JP7471571B2 - Method for producing hydrogen-containing drinking water product and hydrogen-containing drinking water product - Google Patents

Description

The present invention relates to a method for producing a hydrogen-containing drinking water product and a hydrogen-containing drinking water product.

In recent years, hydrogen-containing water (also simply called hydrogen water), which is water in which hydrogen gas has been dissolved, has been attracting attention as it is said to have the effect of inhibiting the oxidation of metals and the spoilage of food due to its high reducing properties, and is also expected to improve various health disorders when used for drinking.

As a method for producing the above-mentioned hydrogen-dissolved water for drinking, for example, there is a method in which hydrogen gas from a gas cylinder is dissolved in raw water, or hydrogen gas generated by electrolysis of water is dissolved in raw water (for example, Patent Document 1). However, if hydrogen gas is simply supplied to the raw water, the dissolved hydrogen concentration is far from the saturated hydrogen concentration because nitrogen gas, oxygen gas, etc. dissolved in the raw water at room temperature and atmospheric pressure hinder the dissolution of hydrogen gas.
In addition, a method has been proposed in which hydrogen gas is filled into a pressure vessel from which air has been removed, and while maintaining the hydrogen gas pressure in the pressure vessel at 2 to 10 atmospheres, raw water is sprayed into the pressure vessel in a shower-like manner to bring the water into contact with the hydrogen gas, thereby efficiently dissolving hydrogen gas (Patent Document 2).
Alternatively, a method has been proposed in which hydrogen gas is injected into water at high pressure to generate ultra-fine bubbles (so-called "nanobubbles" and "microbubbles"), which are then dissolved in the water (Patent Document 3).

JP 2002-254078 A Japanese Patent No. 3606466 JP 2011-230055 A

As described above, various methods for producing hydrogen-containing water have been proposed in order to achieve a higher concentration of dissolved hydrogen. Furthermore, hydrogen-containing water products for drinking have been proposed, in which hydrogen-containing water obtained by the above-mentioned methods is filled into a packaging container with a straw and a cap attached.
In recent years, hydrogen-containing water has been proposed that contains functional ingredients such as amino acids to improve its functionality. However, when these functional ingredients are added to hydrogen-containing water, they are likely to come into contact with air, and there is a concern that the dissolved hydrogen concentration will decrease significantly. Furthermore, if hydrogen is dissolved in raw water after the functional ingredients are added to the raw water, the presence of impurities (functional ingredients) may prevent the desired dissolved hydrogen concentration from being achieved (the dissolved hydrogen concentration decreases due to the addition of the functional ingredients), or the method of dissolving hydrogen may cause problems such as contamination or damage to the device.
In addition, even if it is possible to produce hydrogen-containing water with a high concentration of dissolved hydrogen, if the hydrogen-containing water comes into contact with air while filling and sealing the hydrogen-containing water into a sealable container, or inside the container after it has been sealed, the air will dissolve in the hydrogen-containing water, causing a decrease in the dissolved hydrogen concentration in the hydrogen-containing water.

The present inventors have conducted intensive research to solve the above problems, and have found that by having a water-soluble capsule filled with a functional ingredient present in the system, i.e., in the container, at the same time as filling the hydrogen-containing water produced in the container, or before or after filling, the water-soluble capsule filled with the functional ingredient can be present in the hydrogen-containing water without lowering the dissolved hydrogen concentration of the hydrogen-containing water itself to be filled. That is, by filling the water-soluble capsule with, for example, a water-soluble functional ingredient, when the water-soluble capsule dissolves in the hydrogen-containing water, the functional ingredient dissolves in the hydrogen-containing water, and thus, it has been found that the functional ingredient can be blended into the hydrogen-containing water without lowering the dissolved hydrogen concentration of the hydrogen-containing water at the time of filling. And, by adopting the form of a water-soluble capsule, it has been found that it is possible to simultaneously blend a desired amount of functional ingredient according to the capsule volume, prevent contamination of the production equipment, and quickly dissolve the added capsule (and further the functional ingredient to be filled) in the hydrogen-containing water.
In particular, in the present invention, by adopting an embodiment in which functional raw materials are filled in the form of water-soluble capsules and introduced and dissolved in hydrogen-containing water, it has been found that the dissolved hydrogen concentration can be maintained at a high value even after long-term storage, compared to when the functional raw materials are added alone, or when the water-soluble capsules (or water-soluble capsule material) and the functional raw materials are added separately.
The present inventors have also discovered that a hydrogen-containing water drink product, which contains hydrogen-containing water with an increased dissolved hydrogen concentration and water-soluble capsules filled with functional ingredients dissolved in the hydrogen-containing water, in an openable container, for example a bag-shaped container such as a packaging container with a straw, can maintain a higher dissolved hydrogen concentration even after long-term storage.
Furthermore, the inventors have discovered that by dissolving water-soluble capsules filled with functional ingredients in hydrogen-containing water, it is possible to bring out the good flavor derived from the functional ingredients while suppressing or mitigating undesirable flavors such as odors and excessive bitterness.

That is, the present invention relates to a method for producing a hydrogen-containing water product for drinking, which includes the steps of filling an openable container with hydrogen-containing water and sealing the container, and is characterized in that a water-soluble capsule containing a functional ingredient is placed in the openable container before, during, or after the step of filling the container with hydrogen-containing water.

In the manufacturing method of the present invention, the water-soluble capsule is preferably made of a material containing at least one selected from the group consisting of hydroxypropylmethylcellulose (HPMC), pullulan, and gelatin.

In addition, in the manufacturing method of the present invention, it is preferable that the functional raw material consists of one or a combination of two or more selected from the group consisting of amino acids; polyamines; moisturizing substances; peptides and proteins and substances containing them; vitamins; vitamin-like substances; antioxidants; minerals; sugars; sugar alcohols; synthetic sweeteners; natural sweeteners; acidulants; carbohydrates; stearic acid and its derivatives; vegetables, fruits, plants and plant extracts; mushrooms; tea; herb raw materials and herb extract raw materials; flavonoids; and fragrances.
The present invention also provides a hydrogen-containing water drinkable product, which is filled with hydrogen-containing water together with functional ingredients produced by the production method of the present invention.

The present invention also relates to a hydrogen-containing water product for drinking, which is a hydrogen-containing water product for drinking, containing hydrogen-containing water filled and sealed in an openable container, functional ingredients dissolved in the hydrogen-containing water, and a water-soluble capsule material.

The method for producing a hydrogen-containing water product for drinking of the present invention is characterized in that it does not dissolve functional ingredients in hydrogen-containing water in advance and fill the hydrogen-containing water containing the functional ingredients in the container, but rather introduces the functional ingredients in the form of water-soluble capsules before, during, or after the process of filling the hydrogen-containing water. This method does not involve the mixing process of directly introducing the functional ingredients into the hydrogen-containing water and mixing it, as has been done in the past, and therefore can reduce the contact between the hydrogen-containing water and air, which is a concern in the mixing process. That is, the water-soluble capsules filled with the functional ingredients can be introduced into the hydrogen-containing water and dissolved in the hydrogen-containing water without decreasing the dissolved hydrogen concentration of the hydrogen-containing water produced with a high dissolved hydrogen concentration. And by filling the functional ingredients in the water-soluble capsules, the functional ingredients in the capsules can be blended (dissolved) in the hydrogen-containing water as the water-soluble capsules dissolve.
In addition, in the conventional method of dissolving functional ingredients in raw water before dissolving hydrogen gas, and then dissolving hydrogen in the water containing the functional ingredients, the presence of the functional ingredients as solutes inevitably leads to a decrease in the dissolved hydrogen concentration compared to when hydrogen gas is dissolved without dissolving the functional ingredients. Furthermore, depending on the method of dissolving hydrogen gas, problems such as contamination or damage to the hydrogen dissolving device due to the presence of the functional ingredients may occur.
According to the manufacturing method of the present invention, it is possible to avoid the concern of contamination and damage of such equipment, and to introduce water-soluble capsules filled with functional ingredients into hydrogen-containing water having a high concentration of dissolved hydrogen. By filling the functional ingredients in the water-soluble capsules, it is possible to blend the functional ingredients in the capsules with the hydrogen-containing water while avoiding the contamination and damage of the equipment, which has been a problem in the past.
Furthermore, according to the present invention, by adopting the form of a "water-soluble""capsule""filled with functional ingredients", adding this to hydrogen-containing water makes it easy to mix a fixed amount of functional ingredients into the product, and also reduces contamination of the manufacturing equipment caused by scattering during addition, which can occur when adding functional ingredients in powder form. Furthermore, the capsule form has a large contact surface (i.e. surface area) with the hydrogen-containing water, so dissolution in the hydrogen-containing water proceeds quickly, making it possible to produce a product with little residual water-soluble capsule residue after addition.
In particular, in the present invention, by introducing and dissolving a functional raw material in the form of a water-soluble capsule filled with the functional raw material into hydrogen-containing water, it is possible to produce a product that can maintain a lower oxidation-reduction potential after long-term storage and a higher dissolved hydrogen concentration after long-term storage, compared to when the functional raw material is added alone, or when the water-soluble capsule (or water-soluble capsule material) and the functional raw material are added separately.

The hydrogen-containing drinking water product of the present invention contains functional raw materials and water-soluble capsule material dissolved in the hydrogen-containing water, i.e., is a product in which water-soluble capsules filled with functional raw materials are dissolved in the hydrogen-containing water, and therefore can maintain a lower oxidation-reduction potential and a higher dissolved hydrogen concentration after long-term storage compared to products in which only functional raw materials are dissolved in the hydrogen-containing water or products in which the water-soluble capsules or their capsule material and the functional raw materials are dissolved separately.
Furthermore, the hydrogen-containing drinking water product of the present invention is in the form of water-soluble capsules filled with functional ingredients dissolved in hydrogen-containing water, so that the good flavor derived from the functional ingredients is maintained and enhanced while at the same time suppressing or mitigating undesirable flavors such as odors and excessive bitterness, thereby achieving both the effects of flavor improvement and masking.

FIG. 1 is a perspective view showing one embodiment of a hydrogen-containing drinkable water product produced by the production method of the present invention. FIG. 2 is an enlarged view of the vicinity A of the upper end opening of the straw in the hydrogen-containing drinking water product shown in FIG. FIG. 3 is a perspective view showing a spouted straw used for a hydrogen-containing beverage produced by the production method of the present invention.

As mentioned above, various methods for producing hydrogen-containing water have been investigated to date. However, even if a high concentration of dissolved hydrogen is achieved, there is a problem that the concentration of dissolved hydrogen in the hydrogen-containing water decreases when the hydrogen-containing water comes into contact with air during filling, sealing, and storage.
On the other hand, in recent years, various beverages containing functional ingredients have been attracting attention in order to meet the growing health consciousness and diverse tastes of consumers, and there is an increasing demand for hydrogen-containing water products that contain such various functional ingredients.
However, when functional raw materials are mixed into hydrogen-containing water, contact with air is likely to occur, raising concerns that the dissolved hydrogen concentration will drop significantly. In addition, if hydrogen is dissolved in raw water after the functional raw materials are mixed into the raw water, the presence of impurities (functional raw materials) may make it impossible to achieve the desired dissolved hydrogen concentration (the dissolved hydrogen concentration drops due to the mixing of functional raw materials), or, depending on the method of dissolving hydrogen, problems such as contamination or damage to the equipment may occur.
In particular, when the membrane dissolution method is selected in which hydrogen gas is dissolved in raw water using a hollow fiber membrane, if functional ingredients are mixed into the raw water first and then the membrane dissolution method is carried out, the functional ingredients may clog the membrane, resulting in problems such as a decrease in quality due to membrane deterioration and an increase in costs due to the increased frequency of membrane replacement to ensure quality. Furthermore, if the functional ingredients remain in the pores of the hollow fiber membrane without being completely washed away, the risk of bacterial growth increases.
In addition, since functional raw materials have a certain amount of flavor, when considering the blending of a different type of functional raw material, and especially when considering switching to the production of hydrogen-containing water without blending functional raw materials, it is necessary to completely remove the flavor, etc., derived from the functional raw materials used previously from the manufacturing equipment and piping. However, it requires considerable effort to be sure that the flavor has been completely removed from the manufacturing equipment, etc. This is a problem that accompanies any method of producing hydrogen-containing water, and it is not easy to use equipment for hydrogen-containing water blended with functional raw materials and hydrogen-containing water without blending raw materials in combination. In particular, when blending sweeteners, acidulants, fruit juice, and flavorings into hydrogen-containing water in order to increase its palatability, it is quite difficult to remove the flavor from the manufacturing equipment, etc. involved in the switching of the manufacturing items.

In order to address the issue of providing a hydrogen-containing water drinkable product that maintains a high dissolved hydrogen concentration while also incorporating functional ingredients, the inventors have attempted to minimize the decrease in the dissolved hydrogen concentration of the hydrogen-containing water by adopting a method in which water-soluble capsules filled with functional ingredients are dissolved in the hydrogen-containing water filled in a container.
That is, before or during filling the hydrogen-containing water into the container, or even after filling, a water-soluble capsule filled with a functional ingredient is put into the container, thereby minimizing the decrease in the dissolved hydrogen concentration of the hydrogen-containing water caused by contact with air during blending of the functional ingredient, etc. Furthermore, the water-soluble capsule filled with the functional ingredient is put into the hydrogen-containing water, thereby realizing dissolution of the water-soluble capsule and the functional ingredient in the hydrogen-containing water, without causing problems such as contamination or damage to the manufacturing equipment that may have been caused by blending the functional ingredient in the past, resulting in quality deterioration, increased costs, and increased risk of bacterial growth. In addition, by putting the functional ingredient into the container, contamination of the inside of the piping that sends the hydrogen-containing water to the filling device, the filling machine, and the room can be prevented, and it can also be used to produce hydrogen-containing water without blending the functional ingredient.
Furthermore, by adding and dissolving the functional raw material in hydrogen-containing water in a form in which the functional raw material is filled in capsules, a product is realized that can maintain a lower redox potential and a higher dissolved hydrogen concentration after long-term storage compared to when the functional raw material is added and dissolved alone, or when a water-soluble capsule or water-soluble capsule material and the functional raw material are added and dissolved separately.
Furthermore, as a result of trying to solve these problems, that is, by adopting an embodiment in which water-soluble capsules filled with functional ingredients are dissolved in the hydrogen-containing water in the hydrogen-containing water beverage product of the present invention, it has become possible to bring out the good flavor derived from the functional ingredients while suppressing undesirable flavors such as odor and bitterness.

Furthermore, through various experiments conducted by the applicant, it has been confirmed that, depending on the type of functional ingredient, the present invention, i.e., filling a water-soluble capsule with the functional ingredient and then introducing and dissolving this in hydrogen-containing water, can suppress the aroma and taste of some products, making the aroma and taste less noticeable (making the products more tasteless and odorless).
In recent years, hydrogen water and hydrogen-containing beverages that have added nutritional value and improved flavor through the addition of functional ingredients have been launched on the market, such as beverages in which hydrogen is dissolved not only in water but also in tea or juice, and hydrogen water containing glucosamine and antioxidants. However, some of these ingredients have unique flavors that are specific to the ingredients and even prevent drinking, so flavors are often adjusted by adding flavorings and seasonings (sweeteners, acidulants, etc.).
Hydrogen water has been attracting attention for its antioxidant effects and is becoming more widely recognized as a health drink. However, because hydrogen water (which does not contain tea ingredients or functional ingredients) is tasteless, odorless, colorless and transparent, it has also been perceived by consumers as a beverage similar to "mineral water."
Therefore, some consumers who prefer the above-mentioned "mineral water" tend to avoid hydrogen water, which has had flavorings and seasonings added and its flavor adjusted. Even when hydrogen water is mixed with ingredients that are considered tasteless and odorless, there is still a difference in taste and smell compared to hydrogen water without added ingredients. No knowledge or means have been disclosed to reduce or eliminate this strange feeling, and no attention has been paid to the possibility that a slight strange feeling compared to additive-free hydrogen water may prevent people from drinking hydrogen water, which has various ingredients added to it to add nutritional value or improve flavor.
In this context, the inventors have discovered that by adding water-soluble capsules filled with functional ingredients to hydrogen-containing water, depending on the type of functional ingredient, a product can be produced that has a flavor that is almost identical to that of hydrogen-containing water without added ingredients (a flavor that does not cause any discomfort).

The hydrogen-containing drinking water product and the method for producing the hydrogen-containing drinking water product of the present invention will be described in detail below.

<Hydrogen-containing drinking water products>
The hydrogen-containing drinking water product of the present invention is composed of hydrogen-containing water filled and sealed in an openable container (also simply referred to as a "container"), functional ingredients dissolved in the hydrogen-containing water, and a water-soluble capsule material.
In the present invention, the functional raw material and water-soluble capsule material dissolved in the hydrogen-containing water may be in the form of water-soluble capsules filled with the functional raw material and dissolved in the hydrogen-containing water.
The inventors have also investigated embodiments in which the water-soluble capsules and functional raw materials are dissolved separately in the hydrogen-containing water (without being filled into capsules), and embodiments in which the raw materials for the water-soluble capsules (e.g., pullulan, as described below) and the functional raw materials are dissolved in the hydrogen-containing water, and have confirmed that the above-mentioned effects can be obtained even in these embodiments by varying various manufacturing conditions, etc.

[Water-soluble capsule]
The water-soluble capsule is not particularly limited, and in the present invention, it is preferable to adopt a water-soluble capsule made of a material containing at least one selected from the group consisting of hydroxypropylmethylcellulose (HPMC), pullulan, and gelatin (pork gelatin, fish gelatin). These HPMCs and the like are usually used as the main components constituting the water-soluble capsule, for example, in a proportion of 80% by mass or more.
These water-soluble capsules have characteristics in terms of dissolution behavior and flavor, etc., depending on the capsule material (HPMC, pullulan, gelatin (pork gelatin, fish gelatin)), so the capsule to be adopted may be selected taking into consideration the type of functional raw material to be combined and the selection of the manufacturing method. For example, in cases where a gel-like substance is required even in small amounts at room temperature, such as in a jelly drink, pig or fish gelatin may be considered as a candidate for selection. In cases where a manufacturing method that does not require the sterilization process described below can be selected, and where it is expected that the product will not be exposed to a high-temperature environment during storage or consumption, pullulan or HPMC may be considered as a candidate for selection. In addition, if gelation is not taken into consideration, the product is manufactured through a sterilization process, and general consumption is envisioned, pullulan may be considered as a candidate for selection. The present inventors have conducted tests using various water-soluble capsules and confirmed that there is no significant difference in the long-term stability of the dissolved hydrogen concentration depending on the type of capsule.

Conventionally, when functional raw materials and the like are mixed, various shapes can be adopted, for example, powder, or chunks, such as flakes, granules, plates, spheres, ellipsoids, or hollow spheres or ellipsoids.
However, in the actual manufacturing process, it is necessary to consider the fact that a fixed amount of various compounds, including functional ingredients, is added (blended) to the beverage product (for example, hydrogen-containing water drink), the ease of addition, scattering during addition and overflow of various compounds expected during filling of hydrogen-containing water, contamination of the equipment by overflowing functional ingredients, etc. For this reason, from the standpoint of quality stability and operability, it can be said that a certain amount of lump form is preferable, rather than a powder form which is considered to have excellent solubility.
On the other hand, in order to promote dissolution of the functional ingredients, etc. in the beverage (e.g., hydrogen-containing water) by the heat sterilization process after filling, it is preferable that the contact surface (i.e., surface area) of the compound, including the functional ingredients, with the beverage (e.g., hydrogen-containing water) is large, and for example, a flake-like shape or a hollow spherical or ellipsoidal shape is preferable.

Taking these into consideration, the present invention has come to adopt the shape of a water-soluble capsule (empty capsule) that is formed with a thin layer and hollow structure by filling the functional ingredient into a water-soluble thin container. That is, it has been discovered that the main ingredient is at least one selected from the group consisting of hydroxypropylmethylcellulose (HPMC), pullulan, and gelatin, and that the capsule is formed in a water-soluble capsule form that contains, for example, 80% by mass or more of the above-mentioned hydroxypropylmethylcellulose (HPMC), pullulan, and gelatin, and that the functional ingredient described below is filled in the capsule, which is then placed in the container and dissolved in hydrogen-containing water.

In order to obtain the above-mentioned water-soluble capsule shape, the water-soluble capsule may be configured to contain food or food additives other than the above-mentioned hydroxypropylmethylcellulose (HPMC), pullulan, and gelatin. In this case, the total amount of the other food or food additives can be used at a ratio of, for example, less than 20% by mass (0 to less than 20% by mass) at most with respect to the total mass of the main components such as hydroxypropylmethylcellulose (HPMC), pullulan, or gelatin and the other food or food additives (i.e., the total mass of all the components constituting the water-soluble capsule). As the food or food additive, for example, water, potassium chloride, mold release agents (vegetable oil, lecithin, etc.), surface treatment agents (talc, calcium stearate, etc.), thickening polysaccharides (carrageenan, gellan gum, etc.), and other known substances can be used, and these are preferably water-soluble.
In the present invention, the water-soluble capsule material includes the above-mentioned main raw materials (for example, hydroxypropylmethylcellulose, pullulan, gelatin) and the above-mentioned foods or food additives.

As the various capsules whose main raw materials are hydroxypropylmethylcellulose (HPMC), pullulan, and gelatin, commercially available capsules (empty capsules) manufactured by Capsugel Japan Co., Ltd. and Qualicaps Co., Ltd. can be used.
The water-soluble capsule is, for example, in a ratio of 5 mg to 200 mg by weight per 200 mL of hydrogen-containing water, for example, 10 mg to 200 mg, 20 mg to 200 mg, 30 mg to 200 mg, 35 mg to 100 mg, 40 mg to 90 mg, 40 mg to 80 mg, or 100 mg to 200 mg, 100 mg to 190 mg, 100 mg to 180 mg, 100 mg to 220 mg, 100 mg to 260 mg, 100 mg to 300 mg, 100 mg to 320 mg, 100 mg to 360 mg, 100 mg to 380 mg, 100 mg to 400 mg, 100 mg to 400 mg, 100 mg to 500 mg, 100 mg to
It is preferably present in an amount of from 100 mg to 150 mg.

Water-soluble capsules, preferably those containing at least one selected from the group consisting of hydroxypropylmethylcellulose (HPMC), pullulan, and gelatin, can dissolve in hydrogen-containing water over time at room temperature (20°C ± 5°C). After filling the hydrogen-containing water, the packaging container is sealed and subjected to a heat sterilization process described below, which can sterilize the product and further promote dissolution of the water-soluble capsules in the hydrogen-containing water. The water-soluble capsules may form a gel with the hydrogen-containing water under high temperatures (e.g., heating (sterilization) at 85°C for about 30 minutes), but the gel dissolves and becomes liquid (hydrogen-containing water in which the water-soluble capsules have dissolved) when stored at room temperature.

[Functional ingredients]
The functional raw materials are not particularly limited, and various raw materials that have been used in conventional beverages and the like can be used. For example, amino acids, polyamines, moisturizing substances, peptides and proteins and their containing substances, vitamins, vitamin-like substances, antioxidants, minerals, sugars, sugar alcohols, synthetic sweeteners, natural sweeteners, acidulants, carbohydrates, stearic acid and its derivatives, vegetables, fruits, plants and plant extracts, mushrooms, teas, herbal raw materials and herbal extract raw materials, flavonoids, flavorings, etc. may be used alone or in combination of two or more. The above classifications are for the convenience of this disclosure, and are not limited to these classifications.

Specific examples of functional ingredients are given below, but are not limited to these.
Amino acids: alanine, tryptophan, lysine, methionine, threonine, valine, leucine, isoleucine, histidine, theanine, citrulline, etc. Polyamines: putrescine, spermine, spermidine, etc. Moisturizing substances: glucosamine (amino sugar), ceramide (sphingolipid), hyaluronic acid (mucopolysaccharide), etc. Peptides and proteins and substances containing them: peptides, elastin, elastin peptides (e.g., bonito elastin), silk peptides (e.g., edible silk), collagen (protein), bird's nest (including, for example, Colocaria (registered trademark)), etc. Vitamins: vitamin _B1 , vitamin _B2 , vitamin _B3 (niacin), vitamin _B6 , vitamin _B7 (biotin), vitamin _B9 (folic acid), vitamin _B12 , pantothenic acid, vitamin C (ascorbic acid), sodium vitamin C (sodium ascorbate), and their derivatives, etc. Vitamin-like substances: hesperidin, L-carnitine, L-carnitine tartrate, L-carnitine fumarate, etc. Antioxidants: pyrroloquinoline quinone (PQQ) (coenzyme), low molecular weight polyphenols (e.g. Oligonol (registered trademark)), polyphenols, coenzyme Q ₁₀ etc.・Minerals: magnesium, calcium, zinc, iron, etc.・Sugars: monosaccharides such as glucose (grape sugar), ribose, fructose (fruit sugar), arabinose, etc.; disaccharides such as sucrose (cane sugar), lactose (milk sugar), maltose (malt sugar), trehalose, etc.; oligosaccharides, etc.・Sugar alcohols: erythritol, maltitol, sorbitol, xylitol, etc.・Synthetic sweeteners: aspartame, acesulfame potassium, sucralose, etc.・Natural sweeteners: stevia, maple syrup, honey, fructose, etc.・Acidulants: acetic acid, citric acid Acid, sodium citrate, succinic acid, lactic acid, gluconic acid, malic acid, tartaric acid, phosphoric acid, etc.; Carbohydrates: dextrin, indigestible dextrin, maltodextrin, corn starch, cellulose, and derivatives thereof; Stearic acid and its derivatives: calcium stearate, magnesium stearate, etc.; Vegetables, fruits, trees, plants (roots, stems, leaves, flowers, seeds, and other plant organs, bark and other tissues, fruit structures, etc.) (including powders, liquids, fruit juices, extracts, and fruit juice extracts) and plant extracts: tomatoes, spinach. Coral, red spinach, long life grass (peony root), pepper, cherry blossom, olive, rose, grape, apple, orange, mango, cat's claw, maca, camu camu, beech (oak), sunflower, bergamot, licorice, raw materials for green juice, young barley leaves, young wheat leaves, kale, mulberry, mulberry fruit, angelica tree, superfood, spirulina, maca, wolfberry, wolfberry fruit, cacao, chia seeds, coconut, acai, broccoli, broccoli super sprouts, hemp, hemp seeds, etc., as well as the seeds, shoots (sprouts), extracts, etc. of these, and mushrooms Class: Chaga (Iris obliquus), Agaricus, Maitake, Sparassica napus, Yamabushitake, etc. and extracts of these, etc.・Teas (including powders, liquids, extracts, etc.): tea, sencha, roasted green tea, black tea, oolong tea, brown rice tea, dokudami tea, etc. and extracts of these, etc.・Herb raw materials and herb extract raw materials: chamomile, chamomile, linden, lemongrass, lemon balm, rose buds, rosemary, dokudami, paroassu, hawthorn, European hawthorn, etc.・Flavonoids: rutin, catechin, quercetin, etc.・Flavors, etc.

The amount of functional raw material to be blended can be determined appropriately taking into consideration its solubility, flavor, and other functions. For example, the amount can be 1 mg to 10 g per 1 L of hydrogen-containing water.
The amount of functional raw material to be blended can be changed depending on the size of the water-soluble capsule. In other words, when it is intended to blend a large amount of functional raw material, the desired amount of functional raw material can be divided and filled into multiple water-soluble capsules.

In addition, functional raw materials may contain excipients such as starch, honey, dextrin, fine silicon dioxide, calcium stearate, magnesium stearate, crystalline cellulose, etc., taking into consideration the processing characteristics and ease of processing at the raw material factory, and emulsifiers for the purpose of improving solubility and dispersibility, and these may also be filled together in a water-soluble capsule and dissolved in the hydrogen-containing water.
Furthermore, when the functional raw material is filled into a water-soluble capsule, the above-mentioned excipients and the like may be separately filled into the water-soluble capsule.
Therefore, in the hydrogen-containing drinking water product of the present invention, the above-mentioned excipients and emulsifiers may be contained in the hydrogen-containing water.
The amount of the above excipients and emulsifiers (content per capsule) is not particularly limited, and can be appropriately adjusted depending on the capsule volume, the type of functional raw material, the amount of functional raw material, etc.
For example, in the case of fine silicon dioxide, the amount can be about 0.05% to 2.0% by mass of the total amount of functional ingredients filled in the capsule. When dextrin is also mixed, the amount of dextrin can be counted in the "total amount of functional ingredients."

According to the present invention, as described above, it is possible to blend functional raw materials into hydrogen-containing water without decreasing the dissolved hydrogen concentration in the hydrogen-containing water at the time of filling.
Furthermore, by blending the functional raw material with hydrogen-containing water in the form of water-soluble capsules filled with the functional raw material, the resulting hydrogen-containing water product can maintain a lower redox potential and a higher dissolved hydrogen concentration after long-term storage compared to when the functional raw material is blended alone, or even when the water-soluble capsules or water-soluble capsule material and the functional raw material are dispensed separately.
Furthermore, by adopting the above-mentioned embodiment, it is possible to maintain and enhance the good flavor derived from the functional raw materials, while suppressing or mitigating undesirable flavors such as odor and excessive bitterness, resulting in a product that achieves both the effects of flavor improvement and masking.
Furthermore, depending on the type of functional raw material, this may also lead to suppressing a decrease in the dissolved hydrogen concentration caused by the addition of the functional raw material, and thus makes it possible to suppress an increase in the oxidation-reduction potential and the dissolved hydrogen concentration.

As mentioned above, it has been found that by adding water-soluble capsules filled with functional ingredients to hydrogen-containing water, depending on the type of functional ingredient, the aroma and taste can be suppressed, making it difficult to detect the aroma and taste, resulting in a product that has a flavor that is almost the same as hydrogen-containing water without added ingredients (a flavor that does not cause any discomfort).
In addition, it has been confirmed that, according to the embodiment of the present invention, depending on the combination of functional ingredients, the flavor can be improved and the taste can be increased compared to the case where only one functional ingredient is added.
On the other hand, when fragrances are filled into water-soluble capsules and dissolved in hydrogen-containing water, it has been confirmed that the quality of the fragrance is improved, with the characteristic chemical odor of some fragrances being reduced and the fragrance becoming more natural.
Regarding sweeteners, it has been confirmed that various effects can be obtained depending on the type of sweetener, such as increasing sweetness and allowing the amount used to be reduced, conversely, suppressing sweetness to a moderate level, and improving the overall deliciousness of food and beverages.
It has also been confirmed that various effects can be obtained depending on the type of acidulant, such as the effect of adjusting the strength of the sourness, the masking effect, the effect of reducing bitterness, and the effect of improving the overall palatability of food and beverages.
In this way, in the present invention, by adding water-soluble capsules filled with functional ingredients to hydrogen-containing water, the flavor of the ingredient may be strengthened or weakened depending on the type of functional ingredient. Therefore, the strength of the flavor can be confirmed by selecting appropriate functional ingredients and conducting experiments based on the concept and purpose of product development, consumer preferences, etc.

<Method of manufacturing hydrogen-containing drinking water product>
The present invention relates to a method for producing a hydrogen-containing water product for drinking, which comprises the steps of filling an openable container (also simply referred to as a "container") with hydrogen-containing water and sealing the container, characterized in that a water-soluble capsule containing a functional ingredient is placed in the openable container before, during, or after the step of filling the container with hydrogen-containing water.
Examples of the water-soluble capsules and functional ingredients include those described in "Hydrogen-containing drinking water products."

[Method of producing hydrogen-containing water]
The type of hydrogen-containing water used to produce the hydrogen-containing drinking water product of the present invention, i.e., its production method, is not particularly limited, and can be obtained by various methods such as a bubbling method in which hydrogen gas supplied from a gas cylinder is dissolved in raw water, a pressurization method in which hydrogen gas is filled into a pressure vessel from which air has been removed, and while maintaining the hydrogen gas pressure in the pressure vessel at, for example, 2 to 10 atmospheres, raw water is sprayed into the pressure vessel in a shower-like manner to contact the hydrogen gas and dissolve it in the raw water, an electrolysis method in which hydrogen gas generated by electrolysis of water is dissolved, or a membrane dissolution method using a hollow fiber membrane.
Among these, hydrogen-containing water produced using a membrane dissolution method in which residual gas is removed from raw water through a hollow fiber membrane, and then the degassed water and pressurized hydrogen gas are introduced into a gas permeable membrane module to dissolve the hydrogen gas in the degassed water is preferred because it can increase the dissolved hydrogen concentration more efficiently (see, for example, Japanese Patent No. 4551964, a previous patent application filed by the present inventors).Furthermore, filling a container with hydrogen-containing water produced by the above-mentioned method, particularly by filling the container under pressure, is preferred because it leads to maintaining the efficiently increased dissolved hydrogen concentration at a high value (see, for example, Japanese Patent No. 6052948, a previous patent application filed by the present inventors).

As described above, the manufacturing method of the present invention is not particularly limited with respect to the method, procedure, and manufacturing apparatus, so long as it includes the steps of filling an openable container with hydrogen-containing water and sealing the container, and also includes introducing water-soluble capsules containing a functional raw material into the openable container before, during, or after the step of filling the container with hydrogen-containing water.
For example, as a method for producing a hydrogen-containing water product for drinking of the present invention, a method of producing hydrogen-containing water using the above-mentioned membrane dissolution method, filling the hydrogen-containing water into a container to produce a product, and going through the following steps (A) to (E) can be suitably adopted. In this case, the "step of filling the hydrogen-containing water into an openable container and sealing the container" corresponds to the following steps (C) and (D).
(A) a degassing step in which the raw purified water supplied is degassed through a hollow fiber membrane in a degassing device, and the obtained degassed water is sent to a hydrogen dissolving device;
(B) a hydrogen dissolving step in which pressurized hydrogen gas is dissolved in the degassed water supplied in the hydrogen dissolving device through a hollow fiber membrane, and the resulting hydrogen-containing water is sent to a filling device;
(C) a step of filling a container (e.g., a package with a straw) with the hydrogen-containing water through an inlet of the container in the filling device;
(D) a sealing step of sealing the inlet of the container (packaged with a straw) filled with hydrogen-containing water with a sealing device;
(E) A sterilization step of heat treating the sealed container.

In a particularly preferred embodiment, the step of filling the hydrogen-containing water in step (C) is preferably carried out by filling under pressure, and in order to realize efficient filling under pressure, it is preferable that the following configuration is further provided.
That is, it is desirable that a predetermined pressure (see the description of the pressure applied to the water flow path described below) be applied by operating a pressure pump to the water flow path from the purified water supplied to the degassing device in the degassing step (A) to the hydrogen-containing water injected into the container in the filling step (C), so that the pressurized hydrogen-containing water is supplied to the filling device.
In short, in a preferred embodiment, it is desirable to manufacture the hydrogen-containing water using a manufacturing apparatus that includes at least a water flow path from the purified water supplied to the degassing apparatus (a) to the hydrogen-containing water injected into a container by the filling apparatus (c), and a pressure pump that can apply a predetermined pressure to each apparatus [the degassing apparatus (a), the hydrogen dissolving apparatus (b), and the filling apparatus (c)].
In a preferred embodiment, in the filling step (C), in order to fill the hydrogen-containing water obtained in the hydrogen dissolving step (B) into the container under pressure,
1) a preparation step in which a shaft valve closes a filling port of the filling device, and the hydrogen-containing water under pressure from the hydrogen dissolving step (B) is supplied into a cavity adjacent to the filling port;
2) Then, the inlet of the container is connected to the filling port, and then the gas inside the container is removed by a gas pressure reducing means through a gas passage provided in the stem valve;
3) thereafter, closing the gas passage and opening the valve to inject hydrogen-containing water under pressure directly into the vessel;
4) after the shaft valve closes the filling port, the gas passage is opened, and pressurized air is introduced into the cavity through the gas passage by a gas pressurizing means, thereby discharging the hydrogen-containing water remaining in the filling device into the container; and
5) It is preferable to use an apparatus including a step of immediately proceeding to the sealing step (D) when the connection between the injection port and the filling port is released.
The steps (A) to (E) and the devices used in each step will be described below.

<Deaeration step (A) and deaeration device (a)>
This step is a step of degassing the supplied purified raw water and sending the obtained degassed water to the (b) hydrogen dissolving device in the (B) hydrogen dissolving step.
The degassing device (a) used in this step is a device that degasses the supplied raw purified water through a hollow fiber membrane.
The degassing device (a) is not particularly limited as long as it can degas dissolved gases such as oxygen gas, nitrogen gas, and carbon dioxide gas. For example, a vacuum degassing device or a degassing device equipped with a hollow fiber membrane module can be used. However, it is preferable to use a degassing device equipped with a hollow fiber membrane module because it can efficiently degas dissolved gases in small amounts.

The hollow fiber membrane module is usually composed of a large number of hollow fiber membranes arranged in a bundle with appropriate spaces between the membranes, and is partitioned into a water chamber and a gas chamber by the hollow fiber membranes. The purified water is passed through the water chamber and the gas chamber is depressurized to degas the dissolved gas flowing into the water chamber.
Two or more hollow fiber membrane modules may be used in parallel, and in particular, by using two or more hollow fiber membrane modules in series, trace amounts of dissolved gas can be degassed more efficiently.

In a preferred embodiment, as described above, in the production apparatus that can be used in the present invention, it is expected that pressure will be applied to the water flow path that supplies purified water to the degassing device, and therefore the hollow fiber membrane used in this apparatus is required to have high pressure resistance. However, there are no particular limitations on the type of hollow fiber membrane as long as it has such pressure resistance, and for example, polymer membranes such as polyethylene, polypropylene, polymethylpentene, polydimethylsiloxane (including the form of silicone rubber), polycarbonate-polydimethylsiloxane block copolymer, polyvinylphenol-polydimethylsiloxane-polysulfone block copolymer, poly(4-methylpentene-1-), poly(2,6-dimethylphenylene oxide), and polytetrafluoroethylene can be used.
In a preferred embodiment of the present production method, it is assumed that high pressure is applied to the water flow path that supplies purified water to the degassing device. Therefore, the hollow fiber membranes used in this device may wear out more quickly than in conventional techniques in which low pressure is applied to the water flow path. Therefore, it is desirable to use a hollow fiber membrane of a grade that has better pressure resistance.

To increase the efficiency of degassing, the purified water may be degassed under heating. In that case, it is necessary to cool the water to a lower temperature, at least to room temperature (around 25°C) or lower, when sending it to the hydrogen dissolving device after degassing in order to increase the efficiency of the subsequent hydrogen dissolution.

The purified water used in the degassing apparatus (a) can be obtained, for example, by filtering raw water in a purification apparatus.
The water used as the raw material is not particularly limited as long as it is supplied from a water source suitable for drinking, and examples of the water include tap water (water supplied by a water supply used for waterworks, a dedicated water supply, or a simple dedicated water supply), groundwater, well water, spring water, etc., and pure water (ion-exchanged water) may also be used.

The purification device usually comprises an activated carbon filter and a membrane filter.
The activated carbon filtration device removes moldy odors and trihalomethanes from the raw water, and performs dechlorination, etc. The safety filter filtration device can also remove suspended solids (including activated carbon), bacteria such as E. coli, and pathogenic protozoa such as Cryptosporidium.
Membranes that can be used in the membrane filtration device include microfiltration membranes (MF membranes), ultrafiltration membranes (UF membranes), nanofiltration membranes (NF membranes), and reverse osmosis membranes (RO membranes). In consideration of operability and the remaining mineral components that determine the taste when drinking, it is most desirable to use MF membranes. When NF membranes or RO membranes are used, mineral components dissolved in the raw water, such as sodium ions and potassium ions, tend to be removed, so in order to make the water suitable for drinking, it may be necessary to adjust the remaining rate of these mineral components or add them in a later process. Moreover, in that case, the operation becomes complicated and undesirable.
In addition, when a membrane filtration device using a membrane with a pore size of about 1 μm or less such as an NF membrane is used, bacteria may be removed, and in this case, the water flow path (piping) in each process after membrane filtration can be kept clean, and the inside of the container filled with hydrogen-containing water can be sterilized, and if food hygiene issues can be resolved, it may be possible to produce a hydrogen-containing water product without carrying out the sterilization process (E) in which heat treatment is carried out after filling and sealing. In this case, the hydrogen gas atmosphere formed by the heat treatment in the sterilization process described below is formed by the hydrogen gradually exceeding the saturation concentration vaporizing over time after the product is manufactured.

<Hydrogen dissolving step (B) and hydrogen dissolving device (b)>
This step involves dissolving pressurized hydrogen gas in the degassed water obtained in the (a) degassing apparatus and supplied to the (b) hydrogen dissolving apparatus, and sending the resulting hydrogen-containing water to a filling apparatus (c).
The hydrogen dissolving apparatus (b) used in this step is an apparatus for dissolving pressurized hydrogen gas in the deaerated water supplied from the degassing apparatus (a) in the previous step through a hollow fiber membrane.
As the hydrogen dissolving device (b), a hydrogen dissolving device equipped with a hollow fiber membrane module is used because it has a large amount of hydrogen gas dissolved per unit time and unit space and can easily increase the efficiency of dissolving hydrogen gas.

The hollow fiber membrane module is usually composed of a large number of hollow fiber membranes arranged in a bundle with appropriate spaces between the membranes, and is partitioned into a water chamber and a gas chamber by the hollow fiber membranes. The degassed water is passed through the water chamber and hydrogen gas is supplied to the gas chamber, thereby dissolving hydrogen gas in the degassed water flowing into the water chamber.
Two or more hollow fiber membrane modules may be used in combination.
In a preferred embodiment, in a manufacturing apparatus that can be used in the present invention, it is expected that pressure will be applied to the water flow path that supplies degassed water to the hydrogen dissolution apparatus, and therefore the hollow fiber membranes used in this apparatus are required to have high pressure resistance. However, there are no particular limitations on the type of hollow fiber membrane as long as it has such high pressure resistance, and the hollow fiber membranes used in this apparatus can be the polymer membranes listed as examples of the hollow fiber membranes used in the degassing apparatus described above.

There are no particular limitations on the method of supplying hydrogen gas; for example, hydrogen gas obtained from a commercially available high-purity hydrogen gas cylinder or by electrolysis of water can be pressurized and supplied to the gas chamber of the hollow fiber membrane module. The pressure applied to the hydrogen gas here is, for example, 0.1 MPa to 0.5 MPa, that is, 0.1 MPa to 0.5 MPa as a pressure applied in addition to atmospheric pressure (approximately 0.1 MPa). By applying pressure to the hydrogen gas, the dissolved hydrogen concentration can be further increased.

In a preferred embodiment, in the manufacturing apparatus that can be used in the present invention, it is assumed that high pressure is applied to the water flow path that supplies the degassed water to the hydrogen dissolving apparatus (b). Therefore, compared to the conventional technology in which low pressure is applied to the water flow path, the hollow fiber membrane used in this apparatus may wear out more quickly, so it is desirable to use a hollow fiber membrane of a grade that has better pressure resistance.

As described above, in a preferred embodiment, the manufacturing apparatus (manufacturing process) that can be employed in the present invention is preferably equipped with a pressure pump that can apply pressure to the water flow path from the purified water supplied to the degassing apparatus (a) to the hydrogen-containing water injected into the container in the filling apparatus (c) described below. By providing a pressure pump, hydrogen-containing water with a high dissolved hydrogen concentration that is applied with a pressure significantly higher than that of the conventional apparatus can be fed through the water flow path to the filling apparatus.
The pressure pump is not particularly limited as long as it is capable of applying pressure to the water flow path (piping), and any known pressure pump can be used.

Furthermore, in the manufacturing method of the above preferred embodiment, in order to maintain the pressure applied (loaded) to the water flow path, it is preferable to provide a loop flow path connecting the water flow path after pressure has been loaded by the pressure pump (i.e., the water flow path heading toward the degassing device (a)) with the water flow path before pressure has been loaded by the pressure pump.
A relief valve may be connected to the loop flow path. The relief valve functions to open the loop flow path when the water pressure in the water flow path after pressure is applied by the pressure pump exceeds a certain reference pressure, and to close the loop flow path while the water pressure is lower than the certain reference pressure. In other words, the relief valve plays a role in maintaining the water pressure below the reference pressure by constantly circulating water between the pressure pump and the loop flow path by opening and closing the relief valve.
The reference pressure is, for example, 0.1 MPa to 0.5 MPa, preferably 0.15 MPa to 0.5 MPa, and preferably, for example, 0.15 MPa to 0.4 MPa, for example, 0.15 MPa to 0.3 MPa, for example, 0.2 MPa to 0.4 MPa, from the viewpoint of wear of the hollow fiber membrane and pressure resistance performance of each device. That is, a pressure of 0.1 MPa to 0.5 MPa, for example, a pressure of 0.1 MPa to 0.5 MPa, for example, a pressure of 0.15 MPa to 0.5 MPa is loaded on the water flow path as a pressure (load pressure) further applied on top of atmospheric pressure (about 0.1 MPa).

In a preferred embodiment, the manufacturing apparatus that can be used in the present invention is preferably provided with an orifice in the water flow path before the filling device (c) described below, for example, in the water flow path between the hydrogen dissolving device (b) and the filling device (c). The orifice serves to limit the flow rate of the hydrogen-containing water, which is supplied to the filling device (c) and to which a reference pressure is applied by the pressure pump, to a certain reference flow rate or less. When the injection of hydrogen-containing water into the container begins, the water pressure in the water flow path decreases, but compared to the case where there is no orifice, the amount of pressure decrease can be suppressed by providing the orifice, leading to a stable supply of hydrogen-containing water to the filling device. In this way, the orifice also serves to smoothly and safely fill the container with hydrogen-containing water.

<Filling step (C) and filling device (c)>
This step is a step of filling a container with hydrogen-containing water obtained in the (b) hydrogen dissolving apparatus and supplied to the (c) filling apparatus.
The filling device used in this step is a device that fills the hydrogen-containing water supplied by the hydrogen dissolving device in the previous step into the above-mentioned container through its inlet (for example, the upper end opening).
This step is preferably carried out by pressurized filling, and in order to efficiently carry out the pressurized filling, the filling device (c) preferably has the following configuration.

That is, in a preferred embodiment, the filling device (c) has a cavity in the device body adjacent to the filling port, and is provided with a shaft valve that can reciprocate with its tip facing the filling port. The cavity is preferably connected to a water flow path from the hydrogen dissolving device (b), and the reciprocating movement of the shaft valve preferably provides a valve mechanism that can connect the inlet of the container connected to the filling port to the water flow path from the hydrogen dissolving device (b) and block the communication.
In this case, the cavity in the device body is connected to the gas pressure reducing means and the gas pressure increasing means through a gas passage inside the valve body or along the outer surface of the valve body. It is preferable that the gas passage is structured to be opened and closed by the reciprocating motion of the valve body, that is, the gas passage is connected to the cavity or the cavity is blocked from communication by the reciprocating motion of the valve body.
The valve is set to reciprocate at a constant cycle, whereby the filling port is repeatedly opened and closed at a constant cycle. In conjunction with the reciprocating motion of the valve, the gas passage is also repeatedly opened and closed at a constant cycle.
While the filling port is open, hydrogen-containing water is injected into the container, and the amount of hydrogen-containing water filled in the filling device can be set by the period of reciprocating motion of the shaft valve (opening and closing of the filling port) and the setting of the reference flow rate by the orifice (orifice diameter).

As described above, the manufacturing method of the present invention is characterized in that a water-soluble capsule filled with a functional raw material is placed into an openable container at the same time as or before or after filling the container with hydrogen-containing water.
The water-soluble capsules may be poured into the container through the injection port in the case of a packaging container with a straw or a packaging container with a spout, which will be described later, or through the top opening in the case of a packaging container consisting of a bag-shaped container (with a straw with a spout or without a spout) or a metal can (a bottle can or an easy-open can).

<Sealing step (D) and sealing device (d)>
This step is a step of sealing the inlet of the container filled with hydrogen-containing water by the filling device (c) with a sealing device (d).
The sealing device used in this process is a device that seals the injection port of a container (packaged with a straw) that has been filled with hydrogen-containing water.
The device is not particularly limited as long as it can immediately seal the injection port of the container (packaged with a straw) sent from the filling device, and any known sealing device can be used.

<Sterilization step (E) and heat sterilization device (e)>
In this process, after the sealing process (D) is completed, the sealed hydrogen-containing water container is sent to a suitable heat sterilization device and heat sterilized. Through this process, the final product, the hydrogen-containing water product for drinking, is completed.
As the heat sterilization device, for example, a heat steam sterilization device can be used, and the heating temperature and heating time during sterilization are desirably determined appropriately taking into consideration the F value (the heating temperature (minutes) required to kill a certain number of specific bacterial spores or bacteria at a certain temperature) and product quality. For example, the heating temperature and heating time are 65 to 98°C, 1 minute to 3 hours, for example, 75 to 93°C, 2 minutes to 120 minutes, or 80 to 90°C, 5 minutes to 90 minutes, or 82 to 88°C, 8 minutes to 60 minutes, or 83 to 86°C, 10 minutes to 50 minutes, and for example, 85°C for 30 minutes.
The hydrogen-containing water product for drinking, which is the final product sterilized by heating, meets the standards set forth in the "Standards and Criteria for Foods, Additives, etc." (Notification No. 370 of the Ministry of Health and Welfare, 1959), and meets the criteria for negative coliform bacteria, for example, as set forth in [D. Articles] [Soft Drinks] [1. Ingredient Standards for Soft Drinks] [(1) General Standards]. In addition, from the viewpoint of making it easier for consumers to accept hydrogen-containing water products for drinking with a sense of security, general bacteria may be used as an indicator of product standards for sterilization. For example, in the water quality standards set forth in the "Ministry Ordinance on Water Quality Standards" based on the provisions of Article 4 of the Water Supply Act, the item [general bacteria] has the standard [the number of colonies formed in 1 mL of test water is 100 or less], and the hydrogen-containing water product for drinking of the present invention also meets this standard.

From the viewpoint of food hygiene, hydrogen-containing water products for drinking must be subjected to the above-mentioned heat treatment for sterilization after the hydrogen-containing water is filled and sealed in a storage container. Since the saturated hydrogen concentration decreases with increasing temperature, as the temperature of the hydrogen-containing water inside the container increases due to this heat treatment, the hydrogen dissolved in the hydrogen-containing water cannot maintain its dissolved state, and hydrogen with a concentration above the saturated hydrogen concentration is forced to vaporize. For example, when a packaging container with a straw is used, vaporized hydrogen usually accumulates around the cap at the top of the container and the spout at the top of the straw, forming a hydrogen gas atmosphere.
When the product is cooled after heat treatment, the hydrogen gas inside the container produced after heat treatment redissolves in the hydrogen-containing water depending on the saturated hydrogen concentration at the cooling temperature. In conventional hydrogen-containing water beverage products in which hydrogen-containing water is filled at normal pressure in a general-purpose packaging container with a straw, the hydrogen gas atmosphere essentially disappears when the product is cooled to room temperature after the above-mentioned heat sterilization due to the redissolution of hydrogen gas.

In a preferred embodiment of the manufacturing method of the present invention, the hydrogen-containing water is pressurized and filled into the container, so that the dissolved hydrogen concentration of the hydrogen-containing water at the time of filling is much higher than the saturated hydrogen concentration (saturated hydrogen concentration) of the hydrogen-containing water at the temperature of the hydrogen-containing water at the time of filling. Therefore, the hydrogen gas vaporized by the heat treatment (sterilization process) is not completely dissolved even after being re-dissolved in the hydrogen-containing water after the product is cooled, and the hydrogen gas atmosphere continues to exist in the container even when the product is cooled to room temperature after the heat treatment. If some hydrogen remains in the container as a gas atmosphere (it reacts to a hydrogen sensor or the like when the product is opened), it can be a factor in maintaining the hydrogen concentration of the hydrogen-containing water at a high level, so the remaining hydrogen gas atmosphere is very important in terms of the nature of the hydrogen-containing water.
That is, the hydrogen-containing water product for drinking produced by pressure filling is composed of an openable container, hydrogen-containing water filled and sealed in the container under pressure, water-soluble capsule material dissolved in the hydrogen-containing water, functional ingredients filled in the water-soluble capsules dissolved in the hydrogen-containing water, and a gas atmosphere containing hydrogen gas generated by heat treatment after the pressure filling in the space above the water surface of the hydrogen-containing water in the container. The gas atmosphere exists, for example, after 30 days, preferably after at least 90 days, and more preferably after 180 days. It is particularly preferable that the gas atmosphere has a hydrogen gas partial pressure of 90% or more relative to the total pressure of the atmosphere.
Furthermore, even if there are various gases that lead to a decrease in the dissolved hydrogen concentration due to the presence of this hydrogen gas-containing gas atmosphere, i.e., gas remaining in the container or gas mixed into the hydrogen-containing water, the hydrogen-containing water beverage product produced by employing pressurized filling in the present invention can maintain a high dissolved hydrogen concentration and a low oxidation-reduction potential value compared to products produced by existing technologies or products filled at normal pressure.
As mentioned above, in the manufacturing method of the present invention, water-soluble capsules filled with functional raw materials are added simultaneously with or before or after filling the container, thereby realizing the effect of suppressing the decrease in the dissolved hydrogen concentration of the hydrogen-containing water due to contact with air that occurs when conventional functional raw materials, etc. are mixed with hydrogen-containing water. By combining this with the above-mentioned pressurized filling, it is possible to further maintain a high dissolved hydrogen concentration and a low oxidation-reduction potential value even after long-term storage.

As described above, the hydrogen-containing drinking water product obtained by the manufacturing method of the present invention can realize hydrogen-containing water having a higher dissolved hydrogen concentration, a lower oxidation-reduction potential, and a lower dissolved oxygen concentration compared to conventional products, even after 90 days have passed since production.
In the past, when a hydrogen-containing water product was produced using a general-purpose packaging container with a straw as a storage container, it was difficult to completely maintain the airtightness of the upper end opening (i.e., the mouth part: spout) and the cap of the packaging container with a straw, and the space inside the container communicated with the space outside, even if only slightly. As a result, it was inevitable that air would gradually flow into the container from the outside over time, even if only slightly, and the drop in the dissolved hydrogen concentration caused by the contact between the hydrogen-containing water and the air was unavoidable.
Thus, in conventional hydrogen-containing water products in which hydrogen-containing water is filled and sealed in, for example, a general-purpose packaging container with a straw, there is a problem that the dissolved hydrogen concentration of the hydrogen-containing water decreases as time passes after production. If the bag-shaped container does not have a straw, the problem of air inflow from the straw or the periphery of the cap can be avoided, but on the other hand, it is difficult to drink directly from the bag-shaped container, and when transferring to another container such as a cup, another problem may occur, such as a significant decrease in the dissolved hydrogen concentration due to contact with the air. In any case, there has been a demand for a hydrogen-containing water product that can maintain the dissolved hydrogen concentration as high as possible and maintain a low oxidation-reduction potential (maintain a negative value) even after a long period of time (for example, more than about 3 to 6 months) has passed since production.

According to the present invention, it is possible to provide hydrogen-containing water that maintains high quality, for example, in hydrogen-containing water having a pH of 7.0, the oxidation-reduction potential is approximately -600 mV or less and the dissolved hydrogen concentration is 1.0 ppm or more even 180 days or more after production, and the dissolved oxygen concentration is 1.0 ppm or less even 90 days after production, and further, the dissolved oxygen concentration is 1.3 ppm or less even 180 days after production.
For example, according to the manufacturing method of the present invention, a hydrogen-containing drinking water product can be manufactured in which the oxidation-reduction potential of the filled hydrogen-containing water is {[-59 x (pH value of the hydrogen-containing water in the hydrogen-containing drinking water product after 90 days)]-180} mV or less at least 90 days after production when stored at room temperature, i.e., when the pH of the hydrogen-containing water filled in the hydrogen-containing drinking water product is 7.0 after 90 days, the oxidation-reduction potential of the hydrogen-containing water is -593 mV or less. At the same time, a product can be manufactured in which, when the product is gently shaken up and down after 90 days, a sound of the hydrogen-containing water hitting the inner wall of the container is generated, confirming the presence of a gas atmosphere.
Here, the value of the oxidation-reduction potential (ORP) specified in the present invention refers to a value measured using a 3.3 mol/L silver chloride electrode as a standard (vs. Ag/AgCl (3.3N)), and the potential of a 3.3 mol/L silver chloride electrode (Ag/AgCl (3.3N)) relative to a standard hydrogen electrode (SHE) is +0.206 V (vs. SHE) at 25° C.

The manufacturing method of the present invention makes it possible to blend various ingredients into the hydrogen-containing water filled in the container. In particular, the present invention is characterized in that water-soluble capsules filled with functional ingredients are placed in the container before, during, or after the process of filling the container with the hydrogen-containing water.

The above-mentioned water-soluble capsules (water-soluble capsules filled with functional raw materials) can be mixed into hydrogen-containing water in various ways. For example, after obtaining hydrogen-containing water by the above-mentioned various methods, water-soluble capsules can be added and mixed into the obtained hydrogen-containing water. In this way, water-soluble capsules can be mixed and dissolved in hydrogen-containing water in advance, and then the water-soluble capsules can be filled (pressurized) into a packaging container. However, in this method, there is a concern that the contact between the hydrogen-containing water and air increases during the mixing process in the process of adding, mixing, and dissolving water-soluble capsules into hydrogen-containing water, which reduces the dissolved hydrogen concentration. In addition, a method of dissolving water-soluble capsules in raw water (purified water) and then dissolving hydrogen therein can be considered, but this method cannot achieve the desired dissolved hydrogen concentration, or the presence of impurities (water-soluble capsules) may cause contamination or damage to manufacturing equipment, including hydrogen dissolving equipment.
Therefore, in the method of the present invention, a means is adopted in which water-soluble capsules filled with a functional raw material are placed in the system at the same time as or before or after filling the hydrogen-containing water into the container. In particular, it is preferable to place the water-soluble capsules before or during the step of filling the hydrogen-containing water. For example, a method may be adopted in which water-soluble capsules are placed in the container in advance and then hydrogen-containing water is filled therein.
These water-soluble capsules are placed in the container before, during, or after the hydrogen-containing water is filled into the container. After filling the container with hydrogen-containing water and before sealing the container, the capsules may be pre-treated (for example, by drilling fine holes in the capsules) to prevent them from spilling out of the container due to water pressure or the like.

[Openable container]
The openable container used in the present invention may be in the form of a bag-like container, such as a packaging container with a straw comprising a flexible bag-like container body, a straw with a spout, and a sealing cap, a packaging container with a spout comprising a flexible bag-like container body, a spout, and a sealing cap, or a bag-like container body without a straw or spout. It may also be a metal can such as a bottle can (resealable can) or an easy-open can (pull-tab can, pull-top can).
Various configurations of openable containers are described in detail below.

[Bag-shaped container: packaging container with straw]
The packaging container with a straw, which is one form of bag-like container used in the present invention, is a bag-like container in the form of a so-called "aluminum pouch" that is formed by inserting the lower part of a spouted straw into a flexible bag-like container body made of a laminated film (also called a metal laminate film) containing a metal layer (e.g. metal foil) and a synthetic resin layer, fixing the spouted straw to the container body by heat welding at its upper edge, and screwing a sealing cap onto the upper opening of the spouted straw.

An example of one form of a hydrogen-containing drinkable water product produced by the production method of the present invention is shown in Fig. 1. The hydrogen-containing drinkable water product 1 shown in Fig. 1 is a form in which a straw-equipped package container is used as a bag-shaped container, and hydrogen-containing water 6 is filled into a straw-equipped package container 2 consisting of a container body 3, a spouted straw 4, and a sealing cap 5, and then the upper end opening 42A of the spouted straw 4 is sealed with the cap 5 (water-soluble capsules dissolved in the hydrogen-containing water 6 are not shown).
2 shows an enlarged view of the periphery A of the upper end opening 42A of the spouted straw 4 of the hydrogen-containing water product 1 for drinking shown in FIG. 1. That is, in the hydrogen-containing water product for drinking, when a gas atmosphere exists in the container at the stage of cooling to room temperature after heat treatment, if the spouted straw described later is made transparent or semi-transparent, the presence of the gas atmosphere 7 can be confirmed from the outside of the straw (see FIG. 2(a) : hydrogen-containing water 6, gas atmosphere 7), or, when the hydrogen-containing water product for drinking is lightly shaken up and down, the movement of the hydrogen-containing water 6 in the container, i.e., the movement of the gas atmosphere 7, can be visually confirmed from the outside of the straw (see FIG. 2(b) : hydrogen-containing water 6, gas atmosphere 7). In addition, when the gas atmosphere exists, when the product is lightly shaken up and down, the sound of the hydrogen-containing water hitting the inner wall of the container (for example, onomatopoeic sounds such as splashing and rustling) is generated, and the presence of the gas atmosphere can be confirmed by this sound.
The presence of this gas atmosphere can also be confirmed by using a gas detector. For example, if a hydrogen gas detector is installed near the cap of a hydrogen-containing beverage product and the cap of the product is turned and opened, if a hydrogen gas atmosphere is present, the gas atmosphere present inside the container is released to the outside at the moment the cap is opened or by pressing the container, and the gas detector is activated. On the other hand, if no gas atmosphere is present inside the container, the detector will not be activated even after opening.

[Straw with spout]
FIG. 3 is a perspective view (appearance) showing an example of a spouted straw used in the straw-equipped packaging container of the present invention.
As shown in FIG. 3, the straw 4 with spout is provided with a straw portion 41 which serves as an inlet for the contents, and a mouth portion 42 which serves as a filling port and suction port for the contents, and hydrogen-containing water is filled from the upper end mouth portion 42A by a filling device described later. A male screw portion 43 is formed on the outer periphery of the lower part of the mouth portion 42 so that a sealing cap described later can be screwed on and off freely, and a protrusion portion 48 for engaging the sealing cap is formed below that. Further below that, a flange 47 is formed to fit into the guide rail when the container is fed to the filling device. Although not shown in FIG. 3, a female screw portion is formed on the inner periphery of the sealing cap which seals the upper end mouth portion 42A of the straw 4 with spout to screw into the male screw portion 43 of the mouth portion 42. In addition, a seal material for sealing the upper end mouth portion 42A after filling the contents may be provided at the tip of the mouth portion 42, which can prevent the hydrogen-containing water, which is the content, from leaking from the mouth portion 42 even when sterilized by pressurization and heat. The sealing material is formed of a film made by laminating a synthetic resin film and a metal foil, and can be welded to the upper end mouth portion 42A of the mouth portion 42 by a means such as heat sealing.
A heat-sealed portion 44 is provided below the flange 47 for heat-sealing to the container body 3. A hole 46 is provided above the straw portion 41, which allows the hydrogen-containing water content to be easily sucked out. A lug 45 is formed extending downward from the heat-sealed portion 44 to reinforce the strength of the portion where the hole 46 is formed and to stably position the spouted straw 4 in the container body 3.

The spouted straws used in the present invention can be formed using resin materials such as low-density polyethylene resin, medium-density polyethylene resin, high-density polyethylene resin, linear low-density polyethylene resin, polystyrene resin, ionomer resin, polypropylene resin, acrylic resin, nylon resin, polyester resin, polycarbonate resin, etc.

In addition, the spouted straw used in the present invention may be a spouted straw having improved gas barrier properties of the spouted straw itself.
Examples of spouted straws with improved gas barrier properties include those in which a gas barrier material that blocks hydrogen gas from passing through is disposed on or inside the inner wall of the straw over substantially the entire area of at least the upper part of the straw above the part that is heat-sealed to the container body. The gas barrier material may be disposed inside the spout or straw so as to block the holes in the straw, and holes may be opened in the gas barrier material by utilizing the rotational force when opening the sealing cap described below, or by applying pressure to the bag-shaped container body from the outside, and the gas barrier material may be disposed so that the gas barrier material can be used for drinking.
The gas barrier material is not particularly limited as long as it does not transmit gases such as hydrogen and oxygen, and examples thereof include metal foils (metal films) of aluminum, iron, copper, tin, etc., films of polyvinylidene chloride, etc., films of polyolefin films such as polyethylene and polypropylene coated with polyvinylidene chloride, and films of these polyolefin films subjected to deposition of aluminum, carbon, silica, etc. Among these, from the viewpoints of gas barrier properties, cost, and film operability, aluminum films (aluminum foils) are preferred. In addition, gas barrier properties can also be improved by using multilayer films such as EVOH.

[Sealing cap]
The sealing cap is not particularly limited as long as it has a shape that can be screwed onto the upper end opening of the spouted straw and seal the upper end opening of the straw. Usually, the sealing cap has a female thread on the inner periphery that screws into the male thread 43 of the opening of the spouted straw 4, and is provided with a band that can engage with the protrusion 48 of the spouted straw.
The sealing cap may have improved gas barrier properties, as in the case of the spouted straw. In that case, for example, an inner seal material with hydrogen gas barrier properties that can seal the upper end of the spouted straw may be provided on the inner wall of the top of the sealing cap.
The inner seal material can be formed of a synthetic resin film, a metal foil (film), or a laminated film obtained by laminating these together. As the synthetic resin film, a film using the resin material listed in the spouted straw, various films listed as the gas barrier material, and as the metal foil, the metal foil listed as the gas barrier material can be suitably used.

[Container body]
As the container, a container made of a laminated film (metal laminated film) containing a metal layer and a synthetic resin layer, for example, a container made of an aluminum laminated film (a laminated film containing an aluminum layer and a synthetic resin layer), a so-called pouch container, is preferably used because it has high airtightness and can prevent hydrogen from leaking out. As the shape of the pouch container, various types such as a gusset type (with gusset) and a stand type (without gusset) that are already available on the market can be used.

The product capacity of the container is not particularly limited, but for example, containers with a capacity of 100 mL to 2,000 mL, particularly 150 mL to 550 mL, specifically 150 mL, 180 mL, 200 mL, 220 mL, 250 mL, 280 mL, 300 mL, 330 mL, 350 mL, 400 mL, 450 mL, 500 mL, and 550 mL can be suitably used. In this specification, the "product capacity" refers to the standard capacity (also referred to as the appropriate filling amount or the indicated content amount) when the product is distributed and sold, and is usually several to 15% less than the maximum capacity that can be filled into the container.
The size (diameter) of the cap and the water intake (spout) is almost constant regardless of the product capacity. Therefore, the contact area between the hydrogen gas generated by the heat treatment and accumulated around the cap and the spout and the hydrogen-containing water in the container is smaller in the case of a large-capacity product capacity such as 500 mL or 550 mL than in a low-capacity product (150 mL or 200 mL, etc.). Therefore, in such a large-capacity product, the re-dissolution of the hydrogen gas in the product into the hydrogen-containing water occurs more slowly than in a low-capacity product. Therefore, in a large-capacity product, the hydrogen gas atmosphere remains for a long period of time not only in the hydrogen-containing water product for drinking of the present invention but also in a conventional hydrogen-containing water product for drinking that is filled at normal pressure. Large-capacity products are attracting attention for their excellent long-term storage properties because they can maintain a high dissolved hydrogen concentration for a long period of time compared to low-capacity products. However, in conventional hydrogen-containing drinking water products, even in such large-volume products, the hydrogen gas atmosphere typically substantially disappears within about three months, making it difficult to maintain a state in which hydrogen-containing water and a gas atmosphere continue to coexist inside the container, as in the hydrogen-containing drinking water product of the present invention.

[Bag-shaped container: packaging container with spout]
In the present invention, a spout-equipped packaging container can be used as one form of a bag-shaped container as an openable container. This container is a bag-shaped container formed by fixing a spout to a flexible bag-shaped container body made of a laminated film (metal laminate film) containing a metal layer and a synthetic resin layer by heat welding at the upper edge of the bag-shaped container body, and screwing a sealing cap onto the upper opening of the spout. This container is a form of the straw-equipped packaging container described above, in which there is no straw inside the bag-shaped container, and only a spout (suction mouth) is provided.
The bag-shaped container in this packaging container can be the [container body] of the [Bag-shaped container: packaging container with straw] described above, and its shape and capacity can also be those described for the [container body] above.
The spout used in this packaging container may be formed using various resin materials listed in the [Spout-equipped straw] section of the above [Bag-shaped container: packaging container with straw]. A spout with improved gas barrier properties may also be used, and the gas barrier material listed in the above [Spout-equipped straw] may be used to substantially cover the entire surface or interior of the spout inner wall of the spout above the portion heat-sealed to the container body. The gas barrier material may be attached to the lower part of the spout so as to close the hole in the spout, and the gas barrier material may be provided so that the gas barrier material can be opened by the rotational force when the sealing cap is opened or by the pressure of the hydrogen-containing water inside the spout caused by applying pressure from the outside to the bag-shaped container body, and the gas barrier material can be used for drinking.
Furthermore, the sealing cap used for this packaging container can be the sealing cap of the above-mentioned [Bag-shaped container: packaging container with straw].

In the present invention, particularly when a packaging container with a straw or a packaging container with a spout is used, the bag-shaped container body used therefor has flexibility, so even if it is opened once, it can be easily recapped (resealed) by pressing the container body of the packaging container with a straw (or a packaging container with a spout) from both sides to release the air inside and overflow the hydrogen-containing water, and then fitting the cap, minimizing the amount of air remaining in the container body. Therefore, even if there is leftover drink and it is to be stored (drink in multiple portions), the decrease in the dissolved hydrogen concentration of the hydrogen-containing water can be suppressed to a low level compared to a form consisting of only a bag-shaped container body described below or a metal can.

[Bag-shaped container: packaging container made of a bag-shaped container body]
In the present invention, a bag-shaped container without a straw or spout can be used as the openable bag-shaped container. This container is a flexible bag-shaped container made of a laminated film (metal laminate film) including a metal layer and a synthetic resin layer (without the spout-equipped straw or spout inserted, and without a sealing cap). In this case, after the hydrogen-containing water filling step described below, the upper edge of the container is sealed by heat welding to form a product.
The bag-shaped container in this packaging container can be the [container body] of the [Bag-shaped container: packaging container with straw] described above, and its shape and capacity can also be those described for the [container body] above.
In addition, if a packaging container consisting of a bag-shaped container (a container without a straw) is used, it is difficult to reseal it once it has been opened, so it is a good idea to consider the volume that can be consumed in one go.

[Metal cans: bottle cans, easy-open cans]
In the present invention, in addition to the bag-shaped containers such as the above-mentioned packaging containers with straws, metal cans such as aluminum or steel easy-open cans (pull-tab cans, pull-top cans) and bottle cans (resealable cans) can be used, and their capacities can be those described above under [Container body].
However, among the products filled in these metal cans, easy-open cans (pull-tab cans, pull-top cans) cannot be recapped, so once opened, the hydrogen-containing water continues to come into contact with air, and the dissolved hydrogen concentration of the hydrogen-containing water decreases over time. Therefore, it is desirable to drink the entire can in one go to prevent the decrease in the dissolved hydrogen concentration as much as possible. In addition, in the case of bottle cans (resealable cans), although it is possible to recap the can when the entire can is not yet drunk, it is not possible to recap the can while removing the air that has flowed into the can, so that the dissolved hydrogen concentration of the hydrogen-containing water will decrease. Therefore, in the case of these metal cans, the product volume that can be consumed in one go should be considered, and by setting the product volume to, for example, about 100 mL to 200 mL, it is possible to make a product that can be consumed without any leftovers and maintains the dissolved hydrogen concentration.

In addition, as the product volume increases, for example, in a large-capacity product with a product volume of 550 mL, it is difficult to drink it all at once, so it is expected that it will be consumed in multiple portions. As mentioned above, in a product using the above-mentioned packaging container with a straw or a packaging container with a spout, even if it is opened once, the air remaining in the container body can be minimized by pressing the container body from both sides to release the air inside and overflow the hydrogen-containing water while fitting the cap. However, even if the hydrogen-containing water inside is overflowed every time it is consumed (every time it is opened), it is difficult to reduce the air remaining in the container body to zero, and the phenomenon of the dissolved hydrogen concentration decreasing every time the cap is opened is unavoidable.
As mentioned above, large-capacity hydrogen-containing water products have the advantage of being easy to store for a long time, but this advantage is lost once the product is opened. Therefore, there is a demand for products that do not experience a large decrease in dissolved hydrogen concentration even after multiple openings and recapping.
In response to this demand, the present invention can provide a product in which the dissolved hydrogen concentration in the hydrogen-containing water is higher and maintained longer during storage than in conventional products (particularly products containing functional ingredients) by introducing a water-soluble capsule filled with a functional ingredient into the container before, during, or after filling the container with hydrogen-containing water, and in a preferred embodiment, further combining this with pressurized filling. Therefore, even after multiple cap openings and closings, it is possible to maintain a relatively high dissolved hydrogen concentration.
In this way, the manufacturing method of the present invention can provide a product that is highly appealing to consumers, as it can produce a hydrogen-containing drinking water product that can be consumed in several portions while maintaining a high dissolved hydrogen concentration.

As described above, according to the manufacturing method of the present invention, functional ingredients are filled into the water-soluble capsules and used in the manufacturing method, thereby enabling the blending of the functional ingredients into the hydrogen-containing water without reducing the dissolved hydrogen concentration in the hydrogen-containing water at the time of filling.
That is, in the present invention, functional ingredients are filled in the water-soluble capsules (empty capsules) in advance, and the water-soluble capsules filled with the functional ingredients are poured into a container at the same time as or before or after the container is filled, thereby achieving the blending of the functional ingredients into the hydrogen-containing water. The present invention also covers drinking hydrogen-containing water products filled with hydrogen-containing water together with water-soluble capsules filled with functional ingredients produced by the production method of the present invention.

A more detailed description of a preferred embodiment of the present invention will be given below, but the present invention is not limited thereto.

<Production of hydrogen-containing drinking water product (1)>
The hydrogen-containing drinking water products of Examples 1 and 2 were each produced according to the following procedure.
In this example, a hydrogen-containing drinking water product was produced following the method disclosed by the present inventors in their previous patent applications (Japanese Patent No. 4551964, Japanese Patent Application No. 2014-092648, Japanese Patent No. 6052948, etc.).
Specifically, a hydrogen-containing water product for drinking was produced through the following steps: (1) a purification process in which raw water is filtered and purified in a purification device, and the purified water obtained is sent to a degassing device; (2) a degassing process in which the purified water supplied in the degassing device is degassed through a hollow fiber membrane, and the degassed water obtained is sent to a hydrogen dissolving device; (3) a hydrogen dissolving process in which pressurized hydrogen gas is dissolved in the degassed water supplied in the hydrogen dissolving device through a hollow fiber membrane, and the hydrogen-containing water obtained is sent to a filling device; (4) a filling process in which the hydrogen-containing water supplied in the filling device is filled into a packaging container with a straw through its opening (inlet); (5) a sealing process in which the opening of the packaging container with a straw filled with the hydrogen-containing water is sealed with a sealing cap; and (6) a process in which the product filled and sealed with the hydrogen-containing water is heat-treated (at 85°C for 30 minutes).
The above (4) filling step was carried out by pressurized filling (load pressure: 0.2 MPa to 0.3 MPa) and was adjusted to have the same conditions.
In the filling step, the following capsules and the like were placed in advance into a packaging container with a straw into which hydrogen-containing water was filled, and the hydrogen-containing water was then filled under pressure.
Example 1: A water-soluble capsule filled with functional ingredient 1 (100 mg) was added. Example 2: A water-soluble capsule (empty capsule) and functional ingredient 1 (100 mg) were added separately. In addition, after the (6) heat treatment process, the hydrogen-containing drinking water product was opened as a confirmation sample, and it was confirmed that the water-soluble capsule and functional ingredient had completely dissolved.

The water-soluble capsules and the like used in Examples 1 and 2 are as follows:
・Water-soluble capsule (pullulan):
Product name: "Plantcaps (registered trademark)", size 2, pullulan content 85.5%, capsule weight: 63 mg (pullulan content: 54 mg), Capsugel Japan Co., Ltd. Functional raw material 1:
Sodium ascorbate, product name "Sodium L-ascorbate", Fuso Chemical Co., Ltd.

The inventors have confirmed that the dissolved hydrogen concentration at the time of filling shown in Table 1 below can be realized in product samples (hydrogen-containing water is filled under pressure into a straw-equipped packaging container containing one water-soluble capsule filled with a functional ingredient) produced by producing hydrogen-containing water and filling it under pressure under maximum capacity conditions that can stably maintain mass production using the device shown in Patent No. 6052948 and Figure 1. (Number of samples: 10 in total) Note that, since the production is performed under maximum capacity conditions that can stably maintain mass production, some variation occurs in the dissolved hydrogen concentration, but it has been confirmed that by suppressing the capacity conditions, variation in concentration at the time of filling can be suppressed, and production with a stabilized (constant) concentration can be realized.

<Evaluation of hydrogen-containing drinking water products (1)>
For each of the hydrogen-containing drinking water products of Examples 1 and 2, the dissolved hydrogen concentration, pH, and redox potential (vs. Ag/AgCl (3.3N)) were measured 7, 90, 180, and 360 days after production (storage at room temperature (25°C ± 5°C)) using a 3.3 mol/L silver chloride electrode as a standard (five product samples were measured on each measurement day, and the measurement results were calculated as the average value). As a reference example, a similar evaluation was also carried out on a hydrogen-containing drinking water product (only hydrogen-containing water) that did not contain functional ingredients or water-soluble capsules.
The dissolved hydrogen concentration was measured using a Unisense dissolved hydrogen sensor (a combination of a multimeter and a dissolved hydrogen sensor), and the temperature at the time of filling the packaging container with a straw was adjusted so that the temperature at the time of sensor calibration (water temperature) and the measurement temperature (water temperature) were 20°C ± 2°C.
In order to standardize the measurement conditions, the pH-corrected ORP value was obtained using the following formula based on the measured pH and ORP values, which corrects for the fact that the ORP value is measured as a seemingly low/high value depending on the pH value.
ORP value after pH correction: ORP actual measurement value - (-59 x actual measurement pH)
In addition, based on the pH value of the product measured after 90 days, a reference ORP value was calculated and compared with the actually measured oxidation-reduction potential.
Reference ORP value: {[-59 x (pH value of the hydrogen-containing water in the hydrogen-containing drinking water product after 90 days)] - 170}
The results obtained are shown in Table 2.

The hydrogen-containing drinking water products of Examples 1 and 2, as well as the Reference Example, were lightly shaken (using a special sample that had been stored to check the sound) 7, 90, 180, and 360 days after production (stored at room temperature (25°C ± 5°C)), and sound was detected in all cases. This supports the existence of a gas atmosphere in the space above the water surface of the hydrogen-containing water filled in the container.

As shown in Table 2, the hydrogen-containing drinking water product of Example 1 was able to maintain a lower redox potential and a higher dissolved hydrogen concentration than the hydrogen-containing drinking water product of Example 2.

<Production of hydrogen-containing drinking water product (2)>
In the procedure of <Production of hydrogen-containing drinking water product (1)> above, except that the water-soluble capsules and the like were added as follows, the hydrogen-containing drinking water of Examples 3-1 and 3-2, and Examples 4-1 and 4-2 were produced in the same manner as above.
The following water-soluble capsules and the like were placed in advance into a packaging container with a straw into which hydrogen-containing water was to be filled in the filling step, and the hydrogen-containing water was then filled under pressure into the container.
Example 3-1: Add a water-soluble capsule filled with functional ingredient 1 (100 mg) Example 3-2: Add a water-soluble capsule (empty capsule) and functional ingredient 1 (100 mg) separately Example 4-1: Add a water-soluble capsule filled with functional ingredient 2 (100 mg) Example 4-2: Add a water-soluble capsule (empty capsule) and functional ingredient 2 (100 mg) separately

The water-soluble capsules and the like used in Examples 3-1 and 3-2, and Examples 4-1 and 4-2 are as follows:
・Water-soluble capsule (pullulan):
Product name: "Plantcaps (registered trademark)", size 2, pullulan content 85.5%, capsule weight: 63 mg (pullulan content: 54 mg), Capsugel Japan Co., Ltd. Functional raw material 1:
Sodium ascorbate, product name "Sodium L-ascorbate", Fuso Chemical Co., Ltd.
・Functional ingredients 2:
Mango powder, product name "Mango Powder", Imuraya Foods Co., Ltd.

<Evaluation of hydrogen-containing drinking water products (2): Sensory evaluation (1)>
A sensory evaluation was carried out on the hydrogen-containing drinking water products of Examples 3-1 and 3-2, and Examples 4-1 and 4-2.
The sensory evaluation was conducted using the following evaluation items and evaluation criteria. The sensory evaluation results were conducted by 10 panelists, who selected the numbers of the examples that corresponded to the items shown in Table 3 for each of Functional Raw Material 1 (Examples 3-1 and 3-2) and Functional Raw Material 2 (Examples 4-1 and 4-2) (score: 1), and calculated the total number.
The results obtained are shown in Tables 4 and 5.

As shown in Tables 4 and 5, the product of Example 3-1, which contains functional ingredient 1 (sodium ascorbate), is a product with less bitterness than the product of Example 3-2, while the product of Example 4-1, which contains functional ingredient 2 (mango powder), is a product with less sourness and improved aroma, flavor, and deliciousness than the product of Example 4-2.

<Production of hydrogen-containing drinking water product (3)>
In the procedure of <Production of hydrogen-containing drinking water products (1)> above, except that the water-soluble capsules and the like were added as follows, the hydrogen-containing drinking water products of Examples 5-1 and 5-2, Examples 6-1 and 6-2, Examples 7-1 and 7-2, Examples 8-1 and 8-2, and Examples 9-1 and 9-2 were produced in the same manner as above.
The following water-soluble capsules and the like were placed in advance into a packaging container with a straw into which hydrogen-containing water was to be filled in the filling step, and the hydrogen-containing water was then filled under pressure into the container.
Example 5-1 to Example 9-1: Water-soluble capsules filled with functional ingredients 3 to 7 (100 mg) were added. Example 5-2 to Example 9-2: Water-soluble capsules (empty capsules) and functional ingredients 3 to 7 (100 mg) were added separately.

The water-soluble capsules and the like used in Examples 5-1 to 9-1 and Examples 5-2 to 9-2 are as follows:
・Water-soluble capsule (pullulan):
Product name: "Plantcaps (registered trademark)", size 2, pullulan content 85.5%, capsule weight: 63 mg (pullulan content: 54 mg), Capsugel Japan Co., Ltd. Functional raw material 3:
Grapefruit flavoring, product name "Dry Cotton Grapefruit KC-1646", Takada Fragrance Co., Ltd.
・Functional ingredients 4:
Black tea fragrance, product name "Black Tea Coat AA75975", Ogawa Fragrance Co., Ltd.
・Functional ingredients 5:
Citric acid, product name "Fuso MS Citric Acid", Fuso Chemical Co., Ltd.
・Functional ingredients 6:
Sodium citrate, product name "Purified Sodium Citrate M", Fuso Chemical Co., Ltd.
・Functional ingredients 7:
Stevia, product name "Stevia Fine R-J2", Nippon Paper Crecia Co., Ltd.

<Evaluation of hydrogen-containing drinking water products (3): Sensory evaluation (2)>
Sensory evaluation was carried out on the hydrogen-containing drinking water products of Examples 5-1 and 5-2, Examples 6-1 and 6-2, Examples 7-1 and 7-2, Examples 8-1 and 8-2, and Examples 9-1 and 9-2.
The sensory evaluation was conducted using the following evaluation items and evaluation criteria. The sensory evaluation results were conducted by 10 panelists, who selected the example numbers corresponding to the items shown in Table 6 for each of Functional Raw Material 3 (Examples 5-1 and 5-2), Functional Raw Material 4 (Examples 6-1 and 6-2), Functional Raw Material 5 (Examples 7-1 and 7-2), Functional Raw Material 6 (Examples 8-1 and 8-2), and Functional Raw Material 7 (Examples 9-1 and 9-2) (score: 1), and calculated the total number.
The results are shown in Tables 7 to 11.

As shown in Tables 7 to 11, the product of Example 5-1, which contained functional ingredient 3 (grapefruit flavoring), was a product with improved aroma and flavor compared to the product of Example 5-2, and the product of Example 6-1, which contained functional ingredient 4 (black tea flavoring), was a product with less bitterness and improved aroma and flavor compared to the product of Example 6-2.
Furthermore, the product of Example 7-1, which contained functional ingredient 5 (citric acid), had a more refreshing sour taste and less of a sharp, irritating sour taste than the product of Example 7-2, and the product of Example 8-1, which contained functional ingredient 6 (sodium citrate), had less bitterness than the product of Example 8-2.
The product of Example 9-1, which contained the functional ingredient 7 (stevia), had a mellower sweetness and less bitter aftertaste than the product of Example 9-2.

<Production of hydrogen-containing drinking water product (4)>
The hydrogen-containing drinking water products of Examples 11 to 37 were produced following the above procedure, except that in the procedure of <Production of hydrogen-containing drinking water products (1)>, the water-soluble capsules and the like were added as follows.
The following water-soluble capsules were placed in advance into a packaging container with a straw into which hydrogen-containing water was to be filled in the filling step, and the hydrogen-containing water was then filled under pressure into the container.
The water-soluble capsules used in this example (pre-loaded into a container) are as follows: Functional ingredients 8 to 23 listed in Table 12 were loaded into the water-soluble capsules listed below in the blending amounts (mg) listed in Table 13, and dextrin (Max 1000, Matsutani Chemical Industry Co., Ltd.) and fine silicon dioxide (Silopage 720, Fuji Silysia Chemical Ltd.) were further added to adjust the loading amount to a total of 250 mg to prepare water-soluble capsules for loading.
The water-soluble capsules and the like used in Examples 11 to 37 are as follows:
・Water-soluble capsule (pullulan):
Product name: "Plantcaps (registered trademark)", size 2, pullulan content 85.5%, capsule weight: 63 mg (pullulan content: 54 mg), Capsugel Japan Co., Ltd.

<Evaluation of hydrogen-containing drinking water products (4)>
For each of the hydrogen-containing drinking water products of Examples 11 to 37, the dissolved hydrogen concentration, pH, and oxidation-reduction potential (vs. Ag/AgCl (3.3N)) were measured 7 days, 90 days, 180 days, and 360 days after production (storage at room temperature (25°C ± 5°C)) using a 3.3 mol/L silver chloride electrode as a standard (five product samples were measured on each measurement date, and the measurement results were calculated as the average value).
The dissolved hydrogen concentration was measured using a Unisense dissolved hydrogen sensor (a combination of a multimeter and a dissolved hydrogen sensor), and the temperature at the time of filling the packaging container with a straw was adjusted so that the temperature at the time of sensor calibration (water temperature) and the measurement temperature (water temperature) were 20°C ± 2°C.
In order to standardize the measurement conditions, the pH-corrected ORP value was obtained using the following formula based on the measured pH and ORP values, which corrects for the fact that the ORP value appears to be low or high depending on the pH value.
ORP value after pH correction: ORP actual measurement value - (-59 x actual measurement pH)
Furthermore, based on the above pH-corrected ORP values, the rate of change in ORP value of the product 90 days, 180 days, and 360 days after production was determined relative to the product 7 days after production.
The results are shown in Tables 14 to 18. Table 18 lists the data for the above-mentioned Reference Example (hydrogen-containing water drink product (hydrogen-containing water only) containing no functional ingredients or water-soluble capsules). As Reference Example 2, a water-soluble capsule was produced filled with only dextrin (249 mg) and fine silicon dioxide (1 mg) (total 250 mg), and similarly tested.

The hydrogen-containing drinkable water products of Examples 11 to 37 obtained were lightly shaken (using a special sample stored for checking the sound) 7, 90, 180, and 360 days after production (stored at room temperature (25°C ± 5°C)), and sound was detected in all cases. This supports the existence of a gas atmosphere in the space above the water surface of the hydrogen-containing water filled in the container.

As shown in Tables 14 to 18, the hydrogen-containing drinking water products of Examples 11 to 37 were able to maintain a low redox potential and a high dissolved hydrogen concentration. In particular, Examples 15, 16, and 32 to 35, which contained nicotinamide functional ingredient 10, showed results that allowed the redox potential to be maintained at a low value.

<Production of hydrogen-containing drinking water products (5)>
The hydrogen-containing drinking water products of Examples 38 to 41 were produced following the above procedure, except that in the procedure of <Production of hydrogen-containing drinking water products (1)>, the water-soluble capsules and the like were added as follows.
In the filling step, three water-soluble capsules each described below were placed in advance into the packaging containers with straws into which the hydrogen-containing water was filled, and the hydrogen-containing water was filled under pressure into the containers.
The water-soluble capsules used in this example (pre-loaded into a container) are as follows: Functional ingredients 8 to 15, 19 to 21, and dextrin and micronized silicon dioxide listed in Table 12 were filled into the water-soluble capsules listed below in the blending amounts (mg) listed in Table 19 to prepare water-soluble capsules for loading.
The water-soluble capsules and the like used in Examples 38 to 41 are as follows:
・Water-soluble capsule (pullulan):
Product name: "Plantcaps (registered trademark)", size 2, pullulan content 85.5%, capsule weight: 63 mg (pullulan content: 54 mg), Capsugel Japan Co., Ltd.

<Evaluation of hydrogen-containing drinking water products (5)>
For each of the hydrogen-containing drinking water products of Examples 38 to 41, the dissolved hydrogen concentration, pH, and 3.3 m
The oxidation-reduction potential (vs. Ag/AgCl (3.3N)) was measured using a 1/L silver chloride electrode as a standard (five product samples were measured on each measurement day, and the measurement results were calculated as the average value).
The dissolved hydrogen concentration was measured using a Unisense dissolved hydrogen sensor (a combination of a multimeter and a dissolved hydrogen sensor), and the temperature at the time of filling the packaging container with a straw was adjusted so that the temperature at the time of sensor calibration (water temperature) and the measurement temperature (water temperature) were 20°C ± 2°C.
In order to standardize the measurement conditions, the pH-corrected ORP value was obtained using the following formula based on the measured pH and ORP values, which corrects for the fact that the ORP value is measured as a seemingly low/high value depending on the pH value.
ORP value after pH correction: ORP actual measurement value - (-59 x actual measurement pH)
Furthermore, based on the above pH-corrected ORP values, the rates of change in ORP value of the products 90 days, 180 days, and 360 days after production were determined relative to the products 7 days after production.
The results obtained are shown in Table 20.
Furthermore, when the hydrogen-containing drinking water products of Examples 38 to 41 obtained were lightly shaken (using a special sample stored for checking the sound) 7, 90, 180, and 360 days after production (stored at room temperature (25°C ± 5°C)), sound was detected in all cases. This supports the existence of a gas atmosphere in the space above the water surface of the hydrogen-containing water filled in the container.

In the examples shown, tap water was used as the raw material to produce hydrogen-containing water and drinking hydrogen-containing water products; however, it was confirmed that similar results (effects) were obtained in terms of changes in ORP value, oxidation-reduction potential, and dissolved hydrogen concentration, as well as sensory evaluation, when pure water (ion-exchanged water) was used.
In addition, depending on various formulations, including the example products shown here, such as increasing or decreasing the amount of functional ingredients or changing the combination of multiple types of functional ingredients, the change in redox potential over time will vary, making it possible to achieve a high dissolved hydrogen concentration for a longer period of time.

As mentioned above, the applicant has conducted various experiments and has confirmed that the present invention suppresses the aroma and taste derived from functional ingredients, resulting in products that are closer to being tasteless and odorless.
Hydrogen-containing water itself is tasteless and odorless, and like mineral water, it can help you stay hydrated while maintaining your health, which is one of the major reasons why hydrogen-containing water has become established in the market. For this reason, there are quite a few consumers who think that while hydrogen-containing water is mixed with functional ingredients to make it a more useful product for maintaining health, it would be preferable if the aroma and taste were subdued.
If there is such a demand (reduced odor and taste), and taking into consideration that, as mentioned above, different types of water-soluble capsules have different dissolution behaviors and flavors, etc., appropriate experiments should be carried out and a raw material (and a water-soluble capsule) with reduced odor and taste should be selected from functional raw materials that are in high demand in the market.
Furthermore, the sensory evaluation of sweetness, sourness, bitterness, astringency, spiciness, aroma, etc. may change depending on the combination of ingredients and the increase or decrease in dissolved hydrogen concentration, so after determining the desired direction, it is a good idea to confirm this through appropriate experiments.

Reference Signs List 1: Hydrogen-containing water product for drinking 2: Packaging container with straw 3: Container body 4: Straw with spout 41: Straw part 42: Mouth part 42A: Upper end mouth part 43: Male thread part 44: Heat-sealed part 45: Ear part 46: Hole 47: Flange 48: Projection part 4A: Upper part of straw 5: Sealing cap 6: Hydrogen-containing water 7: Gas atmosphere

Claims (3)

Filling the hydrogen-containing water into an openable container and sealing the container;
A method for producing a hydrogen-containing drinking water product, comprising:
The method is characterized in that a water-soluble capsule containing a functional ingredient is placed in the openable container before, during, or after the step of filling the hydrogen-containing water ,
The functional ingredient is
the active ingredient is one or a combination of two or more selected from the group consisting of amino acids; polyamines; moisturizing substances; peptides and proteins and substances containing them; vitamins; vitamin-like substances; antioxidants; minerals; sugars; sugar alcohols; synthetic sweeteners; natural sweeteners; acidulants; carbohydrates; stearic acid and its derivatives; vegetables, fruits, trees, plants and plant extracts; mushrooms; tea; herbal raw materials and herbal extract raw materials; flavonoids; and flavorings,
A method for producing a hydrogen-containing drinking water product. The method according to claim 1, wherein the water-soluble capsule is made of a material containing at least one selected from the group consisting of hydroxypropylmethylcellulose (HPMC), pullulan, and gelatin. In an openable container,
hydrogen-containing water filled and sealed in said container;
The hydrogen-containing water contains a functional raw material and a water-soluble capsule material dissolved therein.
A hydrogen-containing drinking water product.
Hydrogen-containing drinking water products.

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