent and the liquid medium and the content of the hydrogen gas in the bubble state in the desired hydrogen gas-containing gel.

As an apparatus used in the step (II), any apparatus and equipment used for a known gas-liquid dispersion operation can be used as long as the apparatus can uniformly disperse hydrogen gas as desired bubbles in the liquid composition. The material of the apparatus can be selected in consideration of the corrosion resistance to the gelling agent, the liquid medium, hydrogen gas, etc .; the heat resistance at the use temperature;

In step (II), hydrogen gas is supplied to the liquid composition while the liquid composition is stirred; or, after the hydrogen gas is supplied to the liquid composition without stirring the liquid composition, the liquid composition is shaken. It is preferable to do.
Examples of the stirring method include a method using a stirrer, a method using a homomixer, a method using a line mixer, and the like.
Examples of the shaking method include a method using a shaker.

(Step (III))
Step (III) is a step of obtaining a hydrogen gas-containing gel by gelling a liquid composition containing hydrogen gas in a bubble state after step (II).
A liquid composition containing hydrogen gas in a bubble state is gelled to obtain a hydrogen gas-containing gel.
In order to reduce the volatilization loss of the hydrogen gas contained in the liquid composition as much as possible, the liquid composition is preferably gelled as quickly as possible.

As the gelling method, a method corresponding to the type of the gelling agent may be appropriately selected.
As a gelling method, when the gelling agent has a gelling temperature, such as a gelling agent that can form a physical gel (such as proteins derived from natural products or polysaccharides), the gelling temperature is below the gelling temperature of the gelling agent. And a method of gelling the liquid composition by cooling the liquid composition.
As a gelling method, if the gelling agent is a gelling agent capable of forming a chemical gel and has a crosslinkable group like a polymer having a crosslinkable functional group, gelation with a neutralizing agent or a crosslinker The method of gelatinizing a liquid composition by the crosslinking reaction of an agent is mentioned.

<Application>
Applications of the hydrogen gas-containing gel of the present invention include foods, cosmetics, pharmaceuticals, quasi drugs, livestock feed, aquaculture feed, cell culture substrates and the like.

<Action mechanism>
In the hydrogen gas-containing gel of the present invention described above, the hydrogen gas dissolved in the gel and the hydrogen gas in the bubble state contained in the gel, and the content of the hydrogen gas in the bubble state is 0.1 to Since the volume is 70% by volume [v / w], an amount of hydrogen gas equal to the saturation solubility of hydrogen gas in the liquid medium (water or the like) contained in the gel is dissolved in the gel. That is, the total amount of the hydrogen gas dissolved in the gel and the bubbled hydrogen gas contained in the gel exceeds the saturation solubility of the hydrogen gas in the liquid medium. As described above, the hydrogen gas-containing gel containing a large amount of hydrogen gas can supply a large amount of hydrogen gas, and can fully express various functions (such as a function of removing active oxygen and a function of enhancing biological activity) that the hydrogen gas has.

Further, in the hydrogen gas-containing gel of the present invention described above, the gel melting temperature of the gel is 40 ° C. or higher, or the gel does not have the gel melting temperature, so the gel is difficult to melt or the gel melts. do not do. Therefore, in spite of containing a high concentration of hydrogen gas such that the content of the hydrogen gas in the bubble state in the hydrogen gas-containing gel is 0.1 to 70% by volume [v / w] Hydrogen gas is difficult to escape from the gas-containing gel.

<< Food >>
The food of the present invention contains the hydrogen gas-containing gel of the present invention.
Examples of the use of the food of the present invention include jelly, gummy, pudding, beverage jelly, and koji.

<< Cosmetics >>
The cosmetic of the present invention contains the hydrogen gas-containing gel of the present invention.
Applications of the cosmetics of the present invention include moisture gels, cleansing gels, hair gels, shaving gels, gel creams, gel packs, skin sheets and the like.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

<Measurement>
The measuring method of each physical property in an Example is shown below.

(Hydrogen content of hydrogen gas in the hydrogen gas-containing gel)
Under conditions of atmospheric pressure and 25 ° C., 0.5 to 1 g of the hydrogen gas-containing gel is precisely weighed into a head space GC analysis sample bottle (capacity: 20 mL) used for GC analysis, and 10 mL of water is added and sealed. . The sample bottle was shaken well by hand and then thoroughly mixed with an ultrasonic cleaner. The sample bottle was heated to 70 ° C., and heating was continued at 70 ° C. until bubbles disappeared from the hydrogen gas-containing gel. After the bubbles disappear, the gas phase gas in the sample bottle is collected, the hydrogen gas is quantified by GC analysis (TCD detector), and the hydrogen gas content (volume% [volume% [ v / w%]).

(Gelation temperature)
The gelation temperature was determined as follows.
A 50 mL glass screw bottle with a standard mercury thermometer attached to the outer wall was placed in a thermostatic water bath with a liquid composition of about half the volume of the screw bottle and sealed, and heated to 75 ° C. The temperature at which the liquid composition stopped flowing even when the temperature of the water tank was gradually lowered and the screw bottle was tilted at 45 ° and 90 ° was defined as the gelation temperature.

(Gel melting temperature)
The gel melting temperature was determined as follows.
In a 50 mL glass screw bottle with a standard mercury thermometer attached to the outer wall, about half of the screw bottle's capacity gel and sealed tightly are immersed in a constant temperature water bath and cooled to 10 ° C., and then the constant temperature water bath is gradually The temperature at which the gel began to flow when the screw bottle was tilted to 45 ° and 90 ° was defined as the gel melting temperature.

<Example 1>
Carrageenan, gelatin and water were placed in a container and heated to 90 to 95 ° C. with stirring to prepare a liquid composition having a carrageenan concentration of 3.5% by mass and a gelatin concentration of 5% by mass. The gelation temperature of the liquid composition was 44.5 ° C.
While stirring the liquid composition at 62 to 55 ° C., hydrogen gas was passed through the liquid composition to obtain a liquid composition containing hydrogen gas in a bubble state.
The liquid composition was put into a 50 mL glass container with a lid and cooled to room temperature in a sealed state to obtain a hydrogen gas-containing gel. The hydrogen gas-containing gel contained hydrogen gas dissolved in the gel and hydrogen gas in a bubble state. The content rate of the gaseous hydrogen gas in the hydrogen gas-containing gel was 7.0% by volume [v / w]. The gel melting temperature of the gel was 60 to 65 ° C.
The glass container with a lid containing the hydrogen gas-containing gel was immersed in a constant temperature water bath at 60 ° C. for 1 hour. Immediately after opening the lid of the glass container, the fire was brought close, but it did not ignite.

<Example 2>
Agar, gelatin and water were placed in a container and heated to 90-95 ° C. with stirring to prepare a liquid composition having an agar concentration of 5 mass% and a gelatin concentration of 5 mass%. The gelation temperature of the liquid composition was 36 ° C.
While stirring the liquid composition at 70 to 54 ° C., hydrogen gas was passed through the liquid composition to obtain a liquid composition containing hydrogen gas in a bubble state.
The liquid composition was put into a 50 mL glass container with a lid and cooled to room temperature in a sealed state to obtain a hydrogen gas-containing gel. The hydrogen gas-containing gel contained hydrogen gas dissolved in the gel and hydrogen gas in a bubble state. The content of hydrogen gas in a bubble state in the hydrogen gas-containing gel was 3.9% by volume [v / w]. The gel melting temperature of the gel was 90-95 ° C.
A glass container with a lid containing the hydrogen gas-containing gel was immersed in a constant temperature water bath at 60 ° C. for 1 hour.
Immediately after opening the lid of the glass container, the fire was brought close, but it did not ignite.

<Example 3>
Carrageenan, gelatin and water were placed in a container and heated to 90 to 95 ° C. with stirring to prepare a liquid composition having a carrageenan concentration of 2.5% by mass and a gelatin concentration of 15% by mass. The gelation temperature of the liquid composition was 44 ° C.
While stirring the liquid composition at 62 to 53 ° C., hydrogen gas was passed through the liquid composition to obtain a liquid composition containing hydrogen gas in a bubble state.
The liquid composition was put into a 50 mL glass container with a lid and cooled to room temperature in a sealed state to obtain a hydrogen gas-containing gel. The hydrogen gas-containing gel contained hydrogen gas dissolved in the gel and hydrogen gas in a bubble state. The content rate of the gaseous hydrogen gas in the hydrogen gas-containing gel was 10.3% by volume [v / w]. The gel melting temperature of the gel was 55-60 ° C.
A glass container with a lid containing the hydrogen gas-containing gel was immersed in a constant temperature water bath at 60 ° C. for 1 hour.
Immediately after opening the lid of the glass container, the fire was brought close, but it did not ignite.

<Example 4>
Carboxyvinyl polymer (CBC, Carbopol (registered trademark) 980), polymer emulsifier (Nikko Chemicals, PEMULEN TR-1) and water are placed in a container and stirred, and the carboxyvinyl polymer concentration is 0.5% by mass. A liquid composition having a polymer emulsifier concentration of 0.5% by mass was prepared.
While stirring the liquid composition, hydrogen gas was passed through the liquid composition to obtain a liquid composition containing hydrogen gas in a bubble state.
To this liquid composition, 2.5 mL of a neutralizing agent (10% by mass sodium hydroxide aqueous solution) was added to obtain a hydrogen gas-containing gel. The hydrogen gas-containing gel contained hydrogen gas dissolved in the gel and hydrogen gas in a bubble state. The content rate of the gaseous hydrogen gas in the hydrogen gas-containing gel was 15% by volume [v / w]. The gel was measured for gel melting temperature, but the gel did not melt.
A glass container with a lid containing the hydrogen gas-containing gel was immersed in a constant temperature water bath at 60 ° C. for 1 hour.
Immediately after opening the lid of the glass container, the fire was brought close, but it did not ignite.

<Comparative Example 1>
Gelatin and water were placed in a container and heated to 60 ° C. with stirring to prepare a liquid composition having a gelatin concentration of 35% by mass. The gelation temperature of the liquid composition was 26 ° C.
While stirring the liquid composition at 35 ° C., hydrogen gas was passed through the liquid composition to obtain a liquid composition containing hydrogen gas in a bubble state.
The liquid composition was put into a 50 mL glass container with a lid and cooled to room temperature in a sealed state to obtain a hydrogen gas-containing gel. The hydrogen gas-containing gel contained hydrogen gas dissolved in the gel and hydrogen gas in a bubble state. The content rate of the gaseous hydrogen gas in the hydrogen gas-containing gel was 30% by volume [v / w]. The gel melting temperature of the gel was 30 ° C.
A glass container with a lid containing the hydrogen gas-containing gel was immersed in a constant temperature water bath at 60 ° C. for 1 hour.
Immediately after opening the lid of the glass container, when a fire was brought close, it ignited.

As shown in the examples and comparative examples, if the gel has a gel melting temperature of 40 ° C. or higher, or if the gel does not have a gel melting temperature, there is a risk of ignition even in a high temperature environment in summer, for example. It turns out that it can be used safely.

The hydrogen gas-containing gel of the present invention is useful as a food or cosmetic that can supply a large amount of hydrogen gas and sufficiently develop various functions of hydrogen gas.

Claims

A hydrogen gas-containing gel containing a gel, hydrogen gas dissolved in the gel and hydrogen gas in a bubble state contained in the gel,
The hydrogen gas content in the bubble state in the hydrogen gas-containing gel is 0.1 to 70% by volume [v / w],
The gel containing hydrogen gas, wherein the gel has a gel melting temperature of 40 ° C. or higher, or the gel does not have a gel melting temperature.
The gel includes a network structure formed from a gelling agent and a liquid medium,
The gelling agent is gelatin, agar, carrageenan, pectin, guar gum, tamarind gum, glucomannan, carob bean gum, xanthan gum, pullulan, carboxymethyl cellulose, alginic acid, alginate, alginic acid derivative, carboxyvinyl polymer, carboxyvinyl polymer derivative, polyvinyl alcohol The hydrogen gas-containing gel according to claim 1, which is at least one selected from the group consisting of polyvinyl alcohol derivatives, polyvinyl pyrrolidone and polyvinyl pyrrolidone derivatives, polyacrylic acid and silicone.
Food comprising the hydrogen gas-containing gel according to claim 1 or 2.
Cosmetics comprising the hydrogen gas-containing gel according to claim 1 or 2.