JP2022035075A - Peracetic acid aqueous solution for food additive - Google Patents

Abstract

To provide a peracetic acid aqueous solution for food additive which poses little risk of causing a harmful effect to a living body while lowering possibility of catching fire or explosion.SOLUTION: A peracetic acid aqueous solution for food additive includes 13.0-15.5 mass% of peracetic acid, 5.0-17.0 mass% of hydrogen peroxide, 25.0-50.0 mass% of acetic acid, and water, and has a flash point of 70°C or higher. In particular, it is preferable that an existence mass ratio of the hydrogen peroxide and the peracetic acid in the aqueous solution is hydrogen peroxide/peracetic acid of 0.60 or lower.SELECTED DRAWING: None

Description

The present invention relates to an aqueous solution of peracetic acid used as a food additive.

It has long been known that an aqueous solution of peracetic acid can be synthesized using acetic acid and hydrogen peroxide as raw materials. For example, in the reports of Tokusho 61-10465, Tokusho 37-7459, or FRANK P. GREENSPAN (J. Amer. Chem. Soc., 68, 907 (1946)), reaction conditions and raw material preparation ratios It is described that an aqueous solution of peracetic acid having a peracetic acid concentration of 1 to 50% by weight can be synthesized by selecting the above.

Further, the peracetic acid aqueous solution thus obtained is excellent in sterilization and disinfection due to its oxidizing power, as described in, for example, Japanese Patent Publication No. 61-10465 and Japanese Patent Publication No. 61-14122. It has long been known to have bleaching and other abilities. On the other hand, an aqueous solution of peracetic acid, like other organic peracids, is originally an unstable substance and decomposes violently due to heating or contamination with impurities, so that the storage stability is largely inferior when used. It was a drawback. In order to solve this problem, Patent Document 1 improves the storage stability of the obtained peracetic acid aqueous solution by using a hydrogen peroxide aqueous solution containing a predetermined amount of aluminum.

Generally, the higher the concentration of peracetic acid or hydrogen peroxide, which is a sterilizing component, the higher the sterilizing effect of the peracetic acid aqueous solution. However, hydrogen peroxide, which is one of the components of the peracetic acid aqueous solution, has been found to have weak carcinogenicity when ingested in large amounts, and hydrogen peroxide is not detected in foods when used as a food additive. Is required. It is also important to sufficiently avoid the danger of ignition and explosion when using or transporting the peracetic acid aqueous solution. As described above, there have been many requests for the peracetic acid aqueous solution for food additives in addition to the high sterilizing effect.

WO2019 / 102742

An object of the present invention is to provide an aqueous solution of peracetic acid for food additives, which reduces the possibility of ignition and explosion and has no risk of adversely affecting a living body.

As a result of diligent studies to solve such a problem, the present inventor contains peracetic acid, hydrogen peroxide, acetic acid, and water in a specific amount, thereby reducing the possibility of ignition and explosion and adversely affecting the living body. We have found that it is possible to provide an aqueous solution of peracetic acid for food additives that does not pose a risk, and have completed the present invention.
That is, the present invention is as follows.
<1> Peracetic acid is 13.0 to 15.5% by mass, hydrogen peroxide is 5.0 to 17.0% by mass, acetic acid is 25.0 to 50.0% by mass, and water is contained, and the temperature is 70 ° C. or higher. A peracetic acid aqueous solution for food additives having a flash point of.
<2> The peracetic acid aqueous solution for food additives according to <1> above, wherein the abundance ratio of hydrogen peroxide and peracetic acid in the aqueous solution is hydrogen peroxide / peracetic acid = 0.60 or less in terms of mass ratio. Is.
<3> The peracetic acid aqueous solution for food additives according to <1> or <2> above, which does not have a heat generation start temperature of less than 70 ° C.
<4> Further, the peracetic acid aqueous solution for food additives according to any one of <1> to <3> above, which contains 0.6 to 1.0% by mass of 1-hydroxyethylidene-1,1-diphosphonic acid. be.

According to the present invention, it is possible to provide an aqueous solution of peracetic acid for food additives which has no risk of adversely affecting a living body while reducing the possibility of ignition / explosion.

Hereinafter, the peracetic acid aqueous solution used as the food additive of the present invention will be specifically described. The materials and configurations described below are not limited to the present invention, and can be variously modified within the scope of the purpose of the present invention. In this specification, when the numerical range is indicated by using "-", the numerical values at both ends thereof are included.

In one embodiment of the present invention, peracetic acid is 13.0 to 15.5% by mass, hydrogen peroxide is 5.0 to 17.0% by mass, acetic acid is 25.0 to 50.0% by mass, and water is used. A peracetic acid aqueous solution for food additives, which contains and has a flash point of 70 ° C. or higher.
The peracetic acid aqueous solution of the present invention preferably contains 13.4 to 15.2% by mass of peracetic acid, more preferably 14.0 to 14.5% by mass, and preferably contains hydrogen peroxide from 5.0 to 8. It contains 0% by mass, more preferably 5.0 to 6.5% by mass, preferably acetic acid in an amount of 40.0 to 50.0% by mass, and more preferably 45.0 to 50.0% by mass.
If the concentration of peracetic acid is less than 13.0% by mass, the stability of peracetic acid is lowered, which is not preferable, and if it exceeds 15.5% by mass, the risk of handling increases, which is not preferable. Further, if the concentration of hydrogen peroxide exceeds 17.0% by mass, it is the same and unfavorable, and if the concentration of acetic acid also exceeds 50% by mass, it is not preferable in terms of irritation to the human body and odor.

The aqueous peracetic acid solution of the present invention further preferably contains 1-hydroxyethylidene-1,1-diphosphonic acid in an amount of 0.6 to 1.0% by mass, more preferably 0.6 to 0.8% by mass. .. If the amount of 1-hydroxyethylidene-1,1-diphosphonic acid used is more than 1.0% by mass, the aqueous solution of peracetic acid may not meet the ingredient specifications of food additives, while it is more than 0.6% by mass. If it is too small, the storage stability of the aqueous peracetic acid solution may decrease.

The flash point of the aqueous peracetic acid solution of the present invention is 70 ° C. or higher, but the higher the flash point, the less likely it is to catch fire and the safer it is. Therefore, the flash point is preferably 72 ° C. or higher, more preferably 74. When the flash point is 70 ° C. or higher, the danger of ignition or explosion can be sufficiently avoided during transportation. In the present invention, the upper limit of the flash point is not particularly limited, but is usually less than 200 ° C. In the present invention, the flash point can be measured by the method described in Examples described later.

The abundance ratio of hydrogen peroxide to peracetic acid in the peracetic acid aqueous solution of the present invention is preferably hydrogen peroxide / peracetic acid = 0.60 or less in terms of mass ratio, and hydrogen peroxide / peracetic acid = 0.40. The following is more preferable. The smaller the value of hydrogen peroxide / peracetic acid, the lower the concentration of hydrogen peroxide at the time of sterilization, and the less hydrogen peroxide remains after sterilization, which is preferable. On the contrary, the larger the value of hydrogen peroxide / peracetic acid, the more easily the excess hydrogen peroxide remains in the food, which is not preferable.

The peracetic acid aqueous solution of the present invention preferably does not have a heat generation start temperature of less than 70 ° C. If the temperature does not have a heat generation start temperature of less than 70 ° C., the risk of ignition or explosion can be sufficiently avoided during transportation. The peracetic acid aqueous solution of the present invention does not have a heat generation start temperature, or when it has a heat generation start temperature, it is more preferable to have a heat generation start temperature of 150 ° C. or higher, and a heat generation start temperature of 210 to 250 ° C. Is particularly preferable to have. In the present invention, the heat generation start temperature is in the Fire Service Act Dangerous Goods Class 5 test, and can be measured by the method described in Examples described later.

The method for producing a peracetic acid aqueous solution of the present invention includes a step of mixing a hydrogen peroxide solution and an acetic acid solution, and preferably further includes a step of mixing 1-hydroxyethylidene-1,1-diphosphonic acid.
The hydrogen peroxide aqueous solution preferably contains hydrogen peroxide in an amount of 30 to 40% by mass, more preferably 32 to 38% by mass, and particularly preferably 35 to 36% by mass. It is preferable that the hydrogen peroxide aqueous solution contains 30 to 40% by mass of hydrogen peroxide because it is safe, stable, and conforms to the component specifications of food additives.

本反応の反応速度は、比較的遅く、反応時間短縮のために、プロトン酸触媒を用いることができる。酢酸溶液は、水溶液の形で加えてもよいが、反応時間短縮のためには、より高濃度のものが望ましく、通常、氷酢酸が用いられる。過酸化水素水溶液の濃度は、反応時間短縮のためには、より高濃度のものが望ましいが、取扱時の安全性から考えると、より低濃度のものが望ましく、より好ましくは３２～３８質量％、より好ましくは３５～３６質量％の水溶液が用いられる。 In the method for producing a peracetic acid aqueous solution of the present invention, it is known that the reaction for obtaining a peracetic acid aqueous solution from an acetic acid solution and a hydrogen peroxide aqueous solution is an equilibrium reaction according to the following formula.

The reaction rate of this reaction is relatively slow, and a protonic acid catalyst can be used to shorten the reaction time. The acetic acid solution may be added in the form of an aqueous solution, but in order to shorten the reaction time, a higher concentration is desirable, and glacial acetic acid is usually used. The concentration of the aqueous hydrogen peroxide solution is preferably higher in order to shorten the reaction time, but is preferably lower in consideration of safety during handling, and more preferably 32 to 38% by mass. , More preferably a 35-36 mass% aqueous solution is used.

The 1-hydroxyethidron-1,1-diphosphonic acid (hereinafter, may be referred to as "HEDP") preferably used in the present invention is a protonic acid having a metal-sealing action, and is a stable storage of the obtained peracetic acid aqueous solution. Contributes to improving sex. Various methods can be considered for obtaining the peracetic acid aqueous solution of the present invention, but in general, a hydrogen peroxide solution and an acetic acid solution are preferable in the presence of the above-mentioned 1-hydroxyethylidene-1,1-diphosphonic acid. Is carried out by a method of reacting at a ratio of 1: 1 to 5 mol, more preferably 1: 2 to 4 mol. If necessary, the crude reaction solution can also be diluted with one or more of water, an aqueous hydrogen peroxide solution or an acetic acid solution.

The mixing temperature in the mixing step is preferably 25 to 35 ° C, more preferably 25 to 30 ° C. When the mixing temperature is 25 to 35 ° C., the reaction rate does not become too slow, and volatilization of acetic acid and decomposition of hydrogen peroxide and peracetic acid are suppressed, which is preferable.
The mixing time in the mixing step is preferably 60 minutes or less, more preferably 10 to 60 minutes. If the mixing time exceeds 60 minutes, the power consumption required for mixing becomes large, and the cost may increase.
After mixing in the mixing step, it is preferable to allow it to stand for 1 day or more from the viewpoint of completing the reaction, and it is more preferable to leave it to stand for 1 to 10 days.

Another embodiment of the present invention is a method for sterilizing food by bringing the aqueous solution of peracetic acid of the present invention into contact with the food. Examples of the method of bringing the peracetic acid aqueous solution into contact with the food include, but are not limited to, a method of immersing the food in the peracetic acid aqueous solution and a method of spraying the peracetic acid aqueous solution on the food. ..
Since the aqueous solution of peracetic acid of the present invention has excellent storage stability, it has many advantages when used as a method for disinfecting foods.

Hereinafter, the present embodiment will be described in more detail by way of examples, but the present embodiment is not limited to these examples. The measurement of each physical property value was performed by the method shown below.

<Hydrogen peroxide concentration in peracetic acid aqueous solution>
The hydrogen peroxide concentration in the peracetic acid aqueous solution was measured by redox titration. Specifically, about 0.1 g of the sample was precisely weighed, placed in a 250 mL Erlenmeyer flask, and 75 mL of 0.5 mol / L sulfuric acid was added to prepare a test solution. A few drops of ferroin test solution were added to this test solution, and the mixture was titrated with a 0.1 mol / L cerium (IV) sulfate solution to calculate the hydrogen peroxide concentration.

<Acetic acid and peracetic acid concentration in peracetic acid aqueous solution>
The acetic acid and peracetic acid concentrations in the peracetic acid aqueous solution were measured by neutralization titration. Specifically, about 0.1 g of the sample was precisely weighed, placed in a 100 mL beaker, and about 50 mL of pure water was added to prepare a test solution. This test solution is titrated with a 0.1 mol / L sodium hydroxide solution, and the acetic acid concentration is determined from the amount added at the first inflection, and the peracetic acid concentration is determined from the amount added from the first inflection to the second inflection. Calculated.

<Hydrogen peroxide / peracetic acid>
It was calculated by dividing the hydrogen peroxide concentration by the peracetic acid concentration.

<Flash point of peracetic acid aqueous solution>
The flash point of the peracetic acid aqueous solution was measured by a tag closed flash point test when the flash point was less than 80 ° C. and a Cleveland open flash point test when the flash point was 80 ° C. or higher. According to the method of JIS-K2265, a tag closed type flash point tester and a Cleveland open type flash point tester were used.

<The heat generation start temperature and calorific value of the peracetic acid aqueous solution>
The exothermic start temperature and calorific value of the peracetic acid aqueous solution were measured by a differential scanning calorimeter (DSC6220-ASD2, manufactured by Hitachi High-Tech Science Corporation). Specifically, about 1 mg of a peracetic acid aqueous solution was sealed in a pressure-resistant cell using α-alumina as a reference substance. It was heated at 10 ° C./min, and the heat generation start temperature and the heat generation amount were calculated from the obtained chart.

<Ginger sterilization>
Ginger was cut to a size of about 30 to 80 g and washed with water to remove soil and the like. After removing the water on the surface of the washed ginger pieces with a paper towel, the peracetic acid aqueous solution was immersed in a diluted solution diluted with water so as to have a peracetic acid concentration of 80 ppm for 10 minutes to sterilize the cells. The sterilized ginger pieces were drained so that the weight increase after soaking was 2% or less with respect to the weight before soaking.

<Detection of hydrogen peroxide after sterilization>
・ The following chemicals were prepared for the detection of hydrogen peroxide after sterilization.
Dissolve 27.2 g of monopotassium phosphate (manufactured by Wako Pure Chemical Industries, Ltd.) in water to make 1000 mL, and add 71.6 g of disodium phosphate (manufactured by Wako Pure Chemical Industries, Ltd.) to water. The second solution was prepared by dissolving in 1000 mL. Potassium bromate was dissolved in a mixture of 375 mL of the first solution and 625 mL of the second solution, and nitrogen was aerated for 1 hour or more under ice-cooling to prepare a phosphate buffer solution.
30% hydrogen peroxide solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) diluted with a phosphate buffer solution for calibration curves with hydrogen peroxide concentrations of 0.2 ppm, 0.4 ppm, 0.8 ppm, and 1.0 ppm A standard solution was prepared.
・ The presence or absence of detection of hydrogen peroxide after sterilization was performed as follows.
A high-sensitivity hydrogen peroxide meter (Orientator M5 type, manufactured by Central Science Co., Ltd.) was used to detect hydrogen peroxide after sterilization. Specifically, 100 g of sterilized ginger, 100 mL of phosphate buffer, and a polyethylene zipper bag were placed and shaken for 1 minute. The phosphate buffer solution soaked with ginger was transferred to a polyethylene beaker to prepare a test solution. The range of the high-sensitivity hydrogen peroxide meter was set to 1, and calibration was performed with a standard solution for a calibration curve having a hydrogen peroxide concentration of 1.0 ppm. Accurately 2 mL of a standard solution for a calibration curve having a hydrogen peroxide concentration of 0.2 ppm was taken, placed in a cell of a high-sensitivity hydrogen peroxide meter, and nitrogen gas was flowed while stirring with a stirrer. 20 μL of a nitrogen-aerated catalase solution (catalase for hydrogen peroxide meter, manufactured by Central Science Co., Ltd.) was injected into the cell, and the output value was recorded. Measure the standard solution for the calibration curve with hydrogen peroxide concentration of 0.4 ppm, 0.8 ppm, 1.0 ppm by the same method as the standard solution for the calibration curve with hydrogen peroxide concentration of 0.2 ppm, and measure the calibration curve from the output value. Created. The test solution was measured by the same method as the standard solution for a calibration curve having a hydrogen peroxide concentration of 0.2 ppm, and the hydrogen peroxide concentration was calculated from the calibration curve. If the hydrogen peroxide concentration was less than 0.2 ppm, it was not detected (judgment: none), and if the hydrogen peroxide concentration was 0.2 ppm or more, it was detected (judgment). : Yes).

(Example 1)
83.4 g of pure water and 60% by mass of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) (manufactured by Italmatch Japan Co., Ltd., product name: DayQuest 2010) 15.0 g, glacial acetic acid 527.3 g (Showa Denko KK, product name: 99% pure acetic acid), 35% by mass hydrogen hydrogen solution (Mitsubishi Gas Chemical Co., Ltd., product name: 35% hydrogen peroxide) 374.3 g in a polyethylene container. The mixture was added and mixed, adjusted to the ratio shown in Table 1, and then allowed to stand at 25 ° C. for 10 days to obtain an aqueous peracetic acid solution shown in Table 2. Table 2 shows the flash point, heat generation start temperature, heat generation amount, and detection result of hydrogen peroxide after sterilization of the obtained peracetic acid aqueous solution.

(Example 2)
Except for replacing 45.6 g of pure water and 11.7 g of 60% by mass of 1-hydroxyethylidene-1,1-diphosphonic acid, 597.0 g of glacial acetic acid, and 345.7 g of 35% by mass of hydrogen peroxide solution. The aqueous peracetic acid solution shown in Table 2 was obtained in the same manner as in Example 1. Table 2 shows the flash point, heat generation start temperature, heat generation amount, and detection result of hydrogen peroxide after sterilization of the obtained peracetic acid aqueous solution.

(Example 3)
Except for replacing 28.2 g of pure water, 11.7 g of 60% by mass of 1-hydroxyethylidene-1,1-diphosphonic acid, 603.0 g of glacial acetic acid, and 357.1 g of 35% by mass of hydrogen peroxide solution. The aqueous peracetic acid solution shown in Table 2 was obtained in the same manner as in Example 1. Table 2 shows the flash point, heat generation start temperature, heat generation amount, and detection result of hydrogen peroxide after sterilization of the obtained peracetic acid aqueous solution.

(Comparative Example 1)
63.1 g of pure water, 16.7 g of 1-hydroxyethylidene-1,1-diphosphonic acid of 60% by mass, 374.0 g of glacial acetic acid, and 45% by mass of hydrogen peroxide solution of 35% by mass of hydrogen peroxide solution ( A peracetic acid aqueous solution shown in Table 2 was obtained in the same manner as in Example 1 except that the product name was changed to 546.3 g (manufactured by Mitsubishi Gas Chemicals Co., Ltd., product name: 45% hydrogen peroxide). Table 2 shows the flash point, heat generation start temperature, heat generation amount, and detection result of hydrogen peroxide after sterilization of the obtained peracetic acid aqueous solution.

(Comparative Example 2)
67.7 g of pure water, 11.7 g of 60% by mass of 1-hydroxyethylidene-1,1-diphosphonic acid, 649.5 g of glacial acetic acid, and 45% by mass of hydrogen peroxide solution (45% by mass). An aqueous peracetic acid solution shown in Table 2 was obtained in the same manner as in Example 1 except that the product name was changed to 271.1 g (manufactured by Mitsubishi Gas Chemicals Co., Ltd., product name: 45% hydrogen peroxide). Table 2 shows the flash point of the obtained peracetic acid aqueous solution and the detection result of hydrogen peroxide after sterilization.

(Comparative Example 3)
60.1 g of pure water and 11.7 g of 60% by mass of 1-hydroxyethylidene-1,1-diphosphonic acid, 683.8 g of glacial acetic acid, and 45% by mass of hydrogen peroxide solution (45% by mass) hydrogen peroxide solution ( A peracetic acid aqueous solution shown in Table 2 was obtained in the same manner as in Example 1 except that the product name was 244.4 g (manufactured by Mitsubishi Gas Chemicals Co., Ltd., product name: 45% hydrogen peroxide). Table 2 shows the flash point of the obtained peracetic acid aqueous solution and the detection result of hydrogen peroxide after sterilization.

(Comparative Example 4)
0.1 g of pure water and 11.7 g of 60% by mass of 1-hydroxyethylidene-1,1-diphosphonic acid, 706.1 g of glacial acetic acid, and 45% by mass of hydrogen peroxide solution (45% by mass) hydrogen peroxide solution ( A peracetic acid aqueous solution shown in Table 2 was obtained in the same manner as in Example 1 except that the product name was 282.2 g (manufactured by Mitsubishi Gas Chemicals Co., Ltd., product name: 45% hydrogen peroxide). Table 2 shows the flash point of the obtained peracetic acid aqueous solution and the detection result of hydrogen peroxide after sterilization.

Claims (4)

It contains 13.0 to 15.5% by mass of peracetic acid, 5.0 to 17.0% by mass of hydrogen peroxide, 25.0 to 50.0% by mass of acetic acid, and water, and has a flash point of 70 ° C. or higher. Aqueous solution of peracetic acid for food additives. The peracetic acid aqueous solution for food additives according to claim 1, wherein the abundance ratio of hydrogen peroxide and peracetic acid in the aqueous solution is hydrogen peroxide / peracetic acid = 0.60 or less in terms of mass ratio. The peracetic acid aqueous solution for a food additive according to claim 1 or 2, which does not have a heat generation start temperature of less than 70 ° C. The peracetic acid aqueous solution for a food additive according to any one of claims 1 to 3, further comprising 1-hydroxyethylidene-1,1-diphosphonic acid in an amount of 0.6 to 1.0% by mass.