JP2014189494A - Sterilizing solution, sterilizing solution production apparatus, and sterilizing solution production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sterilizing solution of which decrease in sterilization performance of m-chloroperbenzoic acid (MCPBA) is suppressed by devising a solvent for dissolving MCPBA.SOLUTION: The sterilizing solution for sterilizing objects is composed by comprising MCPBA solution which is a solution in which MCPBA is dissolved into carboxylic acid. By dissolving MCPBA into carboxylic acid, the decrease in oxidation power of MCPBA can be suppressed. Further, by dissolving MCPBA solution and ozone into water, the synergistic effect between MCPBA and ozone enhances the sterilization performance of sterilizing solution as compared with the case where MCPBA alone is present in water and the case where ozone alone is present in water.

Description

  The present invention relates to a sterilizing solution for sterilizing an object, a sterilizing solution manufacturing apparatus, and a sterilizing solution manufacturing method.

  Conventionally, medical devices and the like are sterilized by irradiation with radiation or an electron beam (hereinafter simply referred to as radiation or the like). However, radiation or the like may adversely affect the human body. Therefore, in order to prevent leakage of radiation and the like to the outside, it is necessary to surround the periphery of the irradiation unit with a thick wall such as concrete, and the irradiation device for radiation and the like has been large and expensive.

  Therefore, a method using an m-chloroperbenzoic acid (MCPBA) aqueous solution is disclosed as a sterilization technique for medical devices (Patent Document 1). MCPBA has a strong oxidizing power and has a high bactericidal performance due to its strong oxidizing power. MCPBA is hardly soluble in water, but is soluble in water-soluble alcohols such as ethanol and glycol. For this reason, in the technique of Patent Document 1, when MCPBA is dispersed in water, an ethanol solution in which MCPBA is dissolved in ethanol is added to water.

JP 2003-146807 A

  However, the inventor of the present application has found that if the ethanol solution in which MCPBA is dissolved in ethanol is stored using the technique of Patent Document 1, the sterilization performance of MCPBA is reduced during the storage period. .

  Therefore, in view of such problems, the present invention devised a solvent that dissolves MCPBA to suppress a decrease in the sterilization performance of MCPBA, a sterilization solution production apparatus, and a sterilization solution production. It aims to provide a method.

  As a result of intensive studies, the inventor of the present application has found that when MCPBA and ethanol are mixed, MCPBA gradually oxidizes ethanol, and the oxidizing power of MCPBA gradually decreases with time. That is, the oxidizing power responsible for the sterilization performance of MCPBA is consumed by the oxidation of ethanol, and after mixing MCPBA and ethanol, that is, after the MCPBA ethanol solution is produced, as time passes, It was confirmed that the sterilization performance was lowered.

  Therefore, in order to solve the above-described problems, the sterilizing solution of the present invention is characterized by including an MCPBA solution which is an aqueous solution in which m-chloroperbenzoic acid is dissolved in carboxylic acid.

  The sterilizing solution may be an aqueous solution in which an MCPBA solution and ozone are dissolved in water.

  The carboxylic acid may be one or more selected from the group consisting of formic acid, acetic acid, and propionic acid.

  In order to solve the above-described problems, the sterilizing solution manufacturing apparatus of the present invention includes an MCPBA solution storage tank that stores an MCPBA solution that is a solution in which m-chloroperbenzoic acid is dissolved in carboxylic acid, and ozone is dissolved in water. An ozone water storage tank for storing ozone water and an MCPBA solution stored in the MCPBA solution storage tank are introduced into the ozone water storage tank to produce a sterilizing solution that is an aqueous solution in which the MCPBA solution and ozone are dissolved in water. And an introduction part.

  Moreover, it is good also as providing the ozone generation part which produces | generates ozone, and the bubbling part which manufactures ozone water by bubbling ozone in water in an ozone water storage tank.

  Moreover, it is provided with the ozone generation part which produces | generates ozone, and the ejector which manufactures ozone water by dissolving ozone in water, and the ozone water manufactured by the ejector is stored in an ozone water storage tank Also good.

  In order to solve the above-described problems, the method for producing a sterilizing solution of the present invention includes a step of dissolving m-chloroperbenzoic acid in carboxylic acid to produce an MCPBA solution, dissolving ozone in water, and adding ozone water. And a step of producing a sterilizing solution, which is an aqueous solution in which the MCPBA solution and ozone are dissolved in water, by mixing the MCPBA solution and ozone water.

  According to the present invention, by devising a solvent for dissolving m-chloroperbenzoic acid (MCPBA), it is possible to suppress a decrease in the sterilization performance of MCPBA.

It is a figure for demonstrating the time-dependent change of the abundance of m-chloro perbenzoic acid in ethanol. To explain the time course of the amount of m-chloroperbenzoic acid present in the m-chloroperbenzoic acid-ethanol solution and the amount of m-chloroperbenzoic acid present in the m-chloroperbenzoic acid-acetic acid solution over time FIG. It is a figure for demonstrating a disinfection solution manufacturing apparatus. It is a figure for demonstrating the bactericidal solution manufacturing apparatus concerning the modification 1. FIG. It is a figure for demonstrating the bactericidal solution manufacturing apparatus concerning the modification 2. FIG.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The dimensions, materials, and other specific numerical values shown in the embodiments are merely examples for facilitating the understanding of the invention, and do not limit the present invention unless otherwise specified. In the present specification and drawings, elements having substantially the same function and configuration are denoted by the same reference numerals, and redundant description is omitted, and elements not directly related to the present invention are not illustrated. To do.

(First embodiment)
FIG. 1 is a diagram for explaining the change with time of the abundance of m-chloroperbenzoic acid in ethanol. Two types of solutions (MCPBA-ethanol solutions) in which m-chloroperbenzoic acid (MCPBA) was dissolved in ethanol were produced, and changes with time in the amount of MCPBA were measured.

  More specifically, an MCPBA-ethanol solution having an MCPBA concentration of 0.15 g / mL (indicated by black circles in FIG. 1) and an MCPBA-ethanol solution having an MCPBA concentration of 0.075 g / mL (indicated by white squares in FIG. 1). ) And stored at 30 ° C., and the time course of the amount of MCPBA present was measured. Here, when the amount of MCPBA at the time of completion of the production of the MCPBA-ethanol solution is 1, 1 hour after the completion of production, 3 hours, 24 hours, 30 hours The amount of MCPBA present is measured.

  As shown in FIG. 1, it was found that the amount of MCPBA in the MCPBA-ethanol solution decreased as time passed from the completion of the production of the MCPBA-ethanol solution regardless of the concentration. Specifically, after 1 hour from the completion of the production of the MCPBA-ethanol solution, the abundance of MCPBA decreases to 0.9, after 3 hours it becomes 0.78, and after 24 hours it becomes 0.55. In addition, it was confirmed that after 30 hours, it decreased to 0.48.

…式（１） As the reason why the sterilization performance of MCPBA decreases in the MCPBA-ethanol solution, the inventor of the present application caused an oxidation reaction of ethanol and an oxidation reaction of acetaldehyde by the oxidation power of MCPBA as shown in the following formula (1). It was speculated that the hydroperoxy group responsible for oxidizing power was consumed in the oxidation reaction of ethanol and the oxidation reaction of acetaldehyde.

... Formula (1)

  Therefore, in this embodiment, MCPBA is dissolved in carboxylic acid to produce an MCPBA solution. By making the solvent for dissolving MCPBA a carboxylic acid that is not oxidized any more, it is possible to suppress a decrease in the oxidizing power of MCPBA. That is, since the hydroperoxy group of MCPBA is not consumed for the oxidation reaction of ethanol and the oxidation reaction of acetaldehyde, it is possible to prevent the sterilization performance of MCPBA from being lowered.

  Here, the carboxylic acid is, for example, one or more selected from the group of formic acid, acetic acid, and propionic acid, and among them, acetic acid that is inexpensive and easily available is preferable.

(Example)
A sterilizing solution (MCPBA-acetic acid solution) in which MCPBA was dissolved in acetic acid was used as carboxylic acid, and an MCPBA-ethanol solution as a comparative example was produced.

  FIG. 2 is a diagram for explaining the change over time of the amount of MCPBA in the MCPBA-ethanol solution and the amount of MCPBA in the MCPBA-acetic acid solution. An MCPBA-ethanol solution (indicated by black circles in FIG. 2) having an MCPBA concentration of 0.15 g / mL and an MCPBA-acetic acid solution (indicated by white squares in FIG. 2) having an MCPBA concentration of 0.15 g / mL were prepared. Stored at 0 ° C., the time course of the amount of MCPBA present was measured.

  Here, the amount of MCPBA present after 20 hours and 44 hours from the completion of production, assuming that the amount of MCPBA present at the time of completion of production of the MCPBA-ethanol solution and MCPBA-acetic acid solution is 1. Is measuring.

  As shown in FIG. 2, it was found that the MCPBA-acetic acid solution can suppress a decrease in the amount of MCPBA as compared with the MCPBA-ethanol solution. Specifically, in the MCPBA-ethanol solution, the abundance of MCPBA decreased to 0.63 after 20 hours from the completion of production and to 0.34 after 44 hours. On the other hand, in the MCPBA-acetic acid solution, the abundance of MCPBA was maintained at 0.96 even after 20 hours from the completion of production, and 0.92 after 44 hours. From the above results, it was confirmed that by dissolving MCPBA in acetic acid, a decrease in the amount of MCPBA, that is, a decrease in oxidizing power (bactericidal performance) can be suppressed.

(Second Embodiment)
In addition, the present inventor has found that sterilization performance is significantly improved by making MCPBA present in water together with ozone, as compared with the case where only ozone is present in water or the case where only MCPBA is present in water. It was.

…式（２）
本願発明者は、ＭＣＰＢＡとオゾンとを水中で共存させると、オゾンが有する酸化力によって、式（２）中破線で囲ったように、ＭＣＰＢＡから水酸化物イオン（ＯＨ⁻）が遊離すると推測した。そして、遊離した水酸化物イオンと、オゾンとがさらに反応して、ヒドロキシラジカル（ＯＨ・）が生成されると推測した。このようにして、生成されたヒドロキシラジカルが、ＭＣＰＢＡから水酸化物イオンを遊離したり、水酸化物イオンをヒドロキシラジカルにしたりするため、連鎖的にヒドロキシラジカルを生成できると推測される。 The following formula (2) is a formula for explaining a mechanism for improving the sterilization performance.

... Formula (2)
The inventors of the present application speculated that when MCPBA and ozone coexist in water, hydroxide ions (OH ⁻ ) are liberated from MCPBA as indicated by the broken line in formula (2) due to the oxidizing power of ozone. . And it estimated that the free hydroxide ion and ozone reacted further, and a hydroxy radical (OH *) was produced | generated. Thus, since the produced | generated hydroxyl radical liberates a hydroxide ion from MCPBA, or makes a hydroxide ion into a hydroxyl radical, it is estimated that a hydroxyl radical can be produced | generated in a chain.

  Further, MCPBA, which is perbenzoic acid (peracid), is an unstable substance, and generates hydrogen peroxide when decomposed to become metachlorobenzoic acid (MCBA) having no oxidizing power. At this time, hydrogen peroxide becomes a hydroxy radical in the presence of ozone, and exhibits oxidizing power.

  On the other hand, MCBA is known to become MCPBA again in the presence of ozone. Thus, due to the presence of ozone, MCPBA repeatedly changes from MCBA → MCPBA → MCBA. Therefore, hydrogen peroxide can be continuously generated in the process of this repeated change, and hydroxy radicals can be stably generated from the hydrogen peroxide. In such a system in which ozone is always supplied from the outside, a series of these reactions (repetitive changes between MCPBA and MCBA) occur continuously, and a stable oxidizing power can be exhibited. .

  As described above, by allowing ozone and MCPBA to coexist in water, hydroxy radicals can be generated in a chain. Since the hydroxy radical has a bactericidal performance, the bactericidal performance can be improved as compared with the case where only ozone is present in water or the case where only MCPBA is present in water.

  Therefore, the MCPBA solution (MCPBA-acetic acid solution) described in the first embodiment is used, and in the second embodiment, a sterilizing solution for sterilizing an object such as a medical device such as an endoscope is used as the MCPBA solution. And a solution in which ozone is dissolved.

  As described in the first embodiment, in the MCPBA solution, a decrease in the oxidizing power of MCPBA is hardly observed as compared with the MCPBA-ethanol solution. For this reason, MCPBA and ozone can be made to coexist in water, suppressing the fall of the oxidizing power of MCPBA to the minimum by using the bactericidal solution which dissolved MCPBA solution and ozone in water. Therefore, the sterilization performance of the sterilization solution can be improved by the synergistic effect of the sterilization performance of MCPBA and the sterilization performance of ozone.

  Then, the sterilization solution manufacturing apparatus which manufactures the said sterilization solution is demonstrated.

(Sterilizing solution manufacturing apparatus 100)
FIG. 3 is a diagram for explaining the sterilizing solution manufacturing apparatus 100. As shown in FIG. 3, the sterilizing solution manufacturing apparatus 100 includes an MCPBA solution storage tank 102, an introduction part 104, an oxygen cylinder 110, an ozone generation part 114, a valve 116, an ozone water storage tank 120, and a bubbling part. 130, an ozone decomposition unit 140, a valve 142, and a blower 144.

  The MCPBA solution storage tank 102 stores an MCPBA solution (for example, the MCPBA-acetic acid solution) which is a solution in which MCPBA is dissolved in carboxylic acid.

  The introduction unit 104 is constituted by a pump, for example, and sends the MCPBA solution stored in the MCPBA solution storage tank 102 to an ozone water storage tank 120 described later.

The ozone generator 114 is a so-called ozonizer, and forms a discharge space by applying a predetermined voltage. When oxygen (O ₂ ) is supplied from the oxygen cylinder 110 to this discharge space, oxygen is activated and becomes ozone (O ₃ ). The ozone generated by the ozone generator 114 is sent to the bubbling unit 130 through the valve 116.

  Water is supplied to the ozone water storage tank 120 by supply means (not shown). The bubbling unit 130 bubbles ozone into water (supplying ozone as fine bubbles) in the ozone water storage tank 120. Ozone water in which ozone is dissolved in water can be easily manufactured by the configuration including the bubbling unit 130.

  When the MCPBA solution is introduced into the ozone water storage tank 120 by driving the introduction unit 104, the ozone water stored in the ozone water storage tank 120 and the MCPBA solution are mixed to produce the sterilization solution 122. The Rukoto.

  The ozone decomposing unit 140 is composed of a catalyst that decomposes ozone, and cannot completely dissolve in the sterilizing solution 122, and decomposes ozone introduced from the ozone water storage tank 120 through the valve 142. Exhaust gas generated by decomposing ozone by the ozone decomposing unit 140 is discharged to the outside by the blower 144.

  As described above, according to the sterilizing solution manufacturing apparatus 100 according to the present embodiment, it is possible to efficiently manufacture a sterilizing solution having a high sterilizing effect.

(Modification 1)
FIG. 4 is a diagram for explaining the sterilizing solution manufacturing apparatus 200 according to the first modification. As shown in FIG. 4, the sterilizing solution manufacturing apparatus 200 includes an MCPBA solution storage tank 102, an introduction part 104, an oxygen generation part 210, a pump 212, an ozone generation part 114, a valve 116, and an ozone water storage tank. 120, a bubbling unit 130, an ozonolysis unit 140, a valve 142, and a blower 144. The MCPBA solution storage tank 102, the introduction part 104, the ozone generation part 114, the valve 116, the ozone water storage tank 120, the bubbling part 130, the ozone decomposition part 140, the valve 142, and the blower 144 are the same as those in the sterilization solution manufacturing apparatus 100 described above. Since the functions are substantially the same as those of the constituent elements, the same reference numerals are assigned and redundant description is omitted. Here, the oxygen generator 210 and the pump 212 having different configurations will be mainly described.

  The oxygen generator 210 is, for example, a PSA (Pressure Swing Adsorption) type oxygen separator, and separates and collects oxygen from the air pumped by the pump 212. The oxygen collected in the oxygen generator 210 is sent to the ozone generator 114.

  Thus, according to the sterilizing solution manufacturing apparatus 200 according to the first modification, oxygen (ozone) can be generated from the air without the oxygen cylinder 110, so that the cost required for oxygen can be reduced. Become.

(Modification 2)
FIG. 5 is a diagram for explaining the sterilizing solution manufacturing apparatus 300 according to the second modification. As shown in FIG. 5, the sterilizing solution manufacturing apparatus 300 includes an MCPBA solution storage tank 102, an introduction unit 104, an oxygen cylinder 110, an ozone generation unit 114, a pump 310, an ejector 312, and a concentration measurement unit 320. The ozone control unit 330, the ozone water storage tank 120, the ozone decomposition unit 140, the valve 142, and the blower 144 are configured. Note that the MCPBA solution storage tank 102, the introduction unit 104, the oxygen cylinder 110, the ozone generation unit 114, the ozone water storage tank 120, the ozone decomposition unit 140, the valve 142, and the blower 144 are configured in the sterilization solution manufacturing apparatus 100 described above. Since the functions are substantially the same as those of the elements, the same reference numerals are assigned and redundant description is omitted. Here, the pump 310, the ejector 312, the concentration measuring unit 320, and the ozone control unit 330 having different configurations will be mainly described. .

  The pump 310 circulates water or ozone water to the ozone water storage tank 120. The pump 310 circulates water or ozone water to the ozone water storage tank 120 through a circulation path 310a in which an ejector 312 described later is disposed, or water through a circulation path 310b in which a concentration measuring unit 320 described later is disposed. Or ozone water is circulated through the ozone water storage tank 120.

  The ejector 312 is provided on the circulation path 310a, and dissolves ozone supplied from the ozone generator 114 in water.

  The concentration measuring unit 320 is provided on the circulation path 310b and measures the ozone concentration (dissolved ozone concentration) in the ozone water flowing through the circulation path 310b.

  The ozone control unit 330 is composed of a semiconductor integrated circuit including a CPU (Central Processing Unit), reads programs and parameters for operating the CPU itself from the ROM, and cooperates with the RAM as a work area and other electronic circuits. Thus, the entire sterilizing solution manufacturing apparatus 300 is managed and controlled.

  In Modification 2, the ozone control unit 330 controls the ozone generation unit 114 based on the ozone concentration measured by the concentration measurement unit 320, and adjusts the amount of ozone generated by the ozone generation unit 114.

  As described above, the sterilizing solution manufacturing apparatus 300 according to the modification 2 can maintain the ozone concentration in the sterilizing solution at a concentration suitable for sterilization by the configuration including the concentration measuring unit 320 and the ozone control unit 330. it can.

  In the sterilizing solution manufacturing apparatus 300 illustrated in FIG. 5, the configuration in which oxygen is supplied from the oxygen cylinder 110 to the ozone generation unit 114 has been described. However, instead of the oxygen cylinder 110, an oxygen generation unit 210 and a pump 212 are provided. In addition, oxygen may be supplied from the oxygen generation unit 210 and the pump 212 to the ozone generation unit 114.

(Sterilizing solution manufacturing method)
Then, the sterilization solution manufacturing method concerning 2nd Embodiment is demonstrated. The sterilizing solution manufacturing method of this embodiment includes three steps. MCPBA is dissolved in carboxylic acid to produce an MCPBA solution that is a solution (MCPBA solution production process), and ozone is dissolved in water to produce ozone water (ozone water production process). The MCPBA solution manufacturing process and the ozone water manufacturing process are preferably processed in parallel, but may be processed in time series. And the MCPBA solution manufactured in the MCPBA solution manufacturing process and the ozone water manufactured in the ozone water manufacturing process are mixed to manufacture a sterilizing solution.

  As described above, according to the sterilizing solution manufacturing method according to the present embodiment, by devising a solvent that dissolves m-chloroperbenzoic acid (MCPBA), it is possible to suppress a decrease in the sterilizing performance of MCPBA. . Moreover, since a sterilization solution is manufactured using the MCPBA solution manufactured in this way, a sterilization solution having a high sterilization effect can be efficiently manufactured.

  As mentioned above, although preferred embodiment of this invention was described referring an accompanying drawing, it cannot be overemphasized that this invention is not limited to this embodiment. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the claims, and these are naturally within the technical scope of the present invention. Is done.

  For example, in the above-described embodiment, the sterilizing solution manufacturing apparatus 100, 200, 300 and the sterilizing solution manufacturing method for manufacturing the sterilizing solution by mixing the MCPBA solution and the ozone water have been described. However, the order of mixing is not limited as long as a sterilizing solution that is an aqueous solution in which MCPBA solution and ozone are dissolved in water can be produced. For example, the MCPBA solution may be dissolved in water to produce an MCPBA aqueous solution and stored in a storage tank, and ozone may be dissolved in the MCPBA aqueous solution in the storage tank to manufacture the sterilizing solution.

  INDUSTRIAL APPLICABILITY The present invention can be used for a sterilizing solution for sterilizing an object, a sterilizing solution manufacturing apparatus, and a sterilizing solution manufacturing method.

100, 200, 300 Sterilization solution manufacturing apparatus 102 MCPBA solution storage tank 104 Introduction part 114 Ozone generation part 120 Ozone water storage tank 130 Bubbling part 312 Ejector

Claims (7)

  A bactericidal solution comprising an MCPBA solution which is a solution of m-chloroperbenzoic acid dissolved in a carboxylic acid.   The sterilizing solution according to claim 1, wherein the sterilizing solution is an aqueous solution in which the MCPBA solution and ozone are dissolved in water.   The sterilizing solution according to claim 1 or 2, wherein the carboxylic acid is one or more selected from the group consisting of formic acid, acetic acid, and propionic acid. an MCPBA solution storage tank for storing an MCPBA solution that is a solution of m-chloroperbenzoic acid dissolved in carboxylic acid;
An ozone water storage tank for storing ozone water in which ozone is dissolved in water;
Introducing the MCPBA solution accommodated in the MCPBA solution storage tank into the ozone water storage tank to produce a sterilizing solution that is an aqueous solution in which the MCPBA solution and ozone are dissolved in water;
An apparatus for producing a sterilizing solution, comprising: An ozone generator for generating ozone;
In the ozone water storage tank, a bubbling unit for producing ozone water by bubbling the ozone into water,
The sterilizing solution manufacturing apparatus according to claim 4, comprising: An ozone generator for generating ozone;
An ejector for producing ozone water by dissolving the ozone in water;
With
The sterilizing solution production apparatus according to claim 4, wherein ozone water produced by the ejector is stored in the ozone water storage tank. dissolving m-chloroperbenzoic acid in carboxylic acid to produce an MCPBA solution;
Dissolving ozone in water to produce ozone water;
Mixing the MCPBA solution and the ozone water to produce a bactericidal solution that is an aqueous solution in which the MCPBA solution and ozone are dissolved in water;
A method for producing a sterilizing solution, comprising:

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