JP2013039553A - Weakly acidic hypochlorous acid aqueous solution of long life and method for producing the same - Google Patents
Weakly acidic hypochlorous acid aqueous solution of long life and method for producing the same Download PDFInfo
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本発明は、長寿命の弱酸性次亜塩素酸水溶液とその製造方法に関する。The present invention relates to a long-life weakly acidic hypochlorous acid aqueous solution and a method for producing the same.
ここで取り上げる殺菌消毒剤の弱酸性次亜塩素酸水溶液（ＨＣｌＯ）は、良く知られている食塩水を電気分解して製造する強電解酸性酸化水ではなく、次の化学反応により次亜塩素酸ソーダ（ＮａＣｌＯ）と塩酸（ＨＣｌ）の反応により製造する弱酸性次亜塩素酸水溶液（ＨＣｌＯ）を意味する。
ＮａＣｌＯ ＋ ＨＣｌ ＝ ＨＣｌＯ ＋ ＮａＣｌThe weakly acidic hypochlorous acid aqueous solution (HClO) of the sterilizing disinfectant taken up here is not a strongly electrolyzed acidic oxidized water produced by electrolyzing a well-known saline solution, but hypochlorous acid by the following chemical reaction. It means weakly acidic hypochlorous acid aqueous solution (HClO) produced by the reaction of soda (NaClO) and hydrochloric acid (HCl).
NaClO + HCl = HClO + NaCl
具体的には原水の希釈水に次亜塩素酸ソーダを添加・希釈し、次に同様の希釈水に希塩酸を添加・希釈し、両者を混合または同様の希釈水でさらに希釈して製造されたｐＨ５前後の弱酸性次亜塩素酸水溶液である。Specifically, it was manufactured by adding and diluting sodium hypochlorite to dilution water of raw water, then adding and diluting dilute hydrochloric acid to the same dilution water, and mixing or further diluting with the same dilution water. It is a weakly acidic hypochlorous acid aqueous solution having a pH of around 5.
従来より次亜塩素酸ソーダは殺菌剤や漂白剤として広く用いられており、その酸化力に基づく優れた殺菌、漂白、消臭力があることは公知の事実である。一方最近注目されてきた弱酸性次亜塩素酸は次亜塩素酸ソーダよりもはるかに優れた酸化力に基づく殺菌、漂白、消臭力があり、同一濃度で比較すると次亜塩素酸ソーダの少なくとも１０倍以上の酸化力があり、しかも低濃度で殺菌効果がある。その上酸性であることから特に人体に対して次亜塩素酸ソーダよりはるかに優しいのである。Conventionally, sodium hypochlorite has been widely used as a bactericidal agent and a bleaching agent, and it is a known fact that it has excellent bactericidal, bleaching and deodorizing power based on its oxidizing power. On the other hand, weakly acidic hypochlorous acid, which has recently attracted attention, has sterilization, bleaching, and deodorizing power based on oxidation power far superior to that of sodium hypochlorite. It has an oxidizing power of 10 times or more and has a bactericidal effect at a low concentration. In addition, it is acidic and is much gentler to the human body than sodium hypochlorite.
一般的に次亜塩素酸ソーダの使用濃度が１００ｍｇ／Ｌ以上であるため、次亜塩素酸水溶液も１００ｍｇ／Ｌという非常に高い濃度での使用が試みられており、次亜塩素酸の持つ優れた特性が十分生かされていないのが現状である。次亜塩素酸ソーダはもちろんのこと次亜塩素酸の場合も高濃度での使用は人体を傷つけまた有害な有機塩素化合物の生成を加速する。Since the use concentration of sodium hypochlorite is generally 100 mg / L or more, use of hypochlorous acid aqueous solution at an extremely high concentration of 100 mg / L has been attempted. The current characteristics are not fully utilized. In the case of hypochlorous acid as well as sodium hypochlorite, the use of high concentrations damages the human body and accelerates the generation of harmful organochlorine compounds.
したがって人体や環境のことを考慮すれば可能な限り低濃度で使用することが極めて重要なことである。これが出来ない最大の理由の一つは、低濃度にすると次亜塩素酸水溶液の寿命が短くなるという事象のためである。Therefore, considering the human body and the environment, it is extremely important to use it at the lowest possible concentration. One of the biggest reasons why this is not possible is due to the phenomenon that the life of the hypochlorous acid aqueous solution is shortened at a low concentration.
次亜塩素酸ソーダや次亜塩素酸のような塩素系の殺菌剤の製造時や使用時には有効な塩素と水中や空気中に必ず存在する有機物が反応して有機塩素化合物が生成する。有機塩素化合物は低濃度で毒性が強くかつ発がん性のものが多い。このことは、かつての代表的な農薬であり、現在製造禁止や使用禁止になっているＤＤＴやＢＨＣ、その他近年問題になっているダイオキシンなどいずれも有機塩素化合物であることからも明らかである。有機塩素化合物は現在の土壌汚染、河川水や地下水汚染、海洋汚染など地球環境問題発生の一つの大きな元凶になっている。When producing or using a chlorine-based disinfectant such as sodium hypochlorite or hypochlorous acid, effective chlorine reacts with organic substances present in water or air to produce an organic chlorine compound. Organochlorine compounds are highly toxic and carcinogenic at low concentrations. This is apparent from the fact that these are typical agricultural chemicals in the past, and DDT and BHC, which are currently banned for production and use, and dioxins, which have recently become problematic, are organochlorine compounds. Organochlorine compounds are one of the major causes of global environmental problems such as soil pollution, river water and groundwater pollution, and marine pollution.
有機塩素化合物は有機物であり本来なら土壌に投棄すれば土壌中の微生物が食べて分解してくれるはずのものである。ところが有毒な有機塩素化合物を食べると微生物がやられてしまうため食べてくれない。そのため、いつまでも土壌中に残ることになり、雨が降れば河川に流れ出て河川水汚染、地下に浸透して地下水汚染を引き起こす。現状では一旦有機塩素化合物になると放射性元素より質が悪い。放射性元素には半減期があるが有機塩素化合物にはない。Organochlorine compounds are organic substances that would normally be eaten and decomposed by microorganisms in the soil if discarded into the soil. However, if you eat toxic organochlorine compounds, microorganisms will be killed and you will not eat them. Therefore, it will remain in the soil indefinitely, and if it rains, it will flow into the river and pollute the river water and penetrate into the underground, causing groundwater pollution. At present, once an organochlorine compound is used, the quality is worse than that of radioactive elements. Radioactive elements have a half-life, but organochlorine compounds do not.
このような有機塩素化合物の生成量は塩素の濃度、すなわち次亜塩素酸ソーダや次亜塩素酸の濃度に比例して生成する。したがって製造や使用に当たっては塩素系殺菌剤の濃度は低いほど望ましいのである。このことからも低濃度で殺菌効果の高い次亜塩素酸の方が次亜塩素酸ソーダより有毒な有機塩素化合物の生成量が少なく出来る点でも優れている。さらに使用する次亜塩素酸の濃度を低く出来れば申し分ないのである。The amount of such organic chlorine compound produced is proportional to the chlorine concentration, that is, the concentration of sodium hypochlorite or hypochlorous acid. Therefore, the lower the concentration of the chlorine-based disinfectant is, the more desirable for production and use. For this reason, hypochlorous acid having a low concentration and a high bactericidal effect is superior in that the amount of toxic organochlorine compound produced can be reduced compared to sodium hypochlorite. Furthermore, it would be satisfactory if the concentration of hypochlorous acid used could be lowered.
図１の『ｐＨによる次亜塩素酸の変化』に示すように、ｐＨ５前後で次亜塩素酸の割合が最大になる。As shown in “Change of hypochlorous acid due to pH” in FIG. 1, the ratio of hypochlorous acid becomes maximum around
ところで従来の弱酸性次亜塩素酸水溶液の製造に当っては原水の希釈水に水道水を使用していた。しかし通常の水道水にはミネラル、有機物、微粒子、細菌やその死骸、窒素、酸素、炭酸ガスなど多くのものが含まれている。次亜塩素酸は次亜塩素酸ソーダに比べ酸化力が強いため水中の有機物などと反応し有機塩素化合物を作り易かったり、ミネラル類は次亜塩素酸の自己分解の触媒になったりするため次亜塩素酸の寿命が短くなってしまう。特にこの傾向は次亜塩素酸の濃度が低くなればなるほど顕著になってくる。そのためどうしても高濃度の次亜塩素酸水溶液にせざるを得なかった。図３に『希釈水の種類と次亜塩素酸濃度の経時変化』を示すように、原水である希釈水の純度が水道水、純水、超純水と高くなるほど次亜塩素酸の寿命が長くなる。By the way, in the manufacture of the conventional weakly acidic hypochlorous acid aqueous solution, tap water was used as dilution water of raw water. However, ordinary tap water contains many things such as minerals, organic matter, fine particles, bacteria and their dead bodies, nitrogen, oxygen and carbon dioxide. Hypochlorous acid has a stronger oxidizing power than sodium hypochlorite, so it reacts easily with organic substances in water to make organochlorine compounds, and minerals act as a catalyst for self-decomposition of hypochlorous acid. The life of chlorous acid will be shortened. In particular, this tendency becomes more pronounced as the concentration of hypochlorous acid decreases. Therefore I had to just a high concentration of aqueous solution of hypochlorous acid. As shown in Fig. 3 "Dilution Water Type and Hypochlorous Acid Concentration Changes with Time", the lifetime of hypochlorous acid increases as the purity of the dilution water as raw water increases with tap water, pure water, and ultrapure water. become longer.
ここで取り上げる希釈水の『水道水』、『純水』、『超純水』の一般的な定義を表１および表２に示す。ところで「純水」は製造方法に特別な規定はない。つまり、「蒸留水」、「イオン交換水」、「ＲＯ水」のいずれも「純水」である。当然製法により水質は異なるが、一般的には比抵抗値で１ＭΩ・ｃｍ以上のように定義されており、これまで電解質以外の特別な規定はない。一方「超純水」は、表２に一例を示すように、比抵抗値で１８ＭΩ・ｃｍ（２５℃）以上のほかに溶解や分散している有機物（ＴＯＣ）、微粒子、細菌類、ミネラル類、酸素や窒素等のガス成分なども徹底的に除去し限りなく純度１００％の水に近づけた超高純度水を意味する。尚、「超純水」は通常図２『超純水の製造フロー』のような方法で得られる。Tables 1 and 2 show general definitions of “tap water”, “pure water”, and “ultra pure water” of the dilution water taken up here. By the way, “pure water” has no special provision in the manufacturing method. That is, “distilled water”, “ion exchange water”, and “RO water” are all “pure water”. Of course, the water quality differs depending on the production method, but in general, the specific resistance value is defined as 1 MΩ · cm or more, and there is no special provision other than the electrolyte so far. On the other hand, as shown in Table 2, “ultra-pure water” is a specific resistance value of 18 MΩ · cm (25 ° C.) or higher, dissolved or dispersed organic matter (TOC), fine particles, bacteria, minerals. It means ultra-high-purity water that has been completely removed from gas components such as oxygen and nitrogen, and has been brought close to 100% pure water. The “ultra pure water” is usually obtained by the method shown in FIG.
図４に希釈水に水道水を使用した場合の初期次亜塩素酸濃度の違いによる次亜塩素酸の経時変化を示した。初期次亜塩素酸濃度が低いほど保存中にその濃度が激減してしまうことが分かる。このため低濃度の次亜塩素酸水溶液を保管し使用出来ない問題があった。FIG. 4 shows the temporal change of hypochlorous acid due to the difference in initial hypochlorous acid concentration when tap water is used as dilution water. It can be seen that the lower the initial hypochlorous acid concentration, the more drastically the concentration decreases during storage. Therefore, there is a problem that a low concentration hypochlorous acid aqueous solution cannot be stored and used.
本発明は、以上のような従来の欠点に鑑み、超純水で希釈した次亜塩素酸ソーダに、同様に超純水で希釈した希塩酸を混合して得られた溶液を更に必要に応じ超純水で希釈し、その殺菌消臭力の効能を長期間永続させる最適な濃度の水溶液を生成することを目的としている。In view of the conventional drawbacks as described above, the present invention further adds a solution obtained by mixing dilute hydrochloric acid similarly diluted with ultrapure water to sodium hypochlorite diluted with ultrapure water. The purpose is to produce an aqueous solution with an optimal concentration that is diluted with pure water and maintains the effectiveness of its sterilizing and deodorizing power for a long period of time.
本発明には、比抵抗１８ＭΩ・ｃｍ以上の超純水に約１２％の次亜塩素酸ソーダを添加・希釈した溶液と同様の超純水に約９％の塩酸を添加・希釈して得られる溶液を混合、またはさらに超純水で希釈して、その有効塩素濃度が５０ｍｇ／Ｌ、かつｐＨ５前後の次亜塩素酸水溶液を生成する。The present invention is obtained by adding and diluting about 9% hydrochloric acid to ultrapure water similar to a solution obtained by adding and diluting about 12% sodium hypochlorite to ultrapure water having a specific resistance of 18 MΩ · cm or more. The resulting solution is mixed or further diluted with ultrapure water to produce an aqueous hypochlorous acid solution having an effective chlorine concentration of 50 mg / L and a pH of around 5.
一方、比抵抗１８ＭΩ・ｃｍ以上の超純水に約６％の次亜塩素酸ソーダを添加・希釈した溶液と同様の超純水に約４．５％の塩酸を添加・希釈して得られる溶液を混合、またはさらに超純水で希釈して、その有効塩素濃度が２５ｍｇ／Ｌ、かつｐＨ５前後の次亜塩素酸水溶液を生成する。On the other hand, it is obtained by adding and diluting about 4.5% hydrochloric acid to ultrapure water similar to a solution obtained by adding and diluting about 6% sodium hypochlorite to ultrapure water having a specific resistance of 18 MΩ · cm or more. The solution is mixed or further diluted with ultrapure water to produce an aqueous hypochlorous acid solution having an effective chlorine concentration of 25 mg / L and a pH of around 5.
図５に『弱酸性次亜塩素酸水溶液の製造フロー』を示すように、先ず比抵抗１８ＭΩ・ｃｍ以上の超純水製造装置により製造した超純水に、約１２％の次亜塩素酸ソーダを添加・希釈する。一方同様の超純水に約９％の塩酸を添加・希釈し、両者を混合、必要に応じさらに超純水で希釈して有効塩素濃度１２０ｍｇ／Ｌ以下の次亜塩素酸水溶液を生成する。有効塩素濃度が６０ｍｇ／Ｌ以下の次亜塩素酸水の製造には約６％の次亜塩素酸ソーダと約４．５％の塩酸から製造する。有効塩素濃度３０ｍｇ／Ｌ以下の次亜塩素酸水溶液の製造には約４％の次亜塩素酸ソーダと約３％の塩酸を用いて製造する。As shown in “Flow of production of weakly acidic hypochlorous acid aqueous solution” in FIG. 5, about 12% sodium hypochlorite is first added to ultrapure water produced by an ultrapure water production apparatus having a specific resistance of 18 MΩ · cm or more. Add and dilute. On the other hand, about 9% hydrochloric acid is added and diluted in the same ultrapure water, and both are mixed and further diluted with ultrapure water as necessary to produce a hypochlorous acid aqueous solution having an effective chlorine concentration of 120 mg / L or less. Hypochlorous acid water having an effective chlorine concentration of 60 mg / L or less is produced from about 6% sodium hypochlorite and about 4.5% hydrochloric acid. A hypochlorous acid aqueous solution having an effective chlorine concentration of 30 mg / L or less is produced by using about 4% sodium hypochlorite and about 3% hydrochloric acid.
これまでの説明から明らかなように、本発明により次に列挙する効果が得られる。
（１）ｐＨ５前後でかつ比抵抗が１８ＭΩ・ｃｍ以上の超純水で希釈することにより、その殺菌消臭力の有効期限を永続させることができる。
（２）希釈水に超純水を使用する関係上、調製した次亜塩素酸水溶液中の有機塩素化合物が極めて少なく、かつ次亜塩素酸濃度がたとえば３０ｍｇ／Ｌと低い関係上、殺菌消毒に使用しても有機塩素化合物の生成量が少なく環境にも優しい。As is clear from the above description, the present invention provides the following effects.
(1) By diluting with ultrapure water having a pH of about 5 and a specific resistance of 18 MΩ · cm or more, the expiration date of the sterilizing and deodorizing power can be made permanent.
(2) Due to the use of ultrapure water as dilution water, the amount of organochlorine compound in the prepared hypochlorous acid aqueous solution is extremely small and the concentration of hypochlorous acid is as low as 30 mg / L. Even if it is used, the amount of organic chlorine compounds produced is small and environmentally friendly.
以下、本発明の実施形態を図５『弱酸性次亜塩素酸水溶液の製造フロー』に基づいて説明する。Hereinafter, an embodiment of the present invention will be described with reference to FIG. 5 “Flow for producing weakly acidic hypochlorous acid aqueous solution”.
図３に、図５に示す次亜塩素酸水溶液を製造する装置を用い希釈水として水道水、純水、比抵抗１８ＭΩ・ｃｍ（２５℃）の超純水を用いた場合の有効塩素濃度３０ｍｇ／Ｌの次亜塩素酸水溶液の経時変化を示した。水道水に比べ純水、さらに超純水では次亜塩素酸の持ちがはるかに良いことが分かる。FIG. 3 shows an effective chlorine concentration of 30 mg when tap water, pure water, and ultrapure water having a specific resistance of 18 MΩ · cm (25 ° C.) are used as dilution water using the apparatus for producing the hypochlorous acid aqueous solution shown in FIG. The time course of the / L hypochlorous acid aqueous solution was shown. It can be seen that pure water and ultrapure water have much better hypochlorous acid than tap water.
図４に、図５に示す次亜塩素酸ソーダと塩酸から次亜塩素酸水溶液を製造する装置を用い原水である希釈水に水道水を使用した場合の次亜塩素酸の有効塩素濃度を１０、２０，３０，５０ｍｇ／Ｌと変えた時の次亜塩素酸濃度の経時変化を示した。濃度が低いほど寿命が顕著に短くなることが分かる。FIG. 4 shows the effective chlorine concentration of hypochlorous acid when tap water is used as dilution water as raw water using the apparatus for producing a hypochlorous acid aqueous solution from sodium hypochlorite and hydrochloric acid shown in FIG. , Changes with time of hypochlorous acid concentration when changed to 20, 30, 50 mg / L. It can be seen that the lower the concentration, the significantly shorter the lifetime.
ウイルスなどを感染させた細胞を用いて有効塩素濃度を１００ｍｇ／Ｌの次亜塩素酸で実験するとウイルスだけでなく肝心の細胞まで破壊されてしまい殺菌消毒試験が上手くいかない。次亜塩素酸の濃度を半分の５０ｍｇ／Ｌにすると試験が可能になり、２０ｍｇ／Ｌでも容易に殺菌できた。一方次亜塩素酸の濃度が１０ｍｇ／Ｌになると細菌の存在環境の汚染状況により汚染物に次亜塩素酸が食われてしまい十分殺菌が行われない場合が多かった。Experiments with hypochlorous acid having an effective chlorine concentration of 100 mg / L using cells infected with viruses or the like destroys not only the virus but also the essential cells, and the sterilization test is not successful. The test became possible when the concentration of hypochlorous acid was reduced to 50 mg / L, which was half, and even 20 mg / L could be sterilized easily. On the other hand, when the concentration of hypochlorous acid was 10 mg / L, hypochlorous acid was eaten by the contaminants due to the contamination of the environment where bacteria existed, and sterilization was not often performed.
表３に各種細菌に対する次亜塩素酸水溶液の殺菌効果の試験結果をまとめた。表３中ＶＩＶ水は今回開発した弱酸性次亜塩素酸水溶液を意味する。有効塩素濃度２５ｍｇ／Ｌの次亜塩素酸水溶液で大腸菌を始め通常の細菌は極めて容易に殺菌される。枯草菌のような芽胞を持つ菌は外の殺菌剤でも殺菌し難い菌であるが次亜塩素酸水溶液ではかなり容易に殺菌が進む特性がある。Table 3 summarizes the test results of the bactericidal effect of hypochlorous acid aqueous solution on various bacteria. In Table 3, VIV water means the weakly acidic hypochlorous acid aqueous solution developed this time. Normal bacteria such as Escherichia coli are sterilized very easily with a hypochlorous acid aqueous solution having an effective chlorine concentration of 25 mg / L. Bacteria having spores such as Bacillus subtilis are difficult to sterilize even with other bactericides, but have the property that sterilization proceeds fairly easily with hypochlorous acid aqueous solution.
次亜塩素酸の濃度が高くなると殺菌と同時に菌が存在する環境に必ず存在する有機物と次亜塩素酸が反応して有機塩素化合物を生成する。したがって殺菌が可能なレベルで次亜塩素酸の濃度は低い方が望ましい。一般的には上限濃度は３５ｍｇ／Ｌくらいが適当と思われる。一方濃度が低過ぎると有機物などに次亜塩素酸が食われてしまい殺菌が不完全になる可能性が出てくる。したがって下限は１５ｍｇ／Ｌくらいが適当と予想される。When the concentration of hypochlorous acid becomes high, organic substances that are always present in the environment where bacteria are present simultaneously with sterilization react with hypochlorous acid to produce an organic chlorine compound. Therefore, it is desirable that the concentration of hypochlorous acid be low so that sterilization is possible. In general, the upper limit concentration seems to be about 35 mg / L. On the other hand, if the concentration is too low, hypochlorous acid may be eaten by organic matter and the sterilization may become incomplete. Therefore, the lower limit is expected to be about 15 mg / L.
本発明は、長寿命の弱酸性殺菌消臭水溶液であるため水溶液の形で運搬して利用することができる。またある期間保管や保存し利用することも可能である。したがって高価な製造装置を持たなくても次亜塩素酸水溶液を使用することが出来て多くの病院、介護施設、学校、企業などでの消毒や消臭、また最近社会問題化してきたウイルスに起因する口蹄疫、鳥インフルエンザを始めとした動物の疫病対策や飼育環境の消毒分野でも利用出来る。Since the present invention is a weakly acidic sterilizing and deodorizing aqueous solution having a long life, it can be transported and used in the form of an aqueous solution. It can also be stored and stored for a certain period. Therefore, it is possible to use hypochlorous acid aqueous solution without having expensive manufacturing equipment, resulting in disinfection and deodorization in many hospitals, nursing homes, schools, companies, etc., and due to viruses that have recently become a social problem It can also be used in the field of animal epidemic countermeasures such as foot-and-mouth disease and avian influenza and the disinfection of breeding environments.
［表１］水の純度による分類
［表２］超純水水質の一例
［表３］次亜塩素酸水溶液による殺菌試験結果[Table 1] Classification by water purity [Table 2] Example of ultrapure water quality [Table 3] Sterilization test results with hypochlorous acid aqueous solution
本発明は、長寿命の弱酸性次亜塩素酸水溶液とその製造方法に関する。The present invention relates to a long-life weakly acidic hypochlorous acid aqueous solution and a method for producing the same.
ここで取り上げる殺菌消毒剤の弱酸性次亜塩素酸水溶液（ＨＣｌＯ）は、良く知られている食塩水を電気分解して製造する強電解酸性酸化水ではなく、次の化学反応により次亜塩素酸ソーダ（ＮａＣｌＯ）と塩酸（ＨＣｌ）の反応により製造する弱酸性次亜塩素酸水溶液（ＨＣｌＯ）を意味する。
ＮａＣｌＯ ＋ ＨＣｌ ＝ ＨＣｌＯ ＋ ＮａＣｌThe weakly acidic hypochlorous acid aqueous solution (HClO) of the sterilizing disinfectant taken up here is not a strongly electrolyzed acidic oxidized water produced by electrolyzing a well-known saline solution, but hypochlorous acid by the following chemical reaction. It means weakly acidic hypochlorous acid aqueous solution (HClO) produced by the reaction of soda (NaClO) and hydrochloric acid (HCl).
NaClO + HCl = HClO + NaCl
具体的には原水の希釈水に次亜塩素酸ソーダを添加・希釈し、次に同様の希釈水に希塩酸を添加・希釈し、両者を混合または同様の希釈水でさらに希釈して製造されたｐＨ５前後の弱酸性次亜塩素酸水溶液である。Specifically, it was manufactured by adding and diluting sodium hypochlorite to dilution water of raw water, then adding and diluting dilute hydrochloric acid to the same dilution water, and mixing or further diluting with the same dilution water. It is a weakly acidic hypochlorous acid aqueous solution having a pH of around 5.
従来より次亜塩素酸ソーダは殺菌剤や漂白剤として広く用いられており、その酸化力に基づく優れた殺菌、漂白、消臭力があることは公知の事実である。一方最近注目されてきた弱酸性次亜塩素酸は次亜塩素酸ソーダよりもはるかに優れた酸化力に基づく殺菌、漂白、消臭力があり、同一濃度で比較すると次亜塩素酸ソーダの少なくとも１０倍以上の酸化力があり、しかも低濃度で殺菌効果がある。その上酸性であることから特に人体に対して次亜塩素酸ソーダよりはるかに優しいのである。Conventionally, sodium hypochlorite has been widely used as a bactericidal agent and a bleaching agent, and it is a known fact that it has excellent bactericidal, bleaching and deodorizing power based on its oxidizing power. On the other hand, weakly acidic hypochlorous acid, which has recently attracted attention, has sterilization, bleaching, and deodorizing power based on oxidation power far superior to that of sodium hypochlorite. It has an oxidizing power of 10 times or more, and has a bactericidal effect at a low concentration. In addition, it is acidic and is much gentler to the human body than sodium hypochlorite.
一般的に次亜塩素酸ソーダの使用濃度が１００ｍｇ／Ｌ以上であるため、次亜塩素酸水溶液も１００ｍｇ／Ｌという非常に高い濃度での使用が試みられており、次亜塩素酸の持つ優れた特性が十分生かされていないのが現状である。次亜塩素酸ソーダはもちろんのこと次亜塩素酸の場合も高濃度での使用は人体を傷つけまた有害な有機塩素化合物の生成を加速する。Since the use concentration of sodium hypochlorite is generally 100 mg / L or more, use of hypochlorous acid aqueous solution at an extremely high concentration of 100 mg / L has been attempted. The current characteristics are not fully utilized. In the case of hypochlorous acid as well as sodium hypochlorite, the use of high concentrations damages the human body and accelerates the generation of harmful organochlorine compounds.
したがって人体や環境のことを考慮すれば可能な限り低濃度で使用することが極めて重要なことである。これが出来ない最大の理由の一つは、低濃度にすると次亜塩素酸水溶液の寿命が短くなるという事象のためである。Therefore, considering the human body and the environment, it is extremely important to use it at the lowest possible concentration. One of the biggest reasons why this is not possible is due to the phenomenon that the life of the hypochlorous acid aqueous solution is shortened at a low concentration.
次亜塩素酸ソーダや次亜塩素酸のような塩素系の殺菌剤の製造時や使用時には有効な塩素と水中や空気中に必ず存在する有機物が反応して有機塩素化合物が生成する。有機塩素化合物は低濃度で毒性が強くかつ発がん性のものが多い。このことは、かつての代表的な農薬であり、現在製造禁止や使用禁止になっているＤＤＴやＢＨＣ、その他近年問題になっているダイオキシンなどいずれも有機塩素化合物であることからも明らかである。有機塩素化合物は現在の土壌汚染、河川水や地下水汚染、海洋汚染など地球環境問題発生の一つの大きな元凶になっている。When producing or using a chlorine-based disinfectant such as sodium hypochlorite or hypochlorous acid, effective chlorine reacts with organic substances present in water or air to produce an organic chlorine compound. Organochlorine compounds are highly toxic and carcinogenic at low concentrations. This is apparent from the fact that these are typical agricultural chemicals in the past, and DDT and BHC, which are currently banned for production and use, and dioxins, which have recently become problematic, are organochlorine compounds. Organochlorine compounds are one of the major causes of global environmental problems such as soil pollution, river water and groundwater pollution, and marine pollution.
有機塩素化合物は有機物であり本来なら土壌に投棄すれば土壌中の微生物が食べて分解してくれるはずのものである。ところが有毒な有機塩素化合物を食べると微生物がやられてしまうため食べてくれない。そのため、いつまでも土壌中に残ることになり、雨が降れば河川に流れ出て河川水汚染、地下に浸透して地下水汚染を引き起こす。現状では一旦有機塩素化合物になると放射性元素より質が悪い。放射性元素には半減期があるが有機塩素化合物にはない。Organochlorine compounds are organic substances that would normally be eaten and decomposed by microorganisms in the soil if discarded into the soil. However, if you eat toxic organochlorine compounds, microorganisms will be killed and you will not eat them. Therefore, it will remain in the soil indefinitely, and if it rains, it will flow into the river and pollute the river water and penetrate into the underground, causing groundwater pollution. At present, once an organochlorine compound is used, the quality is worse than that of radioactive elements. Radioactive elements have a half-life, but organochlorine compounds do not.
このような有機塩素化合物の生成量は塩素の濃度、すなわち次亜塩素酸ソーダや次亜塩素酸の濃度に比例して生成する。したがって製造や使用に当たっては塩素系殺菌剤の濃度は低いほど望ましいのである。このことからも低濃度で殺菌効果の高い次亜塩素酸の方が次亜塩素酸ソーダより有毒な有機塩素化合物の生成量が少なく出来る点でも優れている。さらに使用する次亜塩素酸の濃度を低く出来れば申し分ないのである。The amount of such organic chlorine compound produced is proportional to the chlorine concentration, that is, the concentration of sodium hypochlorite or hypochlorous acid. Therefore, the lower the concentration of the chlorine-based disinfectant is, the more desirable for production and use. For this reason, hypochlorous acid having a low concentration and a high bactericidal effect is superior in that the amount of toxic organochlorine compound produced can be reduced compared to sodium hypochlorite. Furthermore, it would be satisfactory if the concentration of hypochlorous acid used could be lowered.
図１の『ｐＨによる次亜塩素酸の変化』に示すように、ｐＨ５前後で次亜塩素酸の割合が最大になる。As shown in “Change of hypochlorous acid due to pH” in FIG. 1, the ratio of hypochlorous acid becomes maximum around
ところで従来の弱酸性次亜塩素酸水溶液の製造に当っては原水の希釈水に水道水を使用していた。しかし通常の水道水にはミネラル、有機物、微粒子、細菌やその死骸、窒素、酸素、炭酸ガスなど多くのものが含まれている。次亜塩素酸は次亜塩素酸ソーダに比べ酸化力が強いため水中の有機物などと反応し有機塩素化合物を作り易かったり、ミネラル類は次亜塩素酸の自己分解の触媒になったりするため次亜塩素酸の寿命が短くなってしまう。特にこの傾向は次亜塩素酸の濃度が低くなればなるほど顕著になってくる。そのためどうしても高濃度の次亜塩素酸水溶液にせざるを得なかった。図３に『希釈水の種類と次亜塩素酸濃度の経時変化』を示すように、原水である希釈水の純度が水道水、純水、超純水と高くなるほど次亜塩素酸の寿命が長くなる。By the way, in the manufacture of the conventional weakly acidic hypochlorous acid aqueous solution, tap water was used as dilution water of raw water. However, ordinary tap water contains many things such as minerals, organic matter, fine particles, bacteria and their dead bodies, nitrogen, oxygen and carbon dioxide. Hypochlorous acid has a stronger oxidizing power than sodium hypochlorite, so it reacts easily with organic substances in water to make organochlorine compounds, and minerals act as a catalyst for self-decomposition of hypochlorous acid. The life of chlorous acid will be shortened. In particular, this tendency becomes more pronounced as the concentration of hypochlorous acid decreases. Therefore I had to just a high concentration of aqueous solution of hypochlorous acid. As shown in Fig. 3 "Dilution Water Type and Hypochlorous Acid Concentration Changes with Time", the lifetime of hypochlorous acid increases as the purity of the dilution water as raw water increases with tap water, pure water, and ultrapure water. become longer.
ここで取り上げる希釈水の『水道水』、『純水』、『超純水』の一般的な定義を表１および表２に示す。ところで「純水」は製造方法に特別な規定はない。つまり、「蒸留水」、「イオン交換水」、「ＲＯ水」のいずれも「純水」である。当然製法により水質は異なるが、一般的には比抵抗値で１ＭΩ・ｃｍ以上のように定義されており、これまで電解質以外の特別な規定はない。一方「超純水」は、表２に一例を示すように、比抵抗値で１８ＭΩ・ｃｍ（２５℃）以上のほかに溶解や分散している有機物（ＴＯＣ）、微粒子、細菌類、ミネラル類、酸素や窒素等のガス成分なども徹底的に除去し限りなく純度１００％の水に近づけた超高純度水を意味する。尚、「超純水」は通常図２『超純水の製造フロー』のような方法で得られる。Tables 1 and 2 show general definitions of “tap water”, “pure water”, and “ultra pure water” of the dilution water taken up here. By the way, “pure water” has no special provision in the manufacturing method. That is, “distilled water”, “ion exchange water”, and “RO water” are all “pure water”. Of course, the water quality differs depending on the production method, but in general, the specific resistance value is defined as 1 MΩ · cm or more, and there is no special provision other than the electrolyte so far. On the other hand, as shown in Table 2, “ultra-pure water” is a specific resistance value of 18 MΩ · cm (25 ° C.) or higher, dissolved or dispersed organic matter (TOC), fine particles, bacteria, minerals. It means ultra-high-purity water that has been completely removed from gas components such as oxygen and nitrogen, and has been brought close to 100% pure water. The “ultra pure water” is usually obtained by the method shown in FIG.
（表１を描きます。）
（表２を描きます。）
図４に希釈水に水道水を使用した場合の初期次亜塩素酸濃度の違いによる次亜塩素酸の経時変化を示した。初期次亜塩素酸濃度が低いほど保存中にその濃度が激減してしまうことが分かる。このため低濃度の次亜塩素酸水溶液を保管し使用出来ない問題があった。FIG. 4 shows the temporal change of hypochlorous acid due to the difference in initial hypochlorous acid concentration when tap water is used as dilution water. It can be seen that the lower the initial hypochlorous acid concentration, the more drastically the concentration decreases during storage. Therefore, there is a problem that a low concentration hypochlorous acid aqueous solution cannot be stored and used.
本発明は、以上のような従来の欠点に鑑み、超純水で希釈した次亜塩素酸ソーダに、同様に超純水で希釈した希塩酸を混合して得られた溶液を更に必要に応じ超純水で希釈し、その殺菌消臭力の効能を長期間永続させる最適な濃度の水溶液を生成することを目的としている。In view of the conventional drawbacks as described above, the present invention further adds a solution obtained by mixing dilute hydrochloric acid similarly diluted with ultrapure water to sodium hypochlorite diluted with ultrapure water. The purpose is to produce an aqueous solution with an optimal concentration that is diluted with pure water and maintains the effectiveness of its sterilizing and deodorizing power for a long period of time.
本発明には、比抵抗１８ＭΩ・ｃｍ以上の超純水に約１２％の次亜塩素酸ソーダを添加・希釈した溶液と同様の超純水に約９％の塩酸を添加・希釈して得られる溶液を混合、またはさらに超純水で希釈して、その有効塩素濃度が５０ｍｇ／Ｌ、かつｐＨ５前後の次亜塩素酸水溶液を生成する。The present invention is obtained by adding and diluting about 9% hydrochloric acid to ultrapure water similar to a solution obtained by adding and diluting about 12% sodium hypochlorite to ultrapure water having a specific resistance of 18 MΩ · cm or more. The resulting solution is mixed or further diluted with ultrapure water to produce an aqueous hypochlorous acid solution having an effective chlorine concentration of 50 mg / L and a pH of around 5.
一方、比抵抗１８ＭΩ・ｃｍ以上の超純水に約６％の次亜塩素酸ソーダを添加・希釈した溶液と同様の超純水に約４．５％の塩酸を添加・希釈して得られる溶液を混合、またはさらに超純水で希釈して、その有効塩素濃度が２５ｍｇ／Ｌ、かつｐＨ５前後の次亜塩素酸水溶液を生成する。On the other hand, it is obtained by adding and diluting about 4.5% hydrochloric acid to ultrapure water similar to a solution obtained by adding and diluting about 6% sodium hypochlorite to ultrapure water having a specific resistance of 18 MΩ · cm or more. The solution is mixed or further diluted with ultrapure water to produce an aqueous hypochlorous acid solution having an effective chlorine concentration of 25 mg / L and a pH of around 5.
図５に『弱酸性次亜塩素酸水溶液の製造フロー』を示すように、先ず比抵抗１８ＭΩ・ｃｍ以上の超純水製造装置により製造した超純水に、約１２％の次亜塩素酸ソーダを添加・希釈する。一方同様の超純水に約９％の塩酸を添加・希釈し、両者を混合、必要に応じさらに超純水で希釈して有効塩素濃度１２０ｍｇ／Ｌ以下の次亜塩素酸水溶液を生成する。有効塩素濃度が６０ｍｇ／Ｌ以下の次亜塩素酸水の製造には約６％の次亜塩素酸ソーダと約４．５％の塩酸から製造する。有効塩素濃度３０ｍｇ／Ｌ以下の次亜塩素酸水溶液の製造には約４％の次亜塩素酸ソーダと約３％の塩酸を用いて製造する。As shown in “Flow of production of weakly acidic hypochlorous acid aqueous solution” in FIG. 5, about 12% sodium hypochlorite is first added to ultrapure water produced by an ultrapure water production apparatus having a specific resistance of 18 MΩ · cm or more. Add and dilute. On the other hand, about 9% hydrochloric acid is added and diluted in the same ultrapure water, and both are mixed and further diluted with ultrapure water as necessary to produce a hypochlorous acid aqueous solution having an effective chlorine concentration of 120 mg / L or less. Hypochlorous acid water having an effective chlorine concentration of 60 mg / L or less is produced from about 6% sodium hypochlorite and about 4.5% hydrochloric acid. A hypochlorous acid aqueous solution having an effective chlorine concentration of 30 mg / L or less is produced by using about 4% sodium hypochlorite and about 3% hydrochloric acid.
これまでの説明から明らかなように、本発明により次に列挙する効果が得られる。
（１）ｐＨ５前後でかつ比抵抗が１８ＭΩ・ｃｍ以上の超純水で希釈することにより、その殺菌消臭力の有効期限を永続させることができる。
（２）希釈水に超純水を使用する関係上、調製した次亜塩素酸水溶液中の有機塩素化合物が極めて少なく、かつ次亜塩素酸濃度がたとえば３０ｍｇ／Ｌと低い関係上、殺菌消毒に使用しても有機塩素化合物の生成量が少なく環境にも優しい。As is clear from the above description, the present invention provides the following effects.
(1) By diluting with ultrapure water having a pH of about 5 and a specific resistance of 18 MΩ · cm or more, the expiration date of the sterilizing and deodorizing power can be made permanent.
(2) Due to the use of ultrapure water as dilution water, the amount of organochlorine compound in the prepared hypochlorous acid aqueous solution is extremely small and the concentration of hypochlorous acid is as low as 30 mg / L. Even if it is used, the amount of organic chlorine compounds produced is small and environmentally friendly.
以下、本発明の実施形態を図５『弱酸性次亜塩素酸水溶液の製造フロー』に基づいて説明する。Hereinafter, an embodiment of the present invention will be described with reference to FIG. 5 “Flow for producing weakly acidic hypochlorous acid aqueous solution”.
図３に、図５に示す次亜塩素酸水溶液を製造する装置を用い希釈水として水道水、純水、比抵抗１８ＭΩ・ｃｍ（２５℃）の超純水を用いた場合の有効塩素濃度３０ｍｇ／Ｌの次亜塩素酸水溶液の経時変化を示した。水道水に比べ純水、さらに超純水では次亜塩素酸の持ちがはるかに良いことが分かる。FIG. 3 shows an effective chlorine concentration of 30 mg when tap water, pure water, and ultrapure water having a specific resistance of 18 MΩ · cm (25 ° C.) are used as dilution water using the apparatus for producing the hypochlorous acid aqueous solution shown in FIG. The time course of the / L hypochlorous acid aqueous solution was shown. It can be seen that pure water and ultrapure water have much better hypochlorous acid than tap water.
図４に、図５に示す次亜塩素酸ソーダと塩酸から次亜塩素酸水溶液を製造する装置を用い原水である希釈水に水道水を使用した場合の次亜塩素酸の有効塩素濃度を１０、２０，３０，５０ｍｇ／Ｌと変えた時の次亜塩素酸濃度の経時変化を示した。濃度が低いほど寿命が顕著に短くなることが分かる。FIG. 4 shows the effective chlorine concentration of hypochlorous acid when tap water is used as dilution water as raw water using the apparatus for producing a hypochlorous acid aqueous solution from sodium hypochlorite and hydrochloric acid shown in FIG. , Changes with time of hypochlorous acid concentration when changed to 20, 30, 50 mg / L. It can be seen that the lower the concentration, the significantly shorter the lifetime.
ウイルスなどを感染させた細胞を用いて有効塩素濃度を１００ｍｇ／Ｌの次亜塩素酸で実験するとウイルスだけでなく肝心の細胞まで破壊されてしまい殺菌消毒試験が上手くいかない。次亜塩素酸の濃度を半分の５０ｍｇ／Ｌにすると試験が可能になり、２０ｍｇ／Ｌでも容易に殺菌できた。一方次亜塩素酸の濃度が１０ｍｇ／Ｌになると細菌の存在環境の汚染状況により汚染物に次亜塩素酸が食われてしまい十分殺菌が行われない場合が多かった。Experiments with hypochlorous acid having an effective chlorine concentration of 100 mg / L using cells infected with viruses or the like destroys not only the virus but also the essential cells, and the sterilization test is not successful. The test became possible when the concentration of hypochlorous acid was reduced to 50 mg / L, which was half, and even 20 mg / L could be sterilized easily. On the other hand, when the concentration of hypochlorous acid was 10 mg / L, hypochlorous acid was eaten by the contaminants due to the contamination of the environment where bacteria existed, and sterilization was not often performed.
表３に各種細菌に対する次亜塩素酸水溶液の殺菌効果の試験結果をまとめた。表３中ＶＩＶ水は今回開発した弱酸性次亜塩素酸水溶液を意味する。有効塩素濃度２５ｍｇ／Ｌの次亜塩素酸水溶液で大腸菌を始め通常の細菌は極めて容易に殺菌される。枯草菌のような芽胞を持つ菌は外の殺菌剤でも殺菌し難い菌であるが次亜塩素酸水溶液ではかなり容易に殺菌が進む特性がある。Table 3 summarizes the test results of the bactericidal effect of hypochlorous acid aqueous solution on various bacteria. In Table 3, VIV water means the weakly acidic hypochlorous acid aqueous solution developed this time. Normal bacteria such as Escherichia coli are sterilized very easily with a hypochlorous acid aqueous solution having an effective chlorine concentration of 25 mg / L. Bacteria having spores such as Bacillus subtilis are difficult to sterilize even with other bactericides, but have the property that sterilization proceeds fairly easily with hypochlorous acid aqueous solution.
（表３を描きます。）
次亜塩素酸の濃度が高くなると殺菌と同時に菌が存在する環境に必ず存在する有機物と次亜塩素酸が反応して有機塩素化合物を生成する。したがって殺菌が可能なレベルで次亜塩素酸の濃度は低い方が望ましい。一般的には上限濃度は３５ｍｇ／Ｌくらいが適当と思われる。一方濃度が低過ぎると有機物などに次亜塩素酸が食われてしまい殺菌が不完全になる可能性が出てくる。したがって下限は１５ｍｇ／Ｌくらいが適当と予想される。When the concentration of hypochlorous acid becomes high, organic substances that are always present in the environment where bacteria are present simultaneously with sterilization react with hypochlorous acid to produce an organic chlorine compound. Therefore, it is desirable that the concentration of hypochlorous acid be low so that sterilization is possible. In general, the upper limit concentration seems to be about 35 mg / L. On the other hand, if the concentration is too low, hypochlorous acid may be eaten by organic matter and the sterilization may become incomplete. Therefore, the lower limit is expected to be about 15 mg / L.
本発明は、長寿命の弱酸性殺菌消臭水溶液であるため水溶液の形で運搬して利用することができる。またある期間保管や保存し利用することも可能である。したがって高価な製造装置を持たなくても次亜塩素酸水溶液を使用することが出来て多くの病院、介護施設、学校、企業などでの消毒や消臭、また最近社会問題化してきたウイルスに起因する口蹄疫、鳥インフルエンザを始めとした動物の疫病対策や飼育環境の消毒分野でも利用出来る。Since the present invention is a weakly acidic sterilizing and deodorizing aqueous solution having a long life, it can be transported and used in the form of an aqueous solution. It can also be stored and stored for a certain period. Therefore, it is possible to use hypochlorous acid aqueous solution without having expensive manufacturing equipment, resulting in disinfection and deodorization in many hospitals, nursing homes, schools, companies, etc., and due to viruses that have recently become a social problem It can also be used in the field of animal epidemic countermeasures such as foot-and-mouth disease and avian influenza and the disinfection of breeding environments.
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| JP2018183082A (en) * | 2017-04-25 | 2018-11-22 | 株式会社東芝 | Method for treating garden stuff using electrolytic water |
| JP2019023207A (en) * | 2015-09-16 | 2019-02-14 | 株式会社フリーキラ製薬 | Antimicrobial agent containing hypochlorite |
| WO2019225599A1 (en) | 2018-05-22 | 2019-11-28 | 株式会社トクヤマデンタル | Method for producing weakly acidic hypochlorous acid aqueous solution |
| JP2021053546A (en) * | 2019-09-27 | 2021-04-08 | 合同会社Ｆｍｃ | Manufacturing equipment and manufacturing method for carbonic acid-containing hypochlorous acid water |
| WO2022138427A1 (en) * | 2020-12-23 | 2022-06-30 | 株式会社トクヤマ | Hypochlorite water |
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| JP2019023207A (en) * | 2015-09-16 | 2019-02-14 | 株式会社フリーキラ製薬 | Antimicrobial agent containing hypochlorite |
| JP2018183082A (en) * | 2017-04-25 | 2018-11-22 | 株式会社東芝 | Method for treating garden stuff using electrolytic water |
| WO2019225599A1 (en) | 2018-05-22 | 2019-11-28 | 株式会社トクヤマデンタル | Method for producing weakly acidic hypochlorous acid aqueous solution |
| JP2021053546A (en) * | 2019-09-27 | 2021-04-08 | 合同会社Ｆｍｃ | Manufacturing equipment and manufacturing method for carbonic acid-containing hypochlorous acid water |
| WO2022138427A1 (en) * | 2020-12-23 | 2022-06-30 | 株式会社トクヤマ | Hypochlorite water |
| KR20220128451A (en) | 2020-12-23 | 2022-09-20 | 가부시끼가이샤 도꾸야마 | hypochlorous acid water |
| JP7164767B1 (en) * | 2020-12-23 | 2022-11-01 | 株式会社トクヤマ | Hypochlorous acid water |
| KR102519332B1 (en) | 2020-12-23 | 2023-04-10 | 가부시끼가이샤 도꾸야마 | hypochlorous acid water |
| CN116709922A (en) * | 2020-12-23 | 2023-09-05 | 株式会社德山 | Hypochlorous acid water |
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