JP3992198B2 - Disinfecting and disinfecting bath water with a new disinfectant composition based on chlorine dioxide - Google Patents

Description

The present invention relates to a bath water by a novel disinfectant that uses a chemical containing a solution containing chlorine dioxide as a main component, an activator that activates the generation of chlorine dioxide, and an active sustaining agent that keeps the activity excited. It relates to sterilization and disinfectant.
Bath water here includes hot spring water, public bath water, facility bath water, 24-hour bath water, and the like.
The sterilization and sterilization disclosed in this specification includes concepts such as “sterilization” and “disinfection”.

In the 1996s, deaths of newborns due to nosocomial infections or problems of Legionella infection by 24-hour baths occurred, and recently, recreational baths in various places in Japan, bathing water for recreational baths in special nursing homes, water use facilities for buildings, for example, Massive outbreaks of Legionella pneumonia with infection sources such as cooling water for air conditioning, water supply / hot water, humidification water, or landscape facility water have been reported, and fatalities have been reported.
Legionellosis is a clinical manifestation of multi-organ disorder accompanied by respiratory distress syndrome that develops mainly due to Legionella spp. Infection to humans also occurs when an aerosol containing this bacterium is inhaled or water contaminated with this bacterium is accidentally swallowed.
Thus, although respiratory tract infection is the main route of infection, wound infection has also been reported.
The main target organ is the lung, but the affected subjects are mainly found in neonates, AIDS patients, malignant tumor patients, and those with metabolic abnormalities who are mainly defective or deficient in the reticuloendothelial system.

Legionella is a natural living organism that grows or proliferates in natural soils and fresh water. It is ubiquitous in human skin and mucous membranes, but never parasitizes.
However, it is characterized by growing as a nutrient source in metabolites of other fungi and algae in the natural world, artificial environment and underwater, and when taken up by bacterial predatory protozoa such as Acanta Amoeba Instead of digesting and disrupting in bacteria, it grows in cells and destroys and kills the host.
Infections do not spread from person to person, and mass infections always infect many people from a common source.

Examples of the infection source include the above-described artificial environment fresh water, for example, hot water supply water, bath water, landscape water, cooling tower water, humidifier, shower water, swirl bath water, and utaze hot water.

Some Legionella spp. Grow while floating and dispersed in water, and it is also recognized that they inhabit biofilms (biofilms) formed on the inner walls of pipes and on the inner surface of the device that come into contact with water. . The growing flora inside the biofilm (biofilm) is not easily affected by ultraviolet light or chemicals and is alive in a conserved state.

As mentioned above, cooling tower water, circulating bath tanks, etc. are considered to be common infectious sources, and the authorities have disclosed Legionellosis prevention guidelines for these infectious sources. Is being introduced to take measures to control Legionella spp.

Legionellosis prevention guidelines are as follows: (1) Escherichia coli group is not detected in 50 ml of bath water according to “Guidelines for water quality standards in public baths”. {Circle around (2)} Legionella bacteria are considered to be less than 10 cfu / 100 ml, that is, an instruction is given to keep them below the detection limit by a prescribed method.

In addition, the basic concept of measures to prevent the development of Legionellosis in bathing facilities in “No. 109004,“ Guidelines for Adding Legionellosis Prevention Measures to Ordinances, etc. ” It is important that measures for hygiene management such as cleaning and disinfection to prevent the generation of biofilms and remove them are important. Sodium hypochlorite, which is commonly used in these biofilms (biofilms), is consumed by contact with free organic substances (contaminants) and membrane surface materials, and is therefore inherent in biofilms (biofilms). It is said that it is difficult to sterilize and remove naturally, because it does not come into contact with microorganisms including Legionella spp.

In addition, in the “Microorganism Management Guidelines for Public Baths”, instructing the bath water to be disinfected, measure the free residual chlorine concentration in the bath frequently and keep it at about 0.2 to 0.4 ppm for 2 hours a day. ing.

In addition, the “Manual for Preventing Legionellosis in Circulating Baths” lists chlorinated drugs, and sodium hypochlorite is displayed as the representative drug.
Guidance is given to prevent the drug concentration from exceeding 1 ppm. When the concentration is high, problems such as by-product of strong carcinogenic trihalomethane, generation of off-flavor due to binding with organic substances, and induction of skin inflammation due to generation of chlorine gas, etc. are problematic.

Legionella is sterilized within 5 minutes at a residual chlorine concentration of 0.5 ppm in purified water, but there are organic contamination and chlorine-consuming substances that are characteristic of bath water, depending on temperature, pH, and inorganic ion concentration. It is usually affected by the above manual and cannot be sterilized and sterilized sufficiently.
(Yuji Ishii Environmental Management Technology 15 293 1997)

In addition, when disinfection is insufficient with chlorinated chemicals according to the above instruction manual, combined use with the ultraviolet irradiation method, ozone method, etc. has been attempted, and the patent publication discloses the combined use method of chlorinated chemicals and ultraviolet rays. . However, in the ultraviolet irradiation method, the bactericidal effect is remarkably reduced due to contamination on the surface of the irradiation tube glass, and when it is exposed to visible light, it is regenerated by light recovery, and when the ozone method is used, the residual carcinogenic ozone is completely removed. It is necessary to disassemble and remove, and it is difficult to use in substantial terms.
JP 10-305285 Japanese Patent Publication No. 10-337569

On the other hand, the removal of bacteria by the barley stone filtration method has a filtration limit of 20 to 50 μm in sand filtration that is widely used at present, and it is impossible to remove microorganisms.

In view of such points, selection of a bactericidal agent that can be substituted for sodium hypochlorite and improvement of its usage have been widely attempted in terms of effectiveness against sterilization / disinfection and side effects.
However, with sodium hypochlorite, as described above, it is almost impossible to expect the effectiveness of sterilization of pipes, bathtubs, and circulators that form a biofilm (biofilm).

The present inventor has so far conducted extensive studies on activated chlorine dioxide that exhibits bactericidal efficacy under any environment against bacteria that have been detached from biofilms (biofilms) and suspended and dispersed.
Regarding the effectiveness of chlorine dioxide for the sterilization of instruments and devices that are forming biofilms, refer to the Kenei No. 95 “Regional Disease Prevention Countermeasure Manual for Circulating Bathtubs” with sodium hypochlorite. It has been reported that slime is removed and disinfected by the combined use, and the effectiveness of disinfection and sterilization of bath water with chlorine dioxide is recognized.

As described above, chlorine dioxide exhibits bactericidal action in a wide pH range and also exhibits bactericidal action even in the presence of organic substances. Furthermore, it is a byproduct of highly carcinogenic trihalomethane, generation of off-flavors due to binding with organic substances, skin No irritation to the skin is observed, and it is environmentally friendly.

However, although chlorine dioxide has excellent characteristics as described above, it has been difficult to maintain its bactericidal efficacy for a long time. In order to overcome these drawbacks, the present inventor has required cleanliness required by the object to be sterilized, suitability of basic conditions at the time of use, antibacterial spectrum range, influence on the living body, persistence and adsorption of disinfection action Investigative research on properties, penetrability, effectiveness in the presence of organic matter, effects on disinfection objects, odor / pigmentation, appearance of resistant bacteria, ease of disposal, and sustainability of efficacy As a result, the present invention disclosed in this specification has been achieved.

Organic fungicides such as quaternary ammonium compounds, pyridium salt compounds or glutaraldehyde, which are said to have a relatively high bactericidal effect, are used for the removal and bactericides of Legionella spp. However, it is necessary to completely eliminate the remaining chemicals due to purification of the bath water or water exchange treatment from the viewpoint of the special and safety of bath water.

Sodium hypochlorite, which is currently widely used, is bath water that has been introduced so as to approximate the legal regulation upper limit set in consideration of the effects of residual chlorine on hypersensitivity, skin irritation allergy, odor, and eyes. However, as mentioned above, Legionella spp. Are detected, and it is known that sufficient bactericidal efficacy is not recognized even when a sufficient amount of sodium hypochlorite is added in hot alkaline bath water. It is.

On the other hand, the strong bactericidal action of chlorine dioxide specifically oxidizes tyrosine, methionine, and cystine residues in the microbial surface layer or biological system, which are in direct contact with bacteria, and important metabolic enzymes and cell membrane compositions. Inactivate its function. At the same time, the target microorganism is killed by destroying the cell with the nascent enzyme generated from chlorine dioxide. In Europe and the United States, this medicine is widely used as a highly safe disinfectant that can replace chlorine, and is already widely used for drinking water sterilization, environmental purification, HACCP food hygiene management, and medical use.

On the other hand, the sterilization mechanism of chlorinated disinfectants such as hypochlorous acid or its salt sodium hypochlorite and calcium hypochlorite is the sterilization action by "chlorination" of the respiratory system of the subject itself. The molecular structure is similar but the bactericidal action mechanism with chlorine dioxide is different.

The present inventor uses a combination of chlorine dioxide and hypochlorous acid or their chlorides, which have different sterilization mechanisms, so that the sharpness of the sharpness of chlorine dioxide is synergistic by the coexistence of hypochlorous acid or its chlorides. It was observed that the bactericidal action was enhanced.

However, as described above, the hypochlorous acid disinfectant can be easily deactivated in the presence of organic substances and in alkaline bath water, and chlorine dioxide may be decomposed in a heating condition of 39 ° C. to 43 ° C. of bath water. is there. The present inventor has conducted further intensive studies in order to maintain the synergistic effect of sterilization by the combined use of chlorine dioxide and a hypochlorous acid agent under such conditions.

As a result, it was recognized that the divalent ions of the group VIII element iron group, specifically, ferrous sulfate, ferrous chloride, or cobaltous chloride suppressed the decomposition of chlorine dioxide in bath water, and the above synergistic effect was maintained. Admitted to be.

The aforementioned activator that synergistically enhances the bactericidal action of chlorine dioxide is called activator MK, and this activator MK contains hypochlorous acid or a salt compound thereof. The compound that maintains the above-mentioned synergistic bactericidal effect is referred to as an active sustaining agent SX, and the active sustaining agent SX is composed of a Group VIII element iron group divalent ion compound. For example, ferrous sulfate, ferrous chloride or ferrous cobalt is included.

The present invention is a novel bactericidal composition agent characterized by using chlorine dioxide, an activator MK, and an active sustaining agent SX in a combination of “trinity”.

The chlorine dioxide agent described in the specification of the present application refers to one containing chlorine dioxide, for example, generated by adding an inorganic acid such as hydrochloric acid or sulfuric acid to a chlorite such as sodium chlorite or potassium chlorite. I can do it.

The chlorine dioxide may be generated from a stabilized chlorine dioxide agent obtained by stabilizing chlorous acid with a stabilizer.
Here, examples of the stabilizer include Na ₂ CO ₃ .3H ₂ O ₂ , NaHCO _3, and NaBO ₃ .
Such a stabilized chlorine dioxide agent is provided by Sukegawa Chemical Co., Ltd.

Further, the chlorine dioxide may be generated from chlorine dioxide in which the generation of chlorine dioxide is activated by an activating agent selected from organic acids, hydrogen peroxide and alcohols. Here, examples of the organic acids include citric acid and the like. Examples of the alcohols include ethanol as a representative example.
Such activated activated chlorine dioxide is also provided by Sukegawa Chemical Co., Ltd.

Examples of the activator MK include organic chlorine disinfectants such as isocyanuric acid and inorganic chlorine disinfectants such as hypochlorous acid or salts thereof, and representative examples include sodium hypochlorite and calcium hypochlorite. I can do it. Hypochlorous acid and its salts also contain functional water such as hypochlorite ions obtained by electrolysis of saline from a hypochlorous acid generator.

The above active sustaining agent SX can be prepared by mixing an aqueous solution of a divalent ion of group VIII element iron group, for example, ferrous chloride, ferrous sulfate, ferrous cobalt sulfate, or cobaltous hydrochloride or the above compound. good.

The above-mentioned new bactericide composition solution is not affected by the pH value of the bath water for the sterilization and bactericidal action of Legionella spp. It is not related to water pollution.

In the present invention, the preferred concentration of chlorine dioxide is 0.5 ppm to 20 ppm, preferably 0.5 ppm to 10 ppm, more preferably 1.0 ppm to 5.0 ppm.

On the other hand, the preferable addition concentration of the activator MK and the active sustaining agent SX in the present invention is 0.01 ppm to 1.0 ppm, more preferably 0.1 ppm to 0.7 ppm, and still more preferably 0.2 ppm to 0.5 ppm. .

For example, in the method of adding a new fungicide composition, in a 24-hour bath white bath water that is circulated for 1 week, 3 chemicals may be added simultaneously on the first day of the replacement, but more preferably, the activator MK is 0.2 ppm daily. The method of adding such is most preferable.

Based on the above facts, the present invention is a novel bactericidal composition comprising chlorine dioxide as a main ingredient, exhibiting a strong disinfecting and bactericidal action against Legionella spp., Escherichia coli (group) and general bacteria in bath water, and bath water In addition to artificial environment water, hot water, cooling tower water, humidifiers, etc., water is intended to be sterilized and disinfected.

The present invention will be described more specifically with the following specific experimental examples, control examples, comparative examples, and examples, but the present invention is not limited thereto.

Control Example 1

The results of microbial contamination for one week in the 24-hour circulation bath are shown in FIG.
The bath is a facility bath of about 10 t, and circulates bath water (42 ° C.), passes through a hair collector and sand filtration during the circulation process, is heated by a heat exchanger, and is circulated to the original bath. Filtration capacity is within legal standards.
More specifically, about 40 to 60 people take a bath every day, complete drainage on Saturday afternoon, and a complete water exchange system in which tap water is newly injected on Monday morning.
Grace, daily bathing time is 2:00 to 5:00 pm, and after 5 o'clock circulation and heating operation are not performed.
As shown in FIG. 1, on the first day (Monday) when the facility tub was changed, general bacteria, 5 × 10 ⁴ cfu / ml, Legionella 6 × 10 ² cfu / ml were detected, and the facility bath equipment Has been polluted by a large amount of general bacteria, Legionella spp., And pipes and attached equipment are already contaminated by microbial (biological) membranes.

Comparative Example 1

Under the same conditions as 0037, it was added so that the chlorine dioxide was 5.0 ppm on the first day of water injection, and the bactericidal effect of chlorine dioxide and its bactericidal effect were examined. The result is shown in FIG.
As shown in FIG. 2, even when 5.0 ppm of chlorine dioxide was added on the first day, an increase in general bacteria, Legionella spp. And Escherichia coli (group) was observed from the next day. unacceptable.

Experimental example 1

表１に示すように、二酸化塩素と次亜塩素酸ソーダとの間に著しい相乗殺菌効果が見られ、初発菌数５．３ｘ１０^５ｃｆｕ／ｍｌが完全に消失した。
図３は、二酸化塩素４．０ｐｐｍ及び次亜塩素酸ソーダ０．４ｐｐｍを初日添加した相乗効果を５日間の生育菌数の変動を求めた。猶、対照例として二酸化塩素及び次亜塩素酸ソーダ単独による殺菌活性を求めた。
この結果、塩素系殺菌剤に二酸化塩素併用することにより浴槽細菌に対して相乗的殺菌効果が認められ、このように有効性及び使用の簡易性から次亜塩素酸ソーダを賦活剤ＭＫとして選択した。The effect of sterilization enhancement by the type of activator in a small closed circulation bath (experimental scale) was examined as follows. The sterile water collected and separated from the public facility bath water with a membrane filter is thoroughly washed and then suspended in sterilized purified water (1.0 × 10 ⁷ cfu / ml suspended in white water). did. Inoculate the above circulating bath water into the circulating bath water aseptically circulated (3.0 ml / min) with a metering pump (2.0 ml of the bath water solution / 200 ml of sterile bath water) and circulate at 42 ° C., 24 hours later The number of bacteria was examined. In this small closed circulation bath, the drugs shown in Table 1 were injected aseptically and test specimens were collected aseptically. The results are shown in Table 1.

As shown in Table 1, a remarkable synergistic bactericidal effect was observed between chlorine dioxide and sodium hypochlorite, and the initial bacterial count of 5.3 × 10 ⁵ cfu / ml completely disappeared.
FIG. 3 shows the synergistic effect of adding 4.0 ppm of chlorine dioxide and 0.4 ppm of sodium hypochlorite on the first day to determine the fluctuation of the number of growing bacteria for 5 days. As a comparative example, bactericidal activity with chlorine dioxide and sodium hypochlorite alone was determined.
As a result, a synergistic bactericidal effect was observed against bathtub bacteria by using chlorine dioxide in combination with the chlorine-based disinfectant. Thus, sodium hypochlorite was selected as the activator MK because of its effectiveness and ease of use. .

Experimental example 2

The concentration of the activator MK was examined for the synergistic effect of the activator MK in the bactericidal and disinfecting action of chlorine dioxide against the bathtub isolate. As a result, as shown in FIG. 4, a remarkable bactericidal synergistic effect was recognized at 0.2 ppm or more.

Experimental example 3

In order to further maintain the bactericidal synergistic effect of the combined use of chlorine dioxide and the activator MK, an activator continuation agent was examined. As shown in FIG. 5 , persistence of the bactericidal effect was observed with chloride, ferrous sulfate, ferrous sulfate, FeCl ₂ , FeSO _4, and monovalent cobalt CoCl ₂ .
As a result of measuring the effective period of the bactericidal efficacy against the bathtub water isolate by the method described in 0039 over time, as shown in FIG. 6, the chloride and ferrous sulfate FeCl ₂ , FeSO ₄ sustained the synergistic bactericidal efficacy. Therefore, FeSO ₄ was used as the active retention agent SX.
FIG. 6 shows the concentration of the active sustaining agent SX and the activity retention effect.

Experimental Example 4

The result of the combination experimental example 4 of chlorine dioxide, activator MK, and active sustaining agent 3 component is shown in FIG.
As shown in this figure, a remarkable bactericidal action was observed against bathtub-separated bacteria by the combined use of three agents.

Experimental Example 5

この結果、二酸化塩素、賦活剤ＭＫ及び活性持続剤ＳＸの併用により、その最小致死濃度は二酸化塩素は０．１６ｐｐｍ、賦活剤はＭＫ０．０２ｐｐｍ及び活性持続剤ＳＸは０．０２ｐｐｍ以下の併用であり、二酸化塩素単独では６０ｐｐｍ、賦活剤単独で０．４４ｐｐｍ及び活性持続剤単独では＞７．５ｐｐｍで、三剤併用により２０〜４００倍の殺菌活性の増強が本実験結果より認められた。Table 2 shows the measurement results of the minimum lethal concentration (MBC) of each drug against the bathtub-isolated bacteria and the combination thereof.

As a result, with the combined use of chlorine dioxide, activator MK and active sustaining agent SX, the minimum lethal concentration is chlorine dioxide 0.16 ppm, activator MK 0.02 ppm and active sustaining agent SX 0.02 ppm or less. In addition, chlorine dioxide alone was 60 ppm, activator alone was 0.44 ppm, and active sustainer alone was> 7.5 ppm, and a combination of the three agents showed an enhancement of bactericidal activity 20 to 400 times from the results of this experiment.

Experimental Example 6

In the small circulation bath described in 0039, the conditions for effective drug introduction for the sterilization and bactericidal action of the new fungicide composition were examined. As shown in FIG. 8, the introduction method for sterilization / sterilization is 5.0 ppm for chlorine dioxide, 0.4 ppm for the activator MK and 0.4 ppm for the active sustaining agent SX, and the activator MK is It has been found that it is most preferable to add only 0.4 ppm daily.

The sterilization and sterilization action by the new sterilization composition with respect to the bath water of the public facility bath (tub approximately 10t) was examined.
The public facility bath is about 40 to 60 bathers per day, and is used continuously for a week with a 24-hour circulation that changes on Monday.
On the first day of water exchange, chlorine dioxide was added at 5.0 ppm, the activator was added at 0.4 ppm, and the active sustaining agent was set at 0.4 ppm, and the next day, only the activator was added at 0.4 ppm.
The transition of general bacteria, Escherichia coli (s), and Legionella spp. Were examined as detection bacteria in the bath.
The transition of general bacteria in bath water is shown in FIG. The number of bacteria detected was about 5.0 × 10 ² cfu / ml even though many people took a bath, and when the isolate was examined, it was almost spore bacteria. At that time, the number of bacteria in Comparative Example 2 was about 1.0 × 10 ⁵ cfu / ml.
On the other hand, Legionella spp. And Escherichia coli are not detected in the bath at all (FIGS. 10 and 11), and by introducing these new bactericidal chemical compositions, Legionella spp. Permitted to be sterilized.

Experimental Example 7

二酸化塩素４００ｐｐｍ、賦活剤ＭＫ（０．２、２．０、２０ｐｐｍ）、活性持続剤ＳＸ（０．２、２．０、２０ｐｐｍ）からなる含浸液のヒト皮膚に対する刺激試験を単回貼付（実施例２〜４）で検討し、その際の対照例として水を用いた（対照例２）。更に、一週間の累積貼付試験（実施例５〜６）及びその対照例として水を用いて（対照例３）検討した。評価方法は日皮学会標準法に準拠した。
この結果を表３に示す。二酸化塩素４００ｐｐｍ、賦活剤ＭＫ２０ｐｐｍ活性持続剤ＳＸ２０ｐｐｍからなる含浸液の１週間累積貼付（実施例６）でも、ヒトの年齢差に係らず、対照例と比較して全く変化は認められず、この含浸液が安全なものであることを確認した。Table 3 shows the irritation test for human skin with the novel fungicide composition solution.

A single application of stimulation test on human skin with impregnating solution consisting of 400ppm chlorine dioxide, activator MK (0.2, 2.0, 20ppm) and active sustaining agent SX (0.2, 2.0, 20ppm) In Examples 2 to 4), water was used as a control example (Control Example 2). Furthermore, the cumulative pasting test for one week (Examples 5 to 6) and water as a control example (Control Example 3) were examined. The evaluation method was in accordance with the Japanese Society of Jerusalem Standards.
The results are shown in Table 3. Even with a one-week cumulative application (Example 6) of an impregnating liquid consisting of 400 ppm chlorine dioxide and activator MK20 ppm active sustaining agent SX20 ppm, no change was observed compared to the control example, regardless of human age difference. The liquid was confirmed to be safe.

As a method for disinfecting and disinfecting microorganisms for bath water, especially Legionella spp. Which is the causative agent of pneumonia, chlorine disinfectant addition method, silver ion disinfection method, ozone disinfection method, ultraviolet disinfection method and the above-mentioned disinfection method Attempts have been made, but no favorable disinfection / bactericidal effect has been observed.
The administrative authorities instruct chlorinated disinfectants as the first choice for disinfection and sterilization of bath water, but sodium hypochlorite is generally formed in bathtubs, hot water pipes and sand filters. It has little bactericidal effect against Legionella spp. That are inherent in biofilms and live there. Sodium hypochlorite is remarkably affected by the pH of the bath water, and in the presence of a large amount of organic matter, its bactericidal power is offset and hardly exhibits bactericidal power. Furthermore, byproduct of trihalomethane, which is a carcinogenic substance, odor, and irritation to human skin are recognized, and as described above, it is general that almost no bactericidal effect is observed at a prescribed use concentration of sodium hypochlorite.
The new sterilizing liquid composition mainly composed of chlorine dioxide described in the specification of the present application is a strong sterilization and sterilization action against peeling of biological membranes (biofilms) on the inner walls of pipes, bathtubs and filtration devices and floating Legionella spp. In a controlled situation, no irritation to human skin, no odor and no side effects due to by-product substances are observed, and the effect of sterilization and sterilization is sustained. It brings a great gospel.

It shows the transition of microorganisms in bath water. (Control 1) It shows the transition of general bacteria, Legionella genus and pH, and chlorine dioxide residual concentration after treatment with chlorine dioxide in bath water. (Comparative Example 1) It shows the transition of general bacteria due to the addition of chemicals in closed bath water. (Experimental example 1) The influence by the density | concentration of the activator MK with respect to the bactericidal action of chlorine dioxide is shown. (Experimental example 2) This shows the influence of iron ions and cobalt ions. (Experimental example 3) This shows the effect of the concentration of the active sustaining agent on the bactericidal / sterilizing effect of chlorine dioxide. (Experimental example 3) The result of the combination experiment with chlorine dioxide, activator MK, and active sustaining agent SX is shown. (Experimental example 4) It is a confirmation result of the bactericidal and sterilizing effect by triple combination use in a circulation type small bathtub. (Experimental example 6) It is explanation of the sterilization of bathtub water by the new sterilization system mainly composed of chlorine dioxide. Example 1 It explains the sterilization of Legionella genus bacteria in bath water by a new sterilization system mainly composed of chlorine dioxide. Example 1 It explains the sterilization of Escherichia coli (s) in bath water by a new sterilization system mainly composed of chlorine dioxide. Example 1

Claims (4)

A method of disinfecting and disinfecting water for circulating baths,
Add chlorine dioxide, hypochlorite and ferrous chloride or ferrous sulfate to the bath water on the first day,
Then, sterilization and sterilization methods bath water which comprises adding daily hypochlorite salt bath water. The chlorine dioxide agent according to claim 1 chlorite is _{Na 2 CO 3 · 3H 2 O} 2, NaHCO 3 and stabilized chlorine dioxide agent stabilized by a stabilizer selected from the group consisting of NaBO ₃ The sterilization / sterilization method for bath water described in 1. The method for sterilizing and disinfecting bath water according to claim 1 or 2, wherein the concentration of chlorine dioxide in the bath water is 0.5 ppm to 20 ppm. 4. The concentration of hypochlorite in the bath water and the concentration of ferrous chloride or ferrous sulfate are 0.01 ppm to 1.0 ppm, respectively. 5. Disinfection and disinfection method for bath water.

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