JP2014024606A - Manufacturing method of filling product of hydrogen water - Google Patents

Manufacturing method of filling product of hydrogen water Download PDF

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JP2014024606A
JP2014024606A JP2013207181A JP2013207181A JP2014024606A JP 2014024606 A JP2014024606 A JP 2014024606A JP 2013207181 A JP2013207181 A JP 2013207181A JP 2013207181 A JP2013207181 A JP 2013207181A JP 2014024606 A JP2014024606 A JP 2014024606A
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hydrogen
hydrogen water
water
filled
filling
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Hiroshi Harada
宏 原田
Tatsuya Suzuki
竜也 鈴木
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NIKKO SEISAKUSHO KK
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B67OPENING, CLOSING OR CLEANING BOTTLES, JARS OR SIMILAR CONTAINERS; LIQUID HANDLING
    • B67CCLEANING, FILLING WITH LIQUIDS OR SEMILIQUIDS, OR EMPTYING, OF BOTTLES, JARS, CANS, CASKS, BARRELS, OR SIMILAR CONTAINERS, NOT OTHERWISE PROVIDED FOR; FUNNELS
    • B67C3/00Bottling liquids or semiliquids; Filling jars or cans with liquids or semiliquids using bottling or like apparatus; Filling casks or barrels with liquids or semiliquids
    • B67C3/02Bottling liquids or semiliquids; Filling jars or cans with liquids or semiliquids using bottling or like apparatus
    • B67C3/04Bottling liquids or semiliquids; Filling jars or cans with liquids or semiliquids using bottling or like apparatus without applying pressure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B67OPENING, CLOSING OR CLEANING BOTTLES, JARS OR SIMILAR CONTAINERS; LIQUID HANDLING
    • B67CCLEANING, FILLING WITH LIQUIDS OR SEMILIQUIDS, OR EMPTYING, OF BOTTLES, JARS, CANS, CASKS, BARRELS, OR SIMILAR CONTAINERS, NOT OTHERWISE PROVIDED FOR; FUNNELS
    • B67C3/00Bottling liquids or semiliquids; Filling jars or cans with liquids or semiliquids using bottling or like apparatus; Filling casks or barrels with liquids or semiliquids
    • B67C3/02Bottling liquids or semiliquids; Filling jars or cans with liquids or semiliquids using bottling or like apparatus
    • B67C3/22Details
    • B67C3/26Filling-heads; Means for engaging filling-heads with bottle necks
    • B67C2003/2657Filling-heads; Means for engaging filling-heads with bottle necks specially adapted for filling cans
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/68Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water

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  • Filling Of Jars Or Cans And Processes For Cleaning And Sealing Jars (AREA)
  • Non-Alcoholic Beverages (AREA)
  • Coloring Foods And Improving Nutritive Qualities (AREA)

Abstract

PROBLEM TO BE SOLVED: To develop a new manufacturing method of a filling product of hydrogen water for extremely reducing discharge of hydrogen from the hydrogen water sealed-filled in a can container.SOLUTION: The present invention is the method for manufacturing the filling product 10 of the hydrogen water, by sealing a can lid part 12 in a can body part 11, by putting the can lid part 12 on the can body part 11 of the can container 10A, after filling hydrogen water W in the metallic can container 10A, by generating the hydrogen water W of dissolving the hydrogen by mixing raw water and hydrogen gas, and seals-fills the hydrogen water W filled in the can container 10A in a state of not contacting with gas except for the hydrogen, in a sealed state of sealing the can lid part 12 in the can body part 11, and fully pours-fills the hydrogen water W in a metallic can body by causing a secondary overflow of overflowing the hydrogen water W from the can body in a step of installing the can lid part 12 in the can container 10A filled with the hydrogen water W in this sealing-filling.

Description

本発明は、缶容器に水素水を充填した製品の製造手法に関するものであって、特に密封充填後の水素水が、水素以外の気体と接触することがないようにし、これにより未開封状態において水素水からの水素の放出を極めて少なくするようにした新規な充填製品の製造手法に係るものである。   The present invention relates to a method for producing a product in which a can container is filled with hydrogen water, and in particular, the hydrogen water after hermetically filling is prevented from coming into contact with a gas other than hydrogen, and thus in an unopened state. The present invention relates to a method for manufacturing a new filled product in which release of hydrogen from hydrogen water is extremely reduced.

健康維持に有効との認識から、水素水の製造販売がなされ注目を集めている。この理由として、様々な疾病の発生・悪化に関連している、いわゆる「酸化ストレス」除去への水素水の関与が挙げられる。生体内において常に発生する活性酸素は、体の免疫機能の一部としての役割を担っているが、必要以上に活性酸素が発生した場合(この状態を「酸化ストレス」と呼ぶ)、自分自身に障害を引き起こす要因として作用するため、過剰な活性酸素は日常的に除去する必要性があると言われている。また一口に「活性酸素」と言っても、その分子形態は様々であることから、活性酸素全ての分子種を一律に除去する仕組みは存在しないと言われている。
活性酸素除去の仕組みに関する最近の研究結果によると、「活性酸素」分子種の一部の除去に分子状水素が関与していることが提示されたことから、簡便に分子状水素を摂取する手法として、水素水の継続的な飲用を実践する人達が増えたのである。ただし生体中での分子状水素の機能・効果については、詳細に解明されたわけではなく、現在、様々な研究機関で鋭意研究中の段階であることから、ここではメカニズムについては記さない。
With the recognition that it is effective for maintaining health, the manufacture and sale of hydrogen water has been made and is attracting attention. This is because hydrogen water is involved in the removal of so-called “oxidative stress”, which is related to the occurrence and deterioration of various diseases. Active oxygen that is always generated in the body plays a role as part of the body's immune function, but if it occurs more than necessary (this condition is called "oxidative stress") It is said that excess active oxygen needs to be removed on a daily basis because it acts as a cause of injury. In addition, even though “active oxygen” is simply referred to, it is said that there is no mechanism for uniformly removing all molecular species of active oxygen because of its various molecular forms.
According to recent research results on the mechanism of removal of active oxygen, it was suggested that molecular hydrogen is involved in the removal of some of the “active oxygen” molecular species. As a result, the number of people who practice continuous drinking of hydrogen water has increased. However, the function and effect of molecular hydrogen in the living body has not been elucidated in detail, and since it is in the stage of earnest research at various research institutions, the mechanism is not described here.

このような水素水への関心が高まるにつれ、水素水製造に関して種々の技術が開発・改良されており、具体的には以下の手法を例示することができる。
(1) 電気分解法
(2) 加圧溶解法
(3) 気液混合ノズル法
(4) マイクロ・ナノバブル法
(5) 気液分離中空糸膜法
いずれの製造手法においても、液温に対する飽和濃度(例えば25℃であれば溶存水素濃度が1.6ppm)、あるいは飽和濃度に近い高濃度の水素水を製造することができ、家庭用・工業用の水素水サーバや水素水製造装置として販売されている。
As interest in such hydrogen water increases, various techniques relating to hydrogen water production have been developed and improved. Specifically, the following methods can be exemplified.
(1) Electrolysis method
(2) Pressure dissolution method
(3) Gas-liquid mixing nozzle method
(4) Micro / Nano Bubble Method
(5) Gas / Liquid Separation Hollow Fiber Membrane Method In any of the production methods, a saturated concentration with respect to the liquid temperature (for example, dissolved hydrogen concentration is 1.6 ppm at 25 ° C) or high concentration hydrogen water close to the saturation concentration is produced. It is sold as a household / industrial hydrogen water server or hydrogen water production apparatus.

一般家庭でも普及してきた、いわゆる「水サーバ」ではあるが、水素水製造技術の発達により、飲料用途の家庭用「水素水サーバ」も数社から製造販売され、上記の健康志向の高まりを背景として普及し始めている。家庭用「水素水サーバ」の場合、サーバから供給された「高濃度水素水」は、時間をおかずに即座に消費することが前提となっているため、水素水の保存に関しての注意点や問題点は少ない。
一方、水素水を手軽に飲用する方法として、「容器に密封状態に詰められた水素水」(以下、これを「容器に充填された水素水」とする)を利用することも可能であり、この目的として幾つかのタイプが市販されている。ここで市販されている「容器に充填された水素水」の形態を分類すると、
(1) ペットボトル充填
(2) アルミパウチ充填
(3) アルミボトル充填
の3つに大きく分類できるが、いずれの形態の水素水であっても、その保存性に関して大きな問題が指摘されている。
Although it is a so-called “water server” that has become widespread in ordinary households, with the development of hydrogen water production technology, domestic “hydrogen water server” for beverage use is also manufactured and sold by several companies. Has begun to spread. In the case of a home-use “hydrogen water server”, “high-concentration hydrogen water” supplied from the server is presumed to be consumed immediately without taking time. There are few points.
On the other hand, as a method of easily drinking hydrogen water, it is possible to use “hydrogen water sealed in a container” (hereinafter referred to as “hydrogen water filled in a container”), Several types are commercially available for this purpose. If you categorize the form of "hydrogen water in a container" that is commercially available here,
(1) Filling plastic bottles
(2) Filling aluminum pouch
(3) Although it can be broadly classified into three types, aluminum bottle filling, any type of hydrogen water has been pointed out as a major problem with respect to its preservability.

すなわち、購入した時点で水素水つまり「容器に充填された水素水」の溶存水素濃度が著しく低い場合、あるいは水素が含まれていない場合が多く、事実、「購入時において容器に充填された水素水の濃度が低い」とか「水素が入っていない」等の多くの書き込み情報がインターネットでアップされており、水素の保存性に関する問題が顕在化している。
なお、このような実情を反映しているのか、水素水の製造方法に関する先行技術文献は、数多く開示されているものの、水素水を保存する方法に関しては、極めて先行技術文献が少ないのが現状である(例えば特許文献1・2参照)。
因みに、上記特許文献1・2は、水素水を生成した後、ただちに凍結保存することにより、水素の放出を抑えるようにしたものである。しかしながら、このような手法では、凍結保存していた水素水を融解させるのに長い時間を要し(例えば室温で12時間)、飲用したい時にすぐ飲めないという大きな欠点がある。また、保存時に凍結を要するため、製造コストが高価となるばかりか、流通や各店舗での保存・陳列においても冷凍設備が必要となり、このような点においても実用上の不便さが解消し切れないという問題があった。
In other words, the dissolved hydrogen concentration of hydrogen water at the time of purchase, that is, “hydrogen water filled in the container” is often extremely low or does not contain hydrogen. Many written information such as “the concentration of water is low” or “no hydrogen” is uploaded on the Internet, and the problem regarding the storage stability of hydrogen is becoming obvious.
In addition, although many prior art documents relating to the method for producing hydrogen water have been disclosed to reflect such actual circumstances, there are very few prior art documents regarding the method for preserving hydrogen water. Yes (see, for example, Patent Documents 1 and 2).
Incidentally, in Patent Documents 1 and 2 described above, hydrogen water is generated and then immediately stored frozen to suppress the release of hydrogen. However, in such a method, it takes a long time to melt the hydrogen water that has been frozen and stored (for example, 12 hours at room temperature), and there is a great drawback that it cannot be drunk immediately when it is desired to drink. In addition, since freezing is required at the time of storage, not only the manufacturing cost is high, but also refrigeration equipment is required for distribution and storage / display in each store, and inconveniences in practical use can be completely eliminated in this respect. There was no problem.

特開2009−208067号公報JP 2009-208067 A 特開2009−208063号公報JP 2009-208063 A

本発明は、このような背景を認識してなされたものであって、まず、凍結することなく、常温雰囲気における水素水の保存手法の開発を目指したものである。具体的には、生成した水素水は缶容器に充填することを前提とし、また水素水を充填した缶容器に蓋をした密封充填状態において、水素水が水素ガス以外の気体と接触しないようにすることで、水素水からの水素の放出を極めて抑えるようにした水素水の充填製品の新規な製造手法の開発を試みたものである。   The present invention has been made in view of such a background. First, the present invention aims to develop a method for storing hydrogen water in a normal temperature atmosphere without freezing. Specifically, it is assumed that the generated hydrogen water is filled in a can container, and in a sealed filling state where a can container filled with hydrogen water is covered, the hydrogen water does not come into contact with a gas other than hydrogen gas. In this way, the inventors have attempted to develop a new method for producing a hydrogen-filled product in which release of hydrogen from hydrogen water is extremely suppressed.

また請求項1記載の、水素水の充填製品の製造方法は、
原水と水素ガスとの混合により水素を溶存させた水素水を生成し、この水素水を金属製の缶容器に充填し、その後、缶容器の缶胴部に缶蓋部を被せて、この缶蓋部を缶胴部に封着して、水素水の充填製品を製造する方法において、
前記缶体内に充填する水素水は、缶蓋部を缶胴部に封着した密封状態において、水素以外の気体と接触しない状態で密封充填されるものであり、
この密封充填にあたっては、
水素水を充填した缶容器に缶蓋部を取り付ける工程において水素水を缶体から溢水させる二次オーバーフローを生じさせ、水素水を金属缶体に満注充填するようにしたことを特徴として成るものである。
Moreover, the manufacturing method of the filling product of hydrogen water of Claim 1 is as follows.
Hydrogen water in which hydrogen is dissolved is produced by mixing raw water and hydrogen gas, and the hydrogen water is filled into a metal can container, and then the can body part of the can container is covered with a can lid part. In a method of manufacturing a hydrogen water filled product by sealing a lid to a can body,
The hydrogen water to be filled in the can body is sealed and filled in a state where the can lid portion is sealed to the can body portion and is not in contact with a gas other than hydrogen,
In this hermetic filling,
In the process of attaching a can lid to a can container filled with hydrogen water, a secondary overflow that causes hydrogen water to overflow from the can body is generated, and hydrogen water is filled in a metal can body. It is.

また請求項2記載の、水素水の充填製品の製造方法は、前記請求項1記載の要件に加え、
前記水素水を缶容器に充填するにあたっては、水素水の充填開始時を除き、注水ノズルの吐出口を、既に缶容器内に注入された水素水の水面下に位置させる水没状態で注入を行うようにしたことを特徴として成るものである。
In addition to the requirement of claim 1, the method for producing a hydrogen water filled product according to claim 2,
When filling the can with the hydrogen water, the injection is performed in a submerged state where the discharge port of the water injection nozzle is located below the surface of the hydrogen water already injected into the can container, except when charging of the hydrogen water is started. This is what makes it a feature.

これら各請求項記載の発明の構成を手段として前記課題の解決が図られる。
すなわち請求項1記載の発明によれば、製造後、ユーザが使用する(例えば飲料用であれば飲むという行為)までの間に、密封充填した水素水からの水素の放出を格段に低い割合に抑制することができ、流通過程における水素水の溶存水素濃度を高いレベルで維持することができる。また、水素水の充填製品の保存は、常温で行えるため、解凍する手間や時間が掛からず、ユーザが飲みたい時にすぐに飲むことができる。また凍結保存ではないため、流通コストも削減でき、これは販売店にとっても設備負担が少なくて済み、保存のためのコストも抑えられる(例えば、倉庫での保管や売り場ショーケース等において冷凍庫などの冷凍設備が不要となる)。なお、この点は、製造者・流通者・販売者(小売業者)・ユーザ等、全てにおいて充填製品が扱い易くなり、商品形態として利便性や手軽さ等を向上させるものである。
また、缶蓋部を取り付ける際の二次オーバーフローを生じさせるため、水素水を金属缶体に確実に満注充填することができる。
The above-described problems can be solved by using the configuration of the invention described in each of the claims.
That is, according to the first aspect of the present invention, the release of hydrogen from the sealed and filled hydrogen water is reduced to a much lower rate after manufacture until the user uses it (for example, the act of drinking if it is for beverages). Therefore, the dissolved hydrogen concentration of the hydrogen water in the distribution process can be maintained at a high level. Moreover, since the product filled with hydrogen water can be stored at room temperature, it does not take time and effort to thaw, and can be drunk immediately when the user wants to drink. In addition, because it is not frozen storage, distribution costs can be reduced, which reduces the equipment burden for the dealer and reduces the cost for storage (for example, storage in a warehouse or a showcase of a store, such as a freezer). Refrigeration equipment is not required). In addition, this point makes it easy to handle filled products in all of manufacturers, distributors, sellers (retailers), users, and the like, and improves convenience, convenience, etc. as a product form.
Moreover, since the secondary overflow at the time of attaching a can lid part is produced, hydrogen water can be reliably filled in a metal can body.

また請求項2記載の発明によれば、水素水を缶容器に充填する際、充填開始時を除き、注水ノズルが水没状態で充填を行うため、できる限り水素水が空気と接触し難い状況をつくることができ、水素の放出を抑える充填方法が得られるものである。なお、このような水没充填が好ましいとの結論は、本発明者が、充填位置の違いによる水素溶存量の相違について行った実験(充填速度は一定)から得たものである。因みに、この実験では、注水ノズルの吐出口を缶容器上端よりも高位置に設定した場合(ノズル吐出口が水没しない状態)、水素水の溶存濃度が水没充填よりも低下することが確認できており、これは、充填の際、空気を巻き込むために、水素中の溶存水素が抜けてしまったためと考えられた。   According to the invention described in claim 2, when filling the can with hydrogen water, since the water injection nozzle is filled in a submerged state except at the start of filling, the situation in which the hydrogen water is difficult to come into contact with air as much as possible. A filling method that can be produced and suppresses the release of hydrogen is obtained. In addition, the conclusion that such submerged filling is preferable is obtained from an experiment (the filling speed is constant) conducted by the present inventor on the difference in the amount of dissolved hydrogen due to the difference in filling position. Incidentally, in this experiment, when the discharge port of the water injection nozzle is set higher than the upper end of the can container (the nozzle discharge port is not submerged), it can be confirmed that the dissolved concentration of hydrogen water is lower than the submerged filling. This was thought to be because dissolved hydrogen in the hydrogen escaped due to air entrainment during filling.

本発明に係る製造装置(水素水の充填製品を製造する装置)の一例を示す正面図並びに平面図である。It is the front view and top view which show an example of the manufacturing apparatus (apparatus which manufactures the filling product of hydrogen water) which concerns on this invention. 本発明に係る充填製品(水素水の充填製品)の一例を示す概観斜視図、並びに該製品の内部の様子を骨格的に示す二種の斜視図(a)・(b)であるが、図(b)は本発明に関連する参考例である。It is a general perspective view showing an example of a filled product (filled product of hydrogen water) according to the present invention, and two perspective views (a) and (b) skeletally showing the inside of the product. (B) is a reference example relevant to the present invention. 水素水を缶容器に充填する際の様子(前半)を段階的に示す説明図である。It is explanatory drawing which shows the mode (first half) at the time of filling hydrogen water into a can container in steps. 水素水を缶容器に充填する際の最終段階と、水素水を充填した缶容器に缶蓋部を取り付ける様子を段階的に示す説明図である。It is explanatory drawing which shows a mode that a can lid part is attached to the final stage at the time of filling a can container with hydrogen water, and the can container filled with hydrogen water. 既に市販されている水素水の充填製品(他社製品)について、溶存水素濃度の経時変化を6ヶ月にわたって示すグラフである。It is a graph which shows the time-dependent change of dissolved hydrogen concentration over 6 months about the filling product (other company's product) of hydrogen water already marketed. 空気に接触する面積を変えた2個の容器に水素水を満たし、それぞれの溶存水素濃度の経時変化を比較して示すグラフである。It is a graph which compares the time-dependent change of each dissolved hydrogen concentration, filling hydrogen water into two containers which changed the area which contacts air. 水素水をペットボトルに満注充填した場合と、ヘッドスペースを設けるように充填した場合とにおいて、溶存水素濃度の経時変化を示すグラフである。It is a graph which shows the time-dependent change of a dissolved hydrogen concentration in the case where it fills with hydrogen water to the PET bottle and the case where it fills so that a head space may be provided. 缶体(スチール缶)に満注充填された水素水(本発明に係る充填製品)を、夏場を想定した37℃の恒温槽に保管し、1週間経過毎に水素水の溶存水素濃度を測定した結果を示すグラフである。Hydrogen water (filled product according to the present invention) fully filled in a can (steel can) is stored in a constant temperature bath at 37 ° C assuming summer and the dissolved hydrogen concentration of hydrogen water is measured every week. It is a graph which shows the result.

本発明を実施するための最良の形態は、以下の実施例に述べるものをその一つとするとともに、更にその技術思想内において改良し得る種々の手法を含むものである。
なお、説明にあたっては、生成された水素水の保存性に関する検討・考察から述べる。すなわち現状の「容器に充填された水素水(本発明に係る「水素水の充填製品10」に相当)」の保存手法の実情と、常温雰囲気で水素水をどのように保存すれば水素水からの水素の放出が抑えられるのかという本発明の基本的な技術思想から示す。そして、その後、充填製品10を製造する際の缶体の名称や水素水について説明(定義)した後、次いで充填製品の製造装置について説明しながら製造方法について併せて説明する。
ここで、本明細書では、容器(本発明では缶容器)に詰められた密封充填状態の水素水を「水素水の充填製品10」とするが、これは単に「充填製品10」と簡略的に称することもある。
BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the present invention includes one described in the following examples, and further includes various methods that can be improved within the technical idea.
In the explanation, we will discuss from the examination and consideration on the preservation of the generated hydrogen water. In other words, the current state of the storage method of “hydrogen water filled in a container (corresponding to“ hydrogen water filling product 10 ”according to the present invention”) and how to store the hydrogen water in a room temperature atmosphere from the hydrogen water. From the basic technical idea of the present invention whether the release of hydrogen is suppressed. Then, after explaining (defining) the name of the can body and hydrogen water when producing the filled product 10, the production method will be described together with the explanation of the filling product producing apparatus.
Here, in this specification, hydrogen water in a hermetically filled state packed in a container (can container in the present invention) is referred to as “filled product 10 of hydrogen water”, which is simply referred to as “filled product 10”. It may be called.

〔水素水の保存性に関しての検討・考察〕
本発明者は、現状の水素水の保存性の問題点を把握する第一歩として、まず市販されている「容器に充填された水素水」の濃度を経時的(ここでは約1ヶ月毎、6ヶ月にわたる)に測定した。得られた結果を図5に示す。ここで、A〜Kの各社製品は、同一ロットの商品(同じ条件で製造された商品)を使用したものである。またサンプルとして購入した「容器に充填された水素水」は、
(1) ペットボトル充填
(2) アルミパウチ充填
(3) アルミボトル充填
の3形態であるが、(1) ペットボトルタイプの製品は、測定時に溶存水素濃度が「0(ゼロ)」のものがあり(例えば他社製品H・Kなど)、経時的に測定することができなかった。
また、市販されている他社製品A〜Kの中には、購入直後であるにも係わらず溶存水素濃度が著しく低いものが存在したが、(2) アルミパウチ充填・(3) アルミボトル充填ともに経時的に溶存水素濃度が減少し、3ヶ月経過で初期濃度の約半分に減少する事例が確認でき、(2) アルミパウチ・(3) アルミボトルの形態では、「水素水」を長期間にわたって保存できないことが明らかになった。なお、溶存水素濃度の測定は、東亜ディーケーケー株式会社製の溶存水素計「DH−35A」を用いて行った。
[Examination and consideration on preservation of hydrogen water]
The present inventor, as a first step to grasp the current problem of storage stability of hydrogen water, first, the concentration of the commercially available “hydrogen water filled in a container” is changed over time (here, approximately every month, Over 6 months). The obtained results are shown in FIG. Here, the products of each company A to K use products of the same lot (products manufactured under the same conditions). In addition, "hydrogen water filled in a container" purchased as a sample is
(1) Filling plastic bottles
(2) Filling aluminum pouch
(3) There are three forms of filling aluminum bottles. (1) Some PET bottle type products have a dissolved hydrogen concentration of “0 (zero)” at the time of measurement (for example, other companies' products H and K). Could not be measured.
In addition, some of the other company's products A to K that are on the market have extremely low dissolved hydrogen concentration even though they are just after purchase. (2) Both aluminum pouch filling and (3) aluminum bottle filling Dissolved hydrogen concentration decreased over time, and it was confirmed that the concentration decreased to about half of the initial concentration after 3 months. (2) Aluminum pouch and (3) Aluminum bottle form “hydrogen water” for a long time It became clear that it could not be saved. The dissolved hydrogen concentration was measured using a dissolved hydrogen meter “DH-35A” manufactured by Toa DKK Corporation.

また、図5の結果では、1ヶ月経過時点で初期測定濃度を上回るものや、2ヶ月経過時点で1ヶ月経過時点の数値(溶存水素濃度)を上回るものが存在するが、これは測定の都度、密閉状態の製品を開栓してしまうため、現実には1ヶ月経過時点と初期測定時点とで同じ製造メーカー・製品でありながら、違うサンプル(個体)を測定しているためである(一回、開栓してしまうと再び蓋をしても、空気接触により水素が逃げ易いため、全く同じサンプルで計測することは不可)。つまり、データ上は、溶存水素濃度が上がっていても、実際に上がっているのではなく、同じ製品の中で生じるサンプル誤差(個体差)がもともと存在していたためであり、全体的な傾向は本図5に示すように、例えば6ヶ月程度の長期にわたって測定したデータを全体的に見渡す必要がある。   In addition, in the results of FIG. 5, there are those that exceed the initial measured concentration after one month, and those that exceed the value (dissolved hydrogen concentration) after one month after two months. This is because, since the product in a sealed state is opened, in reality, the same manufacturer and product are measured at the time of one month and the initial measurement, but different samples (individuals) are measured (one If the lid is opened once, even if the lid is closed again, hydrogen can easily escape due to air contact. In other words, the data shows that even if the dissolved hydrogen concentration is increased, it does not actually increase, but sample errors (individual differences) that occur in the same product originally existed. As shown in FIG. 5, it is necessary to overlook the data measured over a long period of, for example, about 6 months.

次に、水素水の保存性に関して影響を与える因子を明らかにするため、空気に接触する面積を変えた2個の容器に水素水を満たし、溶存水素濃度が時間とともに、どのように変化するかを測定した。得られた結果を図6に示す。図6のグラフから分かることは、空気に触れる面積の広い方が、溶存水素濃度の減少が大きく、この実験では2時間(120分)経過すると、初期濃度の1/4以下にまで低下してしまう点である。この結果から「水素水」は空気と接触すると、「水素水」から水素が抜け出てしまうことが分かり、このため容器に充填された「水素水」を保存するには、空気との接触を遮断することが極めて有効と結論づけられた。   Next, in order to clarify the factors that affect the storage stability of hydrogen water, how the dissolved hydrogen concentration changes with time by filling two containers with different water contact areas with hydrogen water. Was measured. The obtained result is shown in FIG. As can be seen from the graph of FIG. 6, the larger the area in contact with air, the greater the decrease in dissolved hydrogen concentration. In this experiment, after 2 hours (120 minutes), the concentration decreased to 1/4 or less of the initial concentration. It is a point. From this result, it can be seen that “hydrogen water” comes out of “hydrogen water” when it comes into contact with air. Therefore, in order to preserve the “hydrogen water” filled in the container, the contact with air is cut off. It was concluded that it was extremely effective.

次に、ペットボトルに充填した水素水が空気に触れないようにした場合、具体的にはペットボトルに空気を入れないように(ヘッドスペースが生じないように)「水素水」を満注充填した場合に、「水素水」の保存が可能になるか否かの検証を行った。得られた結果を図7に示す。この図から、ペットボトルに水素水を満注充填しても、10時間を経過すると、初期の溶存水素濃度の半分にまで減少してしまうことが分かった。もちろん、ヘッドスペースを設けたものは、満注充填したものよりも更に溶存水素濃度が低下することも明らかとなった。   Next, when hydrogen water filled in a plastic bottle is prevented from touching the air, specifically, "hydrogen water" is filled to prevent air from entering the plastic bottle (so that no headspace is created). In such a case, it was verified whether or not “hydrogen water” could be stored. The obtained results are shown in FIG. From this figure, it was found that even if the PET bottle was fully filled with hydrogen water, it decreased to half of the initial dissolved hydrogen concentration after 10 hours. Of course, it was also found that the dissolved hydrogen concentration was further reduced in the case where the head space was provided than in the case where the full space was filled.

ペットボトルにおいて水素水の溶存水素濃度が減少する点について考察を行ったところ、合成樹脂類の「ガス透過性」が関与していることが考えられた。例えば、ゴムのガス透過性を比較した文献によれば、下記のように水素は窒素の約5倍ものガス透過性を示し、酸素と比較しても約2倍、ゴムを透過してしまうことが分かった。
水素(MW=2) 1.4
ヘリウム(MW=4) 1.0
酸素(MW=32) 0.8
窒素(MW=28) 0.3
When the point that the dissolved hydrogen concentration of hydrogen water decreases in a PET bottle was examined, it was thought that the “gas permeability” of synthetic resins was involved. For example, according to the literature comparing the gas permeability of rubber, hydrogen shows gas permeability about 5 times that of nitrogen as follows, and it penetrates rubber about twice as much as oxygen. I understood.
Hydrogen (MW = 2) 1.4
Helium (MW = 4) 1.0
Oxygen (MW = 32) 0.8
Nitrogen (MW = 28) 0.3

正確な比較データは入手できなかったが、ゴム同様、ペットボトルにもガス透過性があることは各種文献から明らかであり、特に、分子としての大きさが一番小さい水素では、ガス透過力が他のガス種と比較して、より強いことは明白である。そのため、ペットボトルに水素水を満注充填しても、数時間のうちに溶存水素濃度が減少したものと考えられた。   Although accurate comparison data was not available, it is clear from various literatures that, like rubber, PET bottles are also gas permeable, especially for hydrogen, which has the smallest molecular size. Obviously, it is stronger than other gas species. For this reason, it was considered that the dissolved hydrogen concentration decreased within a few hours even when hydrogen water was fully filled in PET bottles.

また、水素を透過させない金属で、一見、完全に密封(シール)されているように見えるアルミキャップボトルであっても溶存水素濃度が減少するものであり、この点について考察を行ったところ、アルミキャップボトルの場合、キャップの内側に貼られた合成樹脂製あるいはシリコン製のパッキンでシール(水素水が漏れないように密閉)しているため、水素水に含有されていた水素が、このパッキンを透過して微量ずつボトル外に抜け出てしまうと考えられた。   Moreover, even if it is an aluminum cap bottle that seems to be completely sealed (sealed) at first glance with a metal that does not allow hydrogen to permeate, the concentration of dissolved hydrogen is reduced. In the case of a cap bottle, since it is sealed (sealed so that hydrogen water does not leak) with a synthetic resin or silicon packing affixed to the inside of the cap, the hydrogen contained in the hydrogen water It was thought that it permeated and slipped out of the bottle little by little.

上記のようにして、水素水の保存性に関する要因を考慮した結果、水素水の保存においては、下記の3項目全てを採り入れた手法が有効であると結論づけ、本願発明に至ったものである。
(A) 水素が透過しない素材である金属缶(スチール製・アルミ製どちらでも可)を使用 する。
(B) 特に密封充填状態では、水素水が、空気等の水素以外の気体と接触しないようにす る。
(C) 缶をパッキンでシールする場合、ガス透過性のある合成樹脂類の使用量を極力少な くする。
その結果、本発明では、ヘッドスペースを生じさせないように、水素水を金属缶に満注充填して、密封充填後の水素水を水素以外のガスと接触させないようにしたものである。すなわち、本発明は、上記(A) 〜(C) の条件を満たす手法により充填製品10を製造し、水素水の溶存水素濃度の低下を抑えるようにしたものである。
As described above, as a result of considering the factors relating to the storage stability of hydrogen water, it was concluded that a technique incorporating all the following three items is effective in storing hydrogen water, and the present invention has been achieved.
(A) Use metal cans (both steel and aluminum) that are impermeable to hydrogen.
(B) Hydrogen water should not come into contact with gases other than hydrogen, such as air, especially in the sealed filling state.
(C) When sealing cans with packing, use as little gas permeable synthetic resins as possible.
As a result, in the present invention, hydrogen water is fully filled in a metal can so as not to generate a head space, and the hydrogen water after hermetically filling is not brought into contact with a gas other than hydrogen. That is, according to the present invention, the filled product 10 is manufactured by a method satisfying the above conditions (A) to (C), and the decrease in the dissolved hydrogen concentration of hydrogen water is suppressed.

次に、充填製品10や、充填製品10を製造する際の缶体の名称について説明する。
なお、以下の説明では、図2(a)に示すように、生成後の水素水Wを缶容器に満注充填し、缶内(上部)にヘッドスペース14を生じさせないようにした充填製品10を例に挙げて説明する。
また、ここでは一例として図2に示すように、缶蓋を開ける際にプルタブが内容物(水素水W)中に入らないフルオープンエンド缶(フルオープン蓋)を想定するが、開栓時にプルタブが内容物中に入ってしまうステイオンタブ缶(SOT缶)でも構わない。
Next, the name of the filling product 10 and the can body when manufacturing the filling product 10 will be described.
In the following description, as shown in FIG. 2A, the filled product 10 in which the produced hydrogen water W is filled in a can container and the head space 14 is not generated in the can (upper part). Will be described as an example.
In addition, as shown in FIG. 2 as an example, a full open end can (full open lid) in which the pull tab does not enter the contents (hydrogen water W) when opening the can lid is assumed. May be a steion tub can (SOT can) that gets into the contents.

充填製品10は、水素水を缶容器10Aに充填した後、蓋をして水素水を外部から密封遮断した缶体を指すものである。ここで缶胴部・缶蓋部に、各々、符号「11」・「12」を付すものであり、また缶蓋部12の開口面から、缶胴部11の上端部までの立ち上がり部を「立ち上がり部13」とするものである。
因みに、缶容器10Aとは、缶胴部11に缶底(底蓋)を具えた有底筒状の状態(つまり缶蓋部12が取り付けられていない状態)を示すものであり、この缶容器10Aを得るにあたっては、缶胴部11と缶底部とを絞り加工で一体に形成しても構わないし(いわゆる2ピース缶)、缶胴部11と缶底部とを別体で形成し接合しても構わないものである(いわゆる3ピース缶)。
The filled product 10 refers to a can body in which hydrogen water is filled in the can container 10A and then the lid is covered to seal off the hydrogen water from the outside. Here, the can body portion and the can lid portion are respectively provided with reference numerals “11” and “12”, and the rising portion from the opening surface of the can lid portion 12 to the upper end portion of the can body portion 11 is “ The rising portion 13 ”is used.
Incidentally, the can container 10A indicates a bottomed cylindrical state in which the can body portion 11 has a can bottom (bottom lid) (that is, a state in which the can lid portion 12 is not attached). In obtaining 10A, the can body portion 11 and the bottom portion may be integrally formed by drawing (a so-called two-piece can), and the can body portion 11 and the can bottom portion may be formed separately and joined. (So-called three-piece cans).

また、水素水Wの用途としては、主に飲料用を想定しており、飲料用の場合には一旦開栓すると時間の経過とともに水素水Wから水素が抜け出てしまうことから、開栓後は時間をおかずに飲むことを前提としている。また、そのために水素水Wを充填する缶の容量も主に100〜350ミリリットル程度の比較的小容量(いわゆる「飲みきりサイズ」)を想定している。しかしながら、水素水の用途としては、もちろん飲用のみに限定されるものではなく、例えば化粧品・化粧水への用途も想定される他、今後は、工業用用途も考えられる。このため容量としても上記「飲みきりサイズ」に限定されるものではなく、大容量の、いわゆるペール缶やドラム缶も缶体として想定でき、この場合には、缶蓋部12を缶胴部11に封着するにあたり、捲締だけなく、別途締め付け金具を用いて固定したり、溶接により固定することも考えられる。
また、このようなことから充填製品10(缶体)としては、飲用であれば、通常、円筒状が一般的であるが、必ずしもこれに限定されるものではない。
In addition, the use of hydrogen water W is mainly intended for beverages, and in the case of beverages, once it is opened, hydrogen will escape from the hydrogen water W over time. The premise is to drink without taking time. For this purpose, the capacity of the can filled with the hydrogen water W is assumed to be a relatively small capacity (so-called “drinking size”) of about 100 to 350 ml. However, the use of hydrogen water is not limited to drinking, of course. For example, it may be used for cosmetics and lotions, and in the future, industrial uses are also conceivable. For this reason, the capacity is not limited to the above-mentioned “drink-out size”, and a large-capacity so-called pail can and drum can can be assumed as a can body. In this case, the can lid portion 12 is replaced with the can body portion 11. For sealing, it is conceivable to fix not only by tightening but also by using a separate fastening metal fitting or by welding.
In addition, for this reason, the filling product 10 (can body) is generally a cylindrical shape as long as it is drinkable, but is not necessarily limited thereto.

なお、水素水Wは、例えば蒸留水等の原水に、水素ガスを溶存させて調整するものであり、できる限り高濃度つまり飽和濃度もしくは飽和濃度に近い状態まで水素を溶存させることが望ましい。また、原水としては、上述した蒸留水の他にも水道水などの適用が考えられる。
更に水素水Wの生成手法には、上述したように種々の手法があり、そのいずれでも飽和濃度に近い高濃度の水素水Wを生成することができるものである。しかしながら、せっかく高濃度に生成した水素水Wであっても、充填手法そのもの、つまりどのように缶容器10Aに詰めるのかによっても水素水Wの溶存水素濃度が変化するため、以下、充填時の好ましい手法(注意点)について説明する。
The hydrogen water W is prepared by dissolving hydrogen gas in raw water such as distilled water, for example, and it is desirable to dissolve hydrogen to the highest possible concentration, that is, to a state close to the saturated concentration. Moreover, as raw water, application of tap water etc. other than the distilled water mentioned above is considered.
Further, as described above, there are various methods for generating the hydrogen water W, and any of them can generate the hydrogen water W having a high concentration close to the saturated concentration. However, even if the hydrogen water W is generated with a high concentration, the dissolved hydrogen concentration of the hydrogen water W varies depending on the filling method itself, that is, how the can container 10A is packed. A method (attention) will be described.

前述したように現在市販されている水素水の溶存水素濃度は、0.1〜1.0ppm程度の製品が多い。しかしながら、水素の保存性の低い容器に充填すると、蓋を密封したままでも経時的に溶存水素濃度が下がり、水素水としての機能が著しく低下してしまう。しかも、水素は水から抜け出し易い性質を持っているため、いくら高濃度の水素水を製造しても充填時に水素を逃がしてしまっては意味がない。
そこで、本実施例では、水素水Wを缶容器10Aに充填する際には、他の気体との接触時間や接触面積を少なくし、また充填速度や充填する際の缶容器10Aと水素水Wの注水ノズル31nとの位置関係を考慮するものである。更に、充填の際には、少なからず水素水Wが他の気体と接触してしまう場合があるが、この接触した水素水Wを缶容器10Aから溢水させることで(満注充填)、水素水Wをより高濃度のまま充填し、且つ密封することができるものである。
As described above, the dissolved hydrogen concentration of hydrogen water currently on the market is often about 0.1 to 1.0 ppm. However, if a container with low hydrogen storage stability is filled, the concentration of dissolved hydrogen decreases with time even when the lid is sealed, and the function as hydrogen water is significantly reduced. Moreover, since hydrogen has the property of easily getting out of the water, no matter how high the concentration of hydrogen water is produced, it is meaningless if hydrogen escapes during filling.
Therefore, in this embodiment, when the hydrogen water W is filled in the can container 10A, the contact time and contact area with other gases are reduced, and the filling speed and the can container 10A and the hydrogen water W at the time of filling are reduced. The positional relationship with the water injection nozzle 31n is taken into consideration. Furthermore, when filling, hydrogen water W may come into contact with other gases, but hydrogen water W that has come into contact with the can container 10A is overflowed (full filling). It is possible to fill and seal W with a higher concentration.

以下、このような充填製品10を製造する装置(以下、「充填製品の製造装置1」とする)について説明しながら、併せて製造方法について説明する。
充填製品の製造装置1は、一例として図1に示すように、原水に水素を所望濃度になるまで溶存・含有させる水素水生成装置2と、生成した水素水Wを缶容器10Aに充填する(注入する)水素水充填装置3と、この缶容器10A(缶胴部11)に缶蓋部12を封着する(取り付ける)缶蓋封着装置4とを具えて成るものである。
ここで水素水Wを得るにあたっては、上述したように種々の手法が存在し、いずれでも採用できるため、以下の説明においては水素水生成装置2については省略し、水素水充填装置3と缶蓋封着装置4とについて説明する。
Hereinafter, the manufacturing method will be described together with an apparatus for manufacturing such a filled product 10 (hereinafter referred to as “filled product manufacturing apparatus 1”).
As an example, as shown in FIG. 1, the filled product manufacturing apparatus 1 fills a can container 10 </ b> A with a hydrogen water generation apparatus 2 that dissolves and contains hydrogen in raw water until a desired concentration is reached, and the generated hydrogen water W ( The hydrogen water filling device 3 (injected) and the can lid sealing device 4 for sealing (attaching) the can lid portion 12 to the can container 10A (can body portion 11) are provided.
Here, in obtaining the hydrogen water W, there are various methods as described above, and any of them can be adopted. Therefore, in the following description, the hydrogen water generating device 2 is omitted, and the hydrogen water filling device 3 and the can lid are omitted. The sealing device 4 will be described.

水素水充填装置3は、一例として図1に示すように、前段の水素水生成装置2により生成された水素水Wを缶容器10Aに注入する充填機本体31と、水素水Wを該充填機本体31に向けて移送するためのポンプ32と、水素水Wを浄化するための濾過フィルタ等の浄化装置33と、水素水Wを殺菌するための殺菌装置34(例えばUV殺菌装置)とを具えて成るものである。もちろん、本充填工程において用いられる缶容器10Aは、内容物である水素水Wの注入が行えるように、缶蓋部12が封着されていない有底筒状を成すものである。   As shown in FIG. 1 as an example, the hydrogen water filling device 3 includes a filling machine main body 31 that injects the hydrogen water W generated by the preceding stage hydrogen water production device 2 into the can container 10A, and the hydrogen water W. A pump 32 for transferring toward the main body 31, a purification device 33 such as a filtration filter for purifying the hydrogen water W, and a sterilization device 34 (for example, a UV sterilization device) for sterilizing the hydrogen water W are provided. It is made up of. Of course, the can container 10A used in the present filling step has a bottomed cylindrical shape in which the can lid portion 12 is not sealed so that the hydrogen water W as the contents can be injected.

また、充填機本体31は、このような缶容器10Aに、水素水Wを注ぎ込む注水ノズル31nを具えるものであり、本実施例では、この注水ノズル31nが昇降動自在に構成される。
更に、本発明では、水素水Wを缶容器10Aに充填する際と、充填後に缶容器10A(缶胴部11)に缶蓋部12を被せる際とのうち、後者において缶容器10Aに充填した水素水Wをオーバーフローさせ、水素水Wを満注充填するものである。もちろん、前者においても水素水Wをオーバーフローさせる場合には、充填機本体31において缶容器10Aをセットする載置台部分に、ドレンパイプ等の排水設備を設けることが好ましい。なお、これらのオーバーフローを区別して示す場合には、充填時に水素水Wを缶容器10Aから溢水させることを一次オーバーフローとし、缶蓋部12を取り付ける際に水素水Wを缶容器10Aから溢水させることを二次オーバーフローとするものである。
The filling machine main body 31 includes a water injection nozzle 31n for pouring the hydrogen water W into such a can container 10A. In this embodiment, the water injection nozzle 31n is configured to be movable up and down.
Furthermore, in the present invention, when filling the can container 10A with the hydrogen water W and when covering the can container 10A (can body part 11) with the can lid part 12 after filling, the latter filled the can container 10A. The hydrogen water W is overflowed and filled with hydrogen water W. Of course, when the hydrogen water W is overflowed also in the former, it is preferable to provide a drainage facility such as a drain pipe in the mounting table portion where the can container 10A is set in the filling machine main body 31. In addition, when distinguishing and indicating these overflows, overflowing the hydrogen water W from the can container 10A at the time of filling is regarded as a primary overflow, and the hydrogen water W is overflowed from the can container 10A when the can lid portion 12 is attached. Is a secondary overflow.

次に、水素水Wを缶容器10Aに充填する際の注入態様の一例と、その効果について説明する。
水素水Wを缶容器10Aに充填するにあたっては、水素水Wの充填開始時を除き、注水ノズル31nの吐出口を、既に缶容器10Aに注入された水素水Wの水面下に位置させる水没状態(注入済の水素水Wに浸けた状態)で充填するものであり(言わば水没充填)、このために注水ノズル31nを昇降動自在に形成するものである。
すなわち、実際の注水ノズル31nの動作としては、例えば図3(a)・(b)に示すように、まず注水ノズル31nを缶容器10Aの底部付近まで下降させ(このときのノズル吐出口と缶底部との離開距離は、充填速度等によって異なり、缶底部からの跳ね返りを考慮して決定される)、この状態で水素水Wの充填を開始するものである。その後、図3(c)・図4(a)に順次示すように、注水ノズル31nの吐出口が缶容器10A内に注入された水素水Wに浸かるようにすることが好ましい。
なお、ここでは充填の進行に伴い、徐々に注水ノズル31n(吐出口)を上昇させて行く形態を図示しており、この際、例えば缶容器10A内に注がれた水素水Wの液面とノズル吐出口との距離を常に一定に維持するように、注水ノズル31nを徐々に上昇させて行くことが可能である。
また、充填時に缶容器10Aをセットする載置台の方が昇降動自在であれば、載置台を昇降動させることで上記と同様の操作が可能となるため、この場合には、必ずしも注水ノズル31nを昇降動自在に構成する必要はない。つまり、注水ノズル31nの昇降動作は、充填時に缶容器10Aをセットする載置台に対して相対的に行えれば良いものである。
Next, an example of an injection mode when the hydrogen water W is filled in the can container 10A and the effect thereof will be described.
In filling the canister 10A with the hydrogen water W, the submerged state in which the discharge port of the water injection nozzle 31n is positioned below the surface of the hydrogen water W already injected into the can container 10A except when the filling of the hydrogen water W is started. In this case, the water injection nozzle 31n is formed so as to be movable up and down.
That is, as an actual operation of the water injection nozzle 31n, for example, as shown in FIGS. 3A and 3B, the water injection nozzle 31n is first lowered to the vicinity of the bottom of the can 10A (the nozzle discharge port and the can at this time). The separation distance from the bottom varies depending on the filling speed and the like, and is determined in consideration of the rebound from the bottom of the can.) In this state, filling of the hydrogen water W is started. Thereafter, as sequentially shown in FIGS. 3C and 4A, the discharge port of the water injection nozzle 31n is preferably immersed in the hydrogen water W injected into the can container 10A.
Here, a mode in which the water injection nozzle 31n (discharge port) is gradually raised as the filling progresses is illustrated. At this time, for example, the liquid level of the hydrogen water W poured into the can 10A It is possible to gradually raise the water injection nozzle 31n so that the distance between the nozzle and the nozzle outlet is always kept constant.
Further, if the mounting table on which the can container 10A is set at the time of filling can be moved up and down, the same operation as described above can be performed by moving the mounting table up and down. In this case, the water injection nozzle 31n is not necessarily used. It is not necessary to configure the slidable up and down. That is, the raising / lowering operation | movement of the water injection nozzle 31n should just be performed relatively with respect to the mounting base which sets 10 A of can containers at the time of filling.

そして、このような注入態様(水没充填)を採ることにより、充填時に缶容器10Aに注入する水素水Wの衝撃、あるいは空気や他の気体との接触が抑えられ、水素水Wからの水素の抜けを極力防止できるものである。
因みに、本発明者は、上述した水没充填を、注水ノズル31n(吐出口)を缶容器10A(缶胴部11)の上端よりも高い位置に設置した場合(つまり充填中にノズル吐出口が水素水Wに水没しない非水没充填)と比較する試験を行っており、水没充填の方が、水素の放出量が少ないことを確認している。これは、非水没充填では、ノズル吐出口が缶容器10Aの上端よりも常に高い位置に設定され、この高位置から水面を叩きながら充填することになるため、充填の際に水素水Wが空気を巻き込むのと同時に水素水Wから水素が抜けて行ったと考えられ、このために本実施例では水没充填を採用したものである。
Further, by adopting such an injection mode (submerged filling), the impact of the hydrogen water W injected into the can container 10A at the time of filling, or contact with air or other gas can be suppressed, and the hydrogen from the hydrogen water W can be suppressed. It can prevent omission as much as possible.
Incidentally, the present inventor performed the above-described submerged filling when the water injection nozzle 31n (discharge port) is installed at a position higher than the upper end of the can container 10A (can body part 11) (that is, the nozzle discharge port is hydrogenated during filling). A test for comparison with non-submerged filling that does not submerge in water W has been conducted, and it has been confirmed that submerged filling has less hydrogen release. This is because in non-submersible filling, the nozzle discharge port is always set at a position higher than the upper end of the can container 10A, and filling is performed while hitting the water surface from this high position. It is considered that hydrogen escaped from the hydrogen water W at the same time as the water was entrained. For this reason, submerged filling was adopted in this embodiment.

因みに本発明者は充填速度の違いが水素溶存濃度の変化に及ぼす影響を調べる実験も行っている。この実験では、一例として2リットル/1分の充填速度と、1リットル/1分の充填速度という速度で比較したものであり、その結果、充填速度の違いによる顕著な差は出現しなかったものの、1リットル/1分という低速度の方が、幾らか高濃度を保てる傾向にあることが分かったものである。   Incidentally, the present inventor has also conducted an experiment to examine the influence of the difference in filling rate on the change in the dissolved hydrogen concentration. In this experiment, for example, a comparison was made at a filling speed of 2 liters / minute and a filling speed of 1 liter / minute, and as a result, no significant difference due to the difference in filling speeds appeared. It has been found that the lower speed of 1 liter / min tends to maintain a somewhat higher concentration.

次に、缶蓋封着装置4について説明する。缶蓋封着装置4は、充填後の缶容器10A(缶胴部11)に缶蓋部12を被せて封着(封緘)する装置であり、換言すれば缶体を密封し、内部に充填(ここでは満注充填)した水素水Wを外部空間から遮断する装置とも言え、ここでは缶詰に蓋をする際に用いられる二重捲締手法を採用する。このため本実施例における缶蓋封着装置4の実質としてはシーマー41となる。因みに二重捲締とは、缶蓋部12(周縁カール部分)を、缶胴部11(上端縁)のフランジ部分に巻き込み、これらをともに圧着・接合する方法である。   Next, the can lid sealing device 4 will be described. The can lid sealing device 4 is a device for sealing (sealing) the can container 10A (can body portion 11) after covering with the can lid portion 12, in other words, sealing the can body and filling the inside. It can also be said to be a device that shuts off the hydrogen water W (full filling here) from the outside space, and here, a double clamping method used when a can is covered is adopted. For this reason, the seamer 41 is a substantial part of the can lid sealing device 4 in this embodiment. Incidentally, the double clamping is a method in which the can lid portion 12 (peripheral curl portion) is wound around the flange portion of the can body portion 11 (upper edge), and these are crimped and joined together.

なお、缶蓋部12の封着時においては、一例として図4(b)・(c)に示すように、水素水Wを充填した缶容器10A(缶胴部11)の上端縁に缶蓋部12を載せた際に(被せた際に)、水素水Wを缶容器10Aからオーバーフローさせるものであり(上述した二次オーバーフロー)、この状態のまま、つまり缶体上部にヘッドスペース14が存在しない状態のまま、缶蓋部12の封着を行うものである。
また、このためシーマー41においては缶容器10A(缶体)を直接あるいは間接的に支持するベース部分においても水素水充填装置3と同様に、二次オーバーフローを許容するためのドレンパイプなどの排水設備を設けることが好ましい。
When the can lid 12 is sealed, as an example, as shown in FIGS. 4 (b) and 4 (c), the can lid is placed on the upper edge of the can container 10 </ b> A (can body 11) filled with hydrogen water W. When the portion 12 is placed (when covered), the hydrogen water W overflows from the can container 10A (secondary overflow described above), and the head space 14 is present in this state, that is, at the top of the can body. The can lid portion 12 is sealed in a state where it is not.
For this reason, in the seamer 41, drainage equipment such as a drain pipe for allowing secondary overflow is also provided in the base portion that directly or indirectly supports the can container 10A (can body) as in the hydrogen water filling device 3. Is preferably provided.

本発明に係る充填製品の製造装置1は、以上のように構成されるものであり、以下、充填製品10(缶体)の実使用における、好ましい缶体の形態(例えば満注充填のため上記図2に示すフルオープンエンド(フルオープン蓋)が好ましい)等について説明する。
ミネラル水等の粘度の低い内容物を満注充填した場合には、開栓する際、内容物の一部が飛び出ることがある。例えばSOT缶(ステイオンタブ缶)では、開栓する際にプルタブが内容物中に入り込むことにより、結果的に内容物を押し出し、飛沫状となって外部に飛び出して周囲を濡らしてしまうことがある。特に、SOT缶では、ユーザ(飲用者)が、片手に缶を持ち、もう一方の手でプルタブの開栓操作をすることが多く、缶体を不安定な状態で持つために、よけいに内容物が飛散し易いと考えられる。
The filled product manufacturing apparatus 1 according to the present invention is configured as described above. Hereinafter, a preferable can body form (for example, the above-mentioned for full filling) in actual use of the filled product 10 (can body). The full open end (full open lid) shown in FIG. 2 is preferable.
When filling with low viscosity contents such as mineral water, a part of the contents may pop out when opening. For example, in a SOT can (steel tub can), when the plug is opened, the pull tab enters the content, and as a result, the content is pushed out and splashes out to the outside and wets the surroundings. is there. In particular, with SOT cans, the user (drinker) often holds the can in one hand and opens the pull tab with the other hand. It is thought that things are easy to scatter.

そして、開栓時におけるこのような内容物の飛散は、消費者からのクレームになることが想定され得る。この問題を解決する手段としては、上記図2に示すように、プルタブが内容物中に入らないフルオープンエンドが好ましいと考えられる。因みに、このフルオープンエンド方式であれば、開栓時に机やテーブル等に缶を安定した状態で置いてから開栓作業を行うことが多いため、より一層、内容物の周囲への飛散が防止できると考えられる。
なお、図2(b)に示すような充填製品10、つまり缶体内(上部)にヘッドスペース14を設け、ここに水素ガスを充填した場合には、フルオープンエンドはもちろんSOT缶でも、開栓時の内容物飛散防止(こぼれ防止)がより確実に行い得るものである。
And it can be assumed that the scattering of the contents at the time of opening the plug becomes a complaint from the consumer. As a means for solving this problem, as shown in FIG. 2, a full open end in which the pull tab does not enter the contents is considered preferable. By the way, with this full-open end method, since the opening operation is often performed after the can is placed in a stable state on a desk or table when opening, the content is further prevented from being scattered around. It is considered possible.
In addition, when the head space 14 is provided in the filling product 10 as shown in FIG. 2B, that is, the inside of the can (upper part) and filled with hydrogen gas, the cap can be opened not only in the full open end but also in the SOT can. Preventing scattering of contents (prevention of spillage) can be performed more reliably.

また、満注充填の充填製品10では、図2に示す「立ち上がり部13」の高さが低いと、開栓時の水素水Wの液面が、缶胴部11の上端(缶の縁)とほぼ同じ高さになってしまい、一口目を飲む際に水素水Wを零さないようにするには、開栓した充填製品10を水平の状態で口まで運ばなければならず、飲みにくいといった問題が起こることも考えられる。
これを解決する手段としては、立ち上がり部13の寸法を、5〜10mm程度確保すれば、これが堰の作用を担い、一口目を飲む際の飲みにくさを解消することができるものであり、更には開栓時の内容物の周囲への飛び散りも防止できるものと考えられる。
Further, in the fully filled product 10, when the height of the “rising portion 13” shown in FIG. 2 is low, the liquid level of the hydrogen water W at the time of opening is the upper end (can edge) of the can body 11. In order not to spill the hydrogen water W when drinking the first mouth, the filled product 10 that has been opened must be transported to the mouth in a horizontal state and is difficult to drink Such a problem may occur.
As a means for solving this, if the dimension of the rising portion 13 is secured about 5 to 10 mm, this bears the action of the weir and can eliminate the difficulty of drinking when drinking the first mouthpiece. It is considered that the contents can be prevented from scattering around the contents when opened.

次に、本発明の製造方法によって製造された充填製品10の保存性の実効性について説明する。
まず、マイクロバブル法により、溶存水素濃度を1.4ppmに高めた蒸留水(水素水W)を200ミリリットル用のスチール製SOT缶(ステイオンタブ缶)に満注充填した後、時間をあけずに、東洋製罐株式会社製のシーマーを用いて2重捲締を行った。
充填された水素水Wを37℃の恒温槽に保管し(夏場を想定)、1週間毎にそのうちの2本を取り出して、溶存水素濃度を測定した。なお、溶存水素濃度の測定は、東亜ディーケーケー株式会社製の溶存水素計「DH−35A」を用いて実施した。
得られた結果を図8に示すものであり、このグラフから溶存水素濃度の減少は、ほとんど見られず、6ヶ月(180日)経過後においても溶存水素濃度は、1.0ppm以上の値を示した。
Next, the effectiveness of the storage stability of the filled product 10 manufactured by the manufacturing method of the present invention will be described.
First, using a micro-bubble method, distilled water (hydrogen water W) whose dissolved hydrogen concentration has been increased to 1.4 ppm is fully filled into a 200 ml steel SOT can (steel tub can), and then no time is spent. In addition, double clamping was performed using a seamer manufactured by Toyo Seikan Co., Ltd.
The filled hydrogen water W was stored in a constant temperature bath at 37 ° C. (assuming summertime), and two of them were taken out every week, and the dissolved hydrogen concentration was measured. The dissolved hydrogen concentration was measured using a dissolved hydrogen meter “DH-35A” manufactured by Toa DKK Corporation.
The obtained results are shown in FIG. 8. From this graph, almost no decrease in the dissolved hydrogen concentration was observed, and the dissolved hydrogen concentration had a value of 1.0 ppm or more even after 6 months (180 days). Indicated.

また、この測定結果から以下の直線回帰式を求め、統計学的に6ヶ月間の水素濃度の変動を算出した。
y=−0.001x+1.2528 (y:水素濃度 x:保存日数)
この回帰式の示すところは、初期値が1.25ppmである場合、6ヶ月後の水素濃度の推定値は、1.07ppmであり、6ヶ月保存における水素濃度の減少率は14%程度にとどまることが分かった。このことは、充填時の溶存水素濃度が1.25ppm以上であれば、真夏の状況下においても1ppm以上の高濃度の水素を保ったまま水素水Wが保存可能であることを示しており、本願発明が水素水Wの保存方法として優れていることが確認できた。
一方、上記図5は、上述したように室温保存した他社製品の溶存水素濃度を約1ヶ月毎に6ヶ月間にわたって測定した結果を示したものである。このうち測定開始時の溶存水素濃度が1ppm以上の製品は、11品目中2品目しかなく、溶存水素濃度を高濃度で保ったまま容器に充填することの難しさが客観的に示されていると同時に、1ppm以上の高濃度を示した製品であっても、3ヶ月保存後には(1ppmをはるかに下回り)0.7〜0.8ppm程度まで減少したことが示されている。本発明に係る充填製品10と同様、上記2製品(上記2品目)の測定結果から各々の直線回帰式を求め、統計学的に3ヶ月保存後の2製品の水素濃度減少率を算出すると、29〜37%であり、6ヶ月保存の場合、59〜75%の水素濃度減少率となった。この点、上述したように本発明に係る充填製品10の6ヶ月保存における水素濃度の減少率は14%程度であり、本発明に係る充填製品10は水素濃度の減少を他社製品と比較して1/4〜1/5に抑えることが明らかとなり、この点が本発明に係る充填製品10の優れた効果である。
なお、初期水素濃度が0.4ppm以下の低濃度の水素水の場合、保存期間における水素濃度の減少率が少なくなる傾向が見られ、保存期間における水素濃度の減少率を比較する場合、1ppm以上の高濃度の水素水での比較が重要な点であることも判明した。
Moreover, the following linear regression formula was calculated | required from this measurement result, and the fluctuation | variation of the hydrogen concentration for 6 months was computed statistically.
y = −0.001x + 1.2528 (y: hydrogen concentration x: number of storage days)
The regression equation shows that when the initial value is 1.25 ppm, the estimated value of the hydrogen concentration after 6 months is 1.07 ppm, and the decrease rate of the hydrogen concentration after 6 months storage is only about 14%. I understood that. This indicates that, if the dissolved hydrogen concentration at the time of filling is 1.25 ppm or more, the hydrogen water W can be stored while maintaining a high concentration of hydrogen of 1 ppm or more even under midsummer conditions. It was confirmed that the present invention is excellent as a method for storing hydrogen water W.
On the other hand, FIG. 5 shows the result of measuring the dissolved hydrogen concentration of another company's product stored at room temperature as described above for about 6 months every 1 month. Of these, products with dissolved hydrogen concentration of 1 ppm or more at the start of measurement are only 2 items out of 11 items, and it is objectively shown that it is difficult to fill the container with the dissolved hydrogen concentration kept high. At the same time, even a product having a high concentration of 1 ppm or more is shown to have decreased to about 0.7 to 0.8 ppm after being stored for 3 months (much less than 1 ppm). As with the filled product 10 according to the present invention, the respective linear regression equations are obtained from the measurement results of the above two products (the above two items), and the hydrogen concentration reduction rate of the two products after three months storage is calculated statistically. It was 29 to 37%, and in the case of storage for 6 months, the decrease rate of hydrogen concentration was 59 to 75%. In this regard, as described above, the reduction rate of the hydrogen concentration in the 6-month storage of the filled product 10 according to the present invention is about 14%, and the filled product 10 according to the present invention compares the decrease in hydrogen concentration with that of other companies. It becomes clear that it suppresses to 1 / 4-1 / 5, and this point is the outstanding effect of the filling product 10 which concerns on this invention.
In the case of low-concentration hydrogen water with an initial hydrogen concentration of 0.4 ppm or less, there is a tendency that the decrease rate of the hydrogen concentration during the storage period tends to decrease. When comparing the decrease rate of the hydrogen concentration during the storage period, 1 ppm or more It was also found that the comparison with high-concentration hydrogen water was an important point.

本発明は、飲用(飲料用)の水素水の保存手法として適用できることはもちろん、飲用以外にも化粧品(化粧水)用の水素水の保存手法としても適用でき、また工業用にも適用できるものである。   The present invention can be applied as a method for preserving hydrogen water for drinking (drinking), as well as a method for preserving hydrogen water for cosmetics (skin water) in addition to drinking, and also applicable to industrial use. It is.

1 充填製品の製造装置
2 水素水生成装置
3 水素水充填装置
4 缶蓋封着装置

10 充填製品
10A 缶容器
11 缶胴部
12 缶蓋部
13 立ち上がり部
14 ヘッドスペース

3 水素水充填装置
31 充填機本体
31n 注水ノズル
32 ポンプ
33 浄化装置
34 殺菌装置

4 缶蓋封着装置
41 シーマー

W 水素水
DESCRIPTION OF SYMBOLS 1 Manufacturing apparatus of filling product 2 Hydrogen water production | generation apparatus 3 Hydrogen water filling apparatus 4 Can lid sealing apparatus

DESCRIPTION OF SYMBOLS 10 Filled product 10A Can container 11 Can body part 12 Can lid part 13 Standing part 14 Head space

3 Hydrogen Water Filling Device 31 Filling Machine Body 31n Water Injection Nozzle 32 Pump 33 Purification Device 34 Sterilization Device

4 Can lid sealing device 41 Seamer

W Hydrogen water

Claims (2)

原水と水素ガスとの混合により水素を溶存させた水素水を生成し、この水素水を金属製の缶容器に充填し、その後、缶容器の缶胴部に缶蓋部を被せて、この缶蓋部を缶胴部に封着して、水素水の充填製品を製造する方法において、
前記缶体内に充填する水素水は、缶蓋部を缶胴部に封着した密封状態において、水素以外の気体と接触しない状態で密封充填されるものであり、
この密封充填にあたっては、
水素水を充填した缶容器に缶蓋部を取り付ける工程において水素水を缶体から溢水させる二次オーバーフローを生じさせ、水素水を金属缶体に満注充填するようにしたことを特徴とする、水素水の充填製品の製造方法。
Hydrogen water in which hydrogen is dissolved is produced by mixing raw water and hydrogen gas, and the hydrogen water is filled into a metal can container, and then the can body part of the can container is covered with a can lid part. In a method of manufacturing a hydrogen water filled product by sealing a lid to a can body,
The hydrogen water to be filled in the can body is sealed and filled in a state where the can lid portion is sealed to the can body portion and is not in contact with a gas other than hydrogen,
In this hermetic filling,
In the process of attaching a can lid to a can container filled with hydrogen water, a secondary overflow that causes hydrogen water to overflow from the can body is produced, and the hydrogen water is filled in a metal can body, Manufacturing method of hydrogen water filled products.
前記水素水を缶容器に充填するにあたっては、水素水の充填開始時を除き、注水ノズルの吐出口を、既に缶容器内に注入された水素水の水面下に位置させる水没状態で注入を行うようにしたことを特徴とする請求項1記載の、水素水の充填製品の製造方法。   When filling the can with the hydrogen water, the injection is performed in a submerged state where the discharge port of the water injection nozzle is located below the surface of the hydrogen water already injected into the can container, except when charging of the hydrogen water is started. The method for producing a product filled with hydrogen water according to claim 1, characterized in that it is configured as described above.
JP2013207181A 2011-08-31 2013-10-02 Manufacturing method of filling product of hydrogen water Pending JP2014024606A (en)

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JP6010716B1 (en) * 2016-06-10 2016-10-19 浩章 皆川 Hydrogen water production apparatus and hydrogen water production method
JP7080275B2 (en) 2020-04-30 2022-06-03 株式会社 伊藤園 Beverages containing hydrogen in containers and their manufacturing methods

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