JP2007031374A

JP2007031374A - Method for producing germicidal disinfectant solution

Info

Publication number: JP2007031374A
Application number: JP2005218755A
Authority: JP
Inventors: Koji Kihira; 孝治木平; Mitsuo Nishino; 光夫西野
Original assignee: SUTAKKU SYSTEM KK
Current assignee: SUTAKKU SYSTEM KK
Priority date: 2005-07-28
Filing date: 2005-07-28
Publication date: 2007-02-08

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a germicidal disinfectant solution, which has pH stabilization effect in carbon dioxide by an aqueous solution of carbonic acid by diluting an aqueous solution of a chlorine agent being sodium hypochlorite with carbonated water and carrying out pH adjustment with an acidic substance, in an example, with a diluted aqueous solution of hydrochloric acid, and does not affect pH even when diluted with a target to be sterilized or a diluent, for example, running water. <P>SOLUTION: An aqueous solution of chlorine agent, for example, an aqueous solution of sodium hypochlorite is diluted with carbonated water or carbon dioxide gas, then an acidic substance such as a dilute aqueous solution of hydrochloric acid is dissolved so as to adjust pH. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は殺菌消毒液の製造方法に関し、詳しくは、次亜塩素酸ナトリウム等の塩素剤水溶液を炭酸水（遊離炭酸濃度５００ｐｐｍ程度）で薄めた後に、酸性物質、例えば希塩酸でｐＨ調整を行うことで、使用時に安定した殺菌消毒液を提供することができる殺菌消毒液の製造方法に関する。 The present invention relates to a method for producing a sterilizing and disinfecting solution. Specifically, after diluting an aqueous chlorine agent solution such as sodium hypochlorite with carbonated water (free carbonic acid concentration of about 500 ppm), the pH is adjusted with an acidic substance such as dilute hydrochloric acid. The present invention also relates to a method for producing a sterilizing / disinfecting solution capable of providing a stable sterilizing / disinfecting solution at the time of use.

塩素を有効成分とする殺菌水は、食材、医療器具、厨房用具、日用器具、室内清掃除菌、人体や動植物の殺菌・除菌等、広い分野の殺菌処理に利用されている。
この塩素を有効成分とする殺菌消毒水は、次亜塩素酸ナトリウムで代表される塩素系殺菌剤であり、その有効塩素濃度にもよるが、ｐＨが１２程度の強アルカリ性であり、その殺菌力は次亜塩素酸（ＨＣｌＯ）の強い酸化作用によるものであることが周知である。一方、次亜塩素酸は弱酸であるため、アルカリ性の次亜塩素酸ナトリウム水溶液ではＮａＣｌＯと水Ｈ_２Ｏの反応により、水中に次亜塩素酸イオン（ＣｌＯ−）とナトリウムイオンに解離していることにより、次亜塩素酸（ＨＣｌＯ）の形になりにくいため、次亜塩素酸の状態に比べて殺菌力が８０〜１００分の一に減少するといわれている。
そこで、次亜塩素酸ナトリウムの希釈水のｐＨ値を７〜３程度に下げて残留塩素が次亜塩素酸ＨＣｌＯの形で存在するようにするため、塩酸等の薬剤を添加（特開平１０−８１６１０号公報）したり、次亜塩素酸ナトリウム水溶液を有隔膜電解槽の陽極室で電解（特開平１０−２４２９４号公報）したり、次亜塩素酸を添加する前の原水又は原水と次亜塩素酸塩の混合水をイオン交換処理すること（特開平６−２０６０７６１０号公報）が従来から試みられている。
更に、簡単な手法の従来における殺菌消毒液は、次亜塩素酸ナトリウムに塩酸などを加え、ｐｈ５〜７の酸性側に調整し殺菌力を増した殺菌消毒液が存在する。 Bactericidal water containing chlorine as an active ingredient is used for sterilization treatments in a wide range of fields such as foodstuffs, medical instruments, kitchen utensils, daily utensils, indoor cleaning sterilization, sterilization / sterilization of human bodies and animals and plants.
This disinfecting water containing chlorine as an active ingredient is a chlorine-based disinfectant typified by sodium hypochlorite, and depending on its effective chlorine concentration, it is a strong alkaline having a pH of about 12, and its disinfecting power Is well known to be due to the strong oxidizing action of hypochlorous acid (HClO). On the other hand, since hypochlorous acid is a weak acid, the alkaline sodium hypochlorite aqueous solution dissociates into hypochlorite ions (ClO-) and sodium ions in water by the reaction of NaClO and water H ₂ O. Thus, since it is difficult to form hypochlorous acid (HClO), the sterilizing power is said to be reduced to 80 to 100 times that of hypochlorous acid.
Therefore, in order to reduce the pH value of the dilute water of sodium hypochlorite to about 7 to 3 so that residual chlorine exists in the form of hypochlorous acid HClO, an agent such as hydrochloric acid is added (Japanese Patent Laid-Open No. 10-101). 81610), electrolysis of a sodium hypochlorite aqueous solution in the anode chamber of the diaphragm electrolyzer (Japanese Patent Laid-Open No. 10-24294), or addition of raw water or raw water and hypochlorous acid before adding hypochlorous acid Attempts have been made to ion-exchange the mixed water of chlorate (JP-A-6-20607610).
Furthermore, as a conventional sterilizing / disinfecting solution of a simple method, there is a disinfecting / disinfecting solution in which hydrochloric acid or the like is added to sodium hypochlorite and adjusted to the acidic side of ph 5-7 to increase the sterilizing power.

特開２００５−２３８号公報（第５頁）Japanese Patent Laying-Open No. 2005-238 (Page 5)

しかしながら、従来技術で説明した殺菌消毒液は、次亜塩素酸ナトリウムに塩酸などを加えてｐＨ５〜７の酸性側に調整して殺菌力を増した殺菌液であるが、酸性側に不安定なため使用時の注意が必要である。即ち、ｐＨを酸性側に調整し、殺菌力を増した次亜塩素系の殺菌剤はｐＨが不安定で、殺菌する対象が酸性を帯びたものに使用すると、ｐＨが急激に下がり塩素ガス発生の危険性がある。
又、希釈して使用する時のｐＨが酸性を帯びている時も同様の危険性がある。
次亜塩素酸ナトリウムに炭酸を加えた実施例（特開２００５−２３８）があるが、これは保存容器から取り出した時点から炭酸ガスが気化し、ｐＨが上がるので殺菌力が低下する不具合がある。
従って、ｐＨが安定するように改良し、濃縮した殺菌消毒液を希釈して使用してもｐＨ値が変化しないような殺菌消毒液の製造方法に解決しなければならない課題を有する。 However, the sterilizing liquid described in the prior art is a sterilizing liquid in which hydrochloric acid or the like is added to sodium hypochlorite to adjust to the acidic side of pH 5-7 to increase the sterilizing power, but is unstable on the acidic side. Therefore, care must be taken during use. In other words, hypochlorite-based disinfectants that have been adjusted to an acidic side and increased sterilizing power have unstable pH, and if the object to be sterilized is acidic, the pH will drop sharply and chlorine gas will be generated. There is a danger of.
There is also a similar danger when the pH of the diluted product is acidic.
There is an example (Japanese Patent Laid-Open No. 2005-238) in which carbonic acid is added to sodium hypochlorite, but this has a problem that the sterilizing power is lowered because the carbon dioxide gas evaporates from the time of taking out from the storage container and the pH rises. .
Accordingly, there is a problem to be solved by a method for producing a sterilizing / disinfecting solution which is improved so that the pH is stabilized and the pH value does not change even if the concentrated sterilizing / disinfecting solution is diluted and used.

上記課題を解決するために、本願発明の殺菌消毒液の製造方法は、次に示す構成にすることである。 In order to solve the above-described problems, a method for producing a sterilizing / disinfecting solution according to the present invention is configured as follows.

（１）殺菌消毒液の製造方法は、塩素剤水溶液を炭酸水或は炭酸ガスで希釈した後に、酸性物質を溶解することによりｐＨ調整を行うようにしたことである。
（２）前記塩素剤水溶液は、少なくとも、ジクロロイソシアヌール酸ナトリウム、次亜塩素酸ナトリウム、高度サラシ粉、クロラミンＴの群より選ばれ、好ましくは次亜塩素酸ナトリウムの水溶液であることを特徴とする（１）に記載の殺菌消毒液の製造方法。
（３）前記酸性物質は、少なくとも、クエン酸、リンゴ酸、酒石酸、マレイン酸、コハク酸、シュウ酸、グリコール酸、酢酸、塩酸、硫酸、硝酸、硫酸水素ナトリウム、スルファミン酸、リン酸より選ばれる少なくとも一種の酸性物質、好ましくは希塩酸水溶液である（１）に記載の殺菌消毒液の製造方法。
（４）前記炭酸水の遊離炭酸濃度は１００ｐｐｍ〜３０００ｐｐｍであることを特徴とする（１）に記載の殺菌消毒液の製造方法。 (1) The method for producing a sterilizing and disinfecting solution is to adjust pH by dissolving an acidic substance after diluting an aqueous chlorine solution with carbonated water or carbon dioxide gas.
(2) The chlorinating agent aqueous solution is at least selected from the group consisting of sodium dichloroisocyanurate, sodium hypochlorite, high-grade salty powder, and chloramine T, and is preferably an aqueous solution of sodium hypochlorite. The manufacturing method of the disinfection liquid as described in (1).
(3) The acidic substance is selected from at least citric acid, malic acid, tartaric acid, maleic acid, succinic acid, oxalic acid, glycolic acid, acetic acid, hydrochloric acid, sulfuric acid, nitric acid, sodium hydrogensulfate, sulfamic acid, and phosphoric acid. The method for producing a sterilizing / disinfecting solution according to (1), wherein the sterilizing / disinfecting solution is at least one acidic substance, preferably a dilute hydrochloric acid aqueous solution.
(4) The method for producing a sterilizing / disinfecting solution according to (1), wherein the carbonated water has a free carbonic acid concentration of 100 ppm to 3000 ppm.

本発明のように、実施例においては次亜塩素酸ナトリウムである塩素剤水溶液に、炭酸水で希釈した後に、酸性物質、実施例において希塩酸水溶液でｐＨ調整を行うようにしたことで、炭酸水溶液による二酸化炭素にｐＨ安定効果があり、殺菌する対象や希釈液、例えば地下水や水道水で希釈したときでもｐＨに影響を与えにくい。 As in the present invention, in the examples, the aqueous chlorine solution, which is sodium hypochlorite, was diluted with carbonated water, and then the pH was adjusted with an acidic substance, dilute hydrochloric acid aqueous solution in the examples. Carbon dioxide has a pH stabilizing effect and hardly affects the pH even when diluted with an object to be sterilized or a diluent such as groundwater or tap water.

本願発明に係る殺菌消毒液の製造方法の実施形態について、以下説明する。 An embodiment of a method for producing a sterilizing / disinfecting solution according to the present invention will be described below.

本発明に係る殺菌消毒液の製造方法は、少なくともジクロロイソシアヌール酸ナトリウム、次亜塩素酸ナトリウム、高度サラシ粉、クロラミンＴの群より選ばれる塩素剤水溶液を炭酸水或は炭酸ガスで希釈した後に、酸性物質を溶解することによりｐＨ調整を行うようにしたことである。
この炭酸水の遊離炭酸濃度は１００ｐｐｍ〜３０００ｐｐｍであり、実施例における塩素剤水溶液は、次亜塩素酸ナトリウムを採用しており、酸性物質はクエン酸、リンゴ酸、酒石酸、マレイン酸、コハク酸、シュウ酸、グリコール酸、酢酸、塩酸、硫酸、硝酸、硫酸水素ナトリウム、スルファミン酸、リン酸より選ばれる少なくとも一種の酸性物質、好ましくは実施例においては希塩酸水溶液を採用している。 The method for producing a sterilizing and disinfecting solution according to the present invention comprises at least diluting a chlorinating agent aqueous solution selected from the group consisting of sodium dichloroisocyanurate, sodium hypochlorite, high-grade salty powder, and chloramine T with carbonated water or carbon dioxide gas. In other words, the pH is adjusted by dissolving an acidic substance.
This carbonated water has a free carbonic acid concentration of 100 ppm to 3000 ppm, and the aqueous chlorine solution in the examples employs sodium hypochlorite, and the acidic substances are citric acid, malic acid, tartaric acid, maleic acid, succinic acid, At least one acidic substance selected from oxalic acid, glycolic acid, acetic acid, hydrochloric acid, sulfuric acid, nitric acid, sodium hydrogen sulfate, sulfamic acid, and phosphoric acid, preferably a dilute aqueous hydrochloric acid solution is used in the examples.

そして、このようにして得られた殺菌消毒液は、有効塩素濃度５ｐｐｍ〜３００ｐｐｍに調整して製造し使用するが、有効塩素濃度５００ｐｐｍ〜２０００ｐｐｍの濃縮殺菌消毒液にすることで、使用時は地下水や水道水などを希釈液として、これらのｐＨを気にすることなく３００ｐｐｍ以下に薄めて使用することができる。特にこれら希釈液のｐＨが低いものを使用する時でも、希釈中の急激なｐＨ値の下降で塩素ガスが発生する危険性を回避できる。
また、この濃縮殺菌消毒液は輸送等の利便性を増し、且つ、保存のための冷蔵庫などの保管容積を減らすことができる。 And the sterilization liquid obtained in this way is manufactured and used by adjusting the effective chlorine concentration to 5 ppm to 300 ppm. By using a concentrated sterilization liquid with an effective chlorine concentration of 500 ppm to 2000 ppm, groundwater is used at the time of use. It can be used by diluting it to 300 ppm or less as a diluting liquid without using the pH. In particular, even when these diluted solutions having a low pH are used, it is possible to avoid the danger of chlorine gas being generated due to a sudden drop in pH value during dilution.
Further, this concentrated sterilizing and disinfecting liquid can increase the convenience of transportation and the like, and can reduce the storage volume of a refrigerator for storage.

本願発明は、先ず塩素剤水溶液を炭酸水或は炭酸ガスで希釈することにより、下記に示す式のように、Ｈ^＋の発生により酸性側或はアルカリ側に傾くのを阻止する働きがあることを発見したことに基づき、この発見した炭酸水（二酸化炭素）を希釈することによりＨ^＋を発生させる工程を取り込んで殺菌消毒液を生成する手法を開示するというものである。 In the present invention, first, the aqueous chlorine solution is diluted with carbonated water or carbon dioxide gas, and as shown in the following formula, it acts to prevent tilting toward the acidic side or alkaline side due to the generation of H ^+. Based on having discovered this, the technique of taking in the process which generate | occur | produces H ^<+> by diluting this discovered carbonated water (carbon dioxide) and disclosing the method of producing | generating a disinfection liquid is disclosed.

上記の式に示すように、Ｈ^＋が入っていることが重要で、殺菌消毒水がアルカリに傾こうとすると、上式の右へ反応が進みアルカリ側に進まないように阻止し、逆に酸に傾こうとすると、左に反応が進み酸性側に行かないように阻止する役目を果たす。
これがｐＨのバッファ効果といわれるもので、少し塩酸が入りすぎても簡単にｐＨが下がることはなく製造時の安全性が確保される。
当然、殺菌消毒水が微生物や有機物などと反応して消費されることによる酸性への移行も防止されることになり使用時の安全性が確保される。 As shown in the above equation, it is important that H ⁺ is contained. If the sterilizing water is inclined to the alkali, the reaction proceeds to the right of the above equation and is prevented from proceeding to the alkali side. If you try to lean on the acid, the reaction proceeds to the left and plays a role in preventing you from going to the acid side.
This is said to be a buffering effect of pH, and even if hydrochloric acid is slightly added, the pH does not drop easily, and safety during production is ensured.
Naturally, the transition to acidity due to the consumption of the sterilized disinfecting water by reacting with microorganisms and organic substances is prevented, and safety during use is ensured.

図１に示すグラフ１１は、上記の如く塩素剤水溶液である次亜塩素ナトリウムを炭酸水で希釈した液体の検体量２００ｃｃに、希塩酸を滴下してｐＨ調整を行う様子をグラフで示したものであり、希塩酸の滴下液は、８.５％の希塩酸でｐＨ０.７８、滴定量は約３０μリットルである。
このような検体量２００ｃｃに希塩酸を滴下すると、図２に示すように、当初ｐＨが５．７４の値であっても、滴下回数が２０数回程度まではｐＨ５．００以上の値を維持することができ、これは塩素ガスが発生するｐＨ４．５０近傍に到達するのに２０数回の滴下量、（３０μリットル×２０数回）の量の希塩酸（酸性物質）を溶解させてもｐＨが下がらないことを意味する。
これに対して、同じく図１に示すグラフ１２は、従来からの炭酸水で希釈しない塩素剤水溶液の検体量２００ｃｃに、希塩酸を滴下してｐＨ調整を行う様子をグラフで示したものであり、希塩酸の滴下液は、８.５％の希塩酸でｐＨ０.７８、滴定量は約３０μリットルである。
このような検体量２００ｃｃに希塩酸を滴下すると、図２に示すように、当初ｐＨが7．５４の値であっても、一度の滴下でｐＨが７．２５になり、次の滴下でｐＨが６．８２となり、３回目の滴下でｐＨが６．１９となり、４回目の滴下ではｐＨが４．３３となって塩素ガスが発生する要件が整うことになる。このようにして、希塩酸を溶解するための量は極めて限定されたものになる。 Graph 11 shown in FIG. 1 is a graph showing how pH adjustment is performed by adding dilute hydrochloric acid dropwise to 200 cc of a liquid sample obtained by diluting sodium hypochlorite, which is a chlorinating agent aqueous solution, with carbonated water as described above. Yes, the drop of dilute hydrochloric acid is 8.5% dilute hydrochloric acid with a pH of 0.78, and the titration is about 30 μl.
When dilute hydrochloric acid is dropped into such a specimen amount of 200 cc, as shown in FIG. 2, even if the initial pH is 5.74, the value of pH 5.00 or more is maintained until the number of drops is about 20 times. This can be achieved by adding 20 times the amount of dripping hydrochloric acid (30 μL × 20 times) of dilute hydrochloric acid (acidic substance) to reach the vicinity of pH 4.50 where chlorine gas is generated. It means not going down.
On the other hand, the graph 12 similarly shown in FIG. 1 is a graph showing how pH adjustment is carried out by adding dilute hydrochloric acid to a specimen amount of 200 cc of a chlorine aqueous solution that is not diluted with conventional carbonated water, The dropping solution of dilute hydrochloric acid is 8.5% dilute hydrochloric acid with a pH of 0.78, and the titer is about 30 μl.
When dilute hydrochloric acid is dropped into such a specimen amount of 200 cc, as shown in FIG. 2, even if the initial pH is 7.54, the pH drops to 7.25 with one drop and the pH drops with the next drop. It becomes 6.82, the pH drops to 6.19 by the third dropping, and the pH becomes 4.33 by the fourth dropping, and the requirement for generating chlorine gas is satisfied. In this way, the amount for dissolving dilute hydrochloric acid is very limited.

このように、次亜塩素酸ナトリウムである塩素剤水溶液に、炭酸水で希釈した後に、酸性物質、実施例において希塩酸水溶液でｐＨ調整を行うようにしたことで、炭酸水溶液による二酸化炭素にｐＨ安定効果があり、殺菌する対象や希釈液、例えば、水道水で希釈したときでもｐＨに影響を与えることがないため、安定した殺菌消毒液を提供することができるのである。 In this way, the aqueous solution of sodium chlorite was diluted with carbonated water, and then diluted with carbonated water, and the pH was adjusted with acidic substances, dilute hydrochloric acid aqueous solution in the examples. Since it is effective and does not affect the pH even when diluted with a subject to be sterilized or a diluted solution such as tap water, a stable sterilized disinfectant can be provided.

次亜塩素酸ナトリウムである塩素剤水溶液に、炭酸水で希釈した後に、酸性物質、実施例において希塩酸水溶液でｐＨ調整を行うようにしたことで、炭酸水溶液による二酸化炭素にｐＨ安定効果があり、殺菌する対象や希釈液、例えば水道水で希釈したときでもｐＨに影響を与えない殺菌消毒液の製造方法を提供する。 By diluting the aqueous chlorine agent solution that is sodium hypochlorite with carbonated water and then adjusting the pH with an acidic substance, dilute hydrochloric acid aqueous solution in the examples, carbon dioxide by the carbonic acid aqueous solution has a pH stabilizing effect, Disclosed is a method for producing a sterilizing and disinfecting solution that does not affect pH even when diluted with a subject to be sterilized, for example, tap water.

本発明の炭酸水で希釈した次亜塩素酸ナトリウム溶液に希塩酸溶液を滴下してｐＨの様子を測定したグラフである。It is the graph which measured the mode of pH by dripping dilute hydrochloric acid solution to the sodium hypochlorite solution diluted with the carbonated water of the present invention. 希塩酸溶液を滴下したときのｐＨの値を一覧表示したものである。It shows a list of pH values when dilute hydrochloric acid solution is dropped.

Explanation of symbols

１１改良したもののグラフ
１２従来のもののグラフ。 11 Improved graph 12 Conventional graph.

Claims

A method for producing a sterilizing / disinfecting solution, wherein pH adjustment is performed by dissolving an acidic substance after diluting an aqueous chlorine solution with carbonated water or carbon dioxide gas.

The chlorinating agent aqueous solution is at least selected from the group consisting of sodium dichloroisocyanurate, sodium hypochlorite, high-grade salty powder, and chloramine T, and is preferably an aqueous solution of sodium hypochlorite. A method for producing a sterilizing and disinfecting solution according to 1.

The acidic substance is at least one selected from citric acid, malic acid, tartaric acid, maleic acid, succinic acid, oxalic acid, glycolic acid, acetic acid, hydrochloric acid, sulfuric acid, nitric acid, sodium hydrogensulfate, sulfamic acid, and phosphoric acid. The method for producing a sterilizing / disinfecting solution according to claim 1, which is an acidic substance, preferably a dilute hydrochloric acid aqueous solution.

The method for producing a sterilizing and disinfecting solution according to claim 1, wherein the carbonated water has a free carbonic acid concentration of 100 ppm to 3000 ppm.