JP5340550B2 - Ozone stabilized aqueous solution and production method thereof - Google Patents

Description

The present invention ozone stabilized aqueous and its manufacturing method.

Currently, ozone water is used in many fields for processing such as sterilization, bleaching, deodorization, virus inactivation, and organic matter removal. The ozone water is prepared by a method in which ozone gas is blown into water, or ozone is generated by electrolysis of water and directly dissolved in water.
However, ozone is a very unstable gas, and its solubility in water is very low. Therefore, ozone is easily diffused into the atmosphere when the gas-liquid interface comes into contact. Therefore, in order to exert the effect of ozone water, a large-scale ozone generator and a device that generates ozone gas with a higher concentration are required, and development thereof is being performed.

By the way, it is known that ozone water usually reacts easily with organic substances, and therefore, when organic substances are mixed during processing such as sterilization, ozone is instantly decomposed and ozone disappears.
Therefore, many studies have been made on ozone water. For example, in Non-Patent Document 1, it is reported that the reactivity with an organic substance is lowered by containing metal ions such as calcium in ozone water. Thus, it can be expected that ozone is stably dissolved in water by using metal ions.
Patent Document 1 discloses a sterilizing detergent composition in which the stability of ozone is improved by adding an anionic or nonionic surfactant to ozone water. According to this, even if ozone water contains the surfactant which is organic substance, stability of ozone concentration improves compared with ozone water which does not contain surfactant.
JP-A-6-313194 Gurol, “Ozone Science & Engineering” (USA), International Ozone Association, 1988, No. 10, p. 277-290

However, the means described in Patent Document 1 and Non-Patent Document 1 do not always have sufficient ozone stability in water.
In particular, during storage of ozone water, or during transportation where vibration and agitation are likely to occur, the stability of ozone in water decreased and ozone was easily diffused.

  The present invention has been made in view of the above circumstances, and includes an ozone stabilizer that improves the stability of ozone in water and suppresses the dispersal of ozone during storage and transportation, and the same. The purpose is to realize an ozone-stabilized aqueous solution and a method for producing the same.

As a result of intensive studies, the present inventors have found that a quaternary ammonium salt type surfactant is effective in stabilizing ozone, and have reached the present invention.
That is, the ozone stabilizer of the present invention is characterized by containing a quaternary ammonium salt type surfactant represented by the following general formula (1).

In Formula (1), R ¹ is selected from the group consisting of an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, a hydroxyalkyl group having 1 to 24 carbon atoms, or an ester group, an amide group, and an ether group. It contains a splitting group that is split by at least one selected, and is an alkyl group having 2 to 24 carbon atoms including these splitting groups, and R ² is an alkyl group having 1 to 24 carbon atoms or ² to 24 carbon atoms. X is CH ₃ SO ₄ , C ₂ H ₅ SO ₄ , CH ₃ COO, C ₂ H ₅ COO, OH, or halogen.

Further, R ^{1 in the} general formula (1) is an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, a hydroxyalkyl group having 6 to 22 carbon atoms, an ester group, an amide group, or an ether group. It is preferable that it is a C6-C24 alkyl group including the parting group interrupted by at least 1 sort (s) chosen from the group which consists of these, including these parting groups.

Moreover, the ozone stabilization aqueous solution of this invention contains the said ozone stabilizer, ozone, and water, It is characterized by the above-mentioned.
Furthermore, the method for producing an ozone-stabilized aqueous solution of the present invention is characterized in that the ozone stabilizer is added to water in which ozone is dissolved.
The method for producing an ozone-stabilized aqueous solution of the present invention is characterized in that ozone is aerated in water containing the ozone stabilizer.

  According to the present invention, an ozone stabilizer that improves the stability of ozone in water and suppresses the dispersion of ozone even during storage and transportation, an ozone-stabilized aqueous solution containing the same, and a method for producing the same Can be realized.

Hereinafter, the present invention will be described in detail.
[Ozone stabilizer]
The ozone stabilizer of the present invention contains a quaternary ammonium salt type surfactant represented by the following general formula (1).

R ¹ is at least one selected from the group consisting of an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, a hydroxyalkyl group having 1 to 24 carbon atoms, an ester group, an amide group, and an ether group. And a C 2 -C 24 alkyl group (hereinafter also referred to as a “C 2 -C 24 split group-containing alkyl group”). . An alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, a hydroxyalkyl group having 6 to 22 carbon atoms, or a splitting group-containing alkyl group having 6 to 24 carbon atoms is preferable.

Examples of the alkyl group having 6 to 22 carbon atoms include hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, icosyl group and docosyl group.
Examples of the alkenyl group having 6 to 22 carbon atoms include a vinyl group and an allyl group.
Examples of the hydroxyalkyl group having 6 to 22 carbon atoms include hydroxyhexyl group, hydroxyoctyl group, hydroxydecyl group, hydroxydodecyl group, hydroxytetradecyl group, hydroxyhexadecyl group, hydroxyoctadecyl group, hydroxyicosyl group, hydroxydocosyl Group and the like.
R ¹ is preferably a dodecyl group, a tetradecyl group, a hexadecyl group or an octadecyl group, particularly preferably a dodecyl group.

R ² is an alkyl group having 1 to 24 carbon atoms or an alkenyl group having 2 to 24 carbon atoms.
Examples of the alkyl group having 1 to 24 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group and hexadecyl group. , Octadecyl group, icosyl group, docosyl group and the like.
Examples of the alkenyl group having 2 to 24 carbon atoms include a vinyl group and an allyl group.
R ² is preferably a methyl group, an ethyl group, or a propyl group, and particularly preferably a methyl group.

X _is a _{CH 3 SO 4, C 2 H} 5 SO 4, CH 3 COO, C 2 H 5 COO, OH or halogen.
Examples of halogen include Cl, Br, and I.
X is preferably CH ₃ SO ₄ or Cl, and particularly preferably Cl.

Examples of such quaternary ammonium salt type surfactants include alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, polyoxyethylene-added alkyl trimethyl ammonium salts, and the like. Of these, alkyltrimethylammonium salts are preferred. More preferred is an alkyltrimethylammonium salt having 6 to 22 carbon atoms in the alkyl group. Specific examples of such alkyltrimethylammonium salts include dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, icosyldecyltrimethylammonium chloride, docosyldecyltrimethylammonium chloride, and the like. Can be mentioned. Of these, dodecyltrimethylammonium chloride and hexadecyltrimethylammonium chloride are preferable.
These quaternary ammonium salt type surfactants may be used alone or in combination of two or more.

 The content of the quaternary ammonium salt type surfactant is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and most preferably 100% by mass in 100% by mass of the ozone stabilizer. preferable. If the content of the quaternary ammonium salt type surfactant is within the above range, the dispersion of ozone can be further suppressed and the stability of ozone in water can be further improved.

The ozone stabilizer of the present invention may contain a component having low reactivity with ozone in addition to the quaternary ammonium salt type surfactant described above.
Examples of components having low reactivity with ozone include inorganic salts, inorganic acids, organic acids, and surfactants.
Inorganic salts include sodium chloride, sodium fluoride, sodium bromide, sodium sulfate, sodium borate, sodium nitrate, sodium acetate, potassium chloride, potassium fluoride, potassium bromide, potassium sulfate, potassium borate, potassium nitrate, potassium acetate, Examples include calcium chloride, calcium fluoride, calcium bromide, calcium sulfate, calcium borate, calcium nitrate, calcium acetate, magnesium chloride, and sodium phosphate.
Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid and the like.
Organic acids include citric acid, lactic acid, acetic acid, tartaric acid, malic acid, gluconic acid, ascorbic acid, fumaric acid, maleic acid, succinic acid, malonic acid, glycolic acid, glutaric acids, adipic acid, phthalic acid, glyceric acid, Examples include aspartic acid, glutamic acid, hydroxyacrylic acid, oxybutyric acid, gallic acid, gluconic acid, amino acid, tannic acid, benzylic acid, salicylic acid, rosmarinic acid and the like.
As surfactants, alkyl amine salts, alkyl quaternary ammonium salts as cationic surfactants; alkyl benzene sulfonates, alkyl phenol sulfonates, alkyl naphthalene sulfonates, alkyl diphenyl sulfonates, alkyl sulfates as anionic surfactants Salts, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl sulfate esters, alkane sulfonates, acylamide alkyl sulfates, alkyl phosphate ester salts, alpha sulfo fatty acid ester salts, higher fatty acid salts; Nonionic surfactants include polyoxyethylene alkyl ether carboxylates, alpha olefin sulfonates, dialkyl sulfosuccinates, monoalkyl-disodium sulfos Ester salt, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, alkylamine oxide, alkyl Glycosides, pluronic surfactants; amphoteric surfactants include alkyldimethylamine oxide, alkyldimethylamino fatty acid betaines, alkylcarboxymethylhydroxyethyl imidazolium betaines, and the like.
These components having low reactivity with ozone may be used alone or in combination of two or more.

 The content of the component having low reactivity with ozone may be 0% by mass. However, when the ozone stabilizer contains a component having low reactivity with ozone, 0.01% in 100% by mass of the ozone stabilizer. -50 mass% is preferable, 0.01-20 mass% is more preferable, 0.01-10 mass% is especially preferable. If the content of a component having low reactivity with ozone exceeds 50% by mass, it may react with ozone.

[Ozone-stabilized aqueous solution]
The ozone-stabilized aqueous solution of the present invention contains the above-described ozone stabilizer, ozone, and water.
The concentration of the ozone stabilizer is preferably 1 to 50 ppm and more preferably 1 to 20 ppm in the ozone-stabilized aqueous solution. If the concentration of the ozone stabilizer is less than 1 ppm, the stabilizing effect may not be exhibited due to adhesion to the container or the like. On the other hand, if the concentration exceeds 50 ppm, the reactivity with ozone is promoted, and the stabilization effect may not be exhibited.
“Ppm” represents a mass-based ratio.

  The concentration of ozone is preferably 0.01 to 5 ppm in the ozone-stabilized aqueous solution. In consideration of the ability of the ozone generator and the influence on the environment, the concentration of ozone is more preferably 0.05 to 0.1 ppm. If the concentration of ozone is less than 0.01 ppm, the effect of ozone may be significantly reduced. On the other hand, if the concentration exceeds 5 ppm, it may not be suitable for actual use due to problems such as ozone odor.

  Such an ozone-stabilized aqueous solution preferably has a pH of 2 to 8 at 25 ° C., more preferably 2 to 4. If the pH is less than 2, it may be difficult to handle under actual use conditions. On the other hand, when the pH exceeds 8, decomposition of ozone may be promoted.

The ozone-stabilized aqueous solution of the present invention may contain other components such as an inorganic salt, an inorganic acid, an organic acid, a surfactant, and a fragrance as long as the effect of the ozone stabilizer is not impaired.
Examples of the inorganic salt, inorganic acid, organic acid, and surfactant include the various inorganic salts, inorganic acids, organic acids, and surfactants exemplified above.
As a fragrance | flavor, a well-known thing can be used suitably.
The concentration of other components is preferably 0.01 to 1000 ppm in the ozone-stabilized aqueous solution.

<Method for producing ozone-stabilized aqueous solution>
The ozone-stabilized aqueous solution of the present invention is a method of adding an ozone stabilizer to water in which ozone is dissolved (hereinafter sometimes referred to as “ozone water”), and aeration of ozone into water containing the ozone stabilizer. It is obtained by the method of making.
In the present invention, the ozone water preparation method is not particularly limited. For example, ozone gas is blown and dissolved in water using an ozone generator (aeration method), ozone is generated by water electrolysis, and direct water The method of making it melt in is mentioned.

  In the method of aeration of ozone in water containing an ozone stabilizer, the ozone stabilizer may be dissolved in water in advance and ozone gas may be aerated. The aeration method of the ozone gas is not particularly limited, and examples thereof include a method of aeration of ozone gas into water using an ozone generator, a method of generating ozone by electrolysis of water and dissolving it directly in water.

  The ozone-stabilized aqueous solution thus obtained can exhibit excellent effects such as sterilization, bleaching, deodorization, virus inactivation, and removal of organic substances.

Thus, according to the ozone stabilizer of the present invention, by containing a quaternary ammonium salt type surfactant having a specific structure, the stability of ozone in water is improved, and the dispersion of ozone is reduced. Can be suppressed. In particular, even when storing ozone water or when vibration or stirring occurs during transportation of ozone water, the addition of the ozone stabilizer of the present invention can improve the stability of ozone in water. It is possible to improve and suppress the dispersion of ozone.
Moreover, according to the ozone stabilizer of this invention, the addition amount to ozone water can be reduced and it becomes an additive useful also in terms of cost.
Furthermore, the ozone stabilizer and ozone-stabilized aqueous solution of the present invention can be put to practical use in a wide variety of fields such as household goods, food, agriculture, and medicine.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.

Here, additives and reagents used in the following Examples and Comparative Examples are shown.
Quaternary ammonium salt type surfactant: dodecyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.).
Quaternary ammonium salt type surfactant: hexadecyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.).
Nonionic surfactant: Laurylamine oxide, “Aromox DM12D-W” (manufactured by Lion Corporation).
Anionic surfactant: sodium dodecyl sulfate (manufactured by Tokyo Chemical Industry Co., Ltd.).
Dye: acidblue92 (manufactured by ACROSORGANICS).

[Test Example 1: Measurement of residual ratio of ozone in ozone water]
<Example 1-1>
Ozone gas is aerated with water produced by an ultrapure water production apparatus (ADVANETC, “DSR-210”) using an ozone generator (Betell Co., Ltd., “Doctor Ozone”). : 0.05-0.1 ppm). After stopping the aeration of ozone gas, the additive shown in Table 1 (dodecyltrimethylammonium chloride; sometimes referred to as “DTAC”) is added as an ozone stabilizer so that the concentration of the additive becomes 10 ppm. did.
The residual rate of ozone in ozone water was measured 20 minutes after the additive was added, using a gas-phase purge / ultraviolet absorption dissolved ozone monitor ("PL-603" manufactured by Sugawara Jitsugyo Co., Ltd.). . The results are shown in Table 1.

<Example 1-2, Comparative Examples 1-1 to 1-3>
Except having changed the kind of additive into what is shown in Table 1, operation similar to Example 1-1 was performed and the residual rate of ozone was measured. The results are shown in Table 1.
In addition, the comparative example 1-1 is a case where an additive is not used, and the residual ratio of ozone in the ozone water after 20 minutes from the adjustment of the ozone water was measured.

As is clear from Table 1, when the ozone stabilizer of the present invention was used as an additive (Examples 1-1 and 1-2), the residual rate of ozone was high even after 20 minutes, and ozone in water. The stability of was sustained.
On the other hand, when the additive was not added (Comparative Example 1-1), the residual rate of ozone was significantly reduced.
In addition, when a nonionic surfactant (laurylamine oxide) or an anionic surfactant (sodium dodecyl sulfate) is used as an additive (Comparative Example 1-2, 1-3), the residual ratio of ozone as compared with the Examples Decreased.
As described above, the ozone stabilizer of the present invention is about twice as stable in ozone as non-ionic surfactants and anionic surfactants, which are conventionally considered to be effective in stabilizing ozone. It was found that the effect was improved.

[Test 2: Dye decolorization test]
<Example 2-1>
Using a ozone-stabilized aqueous solution, a dye decolorization test was performed according to the following procedure, and the decolorization ability (absorbance) of the dye was measured to evaluate the residual ratio of ozone due to changes over time. In addition, DTAC was used as an ozone stabilizer.
In advance, in the same manner as in Example 1-1, an equilibrium concentration of ozone water (concentration: 0.05 to 0.1 ppm) was prepared, and DTAC was added to obtain a test solution (ozone stabilized aqueous solution).
Thereafter, air gas (1 L / min) was aerated, 100 ml of a test solution after 1 minute from the start of aeration was collected and added to an aqueous solution of 100 ppm concentration (acidblue 92). This solution was measured with a spectrophotometer (manufactured by Shimadzu Corporation, “UV-160”), and the absorbance at a wavelength of 570 nm was determined. The same operation (operation for collecting the test solution and measuring the absorbance) was performed every 5 minutes until 20 minutes passed from the start of aeration of the air gas. The results are shown in FIG.
The absorbance of the aqueous dye solution having a concentration of 100 ppm at a wavelength of 570 nm was 0.023.

<Comparative Example 2-1>
A dye decolorization test was conducted in the same manner as in Example 2-1, except that the ozone stabilizer was not added. The results are shown in FIG.

As is clear from FIG. 1, in the case of an ozone-stabilized aqueous solution using DTAC, which is a quaternary ammonium salt type surfactant, as an ozone stabilizer (Example 2-1), when no ozone stabilizer was added ( In the case of ozone water, it was found that the absorbance of the sample at each time was smaller than that of Comparative Example 2-1), and the dye was decolorized. Moreover, even if it was the ozone stabilization aqueous solution after 20-minute progress, the decoloring effect of the pigment | dye was exhibited. Therefore, it has been found that by adding an ozone stabilizer to ozone water, the stability of ozone in water is maintained and the dispersion of ozone is suppressed.
On the other hand, in the case of ozone water, the absorbance increased with time, and the depigmenting effect of the dye decreased. In particular, ozone water after 20 minutes did not exhibit the effect of decoloring the dye, and showed the same value (0.023) as the absorbance of the aqueous dye solution. From this, it was found that when no ozone stabilizer was added, ozone was diffused from the water over time, and all ozone was diffused in about 20 minutes.

[Test Example 3: Decolorization test 1 of dyed fabric]
<Example 3-1>
Using the ozone-stabilized aqueous solution, the decolorization test of the dyed cloth was performed according to the following procedure, and the decolorization ability (Z value) of the ozone-stabilized aqueous solution was measured. In addition, DTAC was used as an ozone stabilizer. Further, as the dyed cloth, a white cloth was immersed in an aqueous dye solution (concentration: 100 ppm) for 10 minutes and then naturally dried.
In the same manner as in Example 1-1, ozone water having an equilibrium concentration (concentration: 1 ppm) was prepared in advance, and DTAC was added to obtain a test solution (ozone stabilized aqueous solution). Next, the test solution was allowed to stir for 1 minute and then sprayed onto a dyed cloth. The dyed cloth after spraying was measured with a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., “Z-90”) to determine the Z value. The results are shown in FIG.

<Comparative Example 3-1>
A decolorization test of the dyed cloth was performed in the same manner as in Example 3-1, except that water produced in the same manner as in Example 1-1 was sprayed onto the dyed cloth. The results are shown in FIG.

<Comparative Example 3-2>
A decoloring test of the dyed cloth was performed in the same manner as in Example 3-1, except that the ozone stabilizer was not added. The results are shown in FIG.

As is clear from FIG. 2, in the case of an ozone-stabilized aqueous solution using DTAC, which is a quaternary ammonium salt type surfactant, as an ozone stabilizer (Example 3-1), water in which ozone gas was not aerated (Comparative Example) 3-1) and ozone water (Comparative Example 3-2) were higher in Z value, and it was found that the dyed cloth was decolorized.
On the other hand, in the case of ozone water, the decolorizing ability (Z value) was almost the same as that of water not aerated with ozone gas. This is considered to be because ozone water was diffused because ozone water was stirred before spraying on the dyed cloth.
As described above, by using the ozone stabilizer of the present invention, it is possible to maintain the stability of ozone in water even when the ozone-stabilized aqueous solution is stirred to make the ozone easily disperse, Could be suppressed.

[Test Example 4: Decolorization test 2 of dyed fabric]
<Example 4-1>
Using the ozone-stabilized aqueous solution, the decolorization test of the dyed cloth was performed according to the following procedure, and the decolorization ability (Z value) of the ozone-stabilized aqueous solution was measured. In addition, the ozone stabilizer and the dyeing cloth used the same thing as the above-mentioned Test example 3.
In the same manner as in Example 1-1, ozone water having an equilibrium concentration (concentration: 1 ppm) was prepared in advance, and DTAC was added to obtain a test solution (ozone stabilized aqueous solution). After the dyed cloth was immersed in the test solution for 3 minutes, the dyed cloth was measured with a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., “Z-90”) to determine the Z value. The results are shown in FIG.

<Comparative Example 4-1>
A decoloring test of the dyed cloth was performed in the same manner as in Example 4-1, except that the dyed cloth was immersed in water produced in the same manner as in Example 1-1. The results are shown in FIG.

<Comparative Example 4-2>
A decolorization test of the dyed cloth was performed in the same manner as in Example 4-1, except that the ozone stabilizer was not added. The results are shown in FIG.

As is clear from FIG. 4, in the case of an ozone-stabilized aqueous solution using DTAC, which is a quaternary ammonium salt type surfactant, as an ozone stabilizer (Example 4-1), water that was not aerated with ozone gas (Comparative Example) 4-1) and ozone water (Comparative Example 4-2) were higher in Z value, and it was found that the dyed cloth was decolorized.
On the other hand, in the case of ozone water, the Z value was higher than that of water not aerated with ozone gas, but the Z value was lower than that of the ozone-stabilized aqueous solution, and the decolorization ability was inferior. This is considered to be because ozone was gradually diffused while the dyed cloth was immersed.
As described above, by using the ozone stabilizer of the present invention, even when the ozone-stabilized aqueous solution was allowed to stand for 3 minutes, the stability of ozone in water could be maintained, and the dispersion of ozone could be suppressed.

6 is a graph showing the results of Test Example 2. 10 is a graph showing the results of Test Example 3. 10 is a graph showing the results of Test Example 4.

Claims (4)

Containing a quaternary ammonium salt type surfactant represented by the following general formula (1) , ozone, and water ;
The concentration of the quaternary ammonium salt type surfactant, ozone stabilized aqueous solution according to claim 1~20ppm der Rukoto.

In formula (1), R ¹ is an alkyl group having 6 to 22 carbon atoms, R ² is a methyl group, and X is Cl. 2. The ozone-stabilized aqueous solution according to claim 1, wherein R ^{1 in the} general formula (1) is a dodecyl group or a hexadecyl group . A method for producing an ozone-stabilized aqueous solution according to claim 1 or 2,
A method for producing an ozone-stabilized aqueous solution, wherein the quaternary ammonium salt surfactant is added to water in which ozone is dissolved so as to have a concentration of 1 to 20 ppm . A method for producing an ozone-stabilized aqueous solution according to claim 1 or 2,
A method for producing an ozone-stabilized aqueous solution, wherein ozone is aerated in water containing 1 to 20 ppm of the quaternary ammonium salt type surfactant .

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