JP6359865B2 - Non-corrosive peracetic acid preparation and its production method - Google Patents

Description

The present invention is mainly used in the field of sterilization and sterilization, and is widely used for the purpose of sterilization and sterilization of objects such as facilities, buildings, equipment, equipment, instruments, tools, containers, etc. The present invention relates to a non-corrosive peracetic acid preparation capable of suppressing the occurrence of corrosion on iron and a method for producing the same.

Peracetic acid formulations have strong bactericidal properties and have been used in various sterilization applications as environmentally friendly peroxides. In particular, sterilization treatment is necessary in recent years because peracetic acid preparations have strong bactericidal activity even at low concentrations, have immediate effect, have a wide antibacterial spectrum, and show excellent bactericidal and bactericidal effects on bacterial spores, fungi, yeast, etc. Widely used in the food and beverage industry.

In general, a peracetic acid stock solution having a peracetic acid concentration of 1 to 10% by weight, a hydrogen peroxide concentration of 3 to 20% by weight, and an acetic acid concentration of 10 to 40% by weight A working solution that can be diluted with a diluent such as water so as to have a concentration of 100 ppm to 5000 ppm is sterilized by spraying, spraying, or immersing the object on the object.

A method for producing a peracetic acid preparation is known as a method of reacting acetic acid with hydrogen peroxide. This reaction proceeds as an equilibrium reaction of peracetic acid, hydrogen peroxide and acetic acid, and a higher concentration of peracetic acid is generated as the concentration of hydrogen peroxide and acetic acid is increased. The ratio of peracetic acid, hydrogen peroxide, and acetic acid changes with time due to dilution, etc., but the ratio of peracetic acid preparation, which is an equilibrium reaction composition, will remain at the original composition ratio even if diluted for a short time after dilution. Can keep. Therefore, if the stock solution of the peracetic acid preparation is diluted and then quickly sprayed and sprayed on the sterilization / sterilization target, the original excellent sterilizing power can be maintained.

Such a peracetic acid preparation having a strong bactericidal action is expected to be useful in other fields such as hospitals, schools and other public facilities, livestock-related such as pig farms and poultry farms, and agricultural and horticultural facilities such as plastic houses. However, use in such fields has not been fully developed yet, mainly because of the following issues.

Peracetic acid is an equilibrium reaction product obtained by an equilibrium reaction represented by [hydrogen peroxide] / [acetic acid] ⇔ [peracetic acid] / [water] by mixing hydrogen peroxide and acetic acid. Contains hydrogen peroxide and acetic acid. When the concentration of hydrogen peroxide in the stock solution is increased to 6% by weight or more in order to increase the concentration of peracetic acid, which is the main bactericidal component, hydrogen peroxide becomes a deleterious substance, and handling such as transportation and storage is restricted. .

In the above, when the concentration of acetic acid instead of hydrogen peroxide in the peracetic acid formulation stock solution is increased, the content of acetic acid with respect to hydrogen peroxide even when using a use solution diluted with water so that the concentration of peracetic acid becomes 100 ppm to 5000 ppm Is high, and causes rust to occur on metals, particularly iron materials that are widely used.

In addition, if the concentration of the peracetic acid formulation stock solution is lowered, the above disadvantages can be avoided, but since the dilution rate cannot be further increased in the usage situation, the volume of the stock solution handled at a time increases, the size of the container increases, etc. This is not a practical solution because it is not easy to handle and transport and store.

The solution to the above problem is as a means to suppress the occurrence of rust (corrosion) due to the concentration of acetic acid, for example, as a means to suppress corrosion against aluminum, peracetic acid and mono-tricarboxylic acid, further chelating agents, stabilizers, antiseptics A composition containing an additive selected from an agent, a pH adjuster, and a buffer has been proposed (Patent Document 1).

In addition, peracetic acid and alkali metal phosphates, stabilizers (phosphonic acid, cyclohexane-1,2-diaminotetramethylenephosphonic acid) can be used as a method to suppress corrosion on aluminum, copper, brass, stainless steel, etc. as medical devices. Etc.) (Patent Document 2), a composition combining peracetic acid with 1,2,3-benzotriazole and alkylene glycol (Patent Document 3), peracetic acid, triazole, azole, benzoate, five-membered ring Although a composition selected from a compound and a composition selected from molybdate, chromate, borate, vanadate, tungstate (Patent Document 4), etc. are disclosed, Since the composition of the peracetic acid preparation is complicated, the manufacturing process can be complicated, and environmental considerations and production costs are not preferable.

A simple method (Patent Document 5) for adjusting a peracetic acid preparation to pH 4.6 to less than 6.2 with a pH adjusting agent such as sodium hydroxide has been proposed. It only mentions application.

Therefore, conventional peracetic acid preparations have strong corrosive properties against iron materials that are most commonly widely used in public facilities, livestock farms, agricultural and horticultural facilities. Even though it is inexpensive, its application in a wide range of fields as a disinfectant and disinfectant has not yet been fully developed.

International Publication No. 2010/095231 Japanese National Patent Publication No. 8-500843 JP 2001-506971 A JP-A-2-83301 JP 2010-95448 A

The present invention provides a non-corrosive peracetic acid preparation that is environmentally friendly, has high sterilization and sterilization power, and can suppress the occurrence of corrosion on metals, particularly iron, and a method for producing the same.

In the working solution of the peracetic acid preparation after dilution, the present inventors have not only the concentration of acetic acid but also the concentration of hydrogen peroxide present at the same time as the cause of the effect of causing rust (corrosion) on iron materials and the like. It was found that a certain correlation with acetic acid concentration is an important factor related to the presence or absence of rust on iron materials. As a result of diligent efforts, the present inventors have completed the present invention by finding a composition ratio of a peracetic acid preparation that suppresses rust generation on iron materials at a practical concentration of sterilization and sterilization of peracetic acid and a simple production method thereof. .

That is, the present invention has the following configuration.

[1] A peracetic acid preparation containing peracetic acid, hydrogen peroxide and acetic acid, wherein the concentration X (ppm) of hydrogen peroxide is 100 ppm to 5000 ppm with respect to the total amount of the peracetic acid preparation, and The concentration X (ppm) of hydrogen oxide and the concentration Y (ppm) of acetic acid are expressed by the following formulas:
Y <1.63X + 890 (Formula 1)
A non-corrosive peracetic acid preparation characterized by satisfying
[2] Furthermore, the concentration X (ppm) of the hydrogen peroxide and the concentration Y (ppm) of the acetic acid contained in the peracetic acid preparation are represented by the following formulas:
Y ≦ 1.63X + 690 [Formula 2]
A non-corrosive peracetic acid preparation characterized by satisfying
[3] A non-corrosive peracetic acid formulation, wherein the concentration of peracetic acid contained is 100 ppm to 5000 ppm with respect to the total amount of the peracetic acid formulation.
[4] A method for producing a non-corrosive peracetic acid formulation comprising a step of adding a hydrogen peroxide stock solution (B stock solution) to a peracetic acid formulation stock solution (A stock solution), uniformly mixing, and further diluting with water. In the equilibrium state, the A stock solution contains less than 6 wt% of hydrogen peroxide with respect to the total amount of the A stock solution, and the acetic acid concentration is 4 to 8 times the peracetic acid concentration. A method for producing a non-corrosive peracetic acid preparation, comprising less than 6 wt% hydrogen peroxide based on the total amount of the stock solution.

The non-corrosive peracetic acid preparation according to the present invention suppresses the occurrence of rust (corrosion) against metals, particularly iron, and can be used as a spraying disinfectant in various places and facilities where iron materials are exposed. Can be used. Further, the peracetic acid preparation containing a peracetic acid concentration of 100 ppm to 5000 ppm has a very good bactericidal ability and can kill a wide range of disease-causing bacteria including spore bacteria.

FIG. 1 is a graph showing the correlation between the hydrogen peroxide concentration and the acetic acid concentration contained in the non-corrosive peracetic acid formulation of the present invention and the composition boundary line of the corrosive / non-corrosive peracetic acid formulation.

The present invention will be described in detail below.
The present invention substantially suppresses the occurrence of corrosion on iron, which is widely used in metals, especially facilities, equipment, equipment, etc., at a practical solution concentration of a peracetic acid preparation having a strong bactericidal power. The present invention relates to a non-corrosive peracetic acid preparation that can be used for a wide range of sterilization and sterilization applications, such as spraying and immersion treatment, and a method for producing the same.

In general, the practical peracetic acid concentration used for sterilization treatment of facilities and equipment is 100 ppm to 5000 ppm. Conventionally, in a peracetic acid preparation having a peracetic acid concentration obtained by diluting a peracetic acid stock solution with water or the like, the concentration of hydrogen peroxide contained is 150 to 9000 ppm, and the concentration of acetic acid is 200 ppm to 11000 ppm. These peracetic acid preparations have strong corrosiveness to iron.

The non-corrosive peracetic acid preparation of the present invention is a working solution obtained by diluting a stock solution with water (for example, distilled water, pure water, deionized water, etc.), and the concentration of hydrogen peroxide with respect to the total amount. Is 100 ppm to 5000 ppm, and the hydrogen peroxide concentration X (ppm) and the acetic acid concentration Y (ppm) are:
Y <1.63X + 890 (Formula 1)
If the composition is in a concentration range that satisfies the above conditions, the generation of sufficient rust can be suppressed for metals, particularly iron, and the conventional bactericidal power and economy can be maintained.

More preferably, with respect to the total amount of the non-corrosive peracetic acid preparation, the hydrogen peroxide concentration contained is 100 ppm to 5000 ppm, and the hydrogen peroxide concentration X (ppm) and the acetic acid concentration Y (ppm) are the following formulas:
Y ≦ 1.63X + 690 [Formula 2]
If it can satisfy | fill, this peracetic acid formulation (use liquid) can suppress generation | occurrence | production of rust reliably with respect to a metal, especially iron.

The concentration of hydrogen peroxide contained is 100 ppm to 5000 ppm, more preferably 200 ppm to 3000 ppm, and particularly preferably 500 ppm to 2500 ppm with respect to the total amount of the non-corrosive peracetic acid preparation.

The concentration of acetic acid contained in the non-corrosive peracetic acid preparation is 1000 ppm to 9000 ppm, more preferably 1200 ppm to 6000 ppm, and particularly preferably 1500 ppm to 5000 ppm.

FIG. 1 shows the premise that the present inventors have a practical peracetic acid concentration, and investigated the corrosive action on iron with a composition having each hydrogen peroxide concentration and acetic acid concentration. It is a graph showing the inhibitory effect on a concentration correlation and corrosion. A peracetic acid formulation having a concentration of hydrogen peroxide and acetic acid that satisfies Equation 1 can suppress the corrosive action on iron. More preferably, a peracetic acid preparation having a concentration of hydrogen peroxide and acetic acid satisfying formula 2 can more reliably suppress the corrosive action on iron.

In the non-corrosive peracetic acid preparation of the present invention, the concentration of peracetic acid is 100 ppm to 5000 ppm, more preferably 200 ppm to 2000 ppm, and particularly preferably 200 ppm to 1000 ppm, based on the total amount in the diluted use solution.

As described above, the non-corrosive peracetic acid preparation of the present invention can suppress the occurrence of sufficient corrosion on metals, particularly iron, while having a strong bactericidal power.

A non-corrosive peracetic acid formulation of the present invention has a peracetic acid concentration of 100 ppm to 5000 ppm, a hydrogen peroxide concentration of 100 ppm to 5000 ppm, and a hydrogen peroxide concentration and an acetic acid concentration satisfying Formula 1 or Formula 2. The mechanism of why corrosion does not occur in metals such as iron is unclear, but the peracetic acid formulation having a concentration relationship between hydrogen peroxide and acetic acid satisfying Formula 1 or Formula 2 in the present invention is the experimental result. This suppresses the generation of rust on the iron surface.

There are several points to be noted regarding the preparation of the stock solution that is the basis of the non-corrosive peracetic acid preparation (use solution) of the present invention. First, hydrogen peroxide is a deleterious substance when its concentration is 6% by weight or more, and it is a dangerous substance when its concentration is 44% by weight or more. It is advantageous to produce a stock solution of 6% by weight or less by using a raw material having a hydrogen peroxide concentration of 44% by weight or less as much as possible in the industry.

However, when the hydrogen peroxide is less than 6% by weight, it is necessary to increase the concentration of acetic acid present at the same time in order to increase the concentration of peracetic acid to 3% by weight or more, preferably 5% by weight or more. In such a peracetic acid formulation stock solution, the concentration of acetic acid is 20% to 40% by weight. Even if such a peracetic acid stock solution is simply diluted with water or the like to make the working solution so that the peracetic acid concentration falls within the concentration range of 100 ppm to 5000 ppm, the concentration of hydrogen peroxide and the concentration of acetic acid in the working solution are It is difficult to satisfy Equation 1 or Equation 2.

Preparation of the stock solution as a raw material for the non-corrosive peracetic acid preparation (use solution) according to the present invention is devised as follows.

Preparation of peracetic acid formulation stock solution (A stock solution) Commercially available hydrogen peroxide, acetic acid and distilled water, etc. are mixed in an appropriate ratio, and the target hydrogen peroxide concentration (less than 6% by weight) and acetic acid / peracetic acid concentration ratio ( (4 times to 8 times) until it reaches an equilibrium state.

Specifically, commercially available 35 wt% to 40 wt% hydrogen peroxide, 68 wt% to 90 wt% acetic acid, homogeneously mixed with distilled water or pure water, deionized water, etc., and allowed to stand for 4 days. Thereafter, a peracetic acid formulation A stock solution is prepared so that the concentration of hydrogen peroxide contained is less than 6% by weight and the concentration of acetic acid contained is 4 to 8 times the concentration of peracetic acid. More preferably, the peracetic acid formulation A stock solution is prepared so that the concentration of acetic acid contained is 6 to 8 times the concentration of peracetic acid.

Preparation of hydrogen peroxide stock solution (B stock solution) Commercially available 35 wt% to 40 wt% hydrogen peroxide is diluted with distilled water or the like to obtain a hydrogen peroxide solution B stock solution having a hydrogen peroxide concentration of less than 6 wt%.

Adjustment of the ratio of the concentration of hydrogen peroxide and acetic acid in the peracetic acid formulation (use solution) of the present invention The above-mentioned peracetic acid formulation stock solution (A stock solution) and hydrogen peroxide stock solution (B stock solution) are mixed and diluted at an appropriate ratio, The concentration of hydrogen peroxide and acetic acid satisfying Formula 1 or Formula 2 of FIG. If the A stock solution is diluted only with water, the ratio of the hydrogen peroxide concentration and the acetic acid concentration in the original A stock solution is maintained as it is, which causes corrosion of the metal. However, when the B stock solution is mixed with the A stock solution, the B stock solution is a solution in which hydrogen peroxide is diluted to less than 6 wt%, and the hydrogen peroxide concentration in the A stock solution is almost the same. The concentration of hydrogen does not change and the concentration of acetic acid can be reduced. Since the ratio of the hydrogen peroxide concentration to the acetic acid concentration in the working solution is lowered, it is considered that this was one of the causes that could suppress the occurrence of corrosion on the metal. By such a method, the concentration ratio of hydrogen peroxide and acetic acid in the peracetic acid preparation can be freely adjusted, so that a composition liquid having a preferable concentration ratio of hydrogen peroxide and acetic acid can be easily prepared. By diluting with water so as to obtain a peracetic acid concentration, a peracetic acid preparation (use liquid) having sufficient sterilizing power and suppressing corrosion against metals can be produced.

Since the peracetic acid formulation stock solution (A stock solution) and the hydrogen peroxide stock solution (B stock solution) basically contain water, even if water is used for dilution, there is no change in the component ratio of each composition. Although it is a ratio which mixes A stock solution and B stock solution, it does not specifically limit, The density | concentration correlation of the hydrogen peroxide of a use liquid finally obtained should just satisfy | fill Formula 1 or Formula 2.

However, because the peracetic acid preparation is an equilibrium reaction represented by [hydrogen peroxide] / [acetic acid] ⇔ [peracetic acid] / [water], it depends on the temperature. In a new equilibrium state, the concentration of peracetic acid changes in a decreasing direction, and there is a possibility that the bactericidal power and the rust generation inhibition ability are impaired.

If the elapsed time after dilution is short, the concentration ratio by mixing can be kept almost as it is, and the sterilizing power and the suppression of rust generation can be maintained. Therefore, it is effective to mix A stock solution and B stock solution and dilute with distilled water or the like immediately before use in an actual use scene. For example, when used as a bactericidal agent / disinfectant, immediately after mixing A stock solution and B stock solution at a predetermined ratio, adding water at a predetermined ratio and diluting it immediately It is preferable to spray or spray the product on the object because a better sterilizing and sterilizing effect and an effect of suppressing generation of rust such as iron can be obtained.

The non-corrosive peracetic acid preparation of the present invention is a peracetic acid preparation containing peracetic acid, hydrogen peroxide, and acetic acid, and may contain other components that enhance the corrosion prevention effect. From the viewpoint of ease of preparation work and cost, the smaller the number of other additives, the more suitable. The final decomposition product of the composition comprising hydrogen peroxide, acetic acid, peracetic acid and water is particularly preferred because it becomes water, oxygen and acetic acid and is non-toxic.

(Measurement and calculation of each composition concentration)
The concentration of peracetic acid was determined by the following method. The conversion method from the “mol%” concentration described below to the “wt%” concentration is omitted.
(1) Measurement of total peracid concentration About 0.1 ml of pure water was added to 0.1 g of a solution containing peracetic acid, 10 ml of 10% sulfuric acid, 10 ml of 1N potassium iodide solution, and 1 to 2 drops of 0.5% ammonium molybdate solution. And titrated with a N / 10 sodium thiosulfate standard solution to obtain a total peracid concentration (mol%). As a measuring instrument, 665 Dosimat (manufactured by Metrohm)) was used.
(2) Measurement of hydrogen peroxide concentration Add about 20 ml of pure water to 0.1 g of a solution containing the same peracetic acid, add (1 + 9) 10 ml of sulfuric acid and 2-3 drops of ferroin indicator, and titrate with N / 10 cerium sulfate standard solution. The hydrogen peroxide concentration (mol%) was obtained. As a measuring instrument, 665 Dosimat (manufactured by Metrohm)) was used.
(3) Calculation of peracetic acid concentration The peracetic acid concentration was calculated by converting the value obtained by subtracting (2) hydrogen peroxide concentration from (1) total peroxide concentration to peracetic acid concentration according to the following equation.
Peracetic acid concentration (mol%) = (total peroxide concentration (mol%))-hydrogen peroxide concentration (mol%))
(4) Measurement of total acid concentration The total acid concentration in the peracetic acid preparation was measured by neutralization titration (1 / 10N NaOH titration method) using sodium hydroxide.
(5) Calculation of acetic acid concentration Acetic acid concentration (mol%) = (total acid concentration (mol%)-peracetic acid concentration (mol%))
(6) Concentration of polyacrylic acid It is a concentration by weight based on the total amount simply calculated from the added amount.

(Preparation of stock solution)
23.5 g of 35 wt% hydrogen peroxide (manufactured by Hodogaya Chemical Co., Ltd.), 54 g of 80 wt% acetic acid (manufactured by Hiyakusei) and 22.5 g of distilled water (DMW) were mixed and allowed to stand at 40 ° C. for 4 days. As a result, a peracetic acid preparation (A stock solution) containing 5.5 wt% peracetic acid, 5.8 wt% hydrogen peroxide, and 37.9 wt% acetic acid was obtained. Further, 35 wt% hydrogen peroxide was diluted with water to obtain 5.9 wt% hydrogen peroxide water (B stock solution). Using these undiluted solutions, a solution for using peracetic acid preparation in the next experiment for examining the corrosiveness to iron was prepared.

(Examination of the effect of suppressing rust generation on iron pieces)
A stock solution, B stock solution and distilled water were mixed at the dilution ratios shown in Table 1 to prepare use solutions at various mixing ratios. The hydrogen peroxide concentration, acetic acid concentration, and peracetic acid concentration of the obtained peracetic acid preparation use liquid are shown in Table 1. Regarding the corrosiveness of the obtained use liquid to iron, three polished iron pieces (5 cm × 3 cm × 0.3 cm) were immersed in 100 ml of each of these use liquids for 10 minutes. Thereafter, the iron piece was taken out and exposed to air with a liquid attached to the surface. Leave at room temperature for 3 hours (until the adhering liquid dries), visually observe the degree of rust generation, the symbol “◎” indicates no complete corrosion on the iron piece surface, and “○” indicates 90% or more of the iron piece. There was no corrosion on the surface area of the steel piece, “Δ” was evaluated as corrosive on the surface area of 10% to less than 30% of the iron piece, and “×” was evaluated as corrosive on the surface area of 30% or more of the iron piece. The results are shown in Table 1. .

  Based on the hydrogen peroxide concentration and the acetic acid concentration of Examples 1 to 6 and Comparative Examples 1 to 3, each composition was plotted in FIG. 1 with the acetic acid concentration as the vertical axis and the hydrogen peroxide concentration as the horizontal axis. The state of occurrence of rust on the iron pieces by the use liquid of each composition is also shown in FIG. Based on the occurrence of rust on the iron pieces by the use liquids of each composition, a boundary line indicating whether or not the corrosion inhibitory effect is present was drawn, and a concentration correlation between hydrogen peroxide and acetic acid capable of suppressing the corrosion action on iron was obtained.

From FIG. 1, the concentration X (ppm) of hydrogen peroxide is in the range of 100 ppm to 5000 ppm with respect to the total amount of the non-corrosive peracetic acid preparation of the present invention, and the concentration X (ppm) of hydrogen peroxide and acetic acid When the concentration of Y (ppm) satisfies the relationship of Y <1.63X + 890, and more preferably satisfies the relationship of Y ≦ 1.63X + 690, the peracetic acid preparation has an excellent bactericidal / sterilizing effect, and in particular, metal The occurrence of corrosion on iron can be suppressed.

Non-corrosive peracetic acid preparations according to the present invention are food-related, sterile packaging containers, equipment / containers, indoor environment sterilization, medical-related, high-level disinfection / endoscope / dialysis line / other medical devices / hospital environment sterilization It is a peracetic acid formulation that is effective in sterilizing harmful bacteria including spore bacteria in fields and applications such as linen-related, agricultural / fishery-related equipment, and pathogen sterilization.

◎ ・ ・ ・ ・ ・ ・ No corrosion on the iron piece surface ○ ・ ・ ・ ・ ・ ・ No corrosion on the area of 90% or more of the iron piece,
Δ ··· Corrosion on an area of 10% to less than 30% of the iron piece,
× ······ Corrosion on more than 30% of the iron piece

Claims (4)

A peracetic acid preparation containing peracetic acid, hydrogen peroxide and acetic acid, wherein the concentration X (ppm) of hydrogen peroxide is 100 ppm to 5000 ppm with respect to the total amount of the peracetic acid preparation, and Concentration X (ppm) and acetic acid concentration Y (ppm) are given by the following formula:
Y <1.63X + 890
And satisfies the, a peracetic acid formulation for peracetic acid concentration is sterilized or sterilizing an object comprising the iron to corrosion by peracetic acid formulation to be 100Ppm～5000ppm, and the corrosion of iron material Peracetic acid formulation for inhibition . The concentration X (ppm) of the hydrogen peroxide and the concentration Y (ppm) of the acetic acid contained in the peracetic acid preparation according to claim 1 are as follows:
Y ≦ 1.63X + 690
And satisfies the, a peracetic acid formulation for peracetic acid concentration is sterilized or sterilizing an object comprising the iron to corrosion by peracetic acid formulation to be 100Ppm～5000ppm, and the corrosion of iron material Peracetic acid formulation for inhibition . Based on the total amount of peracetic acid formulation according to claim 1 or claim 2, the concentration of the peracetic acid containing is characterized in that the 100Ppm～5000ppm, peracetic acid formulation peracetic acid concentration of 100Ppm～5000ppm peracetic acid formulation of a peracetic acid formulation for disinfecting or sterilizing an object comprising the iron to corrosion, and to suppress corrosion of iron material by. A method for producing a non-corrosive peracetic acid formulation comprising a step of adding a hydrogen peroxide stock solution (B stock solution) to a peracetic acid formulation stock solution (A stock solution), uniformly mixing, and further diluting with water. The A stock solution contains less than 6 wt% hydrogen peroxide with respect to the total amount of the A stock solution in an equilibrium state, and the acetic acid concentration is 4 to 8 times the concentration of peracetic acid. The object containing the iron material corroded by the peracetic acid formulation in which the peracetic acid concentration according to any one of claims 1 to 3 is 100 ppm to 5000 ppm , characterized in that it contains less than 6 wt% hydrogen peroxide. a peracetic acid formulation for disinfecting or sterilizing an object, and method for producing peracetic acid formulation to inhibit corrosion of iron material.

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