JP2022182924A - Composition for preparing aqueous chlorous acid - Google Patents

Abstract

To provide removal means effective for pathogens such as fungi.SOLUTION FOR THE PROBLEM: The pH of aqueous hypochlorous acid is adjusted to 5 to 7.5. The concentration of free chlorine molecules is made lower in comparison with the amount of effective chlorine. This is oxidized to make aqueous chlorous acid.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a chlorite water for sterilization and a composition for producing the chlorite water, and more particularly to a composition for microbial decontamination and bleaching with excellent storage stability.

Decontamination of pathogens such as viruses, bacteria, and fungi is an important technology for prognosis and prevention of infectious diseases caused by pathogens. This has been done with disinfectants. However, no method for safely sterilizing the entire room has been known so far, and a method of spraying electrolytic hypochlorous acid is known, but for non-ionizing hypochlorous acid, sodium chloride Although generated by electrolysis of an aqueous solution, it is also known that the non-ionized hypochlorous acid water thus generated exists only temporarily and immediately decomposes into chlorine and water. For this reason, the development of toxicity due to chlorine has become a problem. On the other hand, gaseous chlorine dioxide is also an effective disinfectant, but it also presents safety concerns and limits on its use. Furthermore, chlorous acid produced by dissolving chlorine dioxide in water had the same effect as chlorine dioxide, but it decomposed into chlorine dioxide and hypochlorous acid, so there were problems in stability and effect.

In addition, tablets using trichloroisocyanuric acid, which generate non-electrolyzed, non-ionizing hypochlorous acid with excellent bactericidal action without exhibiting the toxicity of hypochlorous acid or its salts so much when used, and A method has been developed in which the liquid generated by dissolving the is dissolved in water is converted into a dry mist and used for sterilization of a wide area (see, for example, Patent Documents 1 and 2). Moreover, trichloroisocyanuric acid is already known to be applied to disinfectants (see, for example, Patent Documents 3, 4, 5, and 6). Furthermore, it is also known that chlorinated isocyanuric acids, mainly dichloroisocyanuric acid, have deodorizing and bactericidal effects (see Patent Documents 7, 8, 9, 10, and 11). Furthermore, a technology has been developed to improve safety and effectiveness by making these hypochlorous acids non-electric field type in an aqueous solution (see Patent No. 12).

In addition, the technique of reacting chlorous acid and dichloroisocyanuric acid is already known (see Patent 13), and it is also known that such chlorine dioxide is useful for preventing infection (Patent 14, non-patent literature 1).

Moreover, no information is known about non-ionizing chlorous acid, nor is it known that such non-ionizing chlorous acid has an excellent bactericidal action.

Japanese Patent Application No. 2018-047511 Japanese Patent Application No. 2018-047512 JP 2019-089781 A JP 2019-076821 A JP 2019-004413 A JP 2018-162232 A JP-A-2000-247806 Japanese Patent Application Laid-Open No. 2001-300545 JP-A-09-208107 JP-A-10-168425 Japanese Patent Application Laid-Open No. 2002-172155 Japanese Patent No. 6871663 JP 2015-167861 A JP 2013-501146 A

Hitoshi Akai et al., "Air and Sanitary Engineering Papers" Vol.122, 2007, 1-6

The present invention has been made under such circumstances, and an object of the present invention is to provide an effective and safe means for removing pathogens.

In view of this situation, as a result of extensive research efforts in search of effective and safe removal means for pathogens, the present inventors have found that non-ionizing chlorous acid has excellent microbial removal ability and safety. It was found that the

The reason why such non-ionizing chlorous acid exhibits an effective sterilization effect without showing toxicity is that the sterilization effect is in the non-ionizing chlorous acid itself, and chlorine molecules and activity This is because it does not depend on oxygen. Furthermore, due to its high stability, highly toxic free chlorine molecules are less likely to occur. Non-ionizing chlorous acid is stabilized by a buffer salt so that the hydrogen ions are not ionized, and the hydrogen atoms in such chlorous acid exhibit properties similar to hydroxyl groups together with oxygen atoms rather than acid properties. Become. The present inventors have found that such chlorous acid produces less chlorine molecules and less chlorine dioxide.
In addition, the present inventors have found that the decontamination effect against pathogens is higher than that of sodium hypochlorite and electrolytic hypochlorous acid water, which contain chlorine molecules as active ingredients. It has also been found that there is a large difference in toxicity to pathogens.

Therefore, when using chlorous acids, the amount of such non-ionizing chlorous acid present relative to chlorine molecules is an indicator of whether it can be used safely and effectively. There are no published materials addressing the

In view of this situation, as a result of extensive research efforts in search of an effective and safe removal method for pathogens, we have found that the main component is non-ionizing chlorous acid, and the content of free chlorine molecules is low. It was found that such an object can be achieved by discriminating and using chloric acid water.

The present invention has been completed based on the findings first discovered by the inventors described above. That is, the present invention for solving the above problems is as shown below.

<1> A chlorous acid water having a pH of 5 to 7.5 and having a concentration of free chlorine molecules lower than the amount of available chlorine.
<2> The hypochlorous acid water according to <1>, which has a pH of 5 to 7.5 and a concentration of free chlorine molecules of 10 ppm or less.
<3> The hypochlorous acid water according to <3>, wherein the upper limit of determination is 10 ppm.
<4> The chlorous acid water according to any one of <1> to <3>, wherein the concentration of chlorous acid is 50 to 500 ppm.
<5> The chlorous acid water according to any one of <1> to <4>, characterized by containing a buffer salt.
<6> Obtained by oxidizing hypochlorous acid generated by hydrolysis of one or more selected from trichloroisocyanuric acid, dichloroisocyanuric acid and salts thereof in the presence of a buffer salt. , The chlorous acid water according to any one of <1> to <5>.
<7> 1) one or more selected from trichloroisocyanuric acid, dichloroisocyanuric acid, and salts thereof, and 2) a buffer salt are stirred and mixed for 5 minutes or longer to obtain a composition that is transferred to an aqueous medium. The chlorous acid water according to any one of <1> to <6>, which is obtained by oxidizing hypochlorous acid water produced by diluting with an oxidizing agent.
<8> The chlorous acid water according to any one of <1> to <8>, wherein the contained chlorous acid is electrolytic chlorous acid or non-electrolyzed chlorous acid.
<9> The chlorous acid water according to any one of <1> to <8>, wherein the concentration of free chlorine molecules is 0.1 times or less that of hypochlorous acid.
<10> The chlorous acid water according to any one of <1> to <9>, wherein the oxidizing agent is a hydrogen peroxide solution.
<11> A test paper for determining the effect and toxicity of chlorous acid, comprising a test piece for measuring the effective chlorine concentration, a test piece for measuring the pH, and a test piece for measuring the concentration of free chlorine molecules independently. Prepared test paper.
<12> The test paper according to <11>, which is used to determine whether the test paper corresponds to the chlorous acid water according to any one of <1> to <10>.
<13> The test piece for measuring the available chlorine concentration is a test piece for measuring the available chlorine amount by the KI method or a test piece for measuring the available chlorine amount by the DPD method, and a test piece for measuring the molecular weight of free chlorine. The test paper according to <11> or <12>, wherein is a Schillingaldazine test piece.
<14> Attached is a comparative color chart indicating that the preferred ranges for the test paper are 50 to 500 ppm for the concentration of chlorous acid, 5 to 7 for pH, and 0 to 10 ppm for free chlorine molecules. The test paper according to any one of <10> to <13>.
<15> The test paper according to any one of <10> to <14>, wherein the chlorous acid to be determined is electrolytic chlorous acid or non-electrolytic chlorous acid.
<16> Any one of <10> to <15>, wherein the hypochlorous acid to be identified is obtained by hydrolyzing dichloroisocyanurate or trichloroisocyanuric acid in the presence of a buffer salt. The test paper described in .
<17> A chlorous acid water determined to be effective and highly safe by the test paper according to any one of <10> to <16>.
<18> The test paper according to any one of <10> to <16> has a pH of 5 to 7 and a concentration of free chlorine molecules of 0 to 10 ppm, so that it is effective and safe. The chlorous acid water according to <17>, which is determined to be high.
<19> The test paper according to any one of <10> to <16> shows that the concentration of chlorous acid is 50 to 500 ppm, the pH is 5 to 7.5, and the concentration of free chlorine molecules is 10 ppm or less. Chlorous acid water that is determined to be.
<20> The chlorous acid water according to <18> or <19>, wherein the concentration of free chlorine molecules is determined colorimetrically within 2 seconds of contact with the Syringaldazine reagent.
<21> The chlorous acid water according to <20>, wherein the chlorous acid water according to <20> does not exhibit coloration indicating the upper limit of quantitative determination within 2 seconds when contacted with Schillingaldazine test paper.
<22> The chlorous acid water according to any one of <1> to <10> and <17> to <21>, which is used for decontamination of pathogenic microorganisms.
<23> The chlorous acid water according to <22>, wherein the pathogenic microorganism is a fungus.
<24> The chlorous acid water according to <23>, wherein the fungus is yeast.
<25> The chlorous acid water according to any one of <1> to <10> and <17> to <24>, which is used by spraying.
<26> (1) 1) one or more selected from trichloroisocyanuric acid, dichloroisocyanuric acid and salts thereof, 2) a composition containing a buffer salt, and (2) a hydrogen peroxide solution A chlorous acid generation system.
<27> A composition containing 1) one or more selected from trichloroisocyanuric acid, dichloroisocyanuric acid, and salts thereof, and 2) buffer salt is diluted with an aqueous medium, and aqueous hydrogen peroxide is added. A chlorous acid generation system capable of preparing the chlorous acid water according to any one of <1> to <10> and <17> to <25> when oxidized with
<28> A composition containing 1) one or more selected from trichloroisocyanuric acid, dichloroisocyanuric acid, and salts thereof, and 2) a buffer salt is diluted with an aqueous medium, and hydrogen peroxide solution is added. The chlorous acid generation system according to <25>, which can prepare the chlorous acid water according to any one of <1> to <10> and <17> to <25> when oxidized with .
<29> The dilution includes 1) one or more selected from trichloroisocyanuric acid, dichloroisocyanuric acid, and salts thereof, and 2) a buffer salt of 100 to 10,000 times the mass of the composition. The chlorous acid generation system according to <27> or <28>, which is diluted with an aqueous medium.
<30> 1) trichloroisocyanuric acid, dichloroisocyanuric acid, and 10% by mass or more of one or more selected from salts thereof, and 2) 10% by mass or more of a buffer salt. The chlorous acid generation system according to any one of <26> to <29>.
<31> (1) 1) 1 or 2 or more selected from trichloroisocyanuric acid, dichloroisocyanuric acid and salts thereof, and 2) a buffer salt are stirred and mixed for 5 minutes or more. The chlorous acid generation system according to any one of <26> to <30>, wherein the composition is dissolved in an aqueous carrier and (2) oxidized with hydrogen peroxide.
<32> When diluted with an aqueous medium, the pH is 5 to 7.5, the concentration of hypochlorous acid is 50 to 500 ppm, the concentration of free chlorine molecules is less than the concentration of available chlorine, and the free chlorine molecules concentration is 20 ppm or less, and the active ingredient is non-ionizing hypochlorous acid, a composition capable of preparing hypochlorous acid water, and hydrogen peroxide water.
A composition comprising 1) one or more selected from trichloroisocyanuric acid, dichloroisocyanuric acid and salts thereof, and 2) a buffer salt (provided that both the aqueous medium and the composition contain an alkali metal or does not contain alkaline earth metal chlorite.).
<33> The chlorous acid generation system according to <32>, wherein the concentration of the free chlorine molecules is 10 ppm or less.
<34> The chlorous acid generation system according to <32> or <33>, wherein the concentration of the free chlorine molecules is 0.1 times or less the concentration of the hypochlorous acid. .
<35> Any one of <32> to <34>, wherein the concentration of free chlorine molecules is determined by colorimetry within a contact time of 2 seconds with the Syringaldazine reagent. The chlorous acid generation system described.
<36> The chlorine concentration according to any one of <32> to <35>, characterized in that the available chlorine concentration is quantified with a test piece by the KI method or the SMT method. Acid generating system.
<37> A chlorous acid generating system characterized by dissolving chlorite with a buffer salt and adjusting the pH of an aqueous phosphoric acid solution or an aqueous citric acid solution.
<38> The chlorous acid generation system according to any one of <32> to <36>, wherein the chlorous acid water is used for decontamination of fungi.

According to the system comprising the chlorinated water of the present invention, the composition for generating it, and an oxidizing agent such as hydrogen peroxide, it is possible to provide a safe and effective means for removing pathogens such as fungi. Also, the test strip of the present invention can provide means for determining such effective and safe removal means.

1 is a diagram showing a test paper of Example 1. FIG. 1 represents a strip of KI method test strip, 2 a strip of pH test strip, and 3 a strip of Syringaldazine test strip. FIG. 10 is a diagram showing a color chart for discriminating test paper; Appropriate numerical values are enclosed in ellipses.

<Hypochlorous acid water for generating chlorous acid>
Hypochlorous acid water constituting the system of the present invention has a pH of 5 to 7.5. It is more preferably pH 6 or higher, and still more preferably pH 6.3 or higher. In addition, the hypochlorous acid of the present invention preferably has a pH of 7.3 or less, more preferably a pH of 7 or less. The pH value can be measured with a commercially available pH meter or pH test paper.

The concentration of free chlorine molecules of hypochlorous acid used in the present invention is lower than the effective chlorine concentration, specifically 20 ppm or less, preferably 10 ppm or less, more preferably 9 ppm or less, and still more preferably 8 ppm. Below, more preferably 7 ppm or less, more preferably 6 ppm or less, still more preferably 5 ppm or less, still more preferably 4 ppm or less, still more preferably 3 ppm or less, still more preferably 2 ppm or less, still more preferably 1 ppm or less. The concentration of free chlorine molecules in the hypochlorous acid of the present invention may be 0 ppm. This is because the active ingredient of conventional hypochlorous acid is free chlorine molecules, whereas the hypochlorous acid of the present invention is non-ionized hypochlorous acid itself. Accordingly, the chlorous acid derived as described below is also non-ionized and has an extremely low concentration of free chlorine molecules.

The concentration of free chlorine molecules can be measured with a Syringaldazine reagent. Syringaldazine reacts with both molecular chlorine and chlorine bonded to molecules such as non-ionized hypochlorous acid, and there is a difference in reactivity with both. , and then reacts with bound chlorine to develop color. Specifically, it develops color against molecular chlorine in about 1 to 2 seconds, and then reacts with combined chlorine in 3 seconds or more. In other words, the molecular chlorine concentration in the hypochlorous acid water can be known from the color development within 2 seconds after contact. In non-ionized chlorous acid, syringaldazine does not cause a color reaction due to the strong bond between oxygen and chlorine. In other words, the production of non-ionized chlorous acid can be confirmed by not exhibiting a color reaction with syringaldazine.

Further, the hypochlorous acid water used in the present invention may be an embodiment that does not exhibit coloration indicating the upper limit of quantitative determination within 2 seconds when it is brought into contact with Schillingaldazine test paper. As described above, according to the Schillingaldazine test paper, the concentration of molecular chlorine can be known from the color development within 2 seconds after contact. The quantification limit by coloration of commercially available Schillingaldazine test paper (manufactured by Nissan Chemical Industries, Ltd., "residual chlorine test paper Aquacheck 3") is 10 ppm. Therefore, if the hypochlorous acid water does not show coloration indicating the upper limit of determination within 2 seconds when the hypochlorous acid water is brought into contact with the Schillingaldazine test paper, the free chlorine concentration of the hypochlorous acid water is 10 ppm or less. It can be said that there is.

In a preferred embodiment of the present invention, the concentration of hypochlorous acid, which is induced to chlorous acid, is preferably 10 ppm or more, more preferably 20 ppm or more, even more preferably 50 ppm or more, still more preferably 100 ppm or more, and more preferably is 150 ppm or more.
Also, in a preferred embodiment of the present invention, the concentration of hypochlorous acid is preferably 500 ppm or less, more preferably 200 ppm or less, even more preferably 300 ppm or less, even more preferably 500 ppm or less.

The concentration of free chlorine molecules is preferably 0.1 times or less, more preferably 0.05 times or less, and more preferably 0.02 times or less that of hypochlorous acid.

The hypochlorous acid contained in the hypochlorous acid water may be either ionizing hypochlorous acid or non-ionizing hypochlorous acid. An embodiment containing non-ionizing hypochlorous acid is preferred. In a more preferred embodiment, the concentration of non-ionizing hypochlorous acid is within the above preferred hypochlorous acid concentration range.

In a preferred embodiment of the invention, the hypochlorous acid water used in the invention contains a buffer salt. Examples of buffer salts include isocyanuric acid obtained by decomposing dichloroisocyanuric acid and trichloroisocyanuric acid, hydrogencarbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate, citric acid, citrates such as sodium citrate, and phosphoric acid. Preferred examples include phosphates such as disodium hydrogen and monosodium dihydrogen phosphate, lactates such as boric acid, lactic acid, and sodium lactate. Salts of strong acids and strong bases, such as sodium sulfate, potassium sulfate, and sodium chloride, are also classified as buffer salts because they stabilize the system.

The hypochlorous acid water used for generating chlorous acid of the present invention contains 1) one or more selected from trichloroisocyanuric acid, dichloroisocyanuric acid and salts thereof, and 2) a buffer salt. The composition comprising can be prepared by diluting with an aqueous medium. On the other hand, the chlorous acid of the present invention can be derived by adding hydrogen peroxide to a final concentration similar to that of hypochlorous acid.

A composition obtained by stirring and mixing the above components 1) and 2) for preferably 5 minutes or more, more preferably 6 minutes or more, still more preferably 7 minutes or more, still more preferably 8 minutes or more, still more preferably 9 minutes or more. A preferred embodiment is hypochlorous acid water produced by diluting a substance with an aqueous medium. Water or an aqueous solution can be exemplified as the aqueous medium, and an acidic aqueous solution can be suitably exemplified as the aqueous solution. The stirring and mixing may be carried out by any known means, but stirring and mixing by a Henschel mixer can be preferably exemplified.
Other details of the composition will be described later.

The chlorous acid water of the present invention is preferably used for decontamination of pathogenic microorganisms such as fungi. In particular, it is preferably used for decontamination of fungi, more specifically yeasts. Since it can also remove yeasts that make spores and are difficult to remove, it can also be used to remove spore-forming bacteria, bacteria, and viruses. Since it is non-ionizing, it is highly effective and has low biotoxicity.

The chlorous acid water of the present invention is preferably in the form of being sprayed. A spraying means is not particularly limited. It may be sprayed by a pump spray, or may be sprayed in the form of a dry mist by an ultrasonic atomizer. Space disinfection is possible with chlorous acid water provided in the form of a spray.

<Composition>
The present invention also includes a composition capable of preparing hypochlorous acid water.
One embodiment of the present invention is a composition comprising 1) one or more selected from trichloroisocyanuric acid, dichloroisocyanuric acid and salts thereof, and 2) a buffer salt, and an oxidizing substance such as It consists of hydrogen peroxide. That is, after the composition is dissolved in an aqueous carrier to generate hypochlorous acid, it can be derived into chlorous acid by adding an oxidizing substance such as hydrogen peroxide. Such non-ionized chlorous acid does not show a color reaction with syringaldazine, but shows a color reaction by the KI method.

Also, in one embodiment of the present invention, the composition is capable of preparing hypochlorous acid water of the constituent elements of the present invention described above when diluted with an aqueous medium. Specifically, the present invention provides a composition comprising 1) one or more selected from trichloroisocyanuric acid, dichloroisocyanuric acid and salts thereof, and 2) a buffer salt, wherein 3) an aqueous medium A composition having a pH of 5 to 7.5 when diluted with 4) a free chlorine concentration of 10 ppm or less is also a component.
From the viewpoint of maximizing the effect of non-ionizing chlorous acid as an active ingredient, the composition used for chlorite acidity of the present invention is an alkali metal chlorite and an alkaline earth metal chlorite. preferably does not contain

Water or an aqueous solution can be exemplified as the aqueous medium, and an acidic aqueous solution can be suitably exemplified as the aqueous solution. Further, the dilution rate with the aqueous medium is preferably 100 times by mass or more, more preferably 200 times by mass or more, and further preferably 500 times by mass or more. Further, the dilution rate with the aqueous medium is preferably 10,000 times or less, more preferably 8,000 times or less, still more preferably 6,000 times by mass or less, still more preferably 4,000 times by mass or less, still more preferably 2,000 times by mass or less, further preferably 1,000 times. It can be less than twice the mass.
From the viewpoint of maximizing the effect of non-ionizing hypochlorous acid as an active ingredient, the aqueous medium preferably does not contain alkali metal hypochlorite and alkaline earth metal hypochlorite. .

In one embodiment, a composition containing 1) one or more selected from trichloroisocyanuric acid, dichloroisocyanuric acid and salts thereof, and 2) a buffer salt, and 3) 500 times by mass of water and 4) oxidizing a virus decontamination composition having a free chlorine concentration of 10 ppm or less.

As described above, the gist of the present invention is to provide a stable, easy-to-use, and highly safe composition for removing pathogenic microorganisms. As a method for realizing this, trichloroisocyanuric acid, dichloroisocyanuric acid and one or more of their salts are formulated with a buffer salt, and if necessary, dissolved in water at the time of use, non-ionizing hypochlorite It is preferred to generate an acid followed by oxidation with an oxidizing substance such as hydrogen peroxide.
Conversely, a chlorite such as sodium chlorite is dissolved in an aqueous carrier together with a buffer salt, and then the pH is adjusted with an aqueous solution of an organic acid such as phosphoric acid or citric acid. Can produce chlorous acid. Such technology also belongs to the present invention.

The chlorous acid generated in this way is applied to decontamination of pathogenic microorganisms as a non-ionizing aqueous solution. The requirements that such an aqueous solution should have are the following two points (i) and (ii).

(i) pH 5 to 7.5;
The pH is preferably 6 or more, more preferably 6.3 or more. Also, the pH is preferably 7.3 or less, more preferably 7 or less.

(ii) 10 ppm or less when the concentration of free chlorine molecules is 20 ppm or less;
The concentration of free chlorine molecules is preferably 9 ppm or less, more preferably 8 ppm or less, still more preferably 7 ppm or less, still more preferably 6 ppm or less, still more preferably 5 ppm or less, still more preferably 4 ppm or less, still more preferably 3 ppm or less, and further preferably It is preferably 2 ppm or less, more preferably 1 ppm or less. Also, the concentration of free chlorine molecules may be 0 ppm.
Moreover, in terms of the relationship with the effective chlorine concentration, it is preferably 10% or less, more preferably 5% or less, relative to the effective chlorine concentration.
According to the production method of the present invention, which will be described later, free chlorine can be suppressed to about 0.1 to 0.5 ppm.

Furthermore, it is preferable to satisfy the following requirement (iii).
(iii) The available chlorine content by the KI method is 10 ppm or more.
The available chlorine content is preferably 20 ppm or more, more preferably 50 ppm or more, still more preferably 100 ppm or more, still more preferably 150 ppm or more. Also, the available chlorine content is preferably 1000 ppm or less, more preferably 500 ppm or less, still more preferably 200 ppm or less, still more preferably 300 ppm or less, still more preferably 500 ppm or less.

By keeping the composition of the present invention within such a numerical range, it is possible to form non-ionized chlorous acid that does not ionize into hydrogen ions and chlorite ions, thereby enhancing the effect of removing pathogenic microorganisms and enhancing safety. I can. The reason why such an effect is brought about is considered to be that chlorous acid directly acts on pathogenic microorganisms, not chlorine molecules.

Such a composition can take the form of an aqueous solution, or it can be made into a powder composition or a solid formulation composition such as a tablet, and dissolved in an aqueous carrier at the time of use to generate hypochlorous acid and hydrogen peroxide. It can also be used after being oxidized with water. For example, assuming a solid formulation, considering a usage form in which it is dissolved in a 1 L aqueous carrier, in order to generate about 200 ppm of hypochlorous acid, 200 to 300 mg of trichloroisocyanuric acid, or requires 300-500 mg of sodium dichloroisocyanurate. Hydrogen peroxide is preferably 200 to 500 mg in terms of weight.

The content of dichloroisocyanuric acid, trichloroisocyanuric acid and salts thereof in the composition is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, still more preferably 40% by mass or more, More preferably, it is 50% by mass or more.
In addition, the content of dichloroisocyanuric acid, trichloroisocyanuric acid and salts thereof in the composition is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, still more preferably 65% by mass. It is below.
The numerical value of the above content is preferably the content relative to the total amount of components other than water contained in the composition.

In order to generate such non-ionized hypochlorous acid using one or more selected from dichloroisocyanuric acid, trichloroisocyanuric acid and salts thereof, 0.1 to It is preferred to use 5 equivalents of buffer salt. Examples of buffer salts include isocyanuric acid formed by decomposition, hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, citric acid, citrates such as sodium citrate, disodium hydrogen phosphate, dihydrogen phosphate 1 Preferable examples include phosphates such as sodium, boric acid, lactic acid, and lactates such as sodium lactate. Salts of strong acids and strong bases, such as sodium sulfate, potassium sulfate, and sodium chloride, are also classified as buffer salts because they stabilize the system. Such ingredients are processed according to conventional methods and processed into powders, granules and tablets. Any of these can be used as the solid composition of the present invention.

The content of buffer salt in the composition is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more.
In addition, the content of the buffer salt in the composition is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, still more preferably 60% by mass or less, further preferably 50% by mass or less. is.
The numerical value of the above content is preferably the content relative to the total amount of components other than water contained in the composition.

In the composition to induce chlorous acid for removing microorganisms of the present invention, in addition to the above ingredients, it is usually used for formulation for the purpose of adjusting disintegration, improving granulation, suppressing adhesion, etc. can contain optional ingredients. Suitable examples of such components include polyhydric alcohols such as polyethylene glycol, surfactants such as lauromacrogol, cellulose derivatives such as hypromellose, and lubricants such as magnesium stearate. .

These components can be processed into solid formulations such as granules and tablets, concentrated liquid formulations used after dilution, and the like, by processing them according to conventional methods.
In a preferred embodiment of the present invention, ingredients including 1) dichloroisocyanuric acid, trichloroisocyanuric acid and salts thereof, and 2) buffer salts are mixed for preferably 5 minutes or more, more preferably 6 minutes or more, and even more preferably 7 minutes or more. The composition can be prepared by stirring and mixing for at least 8 minutes, more preferably at least 8 minutes, and more preferably at least 9 minutes. Preferably, no water is added in the step of stirring and mixing. Further, the stirring and mixing may be carried out by any known means, but stirring and mixing by a Henschel mixer can be preferably exemplified.
By stirring and mixing within the above time range, the concentration of free chlorine molecules generated when the composition is dissolved in the aqueous medium can be reduced.

The non-ionizing hypochlorous acid generated by dissolving or diluting the composition for inducing chlorous acid of the present invention thus formulated in an aqueous medium is sterilized unlike hypochlorite. Although the toxicity is maintained, the toxicity to the living body is greatly reduced, and the LD50 value of the tablet itself exceeds 1 g/mouse (estimated 100 g/Kg). It can be seen that it is much lower than the electrolytic type such as sodium hypochlorite, which is 1 g/Kg (http://www.jsia.gr.jp/data/naclo.pdf). Further, since the liquid is neutral or slightly acidic (pH 5 to 7.5), preferably neutral (pH 6 to 7), it is not corrosive by alkali.

Such technology will be explained below. For trichloroisocyanuric acid, dichloroisocyanuric acid, and salts thereof, the concentration of final generated non-ionized hypochlorous acid should be set to 100 to 500 ppm, more preferably 150 to 300 ppm, with respect to the determined water content. is preferred. In order to obtain such a form, 50 to 500 mg is preferable, and 100 to 300 mg is more preferable, assuming that it is dissolved in 1 L of water.

The effect of retaining non-ionized hypochlorous acid instead of ionized type when trichloroisocyanuric acid and dichloroisocyanuric acid are dissolved in water is due to the buffer salt. This action continues even after hydrogen peroxide is added to form chlorous acid.

<Test paper>
The present invention is a test paper for determining the effect and toxicity of hypochlorous acid, comprising a test strip for measuring the effective chlorine concentration, a test strip for measuring the pH, and a test strip for measuring the concentration of free chlorine molecules. It also relates to independently provided test strips.

Here, the "test piece" means a test paper including at least a colored portion and a portion thereof. A test in which the coloration part of the test paper for measuring the available chlorine concentration, the coloration part of the test paper for measuring the pH, and the coloration part of the test paper for measuring the concentration of free chlorine molecules are provided on the same test paper. Paper (see Figure 1) is also within the scope of the present invention. A set of test strips comprising the above three test strips independently of each other is also included in the scope of the present invention.

The gist of the present invention is to provide a stable, easy-to-use, and highly safe composition for decontaminating pathogenic microorganisms, as described above. Therefore, the purpose is to identify hypochlorous acid that is highly safe and highly effective, to confirm that hypochlorous acid can be derived into chlorous acid, and to use it for decontamination.

As a method for realizing this, electrolytic hypochlorous acid water, trichloroisocyanuric acid as a buffer salt, dichloroisocyanuric acid and one or more of their salts are formulated together with a buffer salt to form a non-electrolyzed hypochlorous acid aqueous solution. It is preferable to determine the safety and decontamination effect of chlorous acid obtained by oxidizing chloric acid water. Such chlorous acid water is applied to virus decontamination and pathogen decontamination.

Such highly safe and highly effective chlorous acid water must have the following three points (i) to (iii).

(i) pH 5 to 7.5;
The pH is preferably 6 or more, more preferably 6.3 or more. Also, the pH is preferably 7.3 or less, more preferably 7 or less.

(ii) 10 ppm or less when the concentration of free chlorine molecules is 20 ppm or less;
The concentration of free chlorine molecules is preferably 9 ppm or less, more preferably 8 ppm or less, still more preferably 7 ppm or less, still more preferably 6 ppm or less, still more preferably 5 ppm or less, still more preferably 4 ppm or less, still more preferably 3 ppm or less, and further preferably It is preferably 2 ppm or less, more preferably 1 ppm or less. Also, the concentration of free chlorine molecules may be 0 ppm.

(iii) The available chlorine content is 10 ppm or more.
The available chlorine content is preferably 20 ppm or more, more preferably 50 ppm or more, still more preferably 100 ppm or more, still more preferably 150 ppm or more. Also, the available chlorine content is preferably 1000 ppm or less, more preferably 500 ppm or less, still more preferably 200 ppm or less, still more preferably 300 ppm or less, still more preferably 500 ppm or less.

It is preferable to check and determine the above three points (i) to (iii) at the same time. For this purpose, it is preferable to combine test papers coated with a substance that exhibits an appropriate color reaction in these numerical ranges and process them into a single test paper.

(i) As a means for measuring pH, pH test paper that is commonly available on the market can be used, or a test paper prepared by dissolving a reagent such as thymol blue in alcohol or the like and spray-coating it onto paper can be used. can also

(ii) As means for measuring the concentration of free chlorine, it is preferable to use syringaldazine as a coloring agent, and a test paper coated with syringaldazine as a coloring agent can also be used. The test paper can also be prepared by dissolving syringaldazine in a solvent and spraying it onto paper.

Syringaldazine is a color that measures the effective chlorine concentration at low concentrations. Within seconds, the concentration of free chlorine molecules can be determined by colorimetry. The upper limit of the commercially available test paper (“Residual Chlorine Test Paper Aquacheck 3” manufactured by Nissan Chemical Industries, Ltd.) is 10 ppm. Beyond this, the color becomes blackish and does not show any change with increasing density. Furthermore, since it does not show any color reaction to chlorous acid, it is also possible to confirm the degree of conversion of hypochlorous acid to chlorous acid.

(iii) Reagents such as the KI method and DPD are known as means for measuring the amount of available chlorine. Test paper products processed from these are also available on the market, and this can be used, or these reagents can be dissolved in alcohol and coated on a paper medium.

If these test papers are commercially available, the colored part is cut into small pieces of 2 to 6 mm × 2 to 6 mm, and a discrimination test is performed by sequentially attaching to paper pieces of 2 to 10 mm × 30 to 100 mm with double-sided tape. paper can be produced. As for the test paper, it is preferable to attach a reference color chart for comparing the degree of coloration and these numerical values (Fig. 2).

Hypochlorous acid water and chlorous acid water to be determined by the test paper of the present invention may be obtained by hydrolyzing sodium chloride, or sodium dichloroisocyanurate with sodium bicarbonate or sodium carbonate. It may be disassembled. Particularly preferably, dichloroisocyanuric acid and/or its alkali metal salts or trichloroisocyanuric acid, which has little free chlorine molecules, in other words, molecular chlorine, is dissolved in buffers such as carbonates, organic acid salts, and borates. Those generated by hydrolysis in the presence of salts and those oxidized with hydrogen peroxide are preferred.

By keeping the hypochlorous acid water within the numerical range as shown in (i) to (iii) above, non-ionized hypochlorous acid that does not ionize into hydrogen ions and hypochlorous acid ions is formed. , the chlorous acid derived from this can enhance pathogen removal effect and safety. The reason why such an effect is brought about is considered to be that chlorous acid directly acts on the virus, not chlorine molecules.

The present invention also relates to chlorous acid water determined to be effective and highly safe by the above test paper. Specifically, the present invention provides hypochlorous acid water determined by the test paper that the above conditions (i) and (ii), more preferably all of the above (i) to (iii) apply. It also relates to more derived chlorous acid.

When preparing hypochlorous acid by hydrolyzing sodium dichloroisocyanurate and/or trichloroisocyanuric acid in such hypochlorous acid water, 200 to 300 mg of Trichloroisocyanuric acid or 300-500 mg of sodium dichloroisocyanurate is required.

In order to generate such non-ionized hypochlorous acid using one or more selected from dichloroisocyanuric acid, trichloroisocyanuric acid and salts thereof, 0.1 to It is preferred to use 5 equivalents of buffer salt. Examples of buffer salts include isocyanuric acid formed by decomposition, hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, citric acid, citrates such as sodium citrate, disodium hydrogen phosphate, dihydrogen phosphate 1 Preferable examples include phosphates such as sodium, boric acid, lactic acid, and lactates such as sodium lactate. Salts of strong acids and strong bases, such as sodium sulfate, potassium sulfate, and sodium chloride, are also classified as buffer salts because they stabilize the system. Such ingredients are processed according to conventional methods and processed into powders, granules, and tablets. Any of these can be used as the solid composition of the constituents of the present invention.

One embodiment of the chlorous acid water that was determined to be effective and highly safe with the test paper of the present invention is, when the color reaction is performed using the test paper, in comparison with the standard color chart , (i) pH is 6 to 7, more preferably 6.55 to 7, (ii) free chlorine is 20 ppm or less, 0 to 20 ppm in the range, more preferably 10 ppm or less, If it is in the range, it is 0 to 10 ppm, more preferably 8 ppm or less, and in the range, it is 0 to 8 ppm, (iii) the effective chlorine amount is 10 to 1000 ppm, more preferably 50 to 500 ppm. Satisfy 3 points.

EXAMPLES The present invention will be described in more detail below with reference to Examples.

<Preparation of test paper>
On a piece of paper of 6 mm × 50 mm, a commercially available effective chlorine test piece of SBT method 6 mm × 6 mm, a commercially available universal test piece of 6 mm × 6 mm, and 1 mg of syringaldazine were dissolved in 1 ml of dimethylformamide and diluted with 10 ml of methanol. The liquid was evenly sprayed on A4 drawing paper, the solvent was volatilized, and a test paper was prepared.

<Preparation of trichloroisocyanuric acid tablets>
According to the formulation shown below, that is, after mixing the formulation ingredients with a Henschel mixer for 10 minutes, 1 g was weighed and compressed with a tableting machine to obtain tablets. When this tablet was dissolved in 5 liters of tap water, it dissolved immediately, and when the solution was judged with the test paper of Example 1, the pH was 6.5 and the concentration of hypochlorous acid was 100 ppm. The concentration of free chlorine molecules was 0.2 ppm. This product had almost no offensive odor. When 0.5 mL of 3% hydrogen peroxide solution was added to 5 mL of this hypochlorous acid solution, the effective chlorine concentration was slightly less than 100 ppm, and syringaldazine did not exhibit a color reaction.

In the tablet preparation of Example 2, the mixing time was set to 3 minutes, and the other operations were performed in the same manner as in Example 2. When the solution was measured with the test paper of Example 1, the pH was 7.5 and the available chlorine concentration was 100 ppm, free chlorine molecules scaled over over 10 ppm. When diluted and colorimetrically measured within the scale, it was 20 ppm, and this product had a strong irritating odor. When 0.5 mL of 3% hydrogen peroxide solution was added to 5 mL of this hypochlorous acid solution, the effective chlorine concentration was slightly less than 200 ppm, and syringaldazine did not exhibit a color reaction. Also, the irritating odor had disappeared.

The ingredients in Table 2 were processed in the same manner as in Example 2 to obtain a powder formulation composition. 1.3 g of this product was weighed, and 2 L of water was added thereto to prepare an actual working solution. The test paper of Example 1 was brought into contact with this liquid and colorimetrically compared with the standard. The pH was 6, the available chlorine concentration was 200 ppm, and the concentration of free chlorine molecules was 10 ppm. Although this product had a slightly offensive odor, it did not cause irritation. When 0.5 mL of 3% hydrogen peroxide solution was added to 5 mL of this hypochlorous acid solution, the effective chlorine concentration was slightly less than 200 ppm, and syringaldazine did not exhibit a color reaction.

Powder was prepared according to Table 3 in the same manner as in Example 2, and 1.17 g of this powder was weighed and dissolved in 2 L of water in which 0.13 mg of citric acid was dissolved. When the test paper of Example 1 was brought into contact with this and colorimetry with a standard color chart was performed, the pH was 6.0, the effective chlorine concentration was 200 ppm, and the free chlorine molecule concentration was 5 ppm. The offensive odor was extremely mild. I felt little stimulation. From this, it can be seen that when sodium dichloroisocyanurate is used, it is preferable to dissolve it in an acidic aqueous medium to produce a practical solution. When 0.5 mL of 3% hydrogen peroxide solution was added to 5 mL of this hypochlorous acid solution, the effective chlorine concentration was slightly less than 100 ppm, and syringaldazine did not exhibit a color reaction.

The components in Table 4 below were dissolved in 80 mL of water, the pH was adjusted to 7 with a 1 V/V % phosphoric acid aqueous solution, and then the total amount was diluted to 2 L to obtain chlorous acid water. This product had an effective chlorine concentration of 200 ppm by the KI method. In addition, no color reaction was observed with syringaldazine.

The effect on yeast was examined for the hypochlorous acid water containing a little less than 100 ppm of Example 2 and the hypochlorous acid water before induction thereof. That is, 4 ml of a solution of a small amount of dry yeast dissolved in water was dispensed into three tubes, one containing 1 ml of water, one containing 1 ml of the hypochlorous acid water prepared in Example 2, and the remaining one. 1 ml of chlorous acid water was added to the solution, and after 1 minute, the amount of ATP was measured with a Lumitester (ATP measuring instrument) manufactured by Kikkoman Biochemifa. Table 5 shows the results. Only those with chlorite addition saw a decrease in ATP. This is because dry yeast was destroyed by chlorous acid. From this, it can be seen that the chlorous acid water of the present invention has an excellent ability to remove pathogenic microorganisms.

Samples 1 to 3 of the formulation described in Table 6 were prepared on a 10 g scale (using a coffee mill and mixed by stirring 10 times for 30 seconds), 0.15 g was weighed from each, and 500 ml of tap water was added. In addition, samples were prepared. The pH was measured with a pH meter, the free chlorine molecules were colorimetrically determined with Schillingaldazine test paper, and the effective chlorine concentration was colorimetrically determined with test paper according to the KI method.

As shown in Table 6, the hypochlorous acid produced by the composition of the present invention is stable even near neutrality with little dependence on pH. In addition, it is presumed that these are non-ionized hypochlorous acids because the amount of free chlorine molecules is almost unchanged. When 0.5 mL of 3% hydrogen peroxide solution was added to 5 mL of these hypochlorous acid solutions, the available chlorine concentration was slightly less than 100 ppm, and syringaldazine did not exhibit a color reaction.

The present invention can be applied to decontamination of viruses and pathogens such as coronavirus.

1 KI method test strip 2 pH test strip 3 Schillingaldazine test strip

Claims (9)

Hypochlorous acid containing buffer salt and hypochlorous acid generation system consisting of oxidizing compounds. (1) When diluted with an aqueous medium, the pH is 5 to 7.5, the concentration of hypochlorous acid is 50 to 500 ppm, the concentration of free chlorine molecules is less than the concentration of available chlorine, and the free chlorine molecules concentration is 20 ppm or less, and the active ingredient is non-ionizing hypochlorous acid, a composition capable of preparing hypochlorous acid water,
A composition comprising 1) one or more selected from trichloroisocyanuric acid, dichloroisocyanuric acid and salts thereof, and 2) a buffer salt (provided that both the aqueous medium and the composition contain an alkali metal or an alkaline earth metal chlorite) and an oxidizing compound. 3. The system for generating chlorous acid according to claim 1, wherein the generated hypochlorous acid has a concentration of free chlorine molecules of 10 ppm or less. The system for generating chlorous acid according to any one of claims 1 to 3, wherein the concentration of the free chlorine molecules is 0.1 times or less the concentration of the hypochlorous acid. . Chlorous acid according to any one of claims 1 to 4, characterized in that the concentration of free chlorine molecules is determined by colorimetry within a contact time of 2 seconds with a syringaldazine reagent. system for generation. The composition according to any one of claims 1 to 5, wherein the effective chlorine concentration is determined by a test piece by the DPD method or the KI method. (1) When diluted with an aqueous medium, the pH is 5 to 7.5, the concentration of hypochlorous acid is 50 to 500 ppm, the concentration of free chlorine molecules is less than the concentration of available chlorine, and the free chlorine molecules concentration is 20 ppm or less, and the active ingredient is non-ionizing hypochlorous acid, a composition capable of preparing hypochlorous acid water,
A composition comprising 1) one or more selected from trichloroisocyanuric acid, dichloroisocyanuric acid and salts thereof, and 2) a buffer salt (provided that both the aqueous medium and the composition contain an alkali metal or does not contain chlorite of alkaline earth metal.) Chlorite water obtained by adding an oxidizing substance to the hypochlorous acid aqueous solution generated from. 7. The chlorous acid water according to claim 6, wherein the oxidizing substance is hydrogen peroxide water. A chlorous acid generation system characterized by dissolving chlorite with a buffer salt and adjusting the pH of an aqueous phosphoric acid solution or an aqueous citric acid solution.

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