JP6977221B2 - Disinfectant composition, manufacturing method of disinfectant composition - Google Patents
Disinfectant composition, manufacturing method of disinfectant composition Download PDFInfo
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Description
本発明は、除菌剤組成物に関する。特に、低臭気でかつ優れた除菌効力を有し、さらに保存安定性に優れた除菌剤組成物に関する。 The present invention relates to a disinfectant composition. In particular, the present invention relates to a sterilizing agent composition having a low odor, an excellent sterilizing effect, and an excellent storage stability.
過酢酸製剤は、酢酸、過酸化水素、過酢酸の平衡系(下記式(1))からなる除菌剤であり、医療分野では内視鏡や人工透析膜などの洗浄に、飲料工場ではペットボトルの洗浄などに、それぞれ用いられている。
CH3COOH+H2O2 ⇔ CH3COO2H+H2O (1)
The peracetic acid preparation is a disinfectant consisting of an equilibrium system of acetic acid, hydrogen peroxide, and peracetic acid (formula (1) below). It is used for cleaning bottles, etc.
CH 3 COOH + H 2 O 2 ⇔ CH 3 COO 2 H + H 2 O (1)
過酢酸製剤は幅広い微生物種に対して除菌効力を持つが、酢酸に似た強い刺激臭があるため、密閉されていない、若しくは換気が十分に行われていない環境で使用する場合、作業従事者への安全性という点で問題があった。 Although peracetic acid preparations have bactericidal activity against a wide range of microbial species, they have a strong pungent odor similar to acetic acid, so they are engaged in work when used in an environment that is not sealed or is not sufficiently ventilated. There was a problem in terms of safety for people.
過酢酸の代替として、他の無臭性の過カルボン酸の利用が検討されてきた。例えば、特許文献1、2には過グルタル酸を用いた組成物が開示されている。特許文献3には過ジカルボン酸の混合水溶液(過グルタル酸と過コハク酸、または、過グルタル酸と過コハク酸と過アジピン酸)が開示されている。 The use of other odorless percarboxylic acids as an alternative to peracetic acid has been considered. For example, Patent Documents 1 and 2 disclose compositions using perglutaric acid. Patent Document 3 discloses a mixed aqueous solution of a perdicarboxylic acid (perglutaric acid and persuccinic acid, or perglutaric acid and persuccinic acid and peradipic acid).
しかしながら、これらの過カルボン酸は過酢酸に比べ不安定で自己分解しやすく、低温での保存が必要であるため、広く実用化されていない。
そこで本発明は、過酢酸製剤のような刺激臭のない除菌剤組成物であって、優れた除菌効力と優れた保存安定性を有する除菌剤組成物を提供することを課題とする。
However, these percarboxylic acids are more unstable than peracetic acid, are easily autolyzed, and need to be stored at a low temperature, so that they have not been widely put into practical use.
Therefore, it is an object of the present invention to provide a sterilizing agent composition that does not have an irritating odor like a peracetic acid preparation and has excellent sterilizing efficacy and excellent storage stability. ..
本発明者は、上記課題を解決するために鋭意検討した結果、乳酸、過酸化水素、ホスホン酸などの安定化剤、および酸触媒を含む除菌剤組成物が、過カルボン酸を用いた従来の除菌剤組成物が有していた課題を解決できることを見出し、本発明を完成するに至った。 As a result of diligent studies to solve the above problems, the present inventor has made a conventional disinfectant composition containing a stabilizer such as lactic acid, hydrogen peroxide and phosphonic acid, and an acid catalyst using a percarboxylic acid. We have found that the problems of the disinfectant composition of the above can be solved, and have completed the present invention.
本発明の第1の態様に係る除菌剤組成物は、乳酸0.1〜15質量部と、過酸化水素10〜50質量部と、安定化剤3〜12質量部と、酸触媒1〜15質量部とを配合してなる組成物と;水と;を含む。
このように構成すると、過酢酸のような刺激臭がなく、過酢酸と同等以上の除菌効力を持ち、かつ保存安定性に優れた除菌剤組成物となり得る。
The disinfectant composition according to the first aspect of the present invention comprises 0.1 to 15 parts by mass of lactic acid, 10 to 50 parts by mass of hydrogen peroxide, 3 to 12 parts by mass of a stabilizer, and 1 to 1 parts of an acid catalyst. It contains a composition comprising 15 parts by mass; with water;
With this structure, it is possible to obtain a sterilizing agent composition that does not have a pungent odor like peracetic acid, has a sterilizing effect equal to or higher than that of peracetic acid, and has excellent storage stability.
本発明の第2の態様に係る除菌剤組成物は、上記本発明の第1の態様に係る除菌剤組成物において、前記乳酸と前記過酸化水素から生成された過乳酸を含み、前記安定化剤は、有機ホスホン酸およびピリジンカルボン酸のうちの少なくとも1つである。
このように構成すると、各成分が特定の配合比で配合されているため、乳酸と過酸化水素との反応により生成された過乳酸は安定して存在することができる。よって、過乳酸を主成分とした除菌剤組成物となり得る。
The disinfectant composition according to the second aspect of the present invention contains the lactic acid and the perlactic acid produced from the hydrogen peroxide in the disinfectant composition according to the first aspect of the present invention. The stabilizer is at least one of organic phosphonic acid and pyridinecarboxylic acid.
With this configuration, since each component is blended in a specific blending ratio, the perlactic acid produced by the reaction between lactic acid and hydrogen peroxide can be stably present. Therefore, it can be a disinfectant composition containing perlactic acid as a main component.
本発明の第3の態様に係る除菌剤組成物は、乳酸と;過乳酸と;安定化剤と;を含み、前記安定化剤は、有機ホスホン酸およびピリジンカルボン酸のうちの少なくとも1つである。
このように構成すると、過酢酸のような刺激臭がなく、過酢酸と同等以上の除菌効力を持ち、かつ保存安定性に優れた除菌剤組成物となり得る。
The disinfectant composition according to the third aspect of the present invention comprises lactic acid; hyperlactic acid; a stabilizer; the stabilizer is at least one of an organic phosphonic acid and a pyridinecarboxylic acid. Is.
With this structure, it is possible to obtain a sterilizing agent composition that does not have a pungent odor like peracetic acid, has a sterilizing effect equal to or higher than that of peracetic acid, and has excellent storage stability.
本発明の第4の態様に係る除菌剤組成物は、上記本発明の第3の態様に係る除菌剤組成物において、前記乳酸と前記過乳酸の総量0.1〜15質量部と;過酸化水素1〜50質量部と;前記安定化剤3〜12質量部と;酸触媒1〜15質量部と;水と;を含む。
このように構成すると、各成分が特定の組成比で構成されるため、乳酸と過酸化水素との反応により生成された過乳酸は安定して存在することができる。よって、過乳酸を主成分とした除菌剤組成物となり得る。
The disinfectant composition according to the fourth aspect of the present invention is the disinfectant composition according to the third aspect of the present invention, wherein the total amount of the lactic acid and the hydrogen peroxide is 0.1 to 15 parts by mass; It contains 1 to 50 parts by mass of hydrogen peroxide, 3 to 12 parts by mass of the stabilizer, 1 to 15 parts by mass of an acid catalyst, and water.
With this configuration, since each component is composed of a specific composition ratio, the perlactic acid produced by the reaction between lactic acid and hydrogen peroxide can be stably present. Therefore, it can be a disinfectant composition containing perlactic acid as a main component.
本発明の第5の態様に係る除菌剤組成物は、上記本発明の第2の態様または第4の態様に係る除菌剤組成物において、前記乳酸と前記過酸化水素との反応が化学平衡状態に達したときの前記過乳酸の濃度を初期濃度とした場合、初期濃度の前記過乳酸は、前記除菌剤組成物を室温で30日間保管後に初期濃度の70質量%以上が残存する。
このように構成すると、過乳酸は自己分解することなく、30日後であっても除菌剤組成物中に十分に存在するため、除菌効果を十分に発現させることができる。
In the disinfectant composition according to the fifth aspect of the present invention, the reaction between the lactic acid and the hydrogen peroxide is chemical in the disinfectant composition according to the second or fourth aspect of the present invention. When the concentration of the hydrogen peroxide when the equilibrium state is reached is taken as the initial concentration, the initial concentration of the hydrogen peroxide remains 70% by mass or more of the initial concentration after the disinfectant composition is stored at room temperature for 30 days. ..
With this configuration, hyperlactic acid does not self-decompose and is sufficiently present in the sterilizing agent composition even after 30 days, so that the sterilizing effect can be sufficiently exhibited.
本発明の第6の態様に係る除菌剤組成物は、上記本発明の第1の態様〜第5の態様のいずれか1の態様に係る除菌剤組成物において、過酢酸を含まない。なお「含まない」とは、まったく含まないか、または、含んだとしても人の嗅覚で過酢酸の臭気を感知できない程度の量を含むことをいう。
このように構成すると、酢酸に似た強い刺激臭のない除菌剤組成物を得ることができる。
The disinfectant composition according to the sixth aspect of the present invention does not contain peracetic acid in the disinfectant composition according to any one of the first to fifth aspects of the present invention. The term "not contained" means that the substance is not contained at all, or even if it is contained, the amount is such that the odor of peracetic acid cannot be sensed by the human sense of smell.
With this configuration, it is possible to obtain a disinfectant composition having no strong pungent odor similar to acetic acid.
本発明の第7の態様に係る除菌剤組成物の製造方法は、乳酸を0.1〜15質量部と;過酸化水素を10〜50質量部と;安定化剤を3〜12質量部と;酸触媒を1〜15質量部と;水と;を配合するステップを備える。
このように構成すると、過酢酸のような刺激臭がなく、過酢酸と同等以上の除菌効力を持ち、かつ保存安定性に優れた除菌剤組成物を製造することができる。
The method for producing a disinfectant composition according to a seventh aspect of the present invention comprises 0.1 to 15 parts by mass of lactic acid; 10 to 50 parts by mass of hydrogen peroxide; and 3 to 12 parts by mass of a stabilizer. And; a step of blending 1 to 15 parts by mass of an acid catalyst; with water;
With this structure, it is possible to produce a sterilizing agent composition that does not have a pungent odor like peracetic acid, has a sterilizing effect equal to or higher than that of peracetic acid, and has excellent storage stability.
本発明の除菌剤組成物は、過酢酸製剤のような刺激臭がなく、かつ、優れた除菌効力と優れた保存安定性を有することができる。 The sterilizing agent composition of the present invention does not have a pungent odor like a peracetic acid preparation, and can have excellent sterilizing efficacy and excellent storage stability.
以下、図面を参照して本発明の実施の形態について説明する。なお、各図において互いに同一または相当する部分には同一あるいは類似の符号を付し、重複した説明は省略する。また、本発明は、以下の実施の形態に制限されるものではない。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. In each figure, parts that are the same as or correspond to each other are designated by the same or similar reference numerals, and duplicated description will be omitted. Further, the present invention is not limited to the following embodiments.
[除菌剤組成物]
本発明は、過乳酸を主成分とする除菌剤組成物であって、乳酸、過酸化水素、過乳酸の平衡系(下記式(2))に基づいた除菌剤組成物である。なお「主成分」とは、過カルボン酸の総量の50質量%超を占める成分をいう。または60質量%以上であってもよく、好ましくは70質量%以上、より好ましくは80質量%以上、特に好ましくは90質量%以上であってもよい。
配合した乳酸と過酸化水素は、反応して過乳酸を生成する。この反応が平衡状態に達した後には、過乳酸が消費された場合に、平衡状態を維持するために、乳酸と過酸化水素が再度反応して過乳酸をさらに生成する。このように反応が継続的に起こり過乳酸を供給する。
本願の除菌剤組成物では、特定の化合物を特定の割合で配合することにより、過乳酸が自己分解することなく安定した状態で長期にわたり存在することができ、過酢酸製剤のような刺激臭がなく、優れた除菌効力(強力な酸化作用)を有することができる。
CH3CH(OH)COOH+H2O2⇔CH3CH(OH)COO2H+H2O (2)
[Bactericidal composition]
The present invention is a disinfectant composition containing perlactic acid as a main component, and is a disinfectant composition based on an equilibrium system of lactic acid, hydrogen peroxide, and superlactic acid (the following formula (2)). The "main component" refers to a component that accounts for more than 50% by mass of the total amount of the percarboxylic acid. Alternatively, it may be 60% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
The blended lactic acid and hydrogen peroxide react to produce hyperlactic acid. After this reaction reaches equilibrium, when superlactic acid is consumed, lactic acid and hydrogen peroxide react again to produce more superlactic acid in order to maintain the equilibrium state. In this way, the reaction continues and supplies hyperlactic acid.
In the disinfectant composition of the present application, by blending a specific compound in a specific ratio, perlactic acid can exist in a stable state for a long period of time without self-decomposition, and has a pungent odor like a peracetic acid preparation. It can have an excellent sterilizing effect (strong oxidizing action).
CH 3 CH (OH) COOH + H 2 O 2 ⇔ CH 3 CH (OH) COO 2 H + H 2 O (2)
本発明の除菌剤組成物に配合する各成分を(A)成分、(B)成分、(C)成分、(D)成分、(E)成分に分けて以下説明する。
除菌剤組成物は、(A)成分、(B)成分、(C)成分、(D)成分を次の割合で配合する組成物と、(E)成分としての水とを含む。前記組成物では、(A)成分として乳酸が0.1〜15質量部、(B)成分として過酸化水素が15〜50質量部、(C)成分として安定化剤が3〜12質量部、(D)成分として酸触媒が1〜15質量部の割合で配合される。
例えば、(A)成分;乳酸0.1〜15質量%、(B)成分;過酸化水素15〜50質量%、(C)成分;安定化剤3〜12質量%、(D)成分;酸触媒1〜15質量%、残分として(E)成分;水を含み、(A)成分〜(E)成分の総量が100質量%となるように配合してもよい。
Each component to be blended in the disinfectant composition of the present invention will be described below separately for the component (A), the component (B), the component (C), the component (D), and the component (E).
The disinfectant composition contains a composition containing (A) component, (B) component, (C) component, and (D) component in the following proportions, and water as the (E) component. In the composition, lactic acid is 0.1 to 15 parts by mass as a component (A), hydrogen peroxide is 15 to 50 parts by mass as a component (B), and a stabilizer is 3 to 12 parts by mass as a component (C). As the component (D), an acid catalyst is blended in a proportion of 1 to 15 parts by mass.
For example, component (A); lactic acid 0.1 to 15% by mass, component (B); hydrogen peroxide 15 to 50% by mass, component (C); stabilizer 3 to 12% by mass, component (D); acid. The catalyst may be blended so that 1 to 15% by mass of the catalyst, the component (E) as a residue; water is contained, and the total amount of the components (A) to (E) is 100% by mass.
または、(A)成分として乳酸を4.5〜9質量部、(B)成分として過酸化水素を14〜21質量部、(C)成分として安定化剤を0.6〜6質量部、(D)成分として酸触媒を3.5〜11質量部の割合配合してもよい。
例えば、(A)成分;乳酸4.5〜9質量%、(B)成分;過酸化水素14〜21質量%、(C)成分;安定化剤0.6〜6質量%、(D)成分;酸触媒3.5〜11質量%、残分として(E)成分;水を含み、(A)成分〜(E)成分の総量が100質量%となるように配合してもよい。
Alternatively, 4.5 to 9 parts by mass of lactic acid as the component (A), 14 to 21 parts by mass of hydrogen peroxide as the component (B), and 0.6 to 6 parts by mass of the stabilizer as the component (C). D) As a component, an acid catalyst may be blended in a proportion of 3.5 to 11 parts by mass.
For example, component (A); lactic acid 4.5 to 9% by mass, component (B); hydrogen peroxide 14 to 21% by mass, component (C); stabilizer 0.6 to 6% by mass, component (D). The acid catalyst may be blended so that 3.5 to 11% by mass of the acid catalyst, the component (E) as a residue; water is contained, and the total amount of the components (A) to (E) is 100% by mass.
[(A)成分]
(A)成分は過カルボン酸を生成するカルボン酸であり、本発明ではヒドロキシカルボン酸である乳酸を用いる。乳酸は、L乳酸、D乳酸、またはこれらの混合物のいずれであってもよい。
(A)成分:(B)成分:(C)成分:(D)成分の割合において、(A)成分の乳酸の割合は0.1〜15質量部が好ましく、4〜9質量部がより好ましい。乳酸の濃度が0.1質量部以上であると除菌性が低下することがなく、15質量部以下であると生成した過乳酸が分解しにくい。
[(A) component]
The component (A) is a carboxylic acid that produces a hypercarboxylic acid, and in the present invention, lactic acid, which is a hydroxycarboxylic acid, is used. Lactic acid may be L lactic acid, D lactic acid, or a mixture thereof.
In the ratio of (A) component: (B) component: (C) component: (D) component, the ratio of lactic acid of the (A) component is preferably 0.1 to 15 parts by mass, more preferably 4 to 9 parts by mass. .. When the concentration of lactic acid is 0.1 part by mass or more, the sterilizing property does not deteriorate, and when it is 15 parts by mass or less, the generated superlactic acid is hardly decomposed.
[(B)成分]
(B)成分は乳酸と反応させる過酸化水素である。
(A)成分:(B)成分:(C)成分:(D)成分の割合において、(B)成分の過酸化水素の割合は10〜50質量部が好ましく、15〜30質量部がより好ましい。過酸化水素の割合が10質量部以上であると過乳酸が生成しやすくなり、50質量部以下であると過乳酸の安定性の観点から好ましい。
[(B) component]
The component (B) is hydrogen peroxide that reacts with lactic acid.
In the ratio of (A) component: (B) component: (C) component: (D) component, the ratio of hydrogen peroxide of the (B) component is preferably 10 to 50 parts by mass, more preferably 15 to 30 parts by mass. .. When the ratio of hydrogen peroxide is 10 parts by mass or more, superlactic acid is likely to be generated, and when it is 50 parts by mass or less, it is preferable from the viewpoint of the stability of superlactic acid.
[(C)成分]
(C)成分は生成された過乳酸を安定した状態に保つための安定化剤である。
(C)成分の安定化剤としては、1−ヒドロキシエチリデン−1,1−ジホスホン酸、アミノトリ(メチレンホスホン酸)、エチレンジアミンテトラ(メチレンホスホン酸)等の有機ホスホン酸、あるいはピコリン酸、ジピコリン酸、キノリン酸等のピリジンカルボン酸が選択できる。安定化剤は1種類を用いてもよく、複数種類を混合して用いてもよい。
(A)成分:(B)成分:(C)成分:(D)成分の割合において、(C)成分の安定化剤の割合は3〜12質量部が好ましく、5〜10質量部がより好ましい。安定化剤の割合が3質量部以上であると過乳酸が生成しやすくなり、12質量部以下であると生成した過乳酸が分解しにくくなり、また経済的にも好ましい。
[(C) component]
The component (C) is a stabilizer for keeping the produced hyperlactic acid in a stable state.
Examples of the stabilizer of the component (C) include organic phosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid) and ethylenediaminetetra (methylenephosphonic acid), or picolinic acid and dipicolinic acid. A pyridinecarboxylic acid such as quinophosphoric acid can be selected. One type of stabilizer may be used, or a plurality of types may be mixed and used.
In the ratio of the component (A): the component (B): the component (C): the component (D), the ratio of the stabilizer of the component (C) is preferably 3 to 12 parts by mass, more preferably 5 to 10 parts by mass. .. When the ratio of the stabilizer is 3 parts by mass or more, superlactic acid is likely to be generated, and when it is 12 parts by mass or less, the generated superlactic acid is less likely to be decomposed, which is economically preferable.
[(D)成分]
(D)成分は乳酸と過酸化水素の反応を促進させるための酸触媒である。
(D)成分の酸触媒としては、リン酸、硫酸、硝酸、メタンスルホン酸などが使用できる。酸触媒は1種類を用いてもよく、複数種類を混合して用いてもよい。
(A)成分:(B)成分:(C)成分:(D)成分の割合において、(D)成分の酸触媒の割合は1〜15質量部が好ましい。酸触媒の割合が1質量部以上であると過乳酸の生成速度および生成量が低下しにくくなり、15質量部以下であると生成した過乳酸が分解しにくくなり、また経済的にも好ましい。
[(D) component]
The component (D) is an acid catalyst for accelerating the reaction between lactic acid and hydrogen peroxide.
As the acid catalyst of the component (D), phosphoric acid, sulfuric acid, nitric acid, methanesulfonic acid and the like can be used. One type of acid catalyst may be used, or a plurality of types may be mixed and used.
In the ratio of the component (A): the component (B): the component (C): the component (D), the ratio of the acid catalyst of the component (D) is preferably 1 to 15 parts by mass. When the ratio of the acid catalyst is 1 part by mass or more, the production rate and the amount of superlactic acid produced are less likely to decrease, and when the ratio is 15 parts by mass or less, the produced perlactic acid is less likely to be decomposed, which is economically preferable.
[(E)成分]
(E)成分は、(A)成分、(B)成分、(C)成分、(D)成分の各成分が水溶液の場合にそれらの成分とともに添加される水、または、別途添加される水である。
(E)成分の水としては、イオン交換水、軟水、純水、水道水などが挙げられるが、除菌剤組成物中の過乳酸の安定性の観点からは、イオン交換水または純水が好ましい。
[(E) component]
The component (E) is water added together with the components (A), (B), (C), and (D) when they are aqueous solutions, or water added separately. be.
Examples of the water of the component (E) include ion-exchanged water, soft water, pure water, tap water, etc., but from the viewpoint of the stability of hyperlactic acid in the disinfectant composition, ion-exchanged water or pure water is used. preferable.
[その他]
本発明の除菌剤組成物は、(A)成分、(B)成分、(C)成分、(D)成分、(E)成分からなる組成物であってもよく、本発明の効果を損なわない範囲において、本発明の除菌剤組成物に対して当該技術分野で通常使用される他の成分を加えることもできる。このような成分としては、界面活性剤、消泡剤、ハイドロトロープ剤、粘稠剤、香料、色素、pH調整剤などが挙げられる。
[others]
The disinfectant composition of the present invention may be a composition comprising (A) component, (B) component, (C) component, (D) component, and (E) component, and impairs the effect of the present invention. To the extent that it does not exist, other components usually used in the art can be added to the disinfectant composition of the present invention. Examples of such components include surfactants, defoamers, hydrotropes, thickeners, fragrances, pigments, pH adjusters and the like.
[製造方法]
上記(A)成分、(B)成分、(C)成分、(D)成分、(E)成分と、必要に応じて界面活性剤等を計量し、混合することにより、本発明の除菌剤組成物を得ることができる。混合後、乳酸と過酸化水素との反応が平衡状態に達するまでの期間は温度により異なるため適宜調整する。
本発明の除菌剤組成物は、混合後、乳酸と過酸化水素との反応により生成された過乳酸を含み、乳酸と過乳酸の総量0.1〜15質量部と;過酸化水素1〜50質量部と;安定化剤3〜12質量部と;酸触媒1〜15質量部と;水と;を含む。
生成された過乳酸は保存安定性に優れているため、乳酸と過酸化水素との反応が化学平衡状態に達したときの過乳酸の濃度を初期濃度とした場合に、その後、除菌剤組成物を室温で30日間保管した後であっても、過乳酸は自己分解することなく、好ましくは初期濃度の70質量%以上、より好ましくは80質量%以上が残存することができる。
[Production method]
The disinfectant of the present invention is obtained by weighing and mixing the above-mentioned component (A), component (B), component (C), component (D), component (E) and a surfactant or the like, if necessary. The composition can be obtained. After mixing, the period until the reaction between lactic acid and hydrogen peroxide reaches an equilibrium state varies depending on the temperature, so adjust appropriately.
The disinfectant composition of the present invention contains perlactic acid produced by the reaction of lactic acid and hydrogen peroxide after mixing, and the total amount of lactic acid and perlactic acid is 0.1 to 15 parts by mass; hydrogen peroxide 1 to 1 It contains 50 parts by mass; a stabilizer of 3 to 12 parts by mass; an acid catalyst of 1 to 15 parts by mass; and water;
Since the generated superlactic acid has excellent storage stability, when the concentration of superlactic acid when the reaction between lactic acid and hydrogen peroxide reaches a chemical equilibrium state is set as the initial concentration, then the composition of the disinfectant is used. Even after the product is stored at room temperature for 30 days, the perlactic acid does not self-decompose, and preferably 70% by mass or more, more preferably 80% by mass or more of the initial concentration can remain.
本発明の除菌剤組成物は、調製した除菌剤組成物をそのまま除菌剤として使用することができる。または、水を追加して希釈した希釈水溶液、または溶剤などで希釈した希釈混合液として使用してもよい。除菌剤組成物を希釈して使用する場合は、調製した除菌剤組成物を、例えば0.01〜50質量%に希釈してもよく、または0.1〜5質量%に希釈してもよい。 In the disinfectant composition of the present invention, the prepared disinfectant composition can be used as it is as a disinfectant. Alternatively, it may be used as a diluted aqueous solution diluted by adding water, or a diluted mixture diluted with a solvent or the like. When the disinfectant composition is diluted and used, the prepared disinfectant composition may be diluted to, for example, 0.01 to 50% by mass, or 0.1 to 5% by mass. May be good.
上記のとおり、本発明の除菌剤組成物は、過酢酸製剤に比較して臭気(酸臭)が少なく、かつ過酢酸製剤と同等以上の除菌効果を有するため、開放系、若しくは換気が十分に行われていない環境における作業従事者の安全性が過酢酸製剤に比べ著しく改善される。さらに、本発明により得られる過酸化物溶液は常温においても安定しており、低温保管を必要とする過アジピン酸などの過カルボン酸に比べ、保管安定性が大幅に改善される。
このように本発明の除菌剤組成物は、従来の過酢酸製剤や他の過カルボン酸を用いた製剤の代替として使用することができる。例えば、以下の洗浄・除菌・殺菌に用いることができる。人工透析装置、内視鏡、無菌製剤室の空間・床・壁、超純水・純水などの配管やタンク、ペットボトル、食品製造設備などが挙げられる。
As described above, the sterilizing agent composition of the present invention has less odor (acid odor) than the peracetic acid preparation and has a sterilizing effect equal to or higher than that of the peracetic acid preparation. The safety of workers in an inadequate environment is significantly improved compared to the peracetic acid preparation. Further, the peroxide solution obtained by the present invention is stable even at room temperature, and the storage stability is significantly improved as compared with a percarboxylic acid such as peradipic acid which requires low temperature storage.
As described above, the disinfectant composition of the present invention can be used as an alternative to the conventional peracetic acid preparation and other preparations using a percarboxylic acid. For example, it can be used for the following cleaning, sterilization, and sterilization. Examples include artificial dialysis equipment, endoscopes, spaces / floors / walls of sterile pharmaceutical rooms, piping and tanks for ultrapure water / pure water, PET bottles, food manufacturing equipment, and the like.
以下に、本発明を実施例と比較例により具体的に説明する。しかし本発明は、以下の実施例に記載された内容に限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, the present invention is not limited to the contents described in the following examples.
実施例、比較例において配合した各成分を下記に示す。
(A)成分
A:乳酸
(B)成分
B:過酸化水素(過酸化水素水、濃度30%)
(C)成分
C:1−ヒドロキシエタン−1,1−ジホスホン酸(濃度60%)
(D)成分
D−1:メタンスルホン酸
D−2:リン酸
D−3:硫酸
D−4:硝酸(濃度60%)
(E)成分
E:イオン交換水
Each component blended in Examples and Comparative Examples is shown below.
(A) Component A: Lactic acid (B) component B: Hydrogen peroxide (hydrogen peroxide solution,
(C) Component C: 1-hydroxyethane-1,1-diphosphonic acid (concentration 60%)
(D) Component D-1: Methanesulfonic acid D-2: Phosphoric acid D-3: Sulfuric acid D-4: Nitric acid (concentration 60%)
(E) Component E: Ion-exchanged water
[比較例1、2、実施例1〜7]
表1、2に示す割合に基づき除菌剤組成物を調製した。各除菌剤組成物をイオン交換水で希釈して希釈液を調製し、過マンガン酸カリウムとチオ硫酸ナトリウムによる過酸化水素・過酢酸濃度の滴定法に準じて、過酸化物濃度の測定を行った。表1、表2中の比較例、実施例の配合の数値は、純分の質量%濃度を示す。
[Comparative Examples 1 and 2, Examples 1 to 7]
The disinfectant composition was prepared based on the ratios shown in Tables 1 and 2. Dilute each disinfectant composition with ion-exchanged water to prepare a diluted solution, and measure the peroxide concentration according to the titration method of hydrogen peroxide / peracetic acid concentration with potassium permanganate and sodium thiosulfate. gone. The numerical values of the formulations of Comparative Examples and Examples in Tables 1 and 2 indicate the mass% concentration of pure content.
◎:25℃で30日保管後の過乳酸濃度が、化学平衡状態における初期濃度の80質量%以上
○:25℃で30日保管後の過乳酸濃度が、化学平衡状態における初期濃度の70質量%以上80質量%未満
×:25℃で30日保管後の過乳酸濃度が、化学平衡状態における初期濃度の70質量%未満
⊚: The perlactic acid concentration after storage at 25 ° C. for 30 days is 80% by mass or more of the initial concentration in the chemical equilibrium state. % Or more and less than 80% by mass ×: The perlactic acid concentration after storage at 25 ° C. for 30 days is less than 70% by mass of the initial concentration in the chemical equilibrium state.
◎:25℃で30日保管後の過乳酸濃度が、化学平衡状態における初期濃度の80質量%以上
○:25℃で30日保管後の過乳酸濃度が、化学平衡状態における初期濃度の70質量%以上80質量%未満
×:25℃で30日保管後の過乳酸濃度が、化学平衡状態における初期濃度の70質量%未満
⊚: The perlactic acid concentration after storage at 25 ° C. for 30 days is 80% by mass or more of the initial concentration in the chemical equilibrium state. % Or more and less than 80% by mass ×: The perlactic acid concentration after storage at 25 ° C. for 30 days is less than 70% by mass of the initial concentration in the chemical equilibrium state.
[過酸化物の安定性の確認]
過酸化物の測定は過マンガン酸カリウムとチオ硫酸ナトリウムによる過酸化水素・過酢酸濃度の滴定法に準じて行った。チオ硫酸ナトリウムで測定する過酸化物については、乳酸と過酸化水素との反応により過乳酸(乳酸ヒドロペルオキシド,CH3CH(OH)COO2H)が生じている為、過乳酸の濃度として算出した。
[Confirmation of peroxide stability]
The peroxide was measured according to the titration method of hydrogen peroxide / peracetic acid concentration with potassium permanganate and sodium thiosulfate. Peroxide measured with sodium thiosulfate is calculated as the concentration of superlactic acid because superlactic acid (lactic acid hydroperoxide, CH 3 CH (OH) COO 2 H) is generated by the reaction between lactic acid and hydrogen peroxide. did.
[試験方法]
(1)100mlの三角フラスコにサンプル(各除菌剤組成物の2質量%溶液)を5ml採取し、10w/v%硫酸溶液10mlを加えた。0.1N過マンガン酸カリウム溶液で薄桃色を呈するまで滴定した(Aml)。
(2)この液に10w/v%ヨウ化カリウム溶液1mlを添加後、1/70.9Nチオ硫酸ナトリウム標準液で淡黄色になるまで滴定し、1w/v%デンプン溶液を約1ml加え、暗青色が消えるまで滴定した(Bml)。ブランクの測定はイオン交換水1mlを採取し上記操作を行い、1/70.9Nチオ硫酸ナトリウム標準液の滴定量(B0ml)を求めた。
・原体中の過酸化水素濃度(w/v%)=A×1.7×F1
A:0.1N過マンガン酸カリウム溶液の滴定量(ml)
F1:0.1N過マンガン酸カリウム溶液のファクター
・原体中の過乳酸濃度(w/v%)=(B−B0)×0.74×F2
B:1/70.9Nチオ硫酸ナトリウム標準液の滴定量(ml)
B0:ブランクの滴定量(ml)
F2:1/70.9Nチオ硫酸ナトリウム標準液のファクター
※過酢酸の場合は係数(0.74)を0.53にして計算した。
[Test method]
(1) 5 ml of a sample (2% by mass solution of each disinfectant composition) was collected in a 100 ml Erlenmeyer flask, and 10 ml of a 10 w / v% sulfuric acid solution was added. Titrated with 0.1N potassium permanganate solution until pale pink (Aml).
(2) After adding 1 ml of 10 w / v% potassium iodide solution to this solution, titrate with 1 / 70.9 N sodium thiosulfate standard solution until it becomes pale yellow, add about 1 ml of 1 w / v% starch solution, and darken. Titration was performed until the blue color disappeared (B ml). For the measurement of the blank, 1 ml of ion-exchanged water was collected and the above operation was performed to determine the titration amount (B 0 ml) of 1 / 70.9 N sodium thiosulfate standard solution.
-Hydrogen peroxide concentration (w / v%) in the drug substance = A x 1.7 x F1
A: Titration of 0.1N potassium permanganate solution (ml)
Factor of F1: 0.1N potassium permanganate solution ・ Perlactic acid concentration in the original (w / v%) = (BB 0 ) × 0.74 × F2
B: Titration of 1 / 70.9N sodium thiosulfate standard solution (ml)
B 0 : Blank titration (ml)
F2: Factor of 1 / 70.9N sodium thiosulfate standard solution * In the case of peracetic acid, the coefficient (0.74) was set to 0.53.
[結果]
実施例2、実施例6の過酸化水素濃度、および過乳酸濃度の経時変化を6ヶ月調べた結果、市販の過酢酸製剤A(テックP−10、(株)ADEKA製)および過酢酸製剤B(オキシペールAT、保土谷化学工業(株)製)の過酸化水素濃度、過酢酸濃度と同程度の安定性を示した(図1〜図4)。
[result]
As a result of investigating the changes over time of the hydrogen peroxide concentration and the peracetic acid concentration of Examples 2 and 6 for 6 months, the commercially available peracetic acid preparation A (Tech P-10, manufactured by ADEKA Corporation) and the peracetic acid preparation B It showed the same level of stability as the hydrogen peroxide concentration and peracetic acid concentration of (Oxypal AT, manufactured by Hodoya Chemical Industry Co., Ltd.) (FIGS. 1 to 4).
[臭気の比較]
実施例2と市販の過酢酸製剤Aについて臭いの比較を行うため、以下の方法により臭気を評価した。
[Comparison of odors]
In order to compare the odors of Example 2 and the commercially available peracetic acid preparation A, the odors were evaluated by the following method.
[試験方法]
(1)300mlのビーカーを3つ用意し、1つには各濃度に調整した試験液を、他の2つにはイオン交換水(ブランク)をそれぞれ270ml入れ、25℃で静置した。
(2)パネラーに3つの中から臭いがするものを選択させ、どのような臭いがするかを聞き取った。嗅覚の疲弊を考慮し、濃度が薄いものから濃いものへ順に試験を行った。
[Test method]
(1) Three 300 ml beakers were prepared, one was filled with a test solution adjusted to each concentration, and the other two were filled with 270 ml of ion-exchanged water (blank), and allowed to stand at 25 ° C.
(2) We asked the panelists to select the one that smells from the three, and asked what kind of smell it had. Considering the exhaustion of the sense of smell, the tests were conducted in order from the one with the lowest concentration to the one with the highest concentration.
[結果 実施例2]
0.001質量%では半分のパネラーが何らかの臭いを検知した。0.01質量%ではほとんどのパネラーが何らかの臭いを検知した。0.1質量%では半分以上のパネラーが酸っぱい臭いを感知した。1質量%ではすべてのパネラーが臭いを感知した。1質量%溶液については「いい臭いでも不快な臭いでもない」という評価が多かった。
[Result Example 2]
At 0.001% by weight, half of the panelists detected some odor. At 0.01% by weight, most panelists detected some odor. At 0.1% by weight, more than half of the panelists perceived a sour odor. At 1% by weight, all panelists sensed the odor. There were many evaluations that the 1% by mass solution had neither a good odor nor an unpleasant odor.
[結果 市販過酢酸製剤A]
0.001質量%では半分以上のパネラーが何らかの臭いを検知した。0.01質量%以上では全てのパネラーが特定の(酸っぱい)臭いを感知し、「刺激臭」という評価をしたパネラーも見られた。0.1質量%では8人中4人が「刺激臭」を感知した。1質量%溶液については、6人が「刺激臭」と評価した。
[Results Commercially available peracetic acid preparation A]
At 0.001% by weight, more than half of the panelists detected some odor. At 0.01% by mass or more, all panelists sensed a specific (sour) odor, and some panelists evaluated it as a "pungent odor". At 0.1% by weight, 4 out of 8 perceived a "pungent odor". Six people evaluated the 1% by weight solution as a "pungent odor".
◎:不正解または判別不能
○:何か臭いがする(他のサンプルと違う)
△:何の臭いであるか感知(どのような臭いか具体的に言える)
×:刺激臭を感知
◎: Incorrect or indistinguishable ○: Something smells (different from other samples)
△: Sensing what kind of odor (specifically say what kind of odor it is)
×: Detects pungent odor
[除菌効力試験]
以下の試験方法により、過酢酸と過乳酸の除菌効力の比較を行った。除菌効力の差を見るため、菌種として芽胞形成菌であり比較的耐薬品性が高いバチルスサブチリス、バチルスセレウスを選択した。
[Sterilization efficacy test]
The sterilizing efficacy of peracetic acid and perlactic acid was compared by the following test methods. In order to see the difference in eradication efficacy, Bacillus subtilis and Bacillus cereus, which are spore-forming bacteria and have relatively high chemical resistance, were selected as the bacterial species.
[試験菌種]
バチルスサブチリス(Bacillus subtilis):NBRC3134
バチルスセレウス(Bacillus cereus):乳業工場のアルカリ性洗浄液から単離した菌
[Test bacterial species]
Bacillus subtilis: NBRC3134
Bacillus cereus: A bacterium isolated from an alkaline cleaning solution in a dairy factory.
[試験方法 菌液の調整]
(1)標準寒天平板培地に菌を接種し、37℃で7日間培養した。
(2)平板培地上に生じた菌を滅菌生理食塩水40mlに懸濁した。
(3)65℃の水浴中で30分間加熱し、25℃の水で急冷した後、4500rpmで15分間遠心分離し、上清を捨て、沈殿を40mlの生理食塩水に懸濁した。
(4)(3)の工程を計2回繰り返した。
(5)10〜107倍に段階希釈し、105〜107倍希釈液を1mlとって、コンパクトドライ(日水製薬(株)製簡易培地、一般性菌数測定用)に添加した。
(6)37℃、48時間培養後コロニー数が30〜300個の範囲に収まる希釈倍率について計数し、10で割って初発菌数とした。
[Test method Preparation of bacterial solution]
(1) Bacteria were inoculated on a standard agar plate medium and cultured at 37 ° C. for 7 days.
(2) The bacteria generated on the plate medium were suspended in 40 ml of sterile physiological saline.
(3) The mixture was heated in a water bath at 65 ° C. for 30 minutes, rapidly cooled with water at 25 ° C., centrifuged at 4500 rpm for 15 minutes, the supernatant was discarded, and the precipitate was suspended in 40 ml of physiological saline.
(4) The steps of (3) were repeated twice in total.
(5) were serially diluted in 10 to 10 7 times, 10 5 to 10 7 fold dilutions taking 1 ml, was added to the compact dry (Nissui Pharmaceutical Co. simple media, for the number of general bacteria measurement).
(6) After culturing at 37 ° C. for 48 hours, the dilution ratio at which the number of colonies was within the range of 30 to 300 was counted and divided by 10 to obtain the initial number of bacteria.
[試験方法 除菌効力試験]
(7)菌液1mlを除菌剤溶液9mlに接種し、水浴中で25℃に保持した(以下、試験液とする)。
(8)所定時間後、中和液9ml※に対して試験液1mlを添加し、滅菌リン酸緩衝生理食塩水で段階希釈し、各希釈液1mlをコンパクトドライに加えた。
(9)37℃、48時間培養後コロニー数が30〜300個の範囲に収まる希釈倍率について計数し、各試験液中の菌数を求めた。
※レシチン10g、Tween80 30g、L−ヒスチジン1g、チオ硫酸Na5水和物31g、リン酸緩衝液(pH7.2)250mM 100mlを1000mlのイオン交換水でメスアップし、オートクレーブ滅菌したもの。
[Test method sterilization efficacy test]
(7) 1 ml of the bacterial solution was inoculated into 9 ml of the disinfectant solution and kept at 25 ° C. in a water bath (hereinafter referred to as a test solution).
(8) After a predetermined time, 1 ml of the test solution was added to 9 ml * of the neutralizing solution, serially diluted with sterile phosphate buffered saline, and 1 ml of each diluted solution was added to the compact dry.
(9) After culturing at 37 ° C. for 48 hours, the dilution ratio at which the number of colonies was within the range of 30 to 300 was counted, and the number of bacteria in each test solution was determined.
* Lecithin 10 g, Tween80 30 g, L-histidine 1 g, thiosulfate Na pentahydrate 31 g, and phosphate buffer (pH 7.2) 250
[結果]
試験の結果、バチルスサブチリスに対しては、過酢酸と等モル濃度の過乳酸製剤で同等の除菌効力を示した。バチルスセレウスに対しては、過乳酸製剤の除菌効力は等モル濃度の過酢酸よりも高かった。
[result]
As a result of the test, Bacillus subtilis showed the same sterilizing effect as the peracetic acid and the perlactic acid preparation having the same molar concentration. For Bacillus cereus, the eradication efficacy of the perlactic acid preparation was higher than that of the equimolar concentration of peracetic acid.
菌種:バチルスサブチリス(NBRC3134)
初発菌数:8.3×106(CFU/ml)
試験温度:25℃、作用時間:10分
Initial bacteria count: 8.3 × 10 6 (CFU / ml)
Test temperature: 25 ° C, action time: 10 minutes
菌種:バチルスセレウス(乳業工場から単離)
初発菌数:5.6×105(CFU/ml)
試験温度:25℃、作用時間:30分
Initial bacteria count: 5.6 × 10 5 (CFU / ml)
Test temperature: 25 ° C, action time: 30 minutes
Claims (7)
前記乳酸0.1〜15質量部と、前記過酸化水素10〜50質量部と、安定化剤3〜12質量部と、酸触媒(但し、乳酸を除く)1〜15質量部とを配合してなる組成物と;
水と;を含む、
除菌剤組成物。
CH3CH(OH)COOH+H2O2⇔CH3CH(OH)COO2H+H2O (2) A disinfectant composition based on an equilibrium system of lactic acid, hydrogen peroxide, and superlactic acid (formula (2) below) ( excluding quaternary ammonium compounds) .
0.1 to 15 parts by mass of lactic acid, 10 to 50 parts by mass of hydrogen peroxide, 3 to 12 parts by mass of stabilizer, and 1 to 15 parts by mass of acid catalyst (excluding lactic acid) are blended. With the composition of
With water;
Disinfectant composition.
CH 3 CH (OH) COOH + H 2 O 2 ⇔ CH 3 CH (OH) COO 2 H + H 2 O (2)
前記乳酸0.1〜15質量部と、前記過酸化水素10〜50質量部と、安定化剤3〜12質量部と、酸触媒(但し、乳酸を除く)1〜15質量部とを配合してなる組成物と;
水と;からなる、
除菌剤組成物。
CH3CH(OH)COOH+H2O2⇔CH3CH(OH)COO2H+H2O (2) A disinfectant composition based on an equilibrium system of lactic acid, hydrogen peroxide, and superlactic acid (formula (2) below).
0.1 to 15 parts by mass of lactic acid, 10 to 50 parts by mass of hydrogen peroxide, 3 to 12 parts by mass of stabilizer, and 1 to 15 parts by mass of acid catalyst (excluding lactic acid) are blended. With the composition of
Consists of water;
Disinfectant composition.
CH 3 CH (OH) COOH + H 2 O 2 ⇔ CH 3 CH (OH) COO 2 H + H 2 O (2)
前記安定化剤は、有機ホスホン酸およびピリジンカルボン酸のうちの少なくとも1つである、
請求項1または請求項2に記載の除菌剤組成物。 Containing the lactic acid and the hyperlactic acid produced from the hydrogen peroxide,
The stabilizer is at least one of an organic phosphonic acid and a pyridinecarboxylic acid.
The disinfectant composition according to claim 1 or 2.
前記乳酸と前記過乳酸の総量0.1〜15質量部と;
前記過酸化水素1〜50質量部と;
安定化剤3〜12質量部と;
酸触媒(但し、乳酸を除く)1〜15質量部と;
水と;を含み、
前記安定化剤は、有機ホスホン酸およびピリジンカルボン酸のうちの少なくとも1つである、
除菌剤組成物。
CH3CH(OH)COOH+H2O2⇔CH3CH(OH)COO2H+H2O (2) A disinfectant composition based on an equilibrium system of lactic acid, hydrogen peroxide, and superlactic acid (formula (2) below) ( excluding quaternary ammonium compounds) .
With a total amount of 0.1 to 15 parts by mass of the lactic acid and the superlactic acid;
With 1 to 50 parts by mass of hydrogen peroxide;
Stabilizer with 3-12 parts by mass;
With 1 to 15 parts by mass of acid catalyst (excluding lactic acid);
With water;
The stabilizer is at least one of an organic phosphonic acid and a pyridinecarboxylic acid.
Disinfectant composition.
CH 3 CH (OH) COOH + H 2 O 2 ⇔ CH 3 CH (OH) COO 2 H + H 2 O (2)
初期濃度の前記過乳酸は、前記除菌剤組成物を室温で30日間保管後に初期濃度の70質量%以上が残存する、
請求項1〜請求項4のいずれか1項に記載の除菌剤組成物。 When the concentration of the superlactic acid when the reaction between the lactic acid and the hydrogen peroxide reaches a chemical equilibrium state is used as the initial concentration,
The initial concentration of the hyperlactic acid is such that 70% by mass or more of the initial concentration remains after the disinfectant composition is stored at room temperature for 30 days.
The disinfectant composition according to any one of claims 1 to 4.
請求項1〜請求項5のいずれか1項に記載の除菌剤組成物。 Does not contain peracetic acid,
The disinfectant composition according to any one of claims 1 to 5.
乳酸を0.1〜15質量部と;
過酸化水素を10〜50質量部と;
安定化剤を3〜12質量部と;
酸触媒(但し、乳酸を除く)を1〜15質量部と;
水と;を配合するステップを備える、
除菌剤組成物の製造方法。
CH3CH(OH)COOH+H2O2⇔CH3CH(OH)COO2H+H2O (2)
A method for producing a disinfectant composition (excluding quaternary ammonium compounds ) based on an equilibrium system of lactic acid, hydrogen peroxide, and superlactic acid (formula (2) below).
Lactic acid is 0.1 to 15 parts by mass;
Hydrogen peroxide with 10 to 50 parts by mass;
Stabilizer with 3-12 parts by mass;
Add 1 to 15 parts by mass of acid catalyst (excluding lactic acid);
With a step of blending with water;
A method for producing a disinfectant composition.
CH 3 CH (OH) COOH + H 2 O 2 ⇔ CH 3 CH (OH) COO 2 H + H 2 O (2)
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