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JP3607559B2 - Disinfectant composition - Google Patents
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JP3607559B2 - Disinfectant composition - Google Patents

Disinfectant composition Download PDF

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Publication number
JP3607559B2
JP3607559B2 JP2000066815A JP2000066815A JP3607559B2 JP 3607559 B2 JP3607559 B2 JP 3607559B2 JP 2000066815 A JP2000066815 A JP 2000066815A JP 2000066815 A JP2000066815 A JP 2000066815A JP 3607559 B2 JP3607559 B2 JP 3607559B2
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JP
Japan
Prior art keywords
composition
sodium
aqueous solution
acid
ppm
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JP2000066815A
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Japanese (ja)
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JP2001253803A (en
Inventor
清章 吉川
哲也 岡野
登 松尾
純稔 伊藤
成 田村
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Kao Corp
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Kao Corp
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Priority to JP2000066815A priority Critical patent/JP3607559B2/en
Priority to PCT/JP2000/008716 priority patent/WO2001041571A1/en
Priority to US10/149,147 priority patent/US6793846B2/en
Priority to KR1020027007411A priority patent/KR100737951B1/en
Priority to CN00818808A priority patent/CN1433270A/en
Priority to EP00980019A priority patent/EP1236398A4/en
Publication of JP2001253803A publication Critical patent/JP2001253803A/en
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Publication of JP3607559B2 publication Critical patent/JP3607559B2/en
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  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Description

【0001】
【発明の属する技術分野】
本発明は殺菌剤組成物及び殺菌方法に関する。
【0002】
【従来の技術及び発明が解決しようとする課題】
従来、広範な環境における殺菌消毒剤として、次亜塩素酸ナトリウム、次亜塩素酸カルシウム、ジクロロイソシアヌル酸ナトリウム等の塩素系殺菌剤が広く用いられている。中でも次亜塩素酸ナトリウム等の次亜塩素酸塩は、価格面と効果の点で汎用されているが、医療、食品工業等、種々の分野で要求される微生物の殺菌、滅菌に対して、更にその効力を向上させるための多くの提案がなされている。例えば、特開昭57−61099号には、次亜塩素酸塩、アルカリ性物質及び特定の第四級アンモニウム塩型カチオン界面活性剤を、それぞれ特定の重量比で含有する液体殺菌漂白剤組成物が、特開平7−233396号には、次亜塩素酸塩、陰イオン界面活性剤、アルカリ剤及びキレート剤を含有する人工透析機等の医療機器用の殺菌洗浄剤が開示されている。
【0003】
しかしながら、従来の次亜塩素酸塩系殺菌剤は、一般細菌やカビ(菌糸)についてはある程度の効果があるものの、薬品耐性のより高いウイルス、桿菌の形成する芽胞、カビ胞子に対しては簡易な操作では十分な効果が期待できない。
【0004】
また、特開平11−148098号には高度さらし粉(次亜塩素酸カルシウム)のような次亜塩素酸アルカリ土類金属塩を用いた固形殺菌洗浄剤が開示されているが、より高度の殺菌処理について認識されておらず、しかもカルシウム等のアルカリ土類金属がスケール、スカムの発生原因となり、殺菌効率の低下をもたらす。
【0005】
更に、特開平7−328638号には、電解酸化水に表面張力を低減させる薬剤を加えて被殺菌物の外表面に対する密着性を増加させることが記載されており、殺菌効果の面では優れるが、塩素ガスが発生し、安全性に問題がある。
【0006】
なお、特開昭59−93799号には、アミンオキサイドを、次亜塩素酸塩を含有する液体洗浄剤に配合することが、また、特開昭59−98200号には、アミンオキサイドを、次亜塩素酸塩を含有する漂白剤の増粘剤として用いることが開示されているが、これらには殺菌、特に耐性の高い芽胞やウイルスの殺菌に関しての言及はない。
【0007】
本発明は、簡易な処理により、高い殺菌効果が得られ、且つ安全性、作業性に優れた殺菌剤組成物を得ることを目的とする。
【0008】
【課題を解決するための手段】
本発明は、次亜塩素酸(A)とpH調整剤(B)とを含有するpH(25℃)3〜8の水溶液からなる液状殺菌剤組成物に関する。また、本発明は、更に一種以上の界面活性剤(C)を含有する前記殺菌剤組成物に関する。
【0009】
また、本発明は、次亜塩素酸(A)とpH調整剤(B)とを含有し、pH(25℃)3〜8、有効塩素濃度5〜5000ppmの水溶液を微生物と接触させる殺菌方法に関する。
【0010】
【発明の実施の形態】
次亜塩素酸(A)を含む水溶液は、公知の電解酸化水の製法、例えば隔膜方式で電解質含有水溶液を電気分解することや、次亜塩素酸塩を酸析することにより得ることができる。本発明の殺菌剤組成物中の次亜塩素酸(A)の濃度は、有効塩素濃度として5ppm〜5重量%、更に5ppm〜1重量%、特に5ppm〜0.5重量%が好ましい。本発明において、有効塩素濃度は、JIS K−0101“ヨウ素法”により測定されたものである。
【0011】
本発明の殺菌剤組成物のpH(25℃)は3〜8、好ましくは5〜8、より好ましくは5〜7である。このpHは、pH調整剤(B)により調整される。このpH調整剤は、それを添加することにより、本発明の組成物をpH(25℃)3〜8に維持できるものであり、アルカリ剤や緩衝剤として用いられる化合物等から選択することができる。また、pH調整剤(B)は、このようなpH調整機能以外の機能を有するものであってもよい。
【0012】
pH調整剤としては、アルカリ金属の水酸化物、アルカリ土類金属の水酸化物、無機酸又はその塩、有機酸又はその塩等が挙げられる。具体的には、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、塩酸、硫酸ナトリウム、硝酸ナトリウム、塩化ナトリウム、炭酸ナトリウム、炭酸水素カリウム、炭酸水素ナトリウム、炭酸水素カリウム、硫酸マグネシウム、硝酸マグネシウム、塩化マグネシウム、炭酸マグネシウム、リン酸三ナトリウム、リン酸三カリウム、リン酸水素二ナトリウム、リン酸水素二カリウム、リン酸二水素ナトリウム、リン酸二水素カリウム、ポリリン酸ナトリウム、クエン酸、クエン酸ナトリウム、クエン酸カリウム、クエン酸二水素カリウム、フタル酸水素カリウム、コハク酸等が挙げられる。なかでも、水酸化ナトリウム、水酸化カリウム、塩酸、硫酸ナトリウム、硫酸マグネシウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、リン酸三ナトリウム、リン酸三カリウム、リン酸水素二ナトリウム、リン酸水素二カリウム、リン酸二水素ナトリウム、リン酸二水素カリウム及びポリリン酸ナトリウムから選ばれる一種以上が好ましい。
【0013】
本発明の殺菌剤組成物は、一種以上の界面活性剤(C)を含有することが好ましい。界面活性剤としては、陰イオン界面活性剤、陽イオン界面活性剤、非イオン界面活性剤、両性界面活性剤から選ぶことができるが、次亜塩素酸水溶液中で安定なものが使用される。なかでも陽イオン界面活性剤、両性界面活性剤が好ましく、特にアミンオキサイドが好ましい。アミンオキサイドとしては、アルキルジメチルアミンオキサイドが好ましく、特に炭素数8〜18のアルキル基を有するものが好ましい。組成物中の界面活性剤(C)と次亜塩素酸(A)の比率は、(A)(有効塩素濃度として)/(C)=10/1〜1/10(重量比)、更に5/1〜1/5、特に5/1〜1/2が好ましい。
【0014】
本発明の殺菌剤組成物は、殺菌性能向上の観点から、更に有機酸又はその塩(D)を含有してもよい。これらはpH調整剤として機能してもよい。有機酸又はその塩(D)としては、マロン酸、コハク酸、グルタル酸、アジピン酸、セバシン酸等の飽和二塩基酸又はその塩や、フマル酸、マレイン酸等の不飽和二塩基酸又はその塩等が挙げられる。好ましくは飽和二塩基酸又はその塩、より好ましくは炭素数3〜10の飽和二塩基酸又はその塩であり、特にコハク酸又はその塩が好ましい。
【0015】
本発明の殺菌剤組成物は、上記(A)、(B)成分に加えて、増粘剤、香料、着色剤等を含有してもよい。
【0016】
本発明の殺菌剤組成物は、使用の際には、更に希釈した水溶液として用いられるが、この希釈水溶液は、(A)成分を、有効塩素濃度として、5〜5000ppm、更に5〜1000ppm、特に5〜500ppm含有することが好ましい。
【0017】
本発明の殺菌方法は、上記(A)成分と(B)成分、更に(C)成分を含有するpH(25℃)3〜8、好ましくは5〜8、より好ましくは5〜7、有効塩素濃度5〜5000ppm、好ましくは5〜1000ppm、特に5〜500ppmの水溶液を、微生物と接触させることにより行われる。微生物とは、一般細菌、糸状菌、ウイルス、カビ胞子、細菌芽胞等を意味する。
【0018】
水溶液の接触方法は限定されないが、散布、噴霧、浸漬、充填等の方法が挙げられ、適当な担体に水溶液を含浸させたもので対象物を拭き取ってもよい。水溶液の接触時間も限定しないが、微生物によっては、30秒以内、特に10秒以内という短時間の接触時間でも十分な効果が得られる。また、接触させる水溶液の温度も限定しないが、20〜60℃が好ましい。
【0019】
本発明の殺菌剤組成物及びこれを用いた殺菌方法は、殺菌スペクトルが広く、細菌(カビ)のみならず、ウイルスや芽胞に対する効果も高いため、幅広い分野での殺菌方法として有用である。例えば、病院、養護施設、食品加工工場、クリーニング施設、厨房等の壁、床、窓等あるいはそれらで用いられる器具、備品、及び製品用(例えば飲料液用)容器の殺菌に用いられる。
【0020】
【発明の効果】
本発明によれば、殺菌効果が高く、且つ安全性、作業性に優れた殺菌剤組成物及び殺菌方法が得られる。
【0021】
【実施例】
実施例
隔膜方式で得られたいわゆる電解酸化水のうち、陽極側に発生した次亜塩素酸水(pH(25℃)2.7、有効塩素濃度50ppm)を用い、以下の方法で殺菌剤組成物を調製した。なお、次亜塩素酸濃度は、JIS K−0101“ヨウ素法”により測定した有効塩素濃度である。
(1)0.1mol/Lの水酸化ナトリウム水溶液でpH5(実施例1)又はpH11(比較例1)に調整し、殺菌剤組成物を得る。
(2)0.1mol/Lの水酸化ナトリウム水溶液でpH6に調整し、ラウリルジメチルアミンオキサイドを濃度が25ppmとなるように添加し、殺菌剤組成物を得る(実施例2)。
(3)0.1mol/Lのリン酸二水素カリウム−リン酸水素二ナトリウム緩衝液でpH7に調整し、殺菌剤組成物を得る(実施例3)。
【0022】
各殺菌剤組成物を用いて以下の試験を行った。結果を表1に示す。なお、各殺菌剤組成物における塩素ガスの発生は安全性に問題がない程度に低レベルであった。
【0023】
〔1〕殺芽胞試験
芽胞菌である枯草菌(Bacillus subtilis ATCC6633)をSCD寒天培地(日本製薬(株)製)に50日間30℃で培養後、得られた菌を遠心法で2回洗浄して65℃30分の熱処理を行い、細菌芽胞懸濁液(10cell/ml)を得た。
【0024】
この細菌芽胞懸濁液50μlを殺菌剤組成物2mlに接種し、室温にて5分間作用させた後にこの菌接触液を50μl採取し、後培養用SCDLP培地(チオ硫酸ナトリウム3.3%含有)0.2mlの入ったミクロシャーレ(CORNING社製、96−Cell Wells)へ接種した。30℃で48時間培養し、菌の発育を肉眼で観察し、ミクロシャーレ上で菌が生育しているかどうかを観察した。菌の生育がない場合を「◎」、ある場合を「×」とした。
【0025】
〔2〕殺カビ試験
カビ(真菌、Aspergillus niger IFO6341)をPDA培地で25℃で30日間培養した後、得られた菌体をガラス玉法を用い、均一にした後、滅菌ガーゼで異物を除去し、懸濁菌液(10cell/ml)を得た。
【0026】
この懸濁菌液50μlを殺菌剤組成物2mlに接種し、室温にて5分間作用させた後にこの菌接触液を0.1ml採取し、後培養用PDA培地(チオ硫酸ナトリウム3.3%含有)へ接種した。25℃で7時間培養し、カビの発育を肉眼で観察し、上記同様に評価した。
【0027】
【表1】

Figure 0003607559
[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a disinfectant composition and a disinfecting method.
[0002]
[Prior art and problems to be solved by the invention]
Conventionally, chlorine-based disinfectants such as sodium hypochlorite, calcium hypochlorite, and sodium dichloroisocyanurate have been widely used as disinfectants in a wide range of environments. Among them, hypochlorite such as sodium hypochlorite is widely used in terms of price and effect, but for sterilization and sterilization of microorganisms required in various fields such as medical and food industries, Furthermore, many proposals have been made to improve its effectiveness. For example, JP-A-57-61099 discloses a liquid sterilizing bleaching composition containing hypochlorite, an alkaline substance, and a specific quaternary ammonium salt type cationic surfactant in specific weight ratios. JP-A-7-233396 discloses a bactericidal cleaning agent for medical devices such as an artificial dialysis machine containing hypochlorite, an anionic surfactant, an alkali agent and a chelating agent.
[0003]
However, although conventional hypochlorite fungicides have some effects on general bacteria and mold (mycelium), they are easy for viruses with higher chemical resistance, spores formed by gonococci, and mold spores. A sufficient operation cannot be expected.
[0004]
Japanese Patent Application Laid-Open No. 11-148098 discloses a solid sterilizing detergent using an alkaline earth metal hypochlorite such as highly bleached powder (calcium hypochlorite). In addition, alkaline earth metals such as calcium cause scales and scum, resulting in a decrease in sterilization efficiency.
[0005]
Furthermore, JP-A-7-328638 describes that an adhesive for reducing surface tension is added to electrolytically oxidized water to increase the adhesion to the outer surface of an object to be sterilized, which is excellent in terms of sterilization effect. Chlorine gas is generated and there is a safety problem.
[0006]
In JP-A-59-93799, amine oxide is added to a liquid detergent containing hypochlorite, and in JP-A-59-98200, amine oxide is added as follows. Although they are disclosed for use as thickeners for bleach containing chlorite, there is no mention of sterilization, particularly sterilization of highly resistant spores and viruses.
[0007]
It is an object of the present invention to obtain a bactericidal composition having a high bactericidal effect and excellent safety and workability by a simple treatment.
[0008]
[Means for Solving the Problems]
The present invention relates to a liquid fungicide composition comprising an aqueous solution having a pH (25 ° C.) of 3 to 8 containing hypochlorous acid (A) and a pH adjuster (B). Moreover, this invention relates to the said disinfectant composition which contains 1 or more types of surfactant (C) further.
[0009]
In addition, the present invention relates to a sterilization method containing hypochlorous acid (A) and a pH adjuster (B), and bringing an aqueous solution having a pH (25 ° C.) of 3 to 8 and an effective chlorine concentration of 5 to 5000 ppm into contact with microorganisms. .
[0010]
DETAILED DESCRIPTION OF THE INVENTION
An aqueous solution containing hypochlorous acid (A) can be obtained by a known method for producing electrolytic oxidized water, for example, by electrolyzing an electrolyte-containing aqueous solution by a diaphragm system or by acidifying hypochlorite. The concentration of hypochlorous acid (A) in the fungicidal composition of the present invention is preferably 5 ppm to 5% by weight, more preferably 5 ppm to 1% by weight, especially 5 ppm to 0.5% by weight as the effective chlorine concentration. In the present invention, the effective chlorine concentration is measured by JIS K-0101 “Iodine Method”.
[0011]
The pH (25 ° C.) of the fungicide composition of the present invention is 3 to 8, preferably 5 to 8, and more preferably 5 to 7. This pH is adjusted by a pH adjuster (B). This pH adjuster can maintain the composition of the present invention at a pH (25 ° C.) of 3 to 8 by adding it, and can be selected from compounds used as alkali agents and buffers. . Moreover, a pH adjuster (B) may have functions other than such a pH adjustment function.
[0012]
Examples of the pH adjuster include alkali metal hydroxides, alkaline earth metal hydroxides, inorganic acids or salts thereof, organic acids or salts thereof, and the like. Specifically, sodium hydroxide, potassium hydroxide, calcium hydroxide, hydrochloric acid, sodium sulfate, sodium nitrate, sodium chloride, sodium carbonate, potassium bicarbonate, sodium bicarbonate, potassium bicarbonate, magnesium sulfate, magnesium nitrate, chloride Magnesium, magnesium carbonate, trisodium phosphate, tripotassium phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium polyphosphate, citric acid, sodium citrate, Examples include potassium citrate, potassium dihydrogen citrate, potassium hydrogen phthalate, and succinic acid. Among them, sodium hydroxide, potassium hydroxide, hydrochloric acid, sodium sulfate, magnesium sulfate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium hydrogen phosphate, phosphorus One or more selected from dipotassium oxyhydrogen, sodium dihydrogen phosphate, potassium dihydrogen phosphate and sodium polyphosphate are preferred.
[0013]
The fungicidal composition of the present invention preferably contains one or more surfactants (C). The surfactant can be selected from an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant, and those that are stable in a hypochlorous acid aqueous solution are used. Of these, cationic surfactants and amphoteric surfactants are preferable, and amine oxides are particularly preferable. As the amine oxide, alkyldimethylamine oxide is preferable, and those having an alkyl group having 8 to 18 carbon atoms are particularly preferable. The ratio of the surfactant (C) to the hypochlorous acid (A) in the composition is (A) (as effective chlorine concentration) / (C) = 10/1 to 1/10 (weight ratio), further 5 / 1-1 / 5, especially 5 / 1-1 / 2 is preferred.
[0014]
The disinfectant composition of the present invention may further contain an organic acid or a salt (D) thereof from the viewpoint of improving the disinfecting performance. These may function as pH adjusters. Examples of organic acids or salts thereof (D) include saturated dibasic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, and sebacic acid, or salts thereof, unsaturated dibasic acids such as fumaric acid, maleic acid, and the like. Examples include salts. A saturated dibasic acid or a salt thereof is preferable, a saturated dibasic acid having 3 to 10 carbon atoms or a salt thereof is preferable, and a succinic acid or a salt thereof is particularly preferable.
[0015]
The disinfectant composition of the present invention may contain a thickener, a fragrance, a colorant and the like in addition to the components (A) and (B).
[0016]
In use, the fungicidal composition of the present invention is used as a further diluted aqueous solution. This diluted aqueous solution has a component (A) having an effective chlorine concentration of 5-5000 ppm, more preferably 5-1000 ppm, especially It is preferable to contain 5-500 ppm.
[0017]
The sterilization method of the present invention comprises the above components (A) and (B), and further a component (C) at a pH (25 ° C.) of 3 to 8, preferably 5 to 8, more preferably 5 to 7, and effective chlorine. It is carried out by bringing an aqueous solution having a concentration of 5 to 5000 ppm, preferably 5 to 1000 ppm, particularly 5 to 500 ppm into contact with the microorganism. The microorganism means general bacteria, filamentous fungi, viruses, mold spores, bacterial spores and the like.
[0018]
Although the contact method of aqueous solution is not limited, Methods, such as spreading | spraying, spraying, immersion, filling, etc., are mentioned, You may wipe off a target object with what impregnated aqueous solution in the suitable support | carrier. Although the contact time of the aqueous solution is not limited, depending on the microorganism, a sufficient effect can be obtained even with a short contact time of 30 seconds or less, particularly 10 seconds or less. Moreover, although the temperature of the aqueous solution made to contact is also not limited, 20-60 degreeC is preferable.
[0019]
The bactericidal composition and the bactericidal method using the same of the present invention have a wide bactericidal spectrum and have a high effect on not only bacteria (fungi) but also viruses and spores, and thus are useful as a bactericidal method in a wide range of fields. For example, it is used for sterilization of hospitals, nursing homes, food processing factories, cleaning facilities, kitchen walls, floors, windows, etc., or equipment, fixtures, and products (for example, beverages) containers used in them.
[0020]
【The invention's effect】
According to the present invention, a bactericidal composition and a bactericidal method having a high bactericidal effect and excellent safety and workability can be obtained.
[0021]
【Example】
In the so-called electrolytically oxidized water obtained by the diaphragm system, hypochlorous acid water (pH (25 ° C.) 2.7, effective chlorine concentration 50 ppm) generated on the anode side was used, and the disinfectant composition was as follows. A product was prepared. The hypochlorous acid concentration is an effective chlorine concentration measured by JIS K-0101 “iodine method”.
(1) Adjust to pH 5 (Example 1) or pH 11 (Comparative Example 1) with a 0.1 mol / L sodium hydroxide aqueous solution to obtain a bactericide composition.
(2) The pH is adjusted to 6 with a 0.1 mol / L sodium hydroxide aqueous solution, and lauryldimethylamine oxide is added so as to have a concentration of 25 ppm to obtain a fungicide composition (Example 2).
(3) Adjust to pH 7 with 0.1 mol / L potassium dihydrogen phosphate-disodium hydrogen phosphate buffer to obtain a bactericidal composition (Example 3).
[0022]
The following tests were conducted using each fungicide composition. The results are shown in Table 1. In addition, the generation of chlorine gas in each fungicide composition was at a low level to the extent that there was no problem with safety.
[0023]
[1] Spore kill test Bacillus subtilis ATCC6633, a spore bacterium, was cultured on an SCD agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.) for 50 days at 30 ° C., and the resulting bacterium was washed twice by centrifugation. Then, heat treatment was performed at 65 ° C. for 30 minutes to obtain a bacterial spore suspension (10 5 cells / ml).
[0024]
50 μl of this bacterial spore suspension was inoculated into 2 ml of a bactericide composition, allowed to act at room temperature for 5 minutes, and then 50 μl of this bacterial contact solution was collected and used for post-culture SCDLP medium (containing 3.3% sodium thiosulfate) A micro Petri dish (CORNING, 96-Cell Wells) containing 0.2 ml was inoculated. After culturing at 30 ° C. for 48 hours, the growth of the bacteria was observed with the naked eye, and it was observed whether the bacteria were growing on a micro petri dish. The case where there was no growth of the fungus was designated as “◎”, and the case where it was present was designated as “x”.
[0025]
[2] Fungicidal test mold (fungus, Aspergillus niger IFO6341) was cultured in PDA medium for 30 days at 25 ° C., and the resulting cells were homogenized using the glass ball method, and then foreign substances were removed with sterile gauze Suspended bacterial solution (10 5 cells / ml) was obtained.
[0026]
After inoculating 50 ml of this suspension bacterial solution into 2 ml of the bactericidal composition and allowing it to act at room temperature for 5 minutes, 0.1 ml of this bacterial contact solution was collected and PDA medium for postculture (containing 3.3% sodium thiosulfate) ). After culturing at 25 ° C. for 7 hours, mold growth was observed with the naked eye and evaluated in the same manner as described above.
[0027]
[Table 1]
Figure 0003607559

Claims (2)

次亜塩素酸(A)とpH調整剤(B)とアミンオキサイド(C)とを含有するpH(25℃)〜8の水溶液からなる液状殺菌剤組成物。A liquid bactericidal composition comprising an aqueous solution of pH 5 to 8 containing hypochlorous acid (A), a pH adjuster (B), and an amine oxide (C) . 次亜塩素酸(A)とpH調整剤(B)とアミンオキサイド(C)とを含有し、pH(25℃)〜8、有効塩素濃度5〜5000ppmの水溶液を微生物と接触させる殺菌方法。A sterilization method containing an aqueous solution containing hypochlorous acid (A), a pH adjuster (B), and an amine oxide (C) and having a pH (25 ° C) of 5 to 8 and an effective chlorine concentration of 5 to 5000 ppm.
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US10/149,147 US6793846B2 (en) 1999-12-10 2000-12-08 Microbicide compositions
KR1020027007411A KR100737951B1 (en) 1999-12-10 2000-12-08 Fungicide composition
CN00818808A CN1433270A (en) 1999-12-10 2000-12-08 Microbicide compositions
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