JPWO2007102389A1 - Method for producing diluted perglutaric acid - Google Patents
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Abstract
殺菌消毒剤として有用な過グルタル酸組成物において、希釈後の過グルタル酸濃度低下の遅い希釈液を製造する方法を提供することを課題とし、１０〜４５重量％の過グルタル酸、１〜３０重量％のグルタル酸および８〜５０重量％の過酸化水素を含有するｐＨ０．５未満の平衡過グルタル酸濃厚液を水で希釈し、且つ希釈前又は希釈時にアルカリを添加して希釈後にｐＨ１．８〜５．０になるよう調整することによって、過グルタル酸濃度低下の遅い過グルタル酸希釈液を得る。An object of the present invention is to provide a method for producing a dilute solution having a slow decrease in the concentration of perglutaric acid after dilution in a perglutaric acid composition useful as a disinfectant. A concentrated perglutaric acid concentrate having a pH of less than 0.5 containing 5% by weight glutaric acid and 8 to 50% by weight hydrogen peroxide is diluted with water, and an alkali is added before or after dilution to pH 1. By adjusting to 8 to 5.0, a perglutaric acid dilution with a slow decrease in perglutaric acid concentration is obtained.
Description
本発明は、殺菌、消毒等に有用な過グルタル酸希釈液の製造方法及び過グルタル酸希釈液の製造に有用な平衡過グルタル酸組成物に関する。 The present invention relates to a method for producing a perglutaric acid diluted solution useful for sterilization, disinfection, and the like, and an equilibrium perglutaric acid composition useful for producing a perglutaric acid diluted solution.
過グルタル酸組成物は、約８〜４５重量％の過グルタル酸を含む安定な水性ペルオキシ含有濃厚液が知られている（特許文献１参照）。また、過グルタル酸を含む複合過ジカルボン酸含有水溶液が、殺菌、消毒、洗浄用途等に使用できることが知られている（特許文献２参照）。しかしながら、これらの文献では過グルタル酸組成物の希釈時における過グルタル酸濃度低下についてはまったく触れられていない。過酢酸組成物については、リン酸塩およびある種の界面活性剤の添加により希釈時の過酢酸濃度低下を抑制させる方法があるが（特許文献３参照）、過グルタル酸組成物の希釈液の過グルタル酸濃度低下を抑制する方法はない。 As the perglutaric acid composition, a stable aqueous peroxy-containing concentrated liquid containing about 8 to 45% by weight of perglutaric acid is known (see Patent Document 1). In addition, it is known that a complex perdicarboxylic acid-containing aqueous solution containing perglutaric acid can be used for sterilization, disinfection, cleaning, and the like (see Patent Document 2). However, these documents do not mention any decrease in the concentration of perglutaric acid when the perglutaric acid composition is diluted. As for the peracetic acid composition, there is a method of suppressing a decrease in peracetic acid concentration at the time of dilution by adding a phosphate and a certain surfactant (see Patent Document 3). There is no method to suppress a decrease in the perglutaric acid concentration.
前記８〜４５重量％の過グルタル酸を含む過グルタル酸含有濃厚液は、殺菌消毒薬として使用できるが、殺菌消毒に用いる場合、通常はこのような高濃度の過グルタル酸は必要ではなく、安全性、経済性の点から希釈して用いられる。しかしながら、過グルタル酸濃厚液を希釈した場合、平衡移動により過グルタル酸濃度が急速に減少するため、希釈した実用液の殺菌消毒性能が急速に失われることになる。 The concentrated solution containing perglutaric acid containing 8 to 45% by weight of perglutaric acid can be used as a bactericidal disinfectant. However, when used for bactericidal disinfection, usually such a high concentration of perglutaric acid is not necessary, Diluted for safety and economy. However, when the perglutaric acid concentrated liquid is diluted, the perglutaric acid concentration rapidly decreases due to the equilibrium transfer, so that the sterilization performance of the diluted practical liquid is rapidly lost.
１０重量％以下の過グルタル酸含有組成物を平衡組成物として得ることは可能であるが、安全性、経済性に劣る。すなわち、過グルタル酸濃度が低すぎると所望の濃度の過グルタル酸を得るに際し希釈倍率が小さくなり、結果的に不経済となる。
また、１０重量％以下の過酸化水素を含む平衡組成物では、グルタル酸の過グルタル酸への転化率が低く、グルタル酸は高価であることから経済性に劣ることになる。
In addition, in an equilibrium composition containing 10% by weight or less of hydrogen peroxide, the conversion rate of glutaric acid to perglutaric acid is low, and glutaric acid is expensive.
本発明が解決しようとする課題は、希釈した場合に過グルタル酸濃度低下の遅い過グルタル酸濃厚液を得ること、及び殺菌消毒剤として有用な過グルタル酸濃度低下の遅い過グルタル酸希釈液を得ることである。 The problem to be solved by the present invention is to obtain a perglutaric acid concentrated solution with a slow decrease in perglutaric acid concentration when diluted, and a perglutaric acid diluted solution with a slow decrease in perglutaric acid useful as a disinfectant. Is to get.
本発明者らは、前記課題を解決すべく鋭意検討を重ねた結果、少なくとも１０重量％以上の過グルタル酸を含有する平衡過グルタル酸濃厚液を希釈前に又は希釈と同時に特定の値にｐＨ調整することで、平衡移動による過グルタル酸濃度の減少を極めて遅くでき、希釈した実用液の殺菌消毒性能を長時間維持することが可能となることを見出した。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that the equilibrium perglutaric acid concentrated solution containing at least 10% by weight or more of perglutaric acid is adjusted to a specific value before or simultaneously with the dilution. By adjusting, it was found that the reduction of the perglutaric acid concentration due to the equilibrium transfer can be extremely slow, and the sterilization performance of the diluted practical liquid can be maintained for a long time.
すなわち、本発明は、以下に示す過グルタル酸希釈液及びその製造方法、平衡過グルタル酸組成物、それを用いた殺菌消毒剤並びに殺菌消毒方法に関するものである。
（１）以下に示す工程（ａ）〜（ｃ）を含むことを特徴とする、過グルタル酸希釈液の製造方法。
（ａ）１０〜４５重量％の過グルタル酸、１〜３０重量％のグルタル酸、及び８〜５０重量％の過酸化水素を含有するｐＨ０．５未満の平衡過グルタル酸濃厚液を調製する調製工程、
（ｂ）前記平衡過グルタル酸濃厚液をｐＨ０．５以上に調整するｐＨ調整工程、及び
（ｃ）前記平衡過グルタル酸濃厚液を水で希釈する希釈工程。That is, the present invention relates to a perglutaric acid diluted solution and a production method thereof, an equilibrium perglutaric acid composition, a bactericidal disinfectant and a bactericidal disinfecting method using the same, as shown below.
(1) A method for producing a diluted solution of perglutaric acid, comprising the steps (a) to (c) shown below.
(A) Preparation to prepare an equilibrium perglutaric acid concentrate having a pH of less than 0.5, containing 10 to 45% by weight perglutaric acid, 1 to 30% by weight glutaric acid, and 8 to 50% by weight hydrogen peroxide. Process,
(B) a pH adjusting step for adjusting the equilibrium perglutaric acid concentrated solution to a pH of 0.5 or more; and (c) a dilution step for diluting the balanced perglutaric acid concentrated solution with water.
（２）前記調製工程（ａ）が、グルタル酸と濃度２０〜９０重量％の過酸化水素とを、グルタル酸：過酸化水素＝１５〜４０：８５〜６０（重量比）の割合で反応させる工程である、請求項１記載の過グルタル酸希釈液の製造方法。
（３）前記ｐＨ調整工程（ｂ）が、ｐＨ調整剤としてアルカリ成分を添加する工程である、請求項１記載の過グルタル酸希釈液の製造方法。
（４）前記アルカリ成分が水酸化ナトリウムである、請求項３記載の過グルタル酸希釈液の製造方法。(2) In the preparation step (a), glutaric acid and hydrogen peroxide having a concentration of 20 to 90% by weight are reacted at a ratio of glutaric acid: hydrogen peroxide = 15-40: 85-60 (weight ratio). The manufacturing method of the perglutaric-acid dilution liquid of Claim 1 which is a process.
(3) The method for producing a diluted solution of perglutaric acid according to claim 1, wherein the pH adjusting step (b) is a step of adding an alkali component as a pH adjusting agent.
(4) The method for producing a diluted solution of perglutaric acid according to claim 3, wherein the alkali component is sodium hydroxide.
（５）ｐＨが１．８〜５．０である過グルタル酸希釈液を製造する方法である、請求項１記載の過グルタル酸希釈液の製造方法。
（６）１〜２０重量％の過グルタル酸を含有し且つｐＨが１．８〜５．０である過グルタル酸希釈液を製造する方法である、請求項１記載の過グルタル酸希釈液の製造方法。
（７）グルタル酸の過グルタル酸への転化率が６０％以上である、請求項１記載の過グルタル酸希釈液の製造方法。
（８）前記平衡過グルタル酸濃厚液が、酸触媒を０．１〜５重量％含有していることを特徴とする、請求項１記載の過グルタル酸希釈液の製造方法。(5) The manufacturing method of the perglutaric-acid dilution liquid of Claim 1 which is a method of manufacturing the perglutaric-acid dilution liquid whose pH is 1.8-5.0.
(6) The perglutaric acid diluted solution according to claim 1, which is a method for producing a perglutaric acid diluted solution containing 1 to 20% by weight of perglutaric acid and having a pH of 1.8 to 5.0. Production method.
(7) The method for producing a diluted perglutaric acid solution according to claim 1, wherein the conversion rate of glutaric acid to perglutaric acid is 60% or more.
(8) The method for producing a diluted solution of perglutaric acid according to claim 1, wherein the concentrated perglutaric acid concentrated solution contains 0.1 to 5% by weight of an acid catalyst.
（９）１０〜４５重量％の過グルタル酸、１〜３０重量％のグルタル酸、及び８〜５０重量％の過酸化水素を含有する、ｐＨ０．５以上の平衡過グルタル酸組成物。
（１０）アルカリ成分を含有する、請求項１０記載の平衡過グルタル酸組成物。
（１１）前記アルカリ成分が水酸化ナトリウムである、請求項１０記載の平衡過グルタル酸組成物。(9) An equilibrium perglutaric acid composition having a pH of 0.5 or more, comprising 10 to 45% by weight perglutaric acid, 1 to 30% by weight glutaric acid, and 8 to 50% by weight hydrogen peroxide.
(10) The equilibrium perglutaric acid composition according to claim 10, comprising an alkali component.
(11) The equilibrium perglutaric acid composition according to claim 10, wherein the alkali component is sodium hydroxide.
（１２）請求項１記載の方法で得られる過グルタル酸希釈液を用いた殺菌消毒剤。
（１３）請求項１記載の方法で得られる過グルタル酸希釈液を被殺菌消毒物に、１０〜６０℃で１〜６０分接触させる工程を含む、殺菌消毒方法。(12) A disinfectant using a diluted perglutaric acid solution obtained by the method according to claim 1.
(13) A method for sterilizing and disinfecting, comprising the step of bringing the diluted solution of perglutaric acid obtained by the method according to claim 1 into contact with a disinfectant to be sterilized at 10 to 60 ° C for 1 to 60 minutes.
本発明の過グルタル酸希釈液の製造方法によれば、グルタル酸の過グルタル酸への転化速度及び転化率が高く、且つ希釈による過グルタル酸の濃度低下が遅いため、優れた殺菌消毒性能が長時間持続する過グルタル酸希釈液を効率よく経済的に得ることができる。
本発明の平衡過グルタル酸組成物は、希釈しても過グルタル酸の濃度低下が遅いため、高い殺菌消毒性能が長時間持続する実用性に優れた過グルタル酸希釈液を得るための濃厚液として有用である。According to the method for producing a diluted solution of perglutaric acid of the present invention, the conversion rate and conversion rate of glutaric acid to perglutaric acid are high, and the concentration reduction of perglutaric acid due to dilution is slow. A diluted perglutaric acid solution that lasts for a long time can be obtained efficiently and economically.
The balanced perglutaric acid composition of the present invention is a concentrated solution for obtaining a perglutaric acid diluted solution excellent in practicality that maintains a high disinfecting and disinfecting performance for a long time because the concentration decrease of the perglutaric acid is slow even when diluted. Useful as.
１．過グルタル酸希釈液の製造方法
本発明の過グルタル酸希釈液は、以下に示す工程（ａ）〜（ｃ）を含む方法により製造することができる。
（ａ）１０〜４５重量％の過グルタル酸、１〜３０重量％のグルタル酸、及び８〜５０重量％の過酸化水素を含有するｐＨ０．５未満の平衡過グルタル酸濃厚液を調製する調製工程
（ｂ）前記平衡過グルタル酸濃厚液をｐＨ０．５以上に調整するｐＨ調整工程
（ｃ）前記平衡過グルタル酸濃厚液を水で希釈する希釈工程1. The manufacturing method of a perglutaric-acid dilution liquid The perglutaric-acid dilution liquid of this invention can be manufactured by the method containing process (a)-(c) shown below.
(A) Preparation to prepare an equilibrium perglutaric acid concentrate having a pH of less than 0.5, containing 10 to 45% by weight perglutaric acid, 1 to 30% by weight glutaric acid, and 8 to 50% by weight hydrogen peroxide. Step (b) pH adjustment step of adjusting the equilibrium perglutaric acid concentrated solution to pH 0.5 or more (c) Dilution step of diluting the equilibrium perglutaric acid concentrated solution with water
（１）調製工程（ａ）
平衡過グルタル酸濃厚液の調製工程では、グルタル酸に過酸化水素を作用させる。グルタル酸と過酸化水素の反応は平衡反応であり、これにより過グルタル酸が生成する。
グルタル酸のかわりに、無水グルタル酸を用いてもよい。過酸化水素は、好ましくは濃度２０〜９０重量％、より好ましくは３０〜６０重量％の濃度の溶液を用いる。(1) Preparation step (a)
In the step of preparing the equilibrium perglutaric acid concentrated solution, hydrogen peroxide is allowed to act on glutaric acid. The reaction between glutaric acid and hydrogen peroxide is an equilibrium reaction, which produces perglutaric acid.
Instead of glutaric acid, glutaric anhydride may be used. Hydrogen peroxide is preferably a solution having a concentration of 20 to 90% by weight, more preferably 30 to 60% by weight.
反応開始時のグルタル酸と過酸化水素の混合比率（濃度）は、反応後の平衡組成物中の過グルタル酸濃度が１０％重量以上、より好ましくは２０重量％以上となる範囲で適宜選択すれば良い。 The mixing ratio (concentration) of glutaric acid and hydrogen peroxide at the start of the reaction is appropriately selected so that the concentration of perglutaric acid in the equilibrium composition after the reaction is 10% by weight or more, more preferably 20% by weight or more. It ’s fine.
おおむね反応開始時のグルタル酸と濃度２０〜９０重量％の過酸化水素溶液との割合は、グルタル酸：過酸化水素溶液＝１５〜４０：８５〜６０（重量比）、より好ましくはグルタル酸：過酸化水素溶液＝２５〜４０：７５〜６０（重量比）である。また、反応開始時のグルタル酸に対する過酸化水素のモル比率としては、好ましくは１．０〜１０、より好ましくは１．５〜５である。 In general, the ratio of glutaric acid at the start of the reaction to the hydrogen peroxide solution having a concentration of 20 to 90% by weight is glutaric acid: hydrogen peroxide solution = 15 to 40:85 to 60 (weight ratio), more preferably glutaric acid: Hydrogen peroxide solution = 25-40: 75-60 (weight ratio). Further, the molar ratio of hydrogen peroxide to glutaric acid at the start of the reaction is preferably 1.0 to 10, more preferably 1.5 to 5.
グルタル酸に対する過酸化水素の比率が低すぎるとグルタル酸の過グルタル酸への転化率が低下し、経済性に劣る場合がある。 If the ratio of hydrogen peroxide to glutaric acid is too low, the conversion rate of glutaric acid to perglutaric acid is lowered, which may be inferior in economic efficiency.
この際、酸触媒及び／又は安定剤を含有させてもよい。酸触媒としては、例えば硫酸、リン酸、縮合リン酸類等が挙げられる。酸触媒の添加量は、好ましくは０．１〜５重量％、より好ましくは１〜３重量％である。酸触媒の含有量が少なすぎると平衡過グルタル酸濃厚液のｐＨが高くなり、平衡に達するのに長期間を要するため生産性が低下する場合がある。 At this time, an acid catalyst and / or a stabilizer may be contained. Examples of the acid catalyst include sulfuric acid, phosphoric acid, and condensed phosphoric acids. The addition amount of the acid catalyst is preferably 0.1 to 5% by weight, more preferably 1 to 3% by weight. If the content of the acid catalyst is too low, the pH of the concentrated superglutaric acid concentrated solution becomes high, and it may take a long time to reach the equilibrium, so that productivity may be lowered.
安定剤としては、例えばジピコリン酸、１−ヒドロキシエタン−１，１−ジホスホン酸、リン酸塩等が挙げられる。安定剤の添加量は、好ましくは０．０１〜３重量％、より好ましくは０．１〜２重量％である。 Examples of the stabilizer include dipicolinic acid, 1-hydroxyethane-1,1-diphosphonic acid, phosphate, and the like. The added amount of the stabilizer is preferably 0.01 to 3% by weight, more preferably 0.1 to 2% by weight.
グルタル酸と過酸化水素との反応温度は、０〜６０℃の範囲で実施することができるが、通常は常温付近（２０〜４０℃）で実施するのが好ましい。 Although the reaction temperature of glutaric acid and hydrogen peroxide can be carried out in the range of 0 to 60 ° C., it is usually preferred to carry out at around room temperature (20 to 40 ° C.).
グルタル酸と過酸化水素を常温で反応させた場合、約２〜３０日間で平衡に達する。平衡に達した過グルタル酸濃厚液のｐＨは０．５未満である。ｐＨを０．５未満とすることは、例えば前記酸触媒を添加することで容易に達成できる。ｐＨが０．５以上になると、平衡に達するのに長期間を要し製造上好ましくない。 When glutaric acid and hydrogen peroxide are reacted at room temperature, equilibrium is reached in about 2 to 30 days. The pH of the concentrated perglutaric acid solution reaching equilibrium is less than 0.5. Setting the pH to less than 0.5 can be easily achieved, for example, by adding the acid catalyst. When the pH is 0.5 or more, it takes a long time to reach equilibrium, which is not preferable in production.
このようにして得られる平衡過グルタル酸濃厚液中における過グルタル酸濃度は１０〜４５重量％、好ましくは２０〜４５重量％であり、グルタル酸濃度は１〜３０重量％、好ましくは５〜２０重量％であり、過酸化水素濃度は８〜５０重量％、好ましくは１０〜２５重量％である。 The perglutaric acid concentration in the equilibrium perglutaric acid concentrate thus obtained is 10 to 45% by weight, preferably 20 to 45% by weight, and the glutaric acid concentration is 1 to 30% by weight, preferably 5 to 20%. The hydrogen peroxide concentration is 8 to 50% by weight, preferably 10 to 25% by weight.
過グルタル酸濃度が低すぎると、希釈後の過グルタル酸水溶液中の過グルタル酸濃度が低すぎて、十分な殺菌消毒性能が得られないという欠点が生じる。過酸化水素濃度が低すぎるとグルタル酸の過グルタル酸への添加率が低下し、経済的に得策ではない。 If the perglutaric acid concentration is too low, the perglutaric acid concentration in the diluted perglutaric acid aqueous solution is too low, resulting in a disadvantage that sufficient disinfection performance cannot be obtained. If the hydrogen peroxide concentration is too low, the addition rate of glutaric acid to perglutaric acid is lowered, which is not economically advantageous.
また、前記平衡過グルタル酸濃厚液におけるグルタル酸の過グルタル酸への転化率は好ましくは６０％以上である。 Further, the conversion rate of glutaric acid to perglutaric acid in the concentrated perglutaric acid concentrated solution is preferably 60% or more.
（２）ｐＨ調整工程（ｂ）
本発明の過グルタル酸希釈液の製造方法における工程（ｂ）は、前記平衡過グルタル酸濃厚液をｐＨ０．５以上に調整するｐＨ調整工程である。(2) pH adjustment step (b)
Step (b) in the method for producing a diluted perglutaric acid solution of the present invention is a pH adjusting step for adjusting the concentrated perglutaric acid concentrated solution to pH 0.5 or higher.
本発明の方法においては、上記工程（ａ）で調製される平衡過グルタル酸濃厚液をｐＨ０．５未満とし、且つ該平衡過グルタル酸濃厚液の希釈前あるいは希釈時にｐＨを０．５以上に調整することにより、生産性の向上効果だけでなく、驚くべきことに希釈後の過グルタル酸希釈液中における過グルタル酸濃度低下を抑制する効果が得られる。 In the method of the present invention, the concentrated perglutaric acid concentrated solution prepared in the step (a) is set to a pH of less than 0.5, and the pH is adjusted to 0.5 or more before or at the time of dilution of the balanced perglutaric acid concentrated solution. By adjusting, not only the productivity improvement effect, but also an effect of surprisingly suppressing the reduction of the perglutaric acid concentration in the diluted perglutaric acid diluted solution can be obtained.
ｐＨを０．５以上に調整する方法としては、アルカリのｐＨ調整剤を添加するのがよい。アルカリ成分としては、水酸化ナトリウム、リン酸塩（具体的にはリン酸ナトリウム、ピロリン酸ナトリウム等）などが挙げられる。これらのうち、水酸化ナトリウムが好ましい。ｐＨ調整剤の添加量は特に限定されず、希釈後の過グルタル酸希釈液のｐＨが１．８〜５．０になるように適宜選択することができる。 As a method for adjusting the pH to 0.5 or more, an alkaline pH adjuster is preferably added. Examples of the alkali component include sodium hydroxide and phosphate (specifically, sodium phosphate, sodium pyrophosphate, etc.). Of these, sodium hydroxide is preferred. The addition amount of the pH adjusting agent is not particularly limited, and can be appropriately selected so that the diluted perglutaric acid diluted solution has a pH of 1.8 to 5.0.
ｐＨ調整剤の添加は、少なくとも平衡過グルタル酸濃厚液の調製後であれば、すなわちグルタル酸と過酸化水素との反応による過グルタル酸濃厚液が平衡状態に達した後であれば、希釈前であっても、希釈する際であってもよい。 The pH adjuster should be added at least after the preparation of the equilibrated perglutaric acid concentrate, that is, after the perglutaric acid concentrate by the reaction between glutaric acid and hydrogen peroxide has reached an equilibrium state, before dilution. Or it may be at the time of dilution.
（３）希釈工程（ｃ）
本発明の過グルタル酸希釈液の製造方法では、上記工程で得られた平衡過グルタル酸濃厚液を、水で希釈する（希釈工程（ｃ））。希釈の割合は特に限定されず、使用目的に応じて任意の濃度に希釈することができる。好ましくは、希釈後の過グルタル酸濃度が１〜２０重量％、好ましくは１〜１０重量％、さらに好ましくは１〜６重量％になるまで希釈することができる。
本発明の方法で得られる平衡過グルタル酸濃厚液は、過グルタル酸濃度がこのような低濃度範囲となるように希釈しても、平衡移動による過グルタル酸濃度の減少が極めて遅いため、所望の過グルタル酸希釈液濃度を長時間維持することができる。(3) Dilution step (c)
In the method for producing a diluted perglutaric acid solution of the present invention, the concentrated perglutaric acid concentrated solution obtained in the above step is diluted with water (dilution step (c)). The ratio of dilution is not particularly limited, and can be diluted to any concentration depending on the purpose of use. Preferably, it can be diluted until the perglutaric acid concentration after dilution is 1 to 20% by weight, preferably 1 to 10% by weight, more preferably 1 to 6% by weight.
The concentrated perglutaric acid concentrate obtained by the method of the present invention has a very slow decrease in the perglutaric acid concentration due to the equilibrium transfer even if the perglutaric acid concentration is diluted so that it falls within such a low concentration range. The perglutaric acid diluted solution concentration can be maintained for a long time.
上記ｐＨ調整工程（ｂ）と希釈工程（ｃ）とは、いずれを先に行ってもよく、またｐＨ調整工程（ｂ）と希釈工程（ｃ）とを同時に行ってもよい。すなわち、例えば前記調製工程（ａ）において平衡過グルタル酸濃厚液を得た後、これにｐＨ調整剤を添加して平衡過グルタル酸濃厚液のｐＨを０．５以上に調整し、その後これに水を加えて希釈してもよい。また、前記調製工程（ａ）において平衡過グルタル酸濃厚液を得た後、これに水とｐＨ調整剤を同時に添加して過グルタル酸希釈液のｐＨが１．８〜５．０になるよう調整しつつ希釈してもよい。また、前記調製工程（ａ）において平衡過グルタル酸濃厚液を得た後、これに水を加えて希釈した直後にｐＨ調整剤を添加して平衡過グルタル酸希釈液のｐＨを１．８〜５．０に調整してもよい。
これらのうち、平衡過グルタル酸濃厚液をｐＨ調整した後希釈する（先に工程（ｂ）を行った後工程（ｃ）を行う）か、あるいは平衡過グルタル酸濃厚液を希釈する際にｐＨ調整する（工程（ｂ）と工程（ｃ）を同時に行う）方法が好ましい。Any of the pH adjustment step (b) and the dilution step (c) may be performed first, and the pH adjustment step (b) and the dilution step (c) may be performed simultaneously. That is, for example, after obtaining an equilibrium perglutaric acid concentrate in the preparation step (a), a pH adjuster is added thereto to adjust the pH of the equilibrium perglutarate concentrate to 0.5 or more, and then You may dilute by adding water. In addition, after obtaining the concentrated perglutaric acid concentrated solution in the preparation step (a), water and a pH adjuster are added simultaneously so that the pH of the diluted perglutaric acid solution becomes 1.8 to 5.0. You may dilute, adjusting. In addition, after obtaining the concentrated perglutaric acid concentrated solution in the preparation step (a), the pH of the balanced perglutaric acid diluted solution is adjusted to 1.8- You may adjust to 5.0.
Among these, the equilibrium perglutaric acid concentrated solution is adjusted after pH adjustment and then diluted (after step (b) is performed and then step (c) is performed), or when the equilibrium perglutaric acid concentrated solution is diluted. A method of adjusting (performing step (b) and step (c) simultaneously) is preferred.
本発明の方法で得られる過グルタル酸希釈液は、ｐＨが１．８〜５．０、好ましくは３〜４の水溶液である。過グルタル酸を含む液は希釈後に過グルタル酸濃度が急速に低下する傾向にあるが、本発明において希釈後の過グルタル酸含有液のｐＨが上記範囲内になるように調整すると、驚くべきことに前記希釈液中の過グルタル酸濃度の低下が格段に遅くなる。 The perglutaric acid dilution obtained by the method of the present invention is an aqueous solution having a pH of 1.8 to 5.0, preferably 3 to 4. The liquid containing perglutaric acid has a tendency to rapidly decrease the perglutaric acid concentration after dilution, but it is surprising when the pH of the diluted perglutaric acid-containing liquid is adjusted to be within the above range in the present invention. In addition, the decrease in the concentration of perglutaric acid in the diluted solution is much slower.
希釈液中の各成分の濃度は使用目的に応じて任意に設定することが可能であるが、希釈直後において、過グルタル酸濃度が１〜２０重量％、好ましくは１〜１０重量％、さらに好ましくは１〜６重量％であることが望ましい。また、過酸化水素濃度は好ましくは１〜７重量％、より好ましくは１〜５重量％である。さらに前記過グルタル酸希釈液には、好ましくは０．７〜７重量％、より好ましくは１〜５重量％のグルタル酸が含有されている。希釈液中の過グルタル酸濃度が低すぎると殺菌消毒効果が劣り、高すぎると皮膚刺激性が強くなる場合がある。なお、希釈液の各成分濃度は経時的に変化する場合があり、希釈直後以外では上記濃度範囲に必ずしも限定されない。 The concentration of each component in the diluent can be arbitrarily set according to the purpose of use, but immediately after dilution, the concentration of perglutaric acid is 1 to 20% by weight, preferably 1 to 10% by weight, more preferably Is preferably 1 to 6% by weight. The hydrogen peroxide concentration is preferably 1 to 7% by weight, more preferably 1 to 5% by weight. Further, the perglutaric acid diluted solution preferably contains 0.7 to 7% by weight, more preferably 1 to 5% by weight of glutaric acid. If the perglutaric acid concentration in the diluted solution is too low, the sterilizing and disinfecting effect is inferior. Note that the concentration of each component of the diluted solution may change with time, and is not necessarily limited to the above concentration range except immediately after dilution.
２．平衡過グルタル酸組成物
本発明の平衡過グルタル酸組成物は、１０〜４５重量％の過グルタル酸、１〜３０重量％のグルタル酸、及び８〜５０重量％の過酸化水素を含有するｐＨ０．５以上のものである。2. Equilibrium perglutaric acid composition The balanced perglutaric acid composition of the present invention has a pH of 0 containing 10-45 wt% perglutaric acid, 1-30 wt% glutaric acid, and 8-50 wt% hydrogen peroxide. .5 or more.
過グルタル酸のより好ましい濃度は２０〜４５重量％であり、グルタル酸のより好ましい濃度は５〜２０重量％であり、過酸化水素のより好ましい濃度は１０〜２５重量％である。過酸化水素濃度が高すぎる、すなわちグルタル酸の添加量が抑えられると、十分な過グルタル酸濃度を有する平衡過グルタル酸組成物が得られないため、所定の過グルタル酸濃度の溶液を得ようとする場合に希釈倍率を小さくせざるを得なくなる。本発明の平衡過グルタル酸組成物におけるグルタル酸の過グルタル酸への転化率は６０％以上である。 A more preferable concentration of perglutaric acid is 20 to 45% by weight, a more preferable concentration of glutaric acid is 5 to 20% by weight, and a more preferable concentration of hydrogen peroxide is 10 to 25% by weight. If the hydrogen peroxide concentration is too high, that is, if the amount of glutaric acid added is reduced, an equilibrium perglutaric acid composition having a sufficient perglutaric acid concentration cannot be obtained. In this case, the dilution factor must be reduced. The conversion rate of glutaric acid to perglutaric acid in the equilibrium perglutaric acid composition of the present invention is 60% or more.
平衡過グルタル酸組成物は、グルタル酸に過酸化水素を作用させることにより得られる。グルタル酸のかわりに、無水グルタル酸を用いてもよい。過酸化水素は、好ましくは濃度２０〜９０重量％、より好ましくは３０〜６０重量％の濃度の溶液を用いる。 The equilibrium perglutaric acid composition is obtained by allowing hydrogen peroxide to act on glutaric acid. Instead of glutaric acid, glutaric anhydride may be used. Hydrogen peroxide is preferably a solution having a concentration of 20 to 90% by weight, more preferably 30 to 60% by weight.
反応開始時のグルタル酸と過酸化水素の混合比率は、反応後の平衡組成物中の過グルタル酸濃度が１０％重量以上なる範囲で適宜選択すれば良い。おおむね反応開始時のグルタル酸と濃度２０〜９０重量％の過酸化水素溶液との割合は、グルタル酸：過酸化水素溶液＝１５〜４０：８５〜６０（重量比）、より好ましくはグルタル酸：過酸化水素溶液＝２５〜４０：７５〜６０（重量比）である。また、グルタル酸に対する過酸化水素のモル比率としては、好ましくは１．０〜１０、より好ましくは１．５〜５である。
グルタル酸に対する過酸化水素の比率が低すぎるとグルタル酸の過グルタル酸への転化率が低下し、経済性に劣る場合がある。The mixing ratio of glutaric acid and hydrogen peroxide at the start of the reaction may be appropriately selected so that the perglutaric acid concentration in the equilibrium composition after the reaction is 10% by weight or more. In general, the ratio of glutaric acid at the start of the reaction to the hydrogen peroxide solution having a concentration of 20 to 90% by weight is glutaric acid: hydrogen peroxide solution = 15 to 40:85 to 60 (weight ratio), more preferably glutaric acid: Hydrogen peroxide solution = 25-40: 75-60 (weight ratio). Further, the molar ratio of hydrogen peroxide to glutaric acid is preferably 1.0 to 10, more preferably 1.5 to 5.
If the ratio of hydrogen peroxide to glutaric acid is too low, the conversion rate of glutaric acid to perglutaric acid is lowered, which may be inferior in economic efficiency.
本発明の平衡過グルタル酸組成物には、酸触媒及び／又は安定剤が含有されていてもよい。酸触媒としては、例えば硫酸、リン酸、縮合リン酸類等が挙げられる。酸触媒の添加量は、好ましくは０．１〜５重量％、より好ましくは１〜３重量％である。酸触媒の含有量が少なすぎるとグルタル酸と過酸化水素との反応が平衡に達するのに長期間を要するため生産性が低下する場合がある。
安定剤としては、例えばジピコリン酸、１−ヒドロキシエタン−１，１−ジホスホン酸、リン酸塩等が挙げられる。安定剤の添加量は、好ましくは０．０１〜３重量％、より好ましくは０．１〜２重量％である。The equilibrium perglutaric acid composition of the present invention may contain an acid catalyst and / or a stabilizer. Examples of the acid catalyst include sulfuric acid, phosphoric acid, and condensed phosphoric acids. The addition amount of the acid catalyst is preferably 0.1 to 5% by weight, more preferably 1 to 3% by weight. If the content of the acid catalyst is too small, productivity may decrease because it takes a long time for the reaction between glutaric acid and hydrogen peroxide to reach equilibrium.
Examples of the stabilizer include dipicolinic acid, 1-hydroxyethane-1,1-diphosphonic acid, phosphate, and the like. The added amount of the stabilizer is preferably 0.01 to 3% by weight, more preferably 0.1 to 2% by weight.
グルタル酸と過酸化水素との反応温度は、０〜６０℃の範囲で実施することができるが、通常は常温付近（２０〜４０℃）で実施するのが好ましい。
グルタル酸と過酸化水素を常温で反応させた場合、約２〜３０日間で平衡に達する。平衡に達した過グルタル酸濃厚液のｐＨは、通常０．５未満であるが、本発明の平衡過グルタル酸組成物は、これをｐＨ０．５以上に調整したものである。ｐＨを０．５以上にすることにより、驚くべきことに希釈後の過グルタル酸濃度の低下を抑制することができる。ｐＨが０．５未満になると、希釈した場合に過グルタル酸濃度の急速な低下が起こり好ましくない。Although the reaction temperature of glutaric acid and hydrogen peroxide can be carried out in the range of 0 to 60 ° C., it is usually preferred to carry out at around room temperature (20 to 40 ° C.).
When glutaric acid and hydrogen peroxide are reacted at room temperature, equilibrium is reached in about 2 to 30 days. The pH of the concentrated perglutaric acid solution that has reached equilibrium is usually less than 0.5, but the balanced perglutaric acid composition of the present invention is adjusted to pH 0.5 or higher. By making the pH 0.5 or more, it is possible to surprisingly suppress a decrease in the perglutaric acid concentration after dilution. When the pH is less than 0.5, the concentration of perglutaric acid rapidly decreases when diluted, which is not preferable.
ｐＨを０．５以上に調整する方法としては、アルカリのｐＨ調整剤を添加するのがよい。アルカリ成分としては、水酸化ナトリウム、リン酸塩（リン酸ナトリウム、ピロリン酸ナトリウム等）等が挙げられる。これらのうち、水酸化ナトリウムが好ましい。ｐＨ調整剤の添加量は特に限定されず、希釈された過グルタル酸水溶液のｐＨが１．８〜５．０になるように適宜選択することができる。ｐＨ調整剤の添加は、少なくともグルタル酸と過酸化水素との反応が平衡に達した後であればよい。 As a method for adjusting the pH to 0.5 or more, an alkaline pH adjuster is preferably added. Examples of the alkali component include sodium hydroxide and phosphate (such as sodium phosphate and sodium pyrophosphate). Of these, sodium hydroxide is preferred. The addition amount of a pH adjuster is not specifically limited, It can select suitably so that the pH of the diluted perglutaric acid aqueous solution may be 1.8-5.0. The pH adjuster may be added at least after the reaction between glutaric acid and hydrogen peroxide reaches equilibrium.
４．殺菌消毒剤及び殺菌消毒方法
本発明の方法で得られる過グルタル酸希釈液は、殺菌消毒剤として用いることができる。殺菌消毒剤には、必要に応じて一般的な殺菌・消毒用薬剤等に使用される添加剤、例えば界面活性剤、増粘剤、香料、着色剤等が適宜配合されていてもよい。4). Bactericidal disinfectant and bactericidal disinfecting method The perglutaric acid dilution obtained by the method of the present invention can be used as a bactericidal disinfectant. In the sterilizing / disinfecting agent, additives used for general sterilizing / disinfecting agents and the like, for example, surfactants, thickeners, fragrances, coloring agents and the like may be appropriately blended as necessary.
本発明の過グルタル酸希釈液を用いて殺菌消毒する方法としては、被殺菌消毒物に１０〜６０℃にて１〜６０分接触させる工程を含む方法が挙げられ、これにより好適に殺菌消毒を行うことができる。被殺菌消毒物としては、高水準消毒が要求される医療器具等が挙げられる。 Examples of the method for sterilizing and disinfecting using the diluted glutamic acid solution of the present invention include a method including a step of contacting a sterilized material to be sterilized at 10 to 60 ° C. for 1 to 60 minutes. It can be carried out. Examples of the disinfectant to be sterilized include medical instruments that require high-level disinfection.
以下に本発明を用いて行った実施例を示す。この実施例は本発明の範囲を限定するものではない。
まず、過酸化水素と過グルタル酸濃度の算出方法について説明する。本発明の組成物に過マンガン酸カリウム溶液を過マンガン酸のピンク色が消えなくなるまで入れることにより、過酸化水素濃度を滴定により求める。続いてヨードメトリーによりペルオキシカルボキシル基の濃度を測定する。過グルタル酸濃度はモノペルオキシグルタル酸（ＨＯＯＣＣＨ2ＣＨ2ＣＨ2ＣＯＯＯＨ，分子量１４８）に基づき算出する。Examples carried out using the present invention are shown below. This example does not limit the scope of the invention.
First, a method for calculating the hydrogen peroxide and perglutaric acid concentrations will be described. The hydrogen peroxide concentration is determined by titration by adding a potassium permanganate solution to the composition of the present invention until the pink color of permanganate does not disappear. Subsequently, the concentration of the peroxycarboxyl group is measured by iodometry. The perglutaric acid concentration is calculated based on monoperoxyglutaric acid (HOOCCH 2 CH 2 CH 2 COOOH, molecular weight 148).
＜参考例１＞
グルタル酸２５ｇ、３５重量％過酸化水素４０ｍｌ、９５重量％硫酸１ｍｌ、ジピコリン酸０．１ｇ、６０重量％１−ヒドロキシエタン−１，１−ジホスホン酸１ｍｌを混合溶解し、室温にて２日間反応させることにより、２４重量％の過グルタル酸、１２重量％のグルタル酸、１６重量％の過酸化水素、２．４重量％の酸触媒、及び１．３重量％の安定剤（ジピコリン酸及び１−ヒドロキシエタン−１，１−ジホスホン酸）を含むｐＨ−０．２の平衡過グルタル酸濃厚液を得た。グルタル酸の過グルタル酸への転化率は６３％であった。<Reference Example 1>
25 g of glutaric acid, 40 ml of 35 wt% hydrogen peroxide, 1 ml of 95 wt% sulfuric acid, 0.1 g of dipicolinic acid, 1 ml of 60 wt% 1-hydroxyethane-1,1-diphosphonic acid are mixed and reacted for 2 days at room temperature 24% by weight perglutaric acid, 12% by weight glutaric acid, 16% by weight hydrogen peroxide, 2.4% by weight acid catalyst, and 1.3% by weight stabilizer (dipicolinic acid and 1% An equilibrated perglutaric acid concentrated solution having a pH of 0.2 containing -hydroxyethane-1,1-diphosphonic acid) was obtained. The conversion rate of glutaric acid to perglutaric acid was 63%.
＜参考例２＞
グルタル酸４ｇ、３５重量％過酸化水素４０ｍｌ、９５重量％硫酸１ｍｌ、ジピコリン酸０．１ｇ、６０重量％１−ヒドロキシエタン−１，１−ジホスホン酸１ｍｌを混合溶解し、室温にて２日間反応させることにより、５重量％の過グルタル酸、３重量％のグルタル酸、２９重量％の過酸化水素、３．４重量％の酸触媒、及び１．９重量％の安定剤を含む平衡過グルタル酸組成物を得た。グルタル酸の過グルタル酸への転化率は６０％であった。本組成物はそのまま用いる場合（すなわち５重量％の過グルタル酸の濃度）には平衡移動による過グルタル酸濃度低下は生起しないが、高い過酸化水素濃度により強い腐食性を有し非常に危険である。<Reference Example 2>
4 g of glutaric acid, 40 ml of 35% by weight hydrogen peroxide, 1 ml of 95% by weight sulfuric acid, 0.1 g of dipicolinic acid and 1 ml of 60% by weight 1-hydroxyethane-1,1-diphosphonic acid are mixed and reacted for 2 days at room temperature. Equilibrium superglutar containing 5% by weight perglutaric acid, 3% by weight glutaric acid, 29% by weight hydrogen peroxide, 3.4% by weight acid catalyst, and 1.9% by weight stabilizer. An acid composition was obtained. The conversion rate of glutaric acid to perglutaric acid was 60%. When this composition is used as it is (ie, a concentration of 5% by weight of perglutaric acid), it does not cause a decrease in the perglutaric acid concentration due to equilibrium transfer, but it is highly dangerous due to its strong corrosivity due to the high hydrogen peroxide concentration. is there.
＜参考例３＞
グルタル酸２５ｇ、１０重量％過酸化水素４０ｍｌ、９５重量％硫酸１ｍｌ、ジピコリン酸０．１ｇ、６０重量％１−ヒドロキシエタン−１，１−ジホスホン酸１ｍｌを混合溶解し、室温にて２日間反応させることにより、６重量％の過グルタル酸、３１重量％のグルタル酸、５重量％の過酸化水素、２．４重量％の酸触媒、及び１．３重量％の安定剤を含む平衡過グルタル酸組成物を得た。グルタル酸の過グルタル酸への転化率は１５％であった。本組成物はそのまま用いる場合（すなわち６重量％の過グルタル酸の濃度）には平衡移動による過グルタル酸濃度低下は生起しないが、グルタル酸の過グルタル酸への転化率が低いために経済性に劣る。<Reference Example 3>
25 g of glutaric acid, 40 ml of 10% by weight hydrogen peroxide, 1 ml of 95% by weight sulfuric acid, 0.1 g of dipicolinic acid, 1 ml of 60% by weight of 1-hydroxyethane-1,1-diphosphonic acid are mixed and reacted for 2 days at room temperature Equilibrium perglutaric acid containing 6% by weight perglutaric acid, 31% by weight glutaric acid, 5% by weight hydrogen peroxide, 2.4% by weight acid catalyst, and 1.3% by weight stabilizer. An acid composition was obtained. The conversion rate of glutaric acid to perglutaric acid was 15%. When this composition is used as it is (that is, a concentration of 6% by weight of perglutaric acid), a decrease in the concentration of perglutaric acid due to equilibrium transfer does not occur, but it is economical because the conversion rate of glutaric acid to perglutaric acid is low. Inferior to
＜実施例１〜１０、比較例１〜５＞
参考例１の組成物２ｍｌに精製水および２Ｎ−ＮａＯＨを合計８ｍｌ加え、表１に示す希釈液を得た。この希釈液を室温にて静置し、過グルタル酸濃度の経時変化を調べた結果も表１に示す。<Examples 1 to 10, Comparative Examples 1 to 5>
A total of 8 ml of purified water and 2N-NaOH were added to 2 ml of the composition of Reference Example 1 to obtain the diluted solutions shown in Table 1. Table 1 also shows the results of standing this diluted solution at room temperature and examining the change with time in the perglutaric acid concentration.
＜実施例１１、比較例６＞
実施例３、比較例１の希釈直後および希釈してから４、７、１４日後の組成物（過グルタル酸希釈液）を用いて、以下に示す方法で枯草菌芽胞およびクロコウジカビに対する殺菌試験を行なった。<Example 11, Comparative Example 6>
A bactericidal test against Bacillus subtilis spores and Aspergillus niger was performed using the composition (diluted perglutaric acid) immediately after dilution of Example 3 and Comparative Example 1 and 4, 7, and 14 days after the dilution, by the method shown below. I did it.
（１）菌液の調製
試験菌(i)：Bacillus subtilis subsp. subtillis NBRC 3134（枯草菌芽胞）
普通寒天培地［栄研化学株式会社製］で３５℃±１℃、７日間培養した試験菌の菌体を精製水に懸濁させ、７０℃±１℃、２０分間加熱し、栄養細胞を死滅させた。この懸濁液を遠心分離して上澄み液を除いた後、菌体を再度精製水に懸濁させ、１ｍｌ当たりの菌数が約１０8となるように調製し、菌液（芽胞液）とした。
試験菌(ii)：Aspergillus niger IFO 6341（クロコウジカビ）
試験菌をポテトデキストロース寒天培地［栄研化学株式会社製］で２５℃±１℃、７日間培養後、得られた胞子を０．０５％ポリソルベート８０溶液に浮遊させ、１ｍｌ当たりの胞子数が約１０8となるように調製し、菌液とした。(1) Preparation of bacterial solution Test bacteria (i): Bacillus subtilis subsp. Subtillis NBRC 3134 (Bacillus subtilis spores)
Suspended test cells cultured in normal agar medium (Eiken Chemical Co., Ltd.) at 35 ° C ± 1 ° C for 7 days in purified water and heated at 70 ° C ± 1 ° C for 20 minutes to kill vegetative cells I let you. After centrifuging this suspension to remove the supernatant, the cells are suspended again in purified water and prepared so that the number of bacteria per ml is about 10 8. did.
Test bacteria (ii): Aspergillus niger IFO 6341
After culturing the test bacteria on potato dextrose agar medium (Eiken Chemical Co., Ltd.) at 25 ° C. ± 1 ° C. for 7 days, the obtained spores were suspended in 0.05% polysorbate 80 solution, and the number of spores per ml was about 10 8 was prepared and used as a bacterial solution.
（２）殺菌試験
予め２０℃±１℃に保温した試験液５ｍｌに菌液０．０５ｍｌを添加、混合後、試験菌(i)はチオ硫酸ナトリウムを０．５％加えたＳＣＤＬＰ培地［栄研化学株式会社製］、試験菌(ii)はＧＰＬＰ培地［栄研化学株式会社製］１０ｍｌにそれぞれ接種した。
これらの培地を試験菌(i)は３５℃±１℃で４８時間培養、試験菌(ii)は２５℃±１℃で７日間培養後、培地の混濁の有無を肉眼で観察することにより菌の生死を判定した。また、添加菌液の生菌数を、試験菌(i)は標準寒天培地［栄研化学株式会社製］を用いた混釈平板培養法（３５℃±１℃、２日間培養）、試験菌(ii)はポテトデキストロース寒天培地［栄研化学株式会社製］を用いた混釈平板培養法（２５℃、７日間）により測定した。結果を表２に示す。(2) Bactericidal test 0.05 ml of the bacterial solution was added to 5 ml of the test solution previously kept at 20 ° C. ± 1 ° C. and mixed, and then the test strain (i) was an SCDLP medium containing 0.5% sodium thiosulfate [Eiken Chemical Co., Ltd.] and test bacteria (ii) were inoculated into 10 ml of GPLP medium [Eiken Chemical Co., Ltd.].
These culture media were cultured for 48 hours at 35 ° C. ± 1 ° C. for the test bacteria (i), and the test bacteria (ii) were cultured for 7 days at 25 ° C. ± 1 ° C. Judgment of life or death. In addition, the number of viable bacteria in the added bacterial solution, the test bacteria (i) is a pour plate culture method (35 ° C. ± 1 ° C., 2 days culture) using a standard agar medium [manufactured by Eiken Chemical Co., Ltd.] (ii) was measured by a pour plate culture method (25 ° C., 7 days) using a potato dextrose agar medium [Eiken Chemical Co., Ltd.]. The results are shown in Table 2.
＜実施例１２＞
参考例１で得られた組成物に１．４ｇのＮａＯＨを加えることにより２３重量％の過グルタル酸、１１．７重量％のグルタル酸、１５．７重量％の過酸化水素を含むｐＨ０．７の平衡過グルタル酸組成物を得た。得られた平衡過グルタル酸組成物を過グルタル酸濃度が５％となるように精製水で希釈したものの過グルタル酸濃度変化を表３に示す。<Example 12>
By adding 1.4 g of NaOH to the composition obtained in Reference Example 1, pH 0.7 containing 23% by weight perglutaric acid, 11.7% by weight glutaric acid, 15.7% by weight hydrogen peroxide. An equilibrium perglutaric acid composition was obtained. Table 3 shows changes in the concentration of perglutaric acid of the obtained equilibrium perglutaric acid composition diluted with purified water so that the perglutaric acid concentration becomes 5%.
＜比較例７＞
グルタル酸２５ｇ、３５重量％過酸化水素４０ｍｌ、９５重量％硫酸０．２ｍｌ、ジピコリン酸０．１ｇ、６０重量％１−ヒドロキシエタン−１，１−ジホスホン酸１ｍｌを混合溶解し、３５℃にて５日間反応させることにより、２２．５重量％の過グルタル酸、１４．２重量％のグルタル酸、１６．５重量％の過酸化水素を含むｐＨ０．１の平衡過グルタル酸組成物を得た。グルタル酸の過グルタル酸への転化率は５９％であった。得られた平衡過グルタル酸組成物を過グルタル酸濃度が５％となるように精製水で希釈したものの過グルタル酸濃度変化を表３に示す。
<Comparative Example 7>
Glutaric acid 25 g, 35 wt% hydrogen peroxide 40 ml, 95 wt% sulfuric acid 0.2 ml, dipicolinic acid 0.1 g, 60 wt% 1-hydroxyethane-1,1-diphosphonic acid 1 ml were mixed and dissolved at 35 ° C. By reacting for 5 days, an equilibrium perglutaric acid composition having a pH of 0.1 containing 22.5% by weight perglutaric acid, 14.2% by weight glutaric acid, and 16.5% by weight hydrogen peroxide was obtained. . The conversion rate of glutaric acid to perglutaric acid was 59%. Table 3 shows changes in the concentration of perglutaric acid of the obtained equilibrium perglutaric acid composition diluted with purified water so that the perglutaric acid concentration becomes 5%.
本発明の過グルタル酸希釈液の製造方法によれば、グルタル酸の過グルタル酸への転化速度及び転化率が高く、且つ希釈による過グルタル酸の濃度低下が遅いため、優れた殺菌消毒性能が長時間持続する過グルタル酸実用液を効率よく経済的に得ることができる。
本発明の平衡過グルタル酸組成物は、希釈しても過グルタル酸の濃度低下が遅いため、高い殺菌消毒性能が長時間持続する実用性に優れた過グルタル酸希釈液を得るための濃厚液として有用である。According to the method for producing a diluted solution of perglutaric acid of the present invention, the conversion rate and conversion rate of glutaric acid to perglutaric acid are high, and the concentration reduction of perglutaric acid due to dilution is slow. A practical perglutaric acid solution that lasts for a long time can be obtained efficiently and economically.
The balanced perglutaric acid composition of the present invention is a concentrated solution for obtaining a perglutaric acid diluted solution excellent in practicality that maintains a high disinfecting and disinfecting performance for a long time because the concentration decrease of the perglutaric acid is slow even when diluted. Useful as.
Claims (15)
（ａ）１０〜４５重量％の過グルタル酸、１〜３０重量％のグルタル酸、及び８〜５０重量％の過酸化水素を含有するｐＨ０．５未満の平衡過グルタル酸濃厚液を調製する調製工程、
（ｂ）前記平衡過グルタル酸濃厚液をｐＨ０．５以上に調整するｐＨ調整工程、及び
（ｃ）前記平衡過グルタル酸濃厚液を水で希釈する希釈工程。The manufacturing method of the dilute perglutaric acid liquid characterized by including the process (a)-(c) shown below.
(A) Preparation to prepare an equilibrium perglutaric acid concentrate having a pH of less than 0.5, containing 10 to 45% by weight perglutaric acid, 1 to 30% by weight glutaric acid, and 8 to 50% by weight hydrogen peroxide. Process,
(B) a pH adjusting step for adjusting the equilibrium perglutaric acid concentrated solution to a pH of 0.5 or more; and (c) a dilution step for diluting the balanced perglutaric acid concentrated solution with water.
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| PCT/JP2007/053886 WO2007102389A1 (en) | 2006-03-08 | 2007-03-01 | Process for producing dilute perglutaric acid solution |
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| US5683724A (en) * | 1993-03-17 | 1997-11-04 | Ecolab Inc. | Automated process for inhibition of microbial growth in aqueous food transport or process streams |
| JP3537540B2 (en) * | 1994-06-22 | 2004-06-14 | 日本パーオキサイド株式会社 | Aqueous solution containing perdicarboxylic acid |
| JPH11502500A (en) * | 1995-09-08 | 1999-03-02 | ザ、プロクター、エンド、ギャンブル、カンパニー | Method for producing aqueous composition comprising peracid |
| JP3710181B2 (en) * | 1995-12-20 | 2005-10-26 | 日本パーオキサイド株式会社 | Aqueous mold remover composition and two-part mold remover |
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