JP2020151711A - Method for producing magnesium chloride-containing water for beverages - Google Patents
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Abstract
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本発明は、水の長期保存が可能となる飲料用の塩化マグネシウム含有水の製造方法に関する。 The present invention relates to a method for producing magnesium chloride-containing water for beverages, which enables long-term storage of water.
塩化マグネシウムと水との関係に関する文献として、例えば、特公平０５−１１９５２号公報は、牛乳、果汁、飲料水等の液体中の水に対して殺菌力を有する塩化マグネシウムを、液体に少量添加するようにした塩化マグネシウムを利用する殺菌及び消毒方法であり（特許文献１）、文中に「塩化マグネシウムは、水に対して２ｐｐｍの雰囲気下で各種菌をほぼ撲滅させる殺菌力を有している」と記載されている。本発明も、この考え方に基づくものである。 As a document relating to the relationship between magnesium chloride and water, for example, Japanese Patent Publication No. 05-11952 adds a small amount of magnesium chloride having bactericidal activity to water in a liquid such as milk, fruit juice, and drinking water. This is a sterilization and disinfection method using magnesium chloride (Patent Document 1), and the text states that "magnesium chloride has a bactericidal activity that almost eradicates various bacteria in an atmosphere of 2 ppm with respect to water." It is described as. The present invention is also based on this idea.
また、特開平１１−１２３３８５号公報は、塩化マグネシウムではなく、水酸化マグネシウム固溶体についてであり、水酸化マグネシウム固溶体は、水に不溶であるが、わずかにマグネシウムイオンが溶け出て、溶液もアルカリ化する。この状態で殺菌作用があるとの記述であって、溶け出たマグネシウムイオンが細菌に作用しているものと考えられる。また、カルシウム、アルミニウム、亜鉛を含ませた場合も検討している。そして、殺菌処理後に固液分離すれば、固溶体やその他の沈殿物が除け、結果として、清澄化が図れると考えられる水の殺菌、浄化方法および殺菌、浄化剤であり（特許文献２）、その手段として、明細書では、「・Ｍｇ（ＯＨ）２およびＭｇ０．９−１．０Ｃａ０．１−０（ＯＨ）２で表されるマグネシウム化合物の固溶体から選ばれた少なくとも一種を、原水に対し０．０１重量％以上添加して約１時間以上接触させ、その後必要に応じ、固液分離、酸によるＰＨ調整を適宜選択実施する。
・上記マグネシウム化合物が、最大径約０．１〜１０ｍｍに造粒されている。
・細菌増殖が原因で生ずるスライム形成を阻止しながら、富栄養化成分であるリン酸イオン等の有害成分を高度に除去できる。」と記載されている。
Further, Japanese Patent Application Laid-Open No. 11-123385 refers to a magnesium hydroxide solid solution, not magnesium chloride, and the magnesium hydroxide solid solution is insoluble in water, but magnesium ions are slightly dissolved and the solution is also alkalized. To do. It is described that there is a bactericidal action in this state, and it is considered that the dissolved magnesium ions are acting on the bacteria. We are also considering the case where calcium, aluminum, and zinc are included. Then, if solid-liquid separation is performed after the sterilization treatment, the solid solution and other precipitates can be removed, and as a result, water sterilization, purification method and sterilization, purifying agent which are considered to be clarified (Patent Document 2) As a means, in the specification, at least one selected from a solid solution of a magnesium compound represented by “・ Mg (OH) 2 and Mg0.9-1.0Ca0.1-0 (OH) 2” is 0 with respect to raw water. Add 0.01% by weight or more and contact for about 1 hour or more, and then, if necessary, solid-liquid separation and PH adjustment with acid are appropriately selected and carried out.
-The magnesium compound is granulated to a maximum diameter of about 0.1 to 10 mm.
-While blocking slime formation caused by bacterial growth, harmful components such as phosphate ions, which are eutrophicating components, can be highly removed. ".
そこで、特許文献２の実施例を説明すると、「河川水を採取し、含有される固形物を濾過して除去した水１００ｍｌを三角フラスコに分注し、シリコン栓をして湿熱滅菌した。これにＢＥＴ比表面積２８ｍ２／ｇのＭｇ０．９５ Ｚｎ０．０５ Ｏの粉末を表１に示す量それぞれ添加した後、培養した大腸菌を約１０（５）個／ミリリットルとなるように接種し、３５℃で振盪した。菌接種後１、３、５および２４時間後にサンプリングし、含まれる菌数を混釈平板培養法により測定した」である。この混釈培養法とは、例えば、液状検体中の菌数を調べる（固形物は希釈液で溶解して）ときの培養法で、接種検体量が多い場合にも適用できる方法と云われている。 Therefore, to explain the embodiment of Patent Document 2, "River water was sampled, 100 ml of water obtained by filtering and removing the contained solid matter was dispensed into an Erlenmeyer flask, and a silicon stopper was used to sterilize by moist heat. After adding the powders of Mg0.95 Zn0.05 O having a BET specific surface area of 28 m2 / g in the amounts shown in Table 1, the cultured Escherichia coli was inoculated to about 10 (5) pieces / ml, and at 35 ° C. It was shaken. Samples were taken 1, 3, 5 and 24 hours after the inoculation of the bacteria, and the number of the contained bacteria was measured by the warichu plate culture method. " This pour culture method is, for example, a culture method for examining the number of bacteria in a liquid sample (solid matter is dissolved in a diluent), and is said to be a method that can be applied even when the amount of inoculated sample is large. There is.
表１
Table 1
次に、Ａｎｄｒｅａｓ Ｎｏｃｋｅｒ、他４名、“Ａｎｔｉｍｉｃｒｏｂｉａｌ ｐｒｏｐｅｒｔｉｅｓ ｏｆ ｍａｇｎｅｓｉｕｍ ｃｈｌｏｒｉｄｅ ａｔ ｌｏｗ ｐＨ ｉｎ ｔｈｅ ｐｒｅｓｅｎｃｅ ｏｆ ａｎｉｏｎｉｃ ｂａｓｅｓ”、Ｍａｇｎｅｓｉｕｍ Ｒｅｓｅａｒｃｈ、２０１４．Ａｐｒ−Ｊｕｎ、２７（２）、５７−６８ページ（非特許文献１）では、塩化マグネシウムが水に溶ける時に起こる酸性化（ＰＨストレス）で殺菌作用が説明できるのではないかという記述がある。即ち、塩化マグネシウムの菌増殖抑制作用は「ＰＨストレス」の可能性があると述べられている。しかしながら、非特許文献１の如く、中性ＰＨでは塩化マグネシウムの菌増殖抑制作用がでないので、特許文献１と特許文献２の如く、水酸化マグネシウムであって、むしろアルカリ性のＰＨとの構成とは、別物と考えられる。以下に、概要を記述する。 Next, Andreas Nocker and 4 others, "Antimicrobial products of magnesium chloride at low pH in the presence of anionic bases", Magnesium Research, 20. Appr-Jun, 27 (2), pp. 57-68 (Non-Patent Document 1) describes that the bactericidal action may be explained by the acidification (PH stress) that occurs when magnesium chloride dissolves in water. That is, it is stated that the action of magnesium chloride to suppress bacterial growth may be "PH stress". However, as in Non-Patent Document 1, neutral PH does not have a bacterial growth inhibitory effect on magnesium chloride. Therefore, as in Patent Documents 1 and 2, magnesium hydroxide is rather composed of alkaline PH. , Considered different. The outline is described below.
非特許文献１は、「マグネシウムは生命に不可欠な元素であり、すべての生物に普遍的に見いだされる。異なるカチオンは、酵素補因子、シグナル伝達分子、および細胞成分の安定化において重要な役割を果たす。微生物学的実験において、マグネシウム塩が典型的には良い効果と関連することは驚くべきことではない。モデル生物としてのＬｉｓｔｅｒｉ ａｍｏｎｏｃｙｔｏｇｅｎｅｓを用いたこの研究で、我々は、しかしながら、ストレスエンハンサーとしてのＭｇ（ＭｇＣｌ２の形態で）の有用性について焦点を当てている。 ＭｇＣｌ２は、中性付近のＰＨで細菌の生存率に影響を与えないが、細胞懸濁液を酸性ＰＨで塩に曝露すると、培養能および酸化還元活性を強く損なうことが判明した。この原則は、グラム陰性およびグラム陽性の多数の種によって確認された。マグネシウム塩は、リン酸塩、乳酸塩または酢酸塩などのアニオン性塩基（ＴＲＩＳを除く）の存在下では、酸性度を劇的に高め抗菌性であった。ＭｇＣｌ２の抗菌活性は、ＮａＣｌ、 ＫＣｌ、またはＣａＣｌ２の抗菌活性よりもはるかに強かった。 ＭｇＳＯ４で、または細胞がＰＨ≧５のリン酸緩衝液中でＭｇＣｌ２に暴露された場合には、効果は観察されなかった。酸ストレスは微生物生存率に対するＭｇＣｌ２の塩特異的効果によって、強化された。これについてはさらなる検討を要する。表面の消毒に対するその影響とは別に、この観察は、皮膚疾患（健康な皮膚は酸性環境である）の治療のためのＭｇＣｌ２の一般的な治療特性を裏付け、そして、死海からの塩（Ｍｇ２＋およびＣｌ−が、最も豊富に存在する）が治癒特性を有するのかを理解することを助ける。」である。 Non-Patent Document 1 states, "Magnesium is an essential element in life and is universally found in all living organisms. Different cations play important roles in stabilizing enzyme cofactors, signaling molecules, and cellular components. It does not come as a surprise that magnesium salts are typically associated with good effects in microbiological experiments. In this study using Listeria patents as a model organism, we, however, as stress enhancers. The focus is on the usefulness of Mg (in the form of MgCl2). MgCl2 does not affect bacterial viability at near neutral PH, but when the cell suspension is exposed to salts with acidic PH, It was found to severely impair cultivability and oxidative reduction activity. This principle was confirmed by a large number of gram-negative and gram-positive species. Magnesium salts are anionic bases such as phosphates, lactates or acetates. In the presence of (excluding TRIS), the acidity was dramatically increased and antibacterial. The antibacterial activity of MgCl2 was much stronger than the antibacterial activity of NaCl, KCl, or CaCl2. No effect was observed when the cells were exposed to MgCl2 in a phosphate buffer with a pH of ≥ 5. Acid stress was enhanced by the salt-specific effect of MgCl2 on microbial viability, which is further enhanced. Apart from its effect on surface disinfection, this observation confirms the general therapeutic properties of MgCl2 for the treatment of skin diseases (healthy skin is an acidic environment) and from the Dead Sea. It helps to understand whether salts (Mg2 + and Cl- are most abundant) have healing properties. "
非特許文献１の結果は、下記である。 The results of Non-Patent Document 1 are as follows.
低ＰＨでＭｇＣ１２を１５０ｍＭ以上加えると、抗菌効果がでた。（図３）
低ＰＨでＭｇＣｌ２を４００ｍＭ加えると、細胞膜破壊効果がでた。（図４）
低ＰＨでＭｇＣｌ２を４００ｍＭ加えると、グラム陰性菌（大腸菌、チフス菌）もグラム陽性菌（エンテロコッカス、黄色ブドウ球菌）も増殖できなかった。（図５）
大腸菌 チフス菌 エンテロコッカス 黄色ブドウ球菌
図５．ＰＨ７、ＰＨ３、またはＰＨ２における腸菌、チフス菌、エンテロコッカス、黄色ブドウ球菌のＭｇＣｌ２およびＮａＣｌへの暴露の影響。 細胞をそれぞれ４００ｍＭの塩に２０分間暴露した。 塩を含まない細胞懸濁液を対照として用いた。混合緩衝液−塩溶液のＰＨ値を示す。 曝露後、細胞を中性緩衝液に再懸濁し、段階希釈し、一定量をＴＳＡ（栄養培地）にスポットした。代表的なプレートの画像を表示すると、下記である。
When MgC12 was added at a low pH of 150 mM or more, an antibacterial effect was obtained. (Fig. 3)
When 400 mM of MgCl2 was added at low pH, a cell membrane-destroying effect was obtained. (Fig. 4)
When 400 mM of MgCl2 was added at low pH, neither Gram-negative bacteria (Escherichia coli, Typhus) nor Gram-positive bacteria (Enterococcus, Staphylococcus aureus) could grow. (Fig. 5)
Escherichia coli Typhus Enterococcus Staphylococcus aureus Figure 5. Effect of exposure of Enterococcus, Typhus, Enterococcus, Staphylococcus aureus to MgCl2 and NaCl on PH7, PH3, or PH2. Each cell was exposed to 400 mM salt for 20 minutes. A salt-free cell suspension was used as a control. The pH value of the mixed buffer solution-salt solution is shown. After exposure, cells were resuspended in neutral buffer, serially diluted, and a fixed amount was spotted on TSA (Nutrition Medium). An image of a typical plate is shown below.
上記の特許文献１等を考慮した上で、本発明は、下記のことを意図する。
１． 塩化マグネシウムを水に溶かすとＰＨが低下すると考える。即ち、塩化マグネシウム（Ｍｇ２＋およびＣｌ−）＋陽イオンの特別な性質である、他の陽イオンに比べ、イオン半径が最小で最も高い電荷密度である。その結果、水分子との相互作用が強まり、もって、水分子の水素イオン供与性が上がり、ＰＨが下がる。
２． 菌の増殖できる酸性培地へ塩化マグネシウムを加えると、菌の増殖が抑制されること、即ち、培地のＰＨが低下する、例えば、「ＰＨストレス」を利用する。
３． 併せて、塩化マグネシウムの効果の「ＰＨストレス」として、例えば、ＰＨ３（塩化マグネシウムなし）とＰＨ３．３（塩化マグネシウムあり）を比較し、菌の生育はＰＨの高いＰＨ３．３という条件下で抑制される。その一因は、水素イオンと塩化マグネシウムイオンとでなる供与性の働きと考えられる。
４． 従って、他の要因として、膜輸送、イオンとタンパク質や脂質との相互作用等におけるマグネシウムの作用に関することも今後の出願をすべきであるとの結論に基づく。
In consideration of the above-mentioned Patent Document 1 and the like, the present invention intends to:
1. 1. It is considered that the pH decreases when magnesium chloride is dissolved in water. That is, it has the smallest and highest charge density as compared with other cations, which is a special property of magnesium chloride (Mg2 + and Cl−) + cations. As a result, the interaction with the water molecule is strengthened, so that the hydrogen ion donating property of the water molecule is increased and the pH is decreased.
2. 2. When magnesium chloride is added to an acidic medium capable of growing bacteria, the growth of bacteria is suppressed, that is, the pH of the medium is lowered, for example, "PH stress" is utilized.
3. 3. At the same time, as the "PH stress" of the effect of magnesium chloride, for example, PH3 (without magnesium chloride) and PH3.3 (with magnesium chloride) are compared, and the growth of bacteria is suppressed under the condition of high PH 3.3. Will be done. One of the causes is considered to be the donor function of hydrogen ions and magnesium chloride ions.
4. Therefore, it is based on the conclusion that future applications should be filed regarding the action of magnesium on membrane transport, interaction between ions and proteins and lipids, etc. as other factors.
前記課題の解決と、水道水の長期保存と、水資源の不足する地域とか、災害時の生活、かつ人命・生命等保護の観点から、簡易な方法を提供する。その基本が、請求項１−４に記載の発明である。 We will provide a simple method from the viewpoints of solving the above problems, long-term storage of tap water, areas where water resources are scarce, life in the event of a disaster, and protection of human life and life. The basis thereof is the invention according to claim 1-4.
本発明によれば、まろやかな味覚を備え、かつ口あたりがよく、あたかも高原の湧き水の感覚で、美味であったとの飲水者の感覚を得ることができ有益であること、濁りとか臭みもなく、保存性効果も、大いに期待できることが判明した。 According to the present invention, it has a mellow taste, is palatable, and is beneficial because it gives the drinker a sense of deliciousness as if it were spring water from a plateau, without turbidity or odor. , It turned out that the preservation effect can be greatly expected.
本発明によれば、上記特徴と、併せて、通常の生活に利用する水道水の有効利用と、災害時の備蓄水とし活用できて重宝する。 According to the present invention, in addition to the above features, it is useful to be able to effectively use tap water used for normal life and to use it as a stockpile water in the event of a disaster.
本発明によれば、塩化マグネシウムが、水に溶ける時に起こる酸性化（ＰＨストレス）による殺菌作用をもちいて、水の腐敗防止を図る構成とした水である。 According to the present invention, magnesium chloride is a water having a structure for preventing water spoilage by using a bactericidal action due to acidification (PH stress) that occurs when magnesium chloride is dissolved in water.
本発明によれば、水は、少なくとも、１年程度は、味覚、臭気、違和感が発生しないことを特徴とした水であり、請求項１に記載の特徴と、併せて、飲み水としての水道水の有効利用と、災害時の備蓄水とし活用できて重宝する。 According to the present invention, the water is water characterized in that no taste, odor, or discomfort occurs for at least one year, and in addition to the characteristics according to claim 1, water supply as drinking water. It is useful because it can be used effectively as water and as a stockpile in the event of a disaster.
以下、本発明の実施例を説明する。 Hereinafter, examples of the present invention will be described.
実施例１は、下記、検査報告書第１８Ｅ０４９１０１−１／２号に示す結果によると、ペットボトルの水道水２リットルに、塩化マグネシウム（６水和物）１ｇを添加した水（試供品水１）を、平成２８年４月２７日に採取した。その後、平成３０年５月１７日に、株式会社環境公害センターで検査した結果の報告であり、細菌数（生菌数）（／ｍｌ）と、大腸菌群とを示している。検査結果はそれぞれ０、及び陰性であり、飲み水として有効である（遜色ない）。試供品水１の写真を示す。また、出願人の運営するジムの社員が飲料した味評価の結果を表にして示す。
According to the results shown in Inspection Report No. 18E049101-1 / 2 below, Example 1 is water obtained by adding 1 g of magnesium chloride (hexahydrate) to 2 liters of tap water in a PET bottle (sample water 1). ) Was collected on April 27, 2016. After that, on May 17, 2018, it is a report of the result of the inspection at the Environmental Pollution Center Co., Ltd., which shows the number of bacteria (live bacteria number) (/ ml) and coliform bacteria. The test results are 0 and negative, respectively, and they are effective as drinking water (not inferior). A photograph of free sample water 1 is shown. In addition, the results of taste evaluation of beverages made by employees of the gym operated by the applicant are shown in a table.
実施例２は、下記、検査報告書第１８Ｄ１１０５０１−１／２号に示す結果では、ペットボトルの水道水２リットルに、塩化マグネシウム（６水和物）１ｇを添加した水（試供品水１）を、平成２９年４月２０日に採取した。その後平成３０年４月１９日に、株式会社環境公害センターで検査した結果の報告であり、細菌数（生菌数）（／ｍｌ）と、大腸菌群とを示している。検査結果はそれぞれ０、及び陰性であり、飲み水として有効である（遜色ない）。試供品水２の写真を示す。また、出願人の運営するジムの社員が飲料した味評価の結果を表にして示す。
In Example 2, according to the results shown in Inspection Report No. 18D110501 / 1/2 below, water obtained by adding 1 g of magnesium chloride (hexahydrate) to 2 liters of tap water in a PET bottle (sample water 1). Was collected on April 20, 2017. After that, on April 19, 2018, it is a report of the result of the inspection at the Environmental Pollution Center Co., Ltd., which shows the number of bacteria (live bacteria number) (/ ml) and coliform bacteria. The test results are 0 and negative, respectively, and they are effective as drinking water (not inferior). A photograph of free sample water 2 is shown. In addition, the results of taste evaluation of beverages made by employees of the gym operated by the applicant are shown in a table.
実施例３は、下記、検査報告書第１８Ｅ０４９２０１−１／２号に示す結果では、ペットボトルの水道水２リットルに、塩化マグネシウム（６水和物）１ｇを添加した水（試供品水１）を、平成３０年３月１１日に採取した。その後平成３０年５月１７日に、株式会社環境公害センターで検査した結果の報告であり、細菌数（生菌数）（／ｍｌ）と、大腸菌群とを示している。検査結果はそれぞれ０、及び陰性であり、飲み水として有効である（遜色ない）。試供品水３の写真を示す。また、出願人の運営するジムの社員が飲料した味評価の結果を表にして示す。
In Example 3, according to the results shown in Inspection Report No. 18E049201-1 / 2 below, water obtained by adding 1 g of magnesium chloride (hexahydrate) to 2 liters of tap water in a PET bottle (sample water 1). Was collected on March 11, 2018. After that, on May 17, 2018, the result of the inspection at the Environmental Pollution Center Co., Ltd. is reported, showing the number of bacteria (viable cell count) (/ ml) and coliform bacteria. The test results are 0 and negative, respectively, and they are effective as drinking water (not inferior). A photograph of free sample water 3 is shown. In addition, the results of taste evaluation of beverages made by employees of the gym operated by the applicant are shown in a table.
本発明の水を飲水したジムの看護師の感想を示すと、Ｈ３０年５月１９日（土）１３：３０〜１５：００において、準備体操中に、本出願人が保管していた、練習中にいつも飲用している水道水で水分補給した瞬間、何気なく飲用したら「うわっ！薬くさい味がする」とすぐに言葉を発した。しかしながら、瞬時に、まろやかな（マイルドな）水であり、美味であるとの言葉を発した。 To show the impression of the gym nurse who drank the water of the present invention, the practice that the applicant kept during the preparatory exercise on Saturday, May 19, 2018 from 13:30 to 15:00. The moment I rehydrated with the tap water I always drink inside, I immediately said, "Wow! It tastes like medicine" when I drank it casually. However, he instantly said that it was mellow (mild) water and delicious.
この水こそ、本発明の「水道水２リットルに対し、塩化マグネシウム１ｇを配合してあった水道水」であった。 This water was the "tap water in which 1 g of magnesium chloride was mixed with 2 liters of tap water" of the present invention.
尚、この時飲用したのは、開封して３週間後の水道水であった。看護師が驚いたのは、飲用した水（飲水）は、マイルドで、美味であったことに対してであり、看護師はこの味に感動した。殊に、医療従事者として２時間後にも消化器症状が全くなく下痢、嘔吐等ない水道水であった。 What I drank at this time was tap water 3 weeks after opening. What surprised the nurses was that the water they drank (drinking water) was mild and delicious, and the nurses were impressed by this taste. In particular, the tap water had no digestive symptoms and no diarrhea or vomiting even after 2 hours as a medical worker.
尚、本人は、飲水後は普段通り、夜勤に行った。その際に、持ち帰った。人に味わってほしいと思う水であった。飲用者の反応がとても楽しみである。普通に他者に出して反応を感じたい。 After drinking water, he went to night shift as usual. At that time, I brought it home. It was water that I wanted people to taste. I am very much looking forward to the reaction of the drinker. I want to give it to others and feel the reaction.
［付記１］
水道水２リットルに対して、塩化マグネシウム（６水和物）を０．８ｇ−１．５ｇ添加することによる殺菌作用で、１年程度、前記水道水の腐敗、品質劣化の防止が可能になることを特徴とした水。
[Appendix 1]
The bactericidal action of adding 0.8 g-1.5 g of magnesium chloride (hexahydrate) to 2 liters of tap water makes it possible to prevent the tap water from spoiling and deteriorating in quality for about one year. Water characterized by that.
［付記２］
前記品質劣化とは、味覚劣化、悪臭の発生であることを特徴とした付記１に記載の水。
[Appendix 2]
The water according to Appendix 1, characterized in that the quality deterioration is taste deterioration and generation of a foul odor.
Claims (4)
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