WO2019102742A1 - Method for producing peracetic acid composition to be used as food additive - Google Patents

Method for producing peracetic acid composition to be used as food additive Download PDF

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Publication number
WO2019102742A1
WO2019102742A1 PCT/JP2018/038232 JP2018038232W WO2019102742A1 WO 2019102742 A1 WO2019102742 A1 WO 2019102742A1 JP 2018038232 W JP2018038232 W JP 2018038232W WO 2019102742 A1 WO2019102742 A1 WO 2019102742A1
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Prior art keywords
peracetic acid
mass
hydrogen peroxide
acid composition
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PCT/JP2018/038232
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French (fr)
Japanese (ja)
Inventor
和志 杉本
享 印南
哲 岡部
君塚　健一
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三菱瓦斯化学株式会社
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Application filed by 三菱瓦斯化学株式会社 filed Critical 三菱瓦斯化学株式会社
Priority to JP2019556131A priority Critical patent/JP7156306B2/en
Priority to CN201880075959.8A priority patent/CN111372469A/en
Priority to KR1020207013741A priority patent/KR20200089664A/en
Publication of WO2019102742A1 publication Critical patent/WO2019102742A1/en

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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/3463—Organic compounds; Microorganisms; Enzymes
    • A23L3/3481—Organic compounds containing oxygen
    • A23L3/3508—Organic compounds containing oxygen containing carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C409/00—Peroxy compounds
    • C07C409/24—Peroxy compounds the —O—O— group being bound between a >C=O group and hydrogen, i.e. peroxy acids
    • C07C409/26—Peracetic acid

Definitions

  • the present invention relates to a method for producing a peracetic acid composition used as a food additive, and further to a production apparatus for producing a peracetic acid composition used as a food additive, and peracetic acid used as a food additive It relates to a composition.
  • an aqueous peracetic acid solution can be synthesized from acetic acid and hydrogen peroxide as raw materials.
  • Patent Document 1 Patent Document 1
  • JP-B-37-7459 Patent Document 2
  • FRANK P. GREEN SPAN J. Amer. Chem. Soc., 68, 907 (1946)
  • an aqueous peracetic acid solution having a peracetic acid concentration of 1 to 50% by weight can be synthesized depending on the conditions and selection of the raw material feed ratio.
  • the peracetic acid aqueous solution thus obtained is excellent in sterilization and disinfection due to its oxidizing power, as described in, for example, JP-B-61-10465 and JP-B-61-14122. It has also long been known to have the ability to bleach and the like.
  • peracetic acid aqueous solution like other organic peracids, is an inherently unstable substance and is strongly degraded due to heating, contamination with impurities, etc., and therefore storage stability is largely inferior upon use It was a drawback.
  • Stabilizers that directly improve the storage stability of aqueous peracetic acid solutions are known to indirectly improve the storage stability by sealing metal ions present in small amounts, although these have not been known so far.
  • the aqueous peracetic acid solution has excellent ability to disinfect, disinfect, bleach, etc., but its storage stability has been a major drawback in use.
  • methods for improving the storage stability of various peracetic acid aqueous solutions have been proposed so far, but methods for further improving the storage stability have been desired.
  • An object of the present invention is to provide a method for producing a peracetic acid composition which is excellent in storage stability and used as a food additive. Furthermore, this invention makes it a subject to provide the manufacturing apparatus which manufactures the peracetic acid composition used as said food additive, and the peracetic acid composition used as said food additive.
  • a method for producing a peracetic acid composition to be used as a food additive which comprises the step of mixing an aqueous solution of hydrogen peroxide, an acetic acid solution, and a substance containing 1-hydroxyethylidene-1,1-diphosphonic acid.
  • the aqueous hydrogen peroxide solution contains 10 ⁇ g / kg or more of aluminum and 30 to 40% by mass of hydrogen peroxide.
  • the acetic acid solution contains 10 ⁇ g / kg or more of aluminum, 50 ⁇ g / kg or less of iron, 50 mg / kg or less of PO 4 3- and 90 to 99.99 mass% of acetic acid It is a manufacturing method as described in said ⁇ 1> or ⁇ 2>.
  • ⁇ 4> The substance containing 1-hydroxyethylidene-1,1-diphosphonic acid contains 10 ⁇ g / kg or more of aluminum, 7 mg / kg or less of iron, and 50 mg / kg or less of PO 4 3- , And, the method according to any one of the above ⁇ 1> to ⁇ 3>, which contains 55 to 65% by mass of 1-hydroxyethylidene-1,1-diphosphonic acid.
  • ⁇ 5> The method according to any one of ⁇ 1> to ⁇ 4>, wherein a temperature to be mixed in the mixing step is 25 to 35 ° C.
  • ⁇ 6> The method according to any one of ⁇ 1> to ⁇ 5>, wherein the mixing time in the mixing step is 60 minutes or less.
  • ⁇ 7> The method according to any one of ⁇ 1> to ⁇ 6>, wherein the mixture is allowed to stand for one day or more after being mixed in the mixing step.
  • ⁇ 8> The method according to any one of ⁇ 1> to ⁇ 7>, further comprising the step of diluting the obtained peracetic acid composition with water.
  • a manufacturing apparatus used for a method of manufacturing a peracetic acid composition used as a food additive according to any one of ⁇ 1> to ⁇ 8> above Mixing pot for mixing, stirring and dissolving substances containing hydrogen peroxide solution, acetic acid solution and 1-hydroxyethylidene-1,1-diphosphonic acid, hydrogen peroxide aqueous solution feeder, dissolved glacial acetic acid feeder And a 1-hydroxyethylidene-1,1-diphosphonic acid feeding device, which is a production device for producing a peracetic acid composition used as a food additive.
  • ⁇ 10> Contains 50 ⁇ g / kg or more of aluminum, 300 ⁇ g / kg or less of iron, 200 mg / kg or less of PO 4 3- and has a total peroxide concentration of 10 to 18 mass% in terms of hydrogen peroxide , A peracetic acid composition used as a food additive.
  • ⁇ 11> Contains 25 ⁇ g / kg or more of aluminum, 20 ⁇ g / kg or less of iron, 15 mg / kg or less of PO 4 3- and has a total peroxide concentration of 5 to 12 mass% in terms of hydrogen peroxide , A peracetic acid composition used as a food additive.
  • ⁇ 12> The peracetic acid composition according to ⁇ 11>, wherein the equilibrium constant is 2 or more.
  • the manufacturing method of the peracetic acid composition excellent in storage stability and used as a food additive can be provided. Furthermore, this invention can provide the manufacturing apparatus which manufactures the peracetic acid composition used as said food additive, and the peracetic acid composition used as said food additive.
  • One embodiment of the present invention is a peracetic acid composition for use as a food additive comprising the step of mixing a substance comprising hydrogen peroxide aqueous solution, acetic acid solution, and 1-hydroxyethylidene-1,1-diphosphonic acid.
  • the aqueous hydrogen peroxide solution preferably contains 10 to 1000 ⁇ g / kg, more preferably 50 to 500, and particularly preferably 80 to 400 ⁇ g / kg of aluminum.
  • the aqueous hydrogen peroxide solution preferably contains aluminum at 10 ⁇ g / kg or more, since the storage stability of the peracetic acid composition is improved.
  • the aqueous hydrogen peroxide solution preferably contains 32 to 38% by mass, more preferably 35 to 36% by mass of hydrogen peroxide. It is preferable that the aqueous hydrogen peroxide solution contains hydrogen peroxide in an amount of 30 to 40% by mass, since it is safe, stable, and hydrogen peroxide conforming to the component specification of the food additive.
  • the reaction for obtaining a peracetic acid composition from an acetic acid solution and a hydrogen peroxide aqueous solution is known to be 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 higher concentrations are desirable for shortening the reaction time, and usually glacial acetic acid is used.
  • the concentration of the aqueous hydrogen peroxide solution is preferably higher to shorten the reaction time, but lower in terms of safety during handling, preferably 32 to 38% by mass, More preferably, an aqueous solution of 35 to 36% by mass is used.
  • the 1-hydroxyethylidene-1,1-diphosphonic acid (hereinafter sometimes referred to as "HEDP") used in the present invention is a protonic acid having a metal-sealing action, and the storage stability of the obtained peracetic acid composition Contribute to the improvement of
  • HEDP 1-hydroxyethylidene-1,1-diphosphonic acid
  • an aqueous solution of hydrogen peroxide and a solution of acetic acid in the presence of 1-hydroxyethylidene-1,1-diphosphonic acid described above are generally used,
  • the reaction is preferably carried out in a ratio of 1: 1 to 5 moles, more preferably 1: 2 to 4 moles.
  • the reaction crude solution can also be diluted with one or more of water, hydrogen peroxide aqueous solution or acetic acid solution.
  • the amount of 1-hydroxyethylidene-1,1-diphosphonic acid used in the present invention is preferably 0.1 to 1.0% by mass in the peracetic acid composition, and more preferably 0.2 to 0.9%. It is mass%.
  • the peracetic acid composition may not conform to the component specification of the food additive, while 0.1% by mass If it is less than%, the storage stability of the peracetic acid composition may be reduced.
  • the aqueous hydrogen peroxide solution preferably contains 50 ⁇ g / kg or less of iron and 50 mg / kg or less of PO 4 3- .
  • the hydrogen peroxide aqueous solution contains iron more preferably 30 ⁇ g / kg or less, particularly preferably 1 ⁇ g / kg to 30 ⁇ g / kg, and more preferably PO 4 3- or less 40 mg / kg, particularly preferably 1 mg / kg. It contains 40 mg / kg or less.
  • the aqueous hydrogen peroxide solution contains 50 ⁇ g / kg or less of iron because the storage stability of the peracetic acid composition is improved.
  • the aqueous hydrogen peroxide solution contains 50 mg / kg or less of PO 4 3 ⁇ because it becomes hydrogen peroxide conforming to the component specification of the food additive.
  • the acetic acid solution contains 10 ⁇ g / kg or more of aluminum, 50 ⁇ g / kg or less of iron, 50 mg / kg or less of PO 4 3- and 90 to 99.99 mass% of acetic acid.
  • the acetic acid solution contains aluminum, more preferably 10 to 1000 ⁇ g / kg, particularly preferably 50 to 150 ⁇ g / kg, iron more preferably 30 ⁇ g / kg or less, particularly preferably 1 ⁇ g / kg to 30 ⁇ g / kg. , more preferably the PO 4 3- 30mg / kg or less, particularly preferably contains 0 ⁇ 15 mg / kg, acetic acid and more preferably from 95 to 99.99% by weight, particularly preferably contains 99 to 99.99 wt% .
  • the substance containing 1-hydroxyethylidene-1,1-diphosphonic acid used in the present invention contains 10 ⁇ g / kg or more of aluminum, 7 mg / kg or less of iron, and 50 mg / kg or less of PO 4 3- And preferably contains 55 to 65% by mass of 1-hydroxyethylidene-1,1-diphosphonic acid.
  • the substance containing 1-hydroxyethylidene-1,1-diphosphonic acid preferably contains 10 to 1000 ⁇ g / kg of aluminum, more preferably 5 mg / kg or less of iron, particularly preferably 0.1 to 5 mg / kg. It contains and more preferably 30 mg / kg or less, particularly preferably 0 to 15 mg / kg, of PO 4 3- and more preferably 58 to 62% by mass of 1-hydroxyethylidene-1,1-diphosphonic acid.
  • the temperature to be mixed in the mixing step is preferably 25 to 35 ° C., and more preferably 25 to 30 ° C. It is preferable that the mixing temperature is 25 to 35 ° C. in that the reaction rate does not become too slow, and the volatilization of acetic acid and the decomposition of hydrogen peroxide and peracetic acid are suppressed.
  • the mixing time in the mixing step is preferably 60 minutes or less, and more preferably 10 to 60 minutes. If the mixing time exceeds 60 minutes, the power consumption required for mixing may increase and the cost may increase.
  • Another embodiment of the present invention is a production apparatus for use in the method of producing a peracetic acid composition used as the above-mentioned food additive, which comprises a hydrogen peroxide solution, an acetic acid solution, and 1-hydroxyethylidene-1,
  • a mixing kettle for mixing and stirring the substance containing 1-diphosphonic acid, a hydrogen peroxide aqueous solution feeder, a dissolved glacial acetic acid feeder, and a 1-hydroxyethylidene-1,1-diphosphonic acid feeder
  • the peracetic acid composition obtained by the production method of the present invention preferably contains 5 to 20% by mass, more preferably 5 to 15% by mass of peracetic acid, and preferably 4 to 15% by mass of hydrogen peroxide, more preferably 4 It contains 10 to 10% by mass, preferably 10 to 50% by mass, more preferably 30 to 50% by mass of acetic acid. If the concentration of peracetic acid is less than 5% by mass, the stability of peracetic acid decreases, which is not preferable. If it exceeds 20% by mass, the risk of handling increases, which is not preferable.
  • the concentration of hydrogen peroxide is the same and not preferable if it exceeds 15% by mass, and the concentration of acetic acid is also not preferable in terms of irritation to human body and odor if the concentration of acetic acid is also more than 50% by mass.
  • the peracetic acid composition obtained by the production method of the present invention is represented by the following two embodiments. That is, one embodiment of the present invention contains 50 ⁇ g / kg or more (preferably 50 to 300 ⁇ g / kg) of aluminum, 300 ⁇ g / kg or less (preferably 250 ⁇ g / kg or less) of iron, and 200 mg / g of PO 4 3- Used as a food additive that contains no more than kg (preferably 0.1 to 100 mg / kg) and has a total peroxide concentration of 10 to 18% by mass (preferably 11 to 15% by mass) in terms of hydrogen peroxide Peracetic acid composition.
  • another embodiment of the present invention contains 25 ⁇ g / kg or more (preferably 25 to 200 ⁇ g / kg) of aluminum, 20 ⁇ g / kg or less of iron (preferably 15 ⁇ g / kg or less), and PO 4 3- Food additive containing 15 mg / kg or less (preferably 0.1 to 10 mg / kg) and having a total peroxide concentration of 5 to 12% by mass (preferably 6 to 11% by mass) in terms of hydrogen peroxide
  • the equilibrium constant in the peracetic acid composition is preferably 2 or more, more preferably 2 to 3. If the equilibrium constant is less than 2, the storage stability of the peracetic acid composition may be reduced.
  • the peracetic acid composition preferably has no flash point in terms of safety during handling.
  • total peroxide means peracetic acid and hydrogen peroxide in the peracetic acid composition of the present invention, and the sum of their concentrations (mol / L) Is referred to as peroxide concentration (hereinafter sometimes referred to as total peroxide concentration).
  • the peroxide concentration in the peracetic acid composition of the present invention is preferably 1 to 7 mol / L, more preferably 2 to 5 mol / L. If it falls below this range, the peracetic acid concentration, that is, the bactericidal activity may decrease, and if it exceeds this range, the stability may decrease.
  • Another embodiment of the present invention is a method of sterilizing food, which comprises contacting the peracetic acid composition of the present invention with a food.
  • the method of contacting the peracetic acid composition with the food include, but are not limited to, a method of immersing the food in the peracetic acid composition, a method of spraying the peracetic acid composition on the food, and the like. It is not a thing. Since the peracetic acid composition of the present invention is excellent in storage stability, it has many advantages when used in a food sterilization method.
  • ⁇ Peroxide concentration of peracetic acid composition The hydrogen peroxide concentration of the peracetic acid composition was determined by redox titration. Specifically, about 0.1 g of a sample was accurately 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 titration was performed with a 0.1 mol / L cerium (IV) sulfate solution to calculate the hydrogen peroxide concentration.
  • ⁇ Acetic acid and peracetic acid concentration of peracetic acid composition The acetic acid and peracetic acid concentrations of the peracetic acid composition were determined by neutralization titration. Specifically, about 0.1 g of a sample was accurately weighed, placed in a 100 mL beaker, and about 50 mL of pure water was added to make a test solution. This test solution is titrated with a 0.1 mol / L sodium hydroxide solution, and the acetic acid concentration is added from the first inflection point, and the peracetic acid concentration is added from the first inflection point to the second inflection point. Calculated.
  • Total peroxide concentration of peracetic acid composition was determined by iodometric titration. Specifically, accurately measure about 0.1 g of the sample, put in a 250 mL Erlenmeyer flask, add 100 mL of pure water and 10 mL of 1.8 mol / L sulfuric acid, and then add 10 mL of 10 mass% potassium iodide solution, 1 mass% Several drops of ammonium molybdate solution were added to make a test solution.
  • ⁇ Stability of Peracetic Acid Composition> The stability of the peracetic acid composition was calculated from the ratio of the total peroxide concentration at the time of measurement, assuming that the total peroxide concentration at the time of preparation was 100.
  • Flash point of peracetic acid composition was determined by the Cleveland open flash point test.
  • a Cleveland open flash point tester was used according to the method of JIS-K2265.
  • Example 1 0.6 g of pure water 2.8 g and 60 mass% 1-hydroxyethylidene-1,1-diphosphonic acid (Italmatch Japan Co., Ltd. product name: D-Quest 2010) and 29.8 g glacial acetic acid (Showa Denko Product name: 99% pure acetic acid), 35 mass% hydrogen peroxide aqueous solution (Mitsubishi Gas Chemical Co., Ltd., product name: Diapower HP, containing a small amount of aluminum) 16.8 g, SUS304 (alias: 18Cr Test pieces of (-8 Ni, 18 chromium stainless steel) were put in a polyethylene container and mixed. The total peroxide concentration at the time of preparation was 11.9%.
  • Example 2 Potassium aluminum sulfate ⁇ 12 water (Wako Pure Chemical Industries, Ltd. reagent special grade) is added to a 35 mass% hydrogen peroxide aqueous solution (Mitsubishi Gas Chemical Co., Ltd., product name: UELM 35), and 35 mass% after addition
  • the aluminum content in the aqueous hydrogen peroxide solution is 10 ⁇ g / kg, 5.5 mass% of hydrogen peroxide, 48.9 mass% of acetic acid, 13.1 mass of peracetic acid
  • a peracetic acid composition was obtained which was used as a food additive containing%, and 0.8% by weight of 1-hydroxyethylidene-1,1-diphosphonic acid. About the obtained peracetic acid composition, the total peroxide concentration was measured 21 days after preparation, and stability was computed.
  • Example 3 Potassium aluminum sulfate ⁇ 12 water (Wako Pure Chemical Industries, Ltd. reagent special grade) is added to a 35 mass% hydrogen peroxide aqueous solution (Mitsubishi Gas Chemical Co., Ltd., product name: UELM 35), and 35 mass% after addition
  • the aluminum content in the aqueous hydrogen peroxide solution is 100 ⁇ g / kg, 5.5 mass% of hydrogen peroxide, 48.8 mass% of acetic acid, 13.5 mass of peracetic acid
  • a peracetic acid composition was obtained which was used as a food additive containing%, and 0.8% by weight of 1-hydroxyethylidene-1,1-diphosphonic acid. About the obtained peracetic acid composition, the total peroxide concentration was measured 21 days after preparation, and stability was computed.
  • Example 4 The test piece of SUS304 was not inserted, 35% by mass of Mitsubishi Gas Chemical Co., Ltd. instead of 35% by mass of hydrogen peroxide aqueous solution (product name: Diamond Power HP, containing a small amount of aluminum) manufactured by Mitsubishi Gas Chemical Co., Ltd. The same operation as in Example 1 was carried out except using the aqueous hydrogen peroxide solution (product name: 35% hydrogen peroxide), 5.5% by weight of hydrogen peroxide, 47.8% by weight of acetic acid, and 14.4% by weight of peracetic acid.
  • a peracetic acid composition used as a food additive containing 2% by mass and 0.8% by mass of 1-hydroxyethylidene-1,1-diphosphonic acid was obtained.
  • the total peroxide concentration was measured 63 days after preparation, and the stability was calculated.
  • Example 5 The test piece of SUS304 was not inserted, 35% by mass of Mitsubishi Gas Chemical Co., Ltd. instead of 35% by mass of hydrogen peroxide aqueous solution (product name: Diamond Power HP, containing a small amount of aluminum) manufactured by Mitsubishi Gas Chemical Co., Ltd. Aqueous solution of hydrogen peroxide (product name: 35% hydrogen peroxide), 1-hydroxyethylidene-1,1-diphosphonic acid (product name: Dayquest 2010) manufactured by Italmatch Japan Ltd. The same procedure as in Example 1 was repeated except that 1-hydroxyethylidene-1,1-diphosphonic acid (product name: PH-210) manufactured by Co., Ltd. was used, and 5.5% by mass of hydrogen peroxide, acetic acid 48.
  • 1-hydroxyethylidene-1,1-diphosphonic acid product name: PH-210 manufactured by Co., Ltd. was used, and 5.5% by mass of hydrogen peroxide, acetic acid 48.
  • Example 6 0.6 g of pure water 3.4 g and 60% by mass 1-hydroxyethylidene-1,1-diphosphonic acid (Italmatch Japan Ltd., product name: Dayquest 2010), 26.6 g glacial acetic acid (Showa Denko Product name: 99% pure acetic acid), 35% by mass of hydrogen peroxide aqueous solution (Mitsubishi Gas Chemical Co., Ltd., product name: 35% hydrogen peroxide) 19.4 g were mixed in a polyethylene container. The total peroxide concentration at the time of preparation was 13.7%. After mixing, the mixture is allowed to stand at 25 ° C.
  • Example 7 35% by mass hydrogen peroxide aqueous solution (manufactured by Mitsubishi Gas Chemical Co., Ltd., product name: Diapower HP) instead of 35% by mass hydrogen peroxide aqueous solution (manufactured by Mitsubishi Gas Chemical Co., Ltd., product name: 35% hydrogen peroxide)
  • Example 7 35% by mass hydrogen peroxide aqueous solution (manufactured by Mitsubishi Gas Chemical Co., Ltd., product name: Diapower HP) instead of 35% by mass hydrogen peroxide aqueous solution (manufactured by Mitsubishi Gas Chemical Co., Ltd., product name: 35% hydrogen peroxide)
  • 7.5% by mass of hydrogen peroxide 42.1% by mass of acetic acid, 14.1% by mass of peracetic acid, and 1-hydroxyethylidene
  • a peracetic acid composition used as a food additive containing 0.8% by mass of 1,1-diphosphonic acid was obtained.
  • the total peroxide concentration was measured 35 days after preparation, and the stability was calculated.
  • Example 8 Iron standard solution (Wako Pure Chemical Industries, Ltd., Fe 1000) in 35% by mass hydrogen peroxide aqueous solution (Mitsubishi Gas Chemical Co., Ltd., product name: 35% hydrogen peroxide), sodium dihydrogen phosphate dihydrate (Wako Pure Chemical Industries, Ltd., reagent special grade) is added, iron content in 35% by mass of hydrogen peroxide aqueous solution after addition is 100 ⁇ g / kg, and PO 4 3- content is 52.9 mg / kg
  • Example 6 The same procedures as in Example 6 were carried out except that 7.3% by mass of hydrogen peroxide, 42.2% by mass of acetic acid, 13.9% by mass of peracetic acid, and 0-hydroxyethylidene-1,1-diphosphonic acid were used.
  • a peracetic acid composition used as a food additive containing 8% by mass was obtained. For the obtained peracetic acid composition, the total peroxide concentration was measured 35 days after preparation, and the stability was calculated.
  • Example 9 Iron standard solution (Wako Pure Chemical Industries, Ltd., Fe 1000) in 35% by mass hydrogen peroxide aqueous solution (Mitsubishi Gas Chemical Co., Ltd., product name: 35% hydrogen peroxide), sodium dihydrogen phosphate dihydrate (Wako Pure Chemical Industries, Ltd., reagent special grade) is added, iron content in 35% by mass hydrogen peroxide aqueous solution after addition is 510 ⁇ g / kg, and PO 4 3- content is 52.9 mg / kg
  • Example 6 Example 9
  • Example 9 Iron standard solution (Wako Pure Chemical Industries, Ltd., Fe 1000) in 35% by mass hydrogen peroxide aqueous solution (Mitsubishi Gas Chemical Co., Ltd., product name: 35% hydrogen peroxide)
  • sodium dihydrogen phosphate dihydrate (Wako Pure Chemical Industries, Ltd., reagent special grade) is added
  • iron content in 35% by mass hydrogen peroxide aqueous solution after addition is 510 ⁇ g / kg
  • PO 4 3- content
  • Example 10 Pure water 55.0 g and 60 mass% 1-hydroxyethylidene-1,1-diphosphonic acid (Italmatch Japan Ltd. make, product name: DIGEST 2010) 12.8 g, glacial acetic acid 651.0 g (Showa Denko Product name: 99% pure good acetic acid), after mixing 381.1 g of 35% by mass hydrogen peroxide aqueous solution (Mitsubishi Gas Chemical Co., Ltd. product name: 35% hydrogen peroxide) in a polyethylene container By standing at 25 ° C.
  • the peracetic acid composition used as a food additive containing mass% was obtained.
  • the equilibrium constant was 2.4.
  • the obtained peracetic acid composition is diluted 1.2 times with pure water and allowed to stand at 25 ° C. for 10 days, whereby 6.0 mass% of hydrogen peroxide, 42.4 mass% of acetic acid, 9.4 mass of peracetic acid A peracetic acid composition was obtained which was used as a food additive containing%, and 0.6% by weight of 1-hydroxyethylidene-1,1-diphosphonic acid.
  • the equilibrium constant was calculated for the obtained peracetic acid composition, and the flash point was measured.
  • Example 11 The same operation as in Example 10 is carried out except that the obtained peracetic acid composition is diluted 1.3 times with pure water, and 6.0 mass% of hydrogen peroxide, 39.9 mass% of acetic acid, 7.9 mass of peracetic acid A peracetic acid composition used as a food additive containing 5% by weight of 1-hydroxyethylidene-1,1-diphosphonic acid was obtained. The equilibrium constant was calculated for the obtained peracetic acid composition, and the flash point was measured.
  • Example 12 The same operation as in Example 10 is carried out except that the obtained peracetic acid composition is diluted 1.4 times with pure water, and 5.9 mass% of hydrogen peroxide, 37.7 mass% of acetic acid, 6.2 mass of peracetic acid A peracetic acid composition used as a food additive containing 5% by weight of 1-hydroxyethylidene-1,1-diphosphonic acid was obtained. The equilibrium constant was calculated for the obtained peracetic acid composition, and the flash point was measured.
  • Example 1 35% by mass aqueous hydrogen peroxide solution (manufactured by Mitsubishi Gas Chemical Co., Ltd., product name: UELM 35) instead of 35% by mass aqueous hydrogen peroxide solution (manufactured by Mitsubishi Gas Chemical Co., Ltd., product name: Diapower HP, containing a small amount of aluminum)
  • UELM 35 35% by mass aqueous hydrogen peroxide solution
  • Diapower HP containing a small amount of aluminum

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Abstract

According to the present invention, it is possible to provide a method for producing a peracetic acid composition to be used as a food additive, said method comprising a step for mixing an aqueous hydrogen peroxide solution, an acetic acid solution and a substance which contains 1-hydroxyethylidene-1,1-diphosphonic acid, wherein the aqueous hydrogen peroxide solution contains 10 μg/kg or more of aluminum and 30-40 mass% of hydrogen peroxide.

Description

食品添加物として使用される過酢酸組成物の製造方法Process for producing peracetic acid composition used as food additive
　本発明は、食品添加物として使用される過酢酸組成物の製造方法に関し、更には、食品添加物として使用される過酢酸組成物を製造する製造装置、及び食品添加物として使用される過酢酸組成物に関する。 The present invention relates to a method for producing a peracetic acid composition used as a food additive, and further to a production apparatus for producing a peracetic acid composition used as a food additive, and peracetic acid used as a food additive It relates to a composition.
　酢酸と過酸化水素とを原料として、過酢酸水溶液が合成できることは古くから知られている。例えば、特公昭６１－１０４６５号（特許文献１）、特公昭３７－７４５９号公報、或いはFRANK P. GREENSPANの報告（J. Amer. Chem. Soc., 68, 907(1946)）には、反応条件や原料仕込比の選択により、過酢酸濃度が１～５０重量％の過酢酸水溶液が合成できることが記載されている。 It has long been known that an aqueous peracetic acid solution can be synthesized from acetic acid and hydrogen peroxide as raw materials. For example, reaction to JP-B-61-10465 (Patent Document 1), JP-B-37-7459, or the report of FRANK P. GREEN SPAN (J. Amer. Chem. Soc., 68, 907 (1946)). It is described that an aqueous peracetic acid solution having a peracetic acid concentration of 1 to 50% by weight can be synthesized depending on the conditions and selection of the raw material feed ratio.
　また、そのようにして得られた過酢酸水溶液は、例えば、特公昭６１－１０４６５号、特公昭６１－１４１２２号公報に記載されているように、その酸化力のために優れた殺菌、消毒、漂白等の能力を有することも古くから知られている。一方、過酢酸水溶液は、他の有機過酸と同様、元来不安定な物質であり、加熱したり、不純物による汚染などにより、激しく分解するため、使用に際して、貯蔵安定性が劣ることが大きな欠点となっていた。過酢酸水溶液の貯蔵安定性を直接向上させる安定剤は、これまでに知られていないが、微量存在する金属イオンを封止することにより、間接的に貯蔵安定性を向上させることが知られていた。 Moreover, the peracetic acid aqueous solution thus obtained is excellent in sterilization and disinfection due to its oxidizing power, as described in, for example, JP-B-61-10465 and JP-B-61-14122. It has also long been known to have the ability to bleach and the like. On the other hand, peracetic acid aqueous solution, like other organic peracids, is an inherently unstable substance and is strongly degraded due to heating, contamination with impurities, etc., and therefore storage stability is largely inferior upon use It was a drawback. Stabilizers that directly improve the storage stability of aqueous peracetic acid solutions are known to indirectly improve the storage stability by sealing metal ions present in small amounts, although these have not been known so far. The
　上記のように、過酢酸水溶液は優れた殺菌、消毒、漂白等の能力を有しているが、使用に際して、貯蔵安定性が劣ることが大きな欠点となっていた。この問題の解決のため、これまでに、種々の過酢酸水溶液の貯蔵安定性を向上する方法が提案されているが、さらなる貯蔵安定性を向上する方法が望まれていた。 As described above, the aqueous peracetic acid solution has excellent ability to disinfect, disinfect, bleach, etc., but its storage stability has been a major drawback in use. In order to solve this problem, methods for improving the storage stability of various peracetic acid aqueous solutions have been proposed so far, but methods for further improving the storage stability have been desired.
特公昭６１－１０４６５号Japanese Examined Patent Publication No. 61-10465
　本発明は、貯蔵安定性に優れた、食品添加物として使用される過酢酸組成物の製造方法を提供することを課題とする。更に、本発明は、上記食品添加物として使用される過酢酸組成物を製造する製造装置、及び上記食品添加物として使用される過酢酸組成物を提供することを課題とする。 An object of the present invention is to provide a method for producing a peracetic acid composition which is excellent in storage stability and used as a food additive. Furthermore, this invention makes it a subject to provide the manufacturing apparatus which manufactures the peracetic acid composition used as said food additive, and the peracetic acid composition used as said food additive.
　本発明者は、かかる問題点を解決するため鋭意検討した結果、アルミニウムを所定量含有する過酸化水素水溶液、酢酸溶液、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸を混合することにより、得られる過酢酸組成物の貯蔵安定性が飛躍的に向上することを見出し、本発明を完成するに至った。
　即ち、本発明は、以下の通りである。
＜１＞　過酸化水素水溶液、酢酸溶液、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸を含む物質を混合する工程を含む、食品添加物として使用される過酢酸組成物の製造方法であって、
　前記過酸化水素水溶液が、アルミニウムを１０μｇ／ｋｇ以上含有し、かつ、過酸化水素を３０～４０質量％含有する、前記製造方法である。
＜２＞　さらに、前記過酸化水素水溶液が、鉄を５０μｇ／ｋｇ以下含有し、かつ、ＰＯ４ ３－を５０ｍｇ／ｋｇ以下含有する、上記＜１＞に記載の製造方法である。
＜３＞　前記酢酸溶液が、アルミニウムを１０μｇ／ｋｇ以上含有し、鉄を５０μｇ／ｋｇ以下含有し、ＰＯ４ ３－を５０ｍｇ／ｋｇ以下含有し、かつ、酢酸を９０～９９．９９質量％含有する、上記＜１＞又は＜２＞に記載の製造方法である。
＜４＞　前記１－ヒドロキシエチリデン－１，１－ジホスホン酸を含む物質が、アルミニウムを１０μｇ／ｋｇ以上含有し、鉄を７ｍｇ／ｋｇ以下含有し、ＰＯ４ ３－を５０ｍｇ／ｋｇ以下含有し、かつ、１－ヒドロキシエチリデン－１，１－ジホスホン酸を５５～６５質量％含有する、上記＜１＞～＜３＞のいずれかに記載の製造方法である。
＜５＞　前記混合工程において混合する温度が、２５～３５℃である、上記＜１＞～＜４＞のいずれかに記載の製造方法である。
＜６＞　前記混合工程において混合する時間が、６０分以下である、上記＜１＞～＜５＞のいずれかに記載の製造方法である。
＜７＞　前記混合工程において混合をした後に、１日以上静置する、上記＜１＞～＜６＞のいずれかに記載の製造方法である。
＜８＞　さらに、得られた過酢酸組成物を水で希釈する工程を含む、上記＜１＞～＜７＞のいずれかに記載の製造方法である。
＜９＞　上記＜１＞～＜８＞のいずれかに記載の食品添加物として使用される過酢酸組成物の製造方法に用いられる製造装置であって、
　過酸化水素溶液、酢酸溶液、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸を含む物質を混合し、攪拌して溶解するための混合釜、過酸化水素水溶液投入装置、溶解した氷酢酸投入装置、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸投入装置を有する、食品添加物として使用される過酢酸組成物を製造する製造装置である。
＜１０＞　アルミニウムを５０μｇ／ｋｇ以上含み、鉄を３００μｇ／ｋｇ以下含み、ＰＯ４ ３－を２００ｍｇ／ｋｇ以下含み、かつ、過酸化水素換算で全過酸化物濃度が１０～１８質量％である、食品添加物として使用される過酢酸組成物である。
＜１１＞　アルミニウムを２５μｇ／ｋｇ以上含み、鉄を２０μｇ／ｋｇ以下含み、ＰＯ４ ３－を１５ｍｇ／ｋｇ以下含み、かつ、過酸化水素換算で全過酸化物濃度が５～１２質量％である、食品添加物として使用される過酢酸組成物である。
＜１２＞　平衡定数が２以上である、上記＜１１＞に記載の過酢酸組成物である。
＜１３＞　引火点を有さない、上記＜１１＞又は＜１２＞に記載の過酢酸組成物である。
＜１４＞　上記＜１０＞～＜１３＞のいずれかに記載の過酢酸組成物と、食品とを接触させる、食品の殺菌方法である。 As a result of intensive studies to solve such problems, the present inventors obtained by mixing an aqueous hydrogen peroxide solution containing a predetermined amount of aluminum, an acetic acid solution, and 1-hydroxyethylidene-1,1-diphosphonic acid. It has been found that the storage stability of the resulting peracetic acid composition is dramatically improved, and the present invention has been completed.
That is, the present invention is as follows.
<1> A method for producing a peracetic acid composition to be used as a food additive, which comprises the step of mixing an aqueous solution of hydrogen peroxide, an acetic acid solution, and a substance containing 1-hydroxyethylidene-1,1-diphosphonic acid. ,
In the above manufacturing method, the aqueous hydrogen peroxide solution contains 10 μg / kg or more of aluminum and 30 to 40% by mass of hydrogen peroxide.
<2> The method according to <1>, wherein the aqueous hydrogen peroxide solution further contains 50 μg / kg or less of iron and 50 mg / kg or less of PO 4 3- .
<3> The acetic acid solution contains 10 μg / kg or more of aluminum, 50 μg / kg or less of iron, 50 mg / kg or less of PO 4 3- and 90 to 99.99 mass% of acetic acid It is a manufacturing method as described in said <1> or <2>.
<4> The substance containing 1-hydroxyethylidene-1,1-diphosphonic acid contains 10 μg / kg or more of aluminum, 7 mg / kg or less of iron, and 50 mg / kg or less of PO 4 3- , And, the method according to any one of the above <1> to <3>, which contains 55 to 65% by mass of 1-hydroxyethylidene-1,1-diphosphonic acid.
<5> The method according to any one of <1> to <4>, wherein a temperature to be mixed in the mixing step is 25 to 35 ° C.
<6> The method according to any one of <1> to <5>, wherein the mixing time in the mixing step is 60 minutes or less.
<7> The method according to any one of <1> to <6>, wherein the mixture is allowed to stand for one day or more after being mixed in the mixing step.
<8> The method according to any one of <1> to <7>, further comprising the step of diluting the obtained peracetic acid composition with water.
<9> A manufacturing apparatus used for a method of manufacturing a peracetic acid composition used as a food additive according to any one of <1> to <8> above,
Mixing pot for mixing, stirring and dissolving substances containing hydrogen peroxide solution, acetic acid solution and 1-hydroxyethylidene-1,1-diphosphonic acid, hydrogen peroxide aqueous solution feeder, dissolved glacial acetic acid feeder And a 1-hydroxyethylidene-1,1-diphosphonic acid feeding device, which is a production device for producing a peracetic acid composition used as a food additive.
<10> Contains 50 μg / kg or more of aluminum, 300 μg / kg or less of iron, 200 mg / kg or less of PO 4 3- and has a total peroxide concentration of 10 to 18 mass% in terms of hydrogen peroxide , A peracetic acid composition used as a food additive.
<11> Contains 25 μg / kg or more of aluminum, 20 μg / kg or less of iron, 15 mg / kg or less of PO 4 3- and has a total peroxide concentration of 5 to 12 mass% in terms of hydrogen peroxide , A peracetic acid composition used as a food additive.
<12> The peracetic acid composition according to <11>, wherein the equilibrium constant is 2 or more.
It is a peracetic acid composition as described in said <11> or <12> which does not have a <13> flash point.
<14> A method for sterilizing a food, comprising bringing the peracetic acid composition according to any one of the above <10> to <13> into contact with the food.
　本発明によれば、貯蔵安定性に優れた、食品添加物として使用される過酢酸組成物の製造方法を提供することができる。更に、本発明は、上記食品添加物として使用される過酢酸組成物を製造する製造装置、及び上記食品添加物として使用される過酢酸組成物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the peracetic acid composition excellent in storage stability and used as a food additive can be provided. Furthermore, this invention can provide the manufacturing apparatus which manufactures the peracetic acid composition used as said food additive, and the peracetic acid composition used as said food additive.
　以下、本発明の食品添加物として使用される過酢酸組成物の製造方法について具体的に説明する。なお、以下に説明する材料及び構成等は本発明を限定するものではなく、本発明の趣旨の範囲内で種々改変することができるものである。なお、本明細書において、数値範囲を「～」を用いて示した時、その両端の数値を含む。 Hereinafter, the manufacturing method of the peracetic acid composition used as a food additive of this invention is demonstrated concretely. The materials, configurations, and the like described below do not limit the present invention, and various modifications can be made within the scope of the present invention. In the present specification, when a numerical range is indicated using “to”, numerical values at both ends thereof are included.
　本発明の一実施形態は、過酸化水素水溶液、酢酸溶液、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸を含む物質を混合する工程を含む、食品添加物として使用される過酢酸組成物の製造方法であって、前記過酸化水素水溶液が、アルミニウムを１０μｇ／ｋｇ以上含有し、かつ、過酸化水素を３０～４０質量％含有する、前記製造方法である。
　前記過酸化水素水溶液は、アルミニウムを好ましくは１０～１０００μｇ／ｋｇ含有し、より好ましくは５０～５００、特に好ましくは８０～４００μｇ／ｋｇ含有する。前記過酸化水素水溶液が、アルミニウムを１０μｇ／ｋｇ以上含有することにより、前記過酢酸組成物の貯蔵安定性が向上するため好ましい。
　また、前記過酸化水素水溶液は、過酸化水素を好ましくは３２～３８質量％、より好ましくは３５～３６質量％含有する。前記過酸化水素水溶液が、過酸化水素を３０～４０質量％含有することにより、安全で、安定で、食品添加物の成分規格に合致した過酸化水素となるため好ましい。
　本発明の過酢酸組成物の製造方法において、酢酸溶液と過酸化水素水溶液から過酢酸組成物を得る反応は、次の式に従う平衡反応であることが知られている。
Figure JPOXMLDOC01-appb-C000001
 　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、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。 One embodiment of the present invention is a peracetic acid composition for use as a food additive comprising the step of mixing a substance comprising hydrogen peroxide aqueous solution, acetic acid solution, and 1-hydroxyethylidene-1,1-diphosphonic acid. The method according to claim 1, wherein the aqueous hydrogen peroxide solution contains 10 μg / kg or more of aluminum and 30 to 40% by mass of hydrogen peroxide.
The aqueous hydrogen peroxide solution preferably contains 10 to 1000 μg / kg, more preferably 50 to 500, and particularly preferably 80 to 400 μg / kg of aluminum. The aqueous hydrogen peroxide solution preferably contains aluminum at 10 μg / kg or more, since the storage stability of the peracetic acid composition is improved.
The aqueous hydrogen peroxide solution preferably contains 32 to 38% by mass, more preferably 35 to 36% by mass of hydrogen peroxide. It is preferable that the aqueous hydrogen peroxide solution contains hydrogen peroxide in an amount of 30 to 40% by mass, since it is safe, stable, and hydrogen peroxide conforming to the component specification of the food additive.
In the method for producing a peracetic acid composition of the present invention, the reaction for obtaining a peracetic acid composition from an acetic acid solution and a hydrogen peroxide aqueous solution is known to be an equilibrium reaction according to the following formula.
Figure JPOXMLDOC01-appb-C000001
 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 higher concentrations are desirable for shortening the reaction time, and usually glacial acetic acid is used. The concentration of the aqueous hydrogen peroxide solution is preferably higher to shorten the reaction time, but lower in terms of safety during handling, preferably 32 to 38% by mass, More preferably, an aqueous solution of 35 to 36% by mass is used.
　本発明で用いる１－ヒドロキシエチリデン－１，１－ジホスホン酸（以下、「ＨＥＤＰ」と呼ぶことがある）は、金属封止作用を有するプロトン酸であり、得られた過酢酸組成物の貯蔵安定性の向上に寄与する。本発明の過酢酸組成物を得るためには、種々の方法が考えられるが、一般には上記の１－ヒドロキシエチリデン－１，１－ジホスホン酸の存在下で、過酸化水素水溶液及び酢酸溶液を、好ましくは１：１～５モル、より好ましくは１：２～４モルの割合で反応させる方法で行われる。必要な場合には、その反応粗液を水、過酸化水素水溶液あるいは酢酸溶液のうちの１つ以上で希釈することもできる。
　本発明で用いる１－ヒドロキシエチリデン－１，１－ジホスホン酸の使用量は、過酢酸組成物中に好ましくは０．１～１．０質量％であり、より好ましくは０．２～０．９質量％である。１－ヒドロキシエチリデン－１，１－ジホスホン酸の使用量が１．０質量％より多いと、前記過酢酸組成物が食品添加物の成分規格に合致しなくなることがあり、一方、０．１質量％より少ないと、前記過酢酸組成物の貯蔵安定性が低下することがある。 The 1-hydroxyethylidene-1,1-diphosphonic acid (hereinafter sometimes referred to as "HEDP") used in the present invention is a protonic acid having a metal-sealing action, and the storage stability of the obtained peracetic acid composition Contribute to the improvement of Although various methods can be considered to obtain the peracetic acid composition of the present invention, an aqueous solution of hydrogen peroxide and a solution of acetic acid in the presence of 1-hydroxyethylidene-1,1-diphosphonic acid described above are generally used, The reaction is preferably carried out in a ratio of 1: 1 to 5 moles, more preferably 1: 2 to 4 moles. If necessary, the reaction crude solution can also be diluted with one or more of water, hydrogen peroxide aqueous solution or acetic acid solution.
The amount of 1-hydroxyethylidene-1,1-diphosphonic acid used in the present invention is preferably 0.1 to 1.0% by mass in the peracetic acid composition, and more preferably 0.2 to 0.9%. It is mass%. When the amount of 1-hydroxyethylidene-1,1-diphosphonic acid used is more than 1.0% by mass, the peracetic acid composition may not conform to the component specification of the food additive, while 0.1% by mass If it is less than%, the storage stability of the peracetic acid composition may be reduced.
　前記過酸化水素水溶液は、鉄を５０μｇ／ｋｇ以下含有し、かつ、ＰＯ４ ３－を５０ｍｇ／ｋｇ以下含有することが好ましい。前記過酸化水素水溶液は、鉄をより好ましくは３０μｇ／ｋｇ以下、特に好ましくは１μｇ／ｋｇ以上３０μｇ／ｋｇ以下含有し、ＰＯ４ ３－をより好ましくは４０ｍｇ／ｋｇ以下、特に好ましくは１ｍｇ／ｋｇ以上４０ｍｇ／ｋｇ以下含有する。
　前記過酸化水素水溶液が、鉄を５０μｇ／ｋｇ以下含有すると、前記過酢酸組成物の貯蔵安定性が向上するため好ましい。また、前記過酸化水素水溶液が、ＰＯ４ ３－を５０ｍｇ／ｋｇ以下含有すると、食品添加物の成分規格に合致した過酸化水素となるため好ましい。 The aqueous hydrogen peroxide solution preferably contains 50 μg / kg or less of iron and 50 mg / kg or less of PO 4 3- . The hydrogen peroxide aqueous solution contains iron more preferably 30 μg / kg or less, particularly preferably 1 μg / kg to 30 μg / kg, and more preferably PO 4 3- or less 40 mg / kg, particularly preferably 1 mg / kg. It contains 40 mg / kg or less.
It is preferable that the aqueous hydrogen peroxide solution contains 50 μg / kg or less of iron because the storage stability of the peracetic acid composition is improved. Further, it is preferable that the aqueous hydrogen peroxide solution contains 50 mg / kg or less of PO 4 3− because it becomes hydrogen peroxide conforming to the component specification of the food additive.
　前記酢酸溶液は、アルミニウムを１０μｇ／ｋｇ以上含有し、鉄を５０μｇ／ｋｇ以下含有し、ＰＯ４ ３－を５０ｍｇ／ｋｇ以下含有し、かつ、酢酸を９０～９９．９９質量％含有することが好ましい。前記酢酸溶液は、アルミニウムをより好ましくは１０～１０００μｇ／ｋｇ、特に好ましくは５０～１５０μｇ／ｋｇ含有し、鉄をより好ましくは３０μｇ／ｋｇ以下、特に好ましくは１μｇ／ｋｇ以上３０μｇ／ｋｇ以下含有し、ＰＯ４ ３－をより好ましくは３０ｍｇ／ｋｇ以下、特に好ましくは０～１５ｍｇ／ｋｇ含有し、酢酸をより好ましくは９５～９９．９９質量％、特に好ましくは９９～９９．９９質量％含有する。 The acetic acid solution contains 10 μg / kg or more of aluminum, 50 μg / kg or less of iron, 50 mg / kg or less of PO 4 3- and 90 to 99.99 mass% of acetic acid. preferable. The acetic acid solution contains aluminum, more preferably 10 to 1000 μg / kg, particularly preferably 50 to 150 μg / kg, iron more preferably 30 μg / kg or less, particularly preferably 1 μg / kg to 30 μg / kg. , more preferably the PO 4 3- 30mg / kg or less, particularly preferably contains 0 ~ 15 mg / kg, acetic acid and more preferably from 95 to 99.99% by weight, particularly preferably contains 99 to 99.99 wt% .
　本発明で使用される１－ヒドロキシエチリデン－１，１－ジホスホン酸を含む物質は、アルミニウムを１０μｇ／ｋｇ以上含有し、鉄を７ｍｇ／ｋｇ以下含有し、ＰＯ４ ３－を５０ｍｇ／ｋｇ以下含有し、かつ、１－ヒドロキシエチリデン－１，１－ジホスホン酸を５５～６５質量％含有することが好ましい。
　前記１－ヒドロキシエチリデン－１，１－ジホスホン酸を含む物質は、アルミニウムをより好ましくは１０～１０００μｇ／ｋｇ含有し、鉄をより好ましくは５ｍｇ／ｋｇ以下、特に好ましくは０．１～５ｍｇ／ｋｇ含有し、ＰＯ４ ３－をより好ましくは３０ｍｇ／ｋｇ以下、特に好ましくは０～１５ｍｇ／ｋｇ含有し、１－ヒドロキシエチリデン－１，１－ジホスホン酸をより好ましくは５８～６２質量％含有する。 The substance containing 1-hydroxyethylidene-1,1-diphosphonic acid used in the present invention contains 10 μg / kg or more of aluminum, 7 mg / kg or less of iron, and 50 mg / kg or less of PO 4 3- And preferably contains 55 to 65% by mass of 1-hydroxyethylidene-1,1-diphosphonic acid.
The substance containing 1-hydroxyethylidene-1,1-diphosphonic acid preferably contains 10 to 1000 μg / kg of aluminum, more preferably 5 mg / kg or less of iron, particularly preferably 0.1 to 5 mg / kg. It contains and more preferably 30 mg / kg or less, particularly preferably 0 to 15 mg / kg, of PO 4 3- and more preferably 58 to 62% by mass of 1-hydroxyethylidene-1,1-diphosphonic acid.
　前記混合工程において混合する温度は、２５～３５℃が好ましくは、２５～３０℃がより好ましい。混合する温度が２５～３５℃であると、反応速度が遅くなり過ぎず、かつ、酢酸の揮発及び過酸化水素、過酢酸の分解が抑えられる点で好ましい。
　前記混合工程において混合する時間は、６０分以下が好ましく、１０～６０分がより好ましい。混合する時間が、６０分を超えると、混合に要する電力消費量が大きくなり、コストが上がることがある。
　前記混合工程において混合をした後に、１日以上静置することが反応が完了する点で好ましく、１～１０日静置することがより好ましい。
　本発明では、さらに、得られた過酢酸組成物を水で希釈する工程を含むことが、引火しなくなる点で好ましい。 The temperature to be mixed in the mixing step is preferably 25 to 35 ° C., and more preferably 25 to 30 ° C. It is preferable that the mixing temperature is 25 to 35 ° C. in that the reaction rate does not become too slow, and the volatilization of acetic acid and the decomposition of hydrogen peroxide and peracetic acid are suppressed.
The mixing time in the mixing step is preferably 60 minutes or less, and more preferably 10 to 60 minutes. If the mixing time exceeds 60 minutes, the power consumption required for mixing may increase and the cost may increase.
After mixing in the mixing step, it is preferable to stand still for 1 day or more in that the reaction is completed, and it is more preferable to stand for 1 to 10 days.
In the present invention, it is preferable to further include the step of diluting the obtained peracetic acid composition with water in that it does not ignite.
　本発明の別の一実施形態は、上記食品添加物として使用される過酢酸組成物の製造方法に用いられる製造装置であって、過酸化水素溶液、酢酸溶液、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸を含む物質を混合し、攪拌して溶解するための混合釜、過酸化水素水溶液投入装置、溶解した氷酢酸投入装置、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸投入装置を有する、食品添加物として使用される過酢酸組成物を製造する製造装置である。 Another embodiment of the present invention is a production apparatus for use in the method of producing a peracetic acid composition used as the above-mentioned food additive, which comprises a hydrogen peroxide solution, an acetic acid solution, and 1-hydroxyethylidene-1, A mixing kettle for mixing and stirring the substance containing 1-diphosphonic acid, a hydrogen peroxide aqueous solution feeder, a dissolved glacial acetic acid feeder, and a 1-hydroxyethylidene-1,1-diphosphonic acid feeder It is a manufacturing apparatus which manufactures the peracetic acid composition used as a food additive which it has.
　本発明の製造方法により得られる過酢酸組成物は、過酢酸を好ましくは５～２０質量％、より好ましくは５～１５質量％、過酸化水素を好ましくは４～１５質量％、より好ましくは４～１０質量％、酢酸を好ましくは１０～５０質量％、より好ましくは３０～５０質量％含有する。過酢酸の濃度が、５質量％未満では、過酢酸の安定性が低下するため好ましくなく、また２０質量％を超えると取扱い時の危険性が大きくなって好ましくない。また、過酸化水素の濃度は、１５質量％を超えると、同様であり好ましくなく、酢酸の濃度も５０質量％を超えると、人体への刺激性や臭気の面で好ましくない。 The peracetic acid composition obtained by the production method of the present invention preferably contains 5 to 20% by mass, more preferably 5 to 15% by mass of peracetic acid, and preferably 4 to 15% by mass of hydrogen peroxide, more preferably 4 It contains 10 to 10% by mass, preferably 10 to 50% by mass, more preferably 30 to 50% by mass of acetic acid. If the concentration of peracetic acid is less than 5% by mass, the stability of peracetic acid decreases, which is not preferable. If it exceeds 20% by mass, the risk of handling increases, which is not preferable. Further, the concentration of hydrogen peroxide is the same and not preferable if it exceeds 15% by mass, and the concentration of acetic acid is also not preferable in terms of irritation to human body and odor if the concentration of acetic acid is also more than 50% by mass.
　本発明の製造方法により得られる過酢酸組成物は、以下の二つの実施形態によって表されるものである。
　即ち、本発明の一実施形態は、アルミニウムを５０μｇ／ｋｇ以上（好ましくは５０～３００μｇ／ｋｇ）含み、鉄を３００μｇ／ｋｇ以下（好ましくは２５０μｇ／ｋｇ以下）含み、ＰＯ４ ３－を２００ｍｇ／ｋｇ以下（好ましくは０．１～１００ｍｇ／ｋｇ）含み、かつ、過酸化水素換算で全過酸化物濃度が１０～１８質量％（好ましくは１１～１５質量％）である、食品添加物として使用される過酢酸組成物である。 The peracetic acid composition obtained by the production method of the present invention is represented by the following two embodiments.
That is, one embodiment of the present invention contains 50 μg / kg or more (preferably 50 to 300 μg / kg) of aluminum, 300 μg / kg or less (preferably 250 μg / kg or less) of iron, and 200 mg / g of PO 4 3- Used as a food additive that contains no more than kg (preferably 0.1 to 100 mg / kg) and has a total peroxide concentration of 10 to 18% by mass (preferably 11 to 15% by mass) in terms of hydrogen peroxide Peracetic acid composition.
　更に、本発明の別の一実施形態は、アルミニウムを２５μｇ／ｋｇ以上（好ましくは２５～２００μｇ／ｋｇ）含み、鉄を２０μｇ／ｋｇ以下（好ましくは１５μｇ／ｋｇ以下）含み、ＰＯ４ ３－を１５ｍｇ／ｋｇ以下（好ましくは０．１～１０ｍｇ／ｋｇ）含み、かつ、過酸化水素換算で全過酸化物濃度が５～１２質量％（好ましくは６～１１質量％）である、食品添加物として使用される過酢酸組成物である。
　上記過酢酸組成物における平衡定数は２以上が好ましく、２～３がより好ましい。平衡定数が２未満であると、前記過酢酸組成物の貯蔵安定性が低下してしまうことがある。
　上記過酢酸組成物は、引火点を有さないことが、取扱時の安全性の点で好ましい。 Furthermore, another embodiment of the present invention contains 25 μg / kg or more (preferably 25 to 200 μg / kg) of aluminum, 20 μg / kg or less of iron (preferably 15 μg / kg or less), and PO 4 3- Food additive containing 15 mg / kg or less (preferably 0.1 to 10 mg / kg) and having a total peroxide concentration of 5 to 12% by mass (preferably 6 to 11% by mass) in terms of hydrogen peroxide Is a peracetic acid composition used as
The equilibrium constant in the peracetic acid composition is preferably 2 or more, more preferably 2 to 3. If the equilibrium constant is less than 2, the storage stability of the peracetic acid composition may be reduced.
The peracetic acid composition preferably has no flash point in terms of safety during handling.
  本発明における過酸化物（以下、全過酸化物ということがある）とは、本発明の過酢酸組成物における過酢酸と過酸化水素のことをいい、それぞれの濃度（ｍｏｌ／Ｌ）の和を過酸化物濃度（以下、全過酸化物濃度ということがある）という。本発明の過酢酸組成物における過酸化物濃度は、好ましくは１～７ｍｏｌ／Ｌであり、より好ましくは２～５ｍｏｌ／Ｌである。この範囲を下回った場合には、過酢酸濃度、即ち殺菌力が低下し、この範囲を上回った場合には安定性が低下することがある。 The peroxide in the present invention (hereinafter sometimes referred to as "total peroxide") means peracetic acid and hydrogen peroxide in the peracetic acid composition of the present invention, and the sum of their concentrations (mol / L) Is referred to as peroxide concentration (hereinafter sometimes referred to as total peroxide concentration). The peroxide concentration in the peracetic acid composition of the present invention is preferably 1 to 7 mol / L, more preferably 2 to 5 mol / L. If it falls below this range, the peracetic acid concentration, that is, the bactericidal activity may decrease, and if it exceeds this range, the stability may decrease.
　本発明の別の一実施形態は、本発明の過酢酸組成物と、食品とを接触させる、食品の殺菌方法である。過酢酸組成物と食品とを接触させる方法としては、例えば、過酢酸組成物中に食品を浸漬させる方法や、食品に過酢酸組成物を噴霧させる方法などが挙げられるが、これらに限定されるものではない。
　本発明の過酢酸組成物は、貯蔵安定性に優れているため、食品の殺菌方法に使用した場合にも利点が多い。 Another embodiment of the present invention is a method of sterilizing food, which comprises contacting the peracetic acid composition of the present invention with a food. Examples of the method of contacting the peracetic acid composition with the food include, but are not limited to, a method of immersing the food in the peracetic acid composition, a method of spraying the peracetic acid composition on the food, and the like. It is not a thing.
Since the peracetic acid composition of the present invention is excellent in storage stability, it has many advantages when used in a food sterilization method.
　以下、実施例により本実施形態を更に詳細に説明するが、本実施形態はこれらの実施例に限定されるものではない。各物性値の測定は、以下に示す方法で行った。 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.
＜過酢酸組成物の過酸化水素濃度＞
　過酢酸組成物の過酸化水素濃度は酸化還元滴定により行った。具体的には試料約０．１ｇを精密に量り、２５０ｍＬの三角フラスコに入れ、０．５ｍｏｌ／Ｌ硫酸を７５ｍＬ加えて検液とした。この検液にフェロイン試液を数滴加えて、０．１ｍｏｌ／Ｌ硫酸セリウム（ＩＶ）溶液で滴定し、過酸化水素濃度を算出した。 <Peroxide concentration of peracetic acid composition>
The hydrogen peroxide concentration of the peracetic acid composition was determined by redox titration. Specifically, about 0.1 g of a sample was accurately 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 titration was performed with a 0.1 mol / L cerium (IV) sulfate solution to calculate the hydrogen peroxide concentration.
＜過酢酸組成物の酢酸及び過酢酸濃度＞
　過酢酸組成物の酢酸及び過酢酸濃度は中和滴定により行った。具体的には試料約０．１ｇを精密に量り、１００ｍＬビーカーに入れ、純水約５０ｍＬを加えて検液とした。この検液を０．１ｍｏｌ／Ｌ水酸化ナトリウム溶液で滴定し、第一変曲点での添加量から酢酸濃度、第一変曲点から第二変曲点までの添加量から過酢酸濃度を算出した。 <Acetic acid and peracetic acid concentration of peracetic acid composition>
The acetic acid and peracetic acid concentrations of the peracetic acid composition were determined by neutralization titration. Specifically, about 0.1 g of a sample was accurately weighed, placed in a 100 mL beaker, and about 50 mL of pure water was added to make a test solution. This test solution is titrated with a 0.1 mol / L sodium hydroxide solution, and the acetic acid concentration is added from the first inflection point, and the peracetic acid concentration is added from the first inflection point to the second inflection point. Calculated.
＜過酢酸組成物の全過酸化物濃度＞
　過酢酸組成物の全過酸化物濃度は、ヨウ素還元滴定法により行った。具体的には試料約０．１ｇを精密に量り、２５０ｍＬの三角フラスコに入れ、純水１００ｍＬ、１．８ｍｏｌ／Ｌ硫酸１０ｍＬを加えた後、１０質量％のヨウ化カリウム溶液１０ｍＬ、１質量％モリブデン酸アンモニウム溶液を数滴加えて検液とした。この検液に０．１ｍｏｌ／Ｌチオ硫酸ナトリウム溶液を滴下し、指示薬にでんぷんを使用して液の青紫色が消失し無色となったところを終点として、遊離したヨウ素を定量した。そのヨウ素量から、過酸化水素換算で全過酸化物濃度を算出した。 <Total peroxide concentration of peracetic acid composition>
The total peroxide concentration of the peracetic acid composition was determined by iodometric titration. Specifically, accurately measure about 0.1 g of the sample, put in a 250 mL Erlenmeyer flask, add 100 mL of pure water and 10 mL of 1.8 mol / L sulfuric acid, and then add 10 mL of 10 mass% potassium iodide solution, 1 mass% Several drops of ammonium molybdate solution were added to make a test solution. A 0.1 mol / L sodium thiosulfate solution was added dropwise to this test solution, and starch was used as an indicator, and the released iodine was quantified as an end point when the bluish purple color of the solution disappeared and became colorless. From the amount of iodine, the total peroxide concentration was calculated in terms of hydrogen peroxide.
＜過酢酸組成物の安定度＞
　過酢酸組成物の安定度は仕込み時の全過酸化物濃度を１００とし、測定時の全過酸化物濃度の比率により算出した。 <Stability of Peracetic Acid Composition>
The stability of the peracetic acid composition was calculated from the ratio of the total peroxide concentration at the time of measurement, assuming that the total peroxide concentration at the time of preparation was 100.
＜過酢酸組成物の平衡定数＞
　過酢酸組成物の平衡定数は下記の式よりで算出した。
　平衡定数＝過酢酸濃度（ｍｏｌ／Ｌ）×水の濃度（ｍｏｌ／Ｌ）
÷過酸化水素濃度（ｍｏｌ／Ｌ）÷酢酸濃度（ｍｏｌ／Ｌ） <Equilibrium constant of peracetic acid composition>
The equilibrium constant of the peracetic acid composition was calculated by the following equation.
Equilibrium constant = peracetic acid concentration (mol / L) × water concentration (mol / L)
Peroxide concentration (mol / L) Peracetic acid concentration (mol / L)
＜過酢酸組成物の引火点＞
　過酢酸組成物の引火点はクリーブランド開放式引火点試験により測定した。ＪＩＳ－Ｋ２２６５の方法に準じ、クリーブランド開放式引火点試験器を使用した。 <Flash point of peracetic acid composition>
The flash point of the peracetic acid composition was determined by the Cleveland open flash point test. A Cleveland open flash point tester was used according to the method of JIS-K2265.
（実施例１）
　純水２．８ｇと６０質量％の１－ヒドロキシエチリデン－１，１－ジホスホン酸（イタルマッチジャパン株式会社製、製品名：デイクエスト２０１０）を０．６ｇ、氷酢酸を２９．８ｇ（昭和電工株式会社製、製品名：９９％純良酢酸）、３５質量％の過酸化水素水溶液（三菱ガス化学株式会社製、製品名：ダイヤパワーＨＰ、アルミニウム微量含有）を１６．８ｇ、ＳＵＳ３０４（別名：18Cr-8Ni、１８クロムステンレス）のテストピースをポリエチレン容器内に入れ混合した。調合時の全過酸化物濃度は１１．９％であった。混合後、２５℃で１０日間静置することで過酸化水素５．５質量％、酢酸４８．７質量％、過酢酸１３．４質量％、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸０．８質量％を含有する食品添加物として使用される過酢酸組成物を得た。ＳＵＳ３０４のテストピースを入れた目的は、ＳＵＳ容器で過酢酸組成物を製造することを想定したためである。得られた過酢酸組成物については、調合してから２１日後に全過酸化物濃度を測定し、安定度を算出した。 Example 1
0.6 g of pure water 2.8 g and 60 mass% 1-hydroxyethylidene-1,1-diphosphonic acid (Italmatch Japan Co., Ltd. product name: D-Quest 2010) and 29.8 g glacial acetic acid (Showa Denko Product name: 99% pure acetic acid), 35 mass% hydrogen peroxide aqueous solution (Mitsubishi Gas Chemical Co., Ltd., product name: Diapower HP, containing a small amount of aluminum) 16.8 g, SUS304 (alias: 18Cr Test pieces of (-8 Ni, 18 chromium stainless steel) were put in a polyethylene container and mixed. The total peroxide concentration at the time of preparation was 11.9%. After mixing, the mixture is allowed to stand at 25 ° C. for 10 days to obtain 5.5% by mass of hydrogen peroxide, 48.7% by mass of acetic acid, 13.4% by mass of peracetic acid, and 0-hydroxyethylidene-1,1-diphosphonic acid A peracetic acid composition used as a food additive containing 8% by mass was obtained. The purpose of placing the test piece of SUS304 is to assume that the peracetic acid composition is produced in a SUS container. About the obtained peracetic acid composition, the total peroxide concentration was measured 21 days after preparation, and stability was computed.
（実施例２）
　３５質量％の過酸化水素水溶液（三菱ガス化学株式会社製、製品名：UELM35）に硫酸カリウムアルミニウム・１２水（和光純薬工業株式会社製、試薬特級）を添加し、添加後の３５質量％の過酸化水素水溶液中のアルミニウム含有量を１０μｇ／ｋｇとしたこと以外は実施例１と同様に操作し、過酸化水素５．５質量％、酢酸４８．９質量％、過酢酸１３．１質量％、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸０．８質量％を含有する食品添加物として使用される過酢酸組成物を得た。得られた過酢酸組成物については、調合してから２１日後に全過酸化物濃度を測定し、安定度を算出した。 (Example 2)
Potassium aluminum sulfate · 12 water (Wako Pure Chemical Industries, Ltd. reagent special grade) is added to a 35 mass% hydrogen peroxide aqueous solution (Mitsubishi Gas Chemical Co., Ltd., product name: UELM 35), and 35 mass% after addition The same operation as in Example 1 is carried out except that the aluminum content in the aqueous hydrogen peroxide solution is 10 μg / kg, 5.5 mass% of hydrogen peroxide, 48.9 mass% of acetic acid, 13.1 mass of peracetic acid A peracetic acid composition was obtained which was used as a food additive containing%, and 0.8% by weight of 1-hydroxyethylidene-1,1-diphosphonic acid. About the obtained peracetic acid composition, the total peroxide concentration was measured 21 days after preparation, and stability was computed.
（実施例３）
　３５質量％の過酸化水素水溶液（三菱ガス化学株式会社製、製品名：UELM35）に硫酸カリウムアルミニウム・１２水（和光純薬工業株式会社製、試薬特級）を添加し、添加後の３５質量％の過酸化水素水溶液中のアルミニウム含有量を１００μｇ／ｋｇとしたこと以外は実施例１と同様に操作し、過酸化水素５．５質量％、酢酸４８．８質量％、過酢酸１３．５質量％、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸０．８質量％を含有する食品添加物として使用される過酢酸組成物を得た。得られた過酢酸組成物については、調合してから２１日後に全過酸化物濃度を測定し、安定度を算出した。 (Example 3)
Potassium aluminum sulfate · 12 water (Wako Pure Chemical Industries, Ltd. reagent special grade) is added to a 35 mass% hydrogen peroxide aqueous solution (Mitsubishi Gas Chemical Co., Ltd., product name: UELM 35), and 35 mass% after addition The same operation as in Example 1 is carried out except that the aluminum content in the aqueous hydrogen peroxide solution is 100 μg / kg, 5.5 mass% of hydrogen peroxide, 48.8 mass% of acetic acid, 13.5 mass of peracetic acid A peracetic acid composition was obtained which was used as a food additive containing%, and 0.8% by weight of 1-hydroxyethylidene-1,1-diphosphonic acid. About the obtained peracetic acid composition, the total peroxide concentration was measured 21 days after preparation, and stability was computed.
（実施例４）
　ＳＵＳ３０４のテストピースを入れなかったこと、三菱ガス化学株式会社製の３５質量％の過酸化水素水溶液（製品名：ダイヤパワーＨＰ、アルミニウム微量含有）の代わりに三菱ガス化学株式会社製の３５質量％の過酸化水素水溶液（製品名：35％過酸化水素）を使用したこと以外は実施例１と同様に操作し、過酸化水素５．５質量％、酢酸４７．８質量％、過酢酸１４．２質量％、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸０．８質量％を含有する食品添加物として使用される過酢酸組成物を得た。得られた過酢酸組成物については、調合してから６３日後に全過酸化物濃度を測定し、安定度を算出した。 (Example 4)
The test piece of SUS304 was not inserted, 35% by mass of Mitsubishi Gas Chemical Co., Ltd. instead of 35% by mass of hydrogen peroxide aqueous solution (product name: Diamond Power HP, containing a small amount of aluminum) manufactured by Mitsubishi Gas Chemical Co., Ltd. The same operation as in Example 1 was carried out except using the aqueous hydrogen peroxide solution (product name: 35% hydrogen peroxide), 5.5% by weight of hydrogen peroxide, 47.8% by weight of acetic acid, and 14.4% by weight of peracetic acid. A peracetic acid composition used as a food additive containing 2% by mass and 0.8% by mass of 1-hydroxyethylidene-1,1-diphosphonic acid was obtained. For the obtained peracetic acid composition, the total peroxide concentration was measured 63 days after preparation, and the stability was calculated.
（実施例５）
　ＳＵＳ３０４のテストピースを入れなかったこと、三菱ガス化学株式会社製の３５質量％の過酸化水素水溶液（製品名：ダイヤパワーＨＰ、アルミニウム微量含有）の代わりに三菱ガス化学株式会社製の３５質量％の過酸化水素水溶液（製品名：35％過酸化水素）を使用したこと、イタルマッチジャパン株式会社製の１－ヒドロキシエチリデン－１，１－ジホスホン酸（製品名：デイクエスト２０１０）の代わりにキレスト株式会社製の１－ヒドロキシエチリデン－１，１－ジホスホン酸（製品名：ＰＨ－２１０）を使用したこと以外は実施例１と同様に操作し、過酸化水素５．５質量％、酢酸４８．０質量％、過酢酸１４．０質量％、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸０．８質量％含有する食品添加物として使用される過酢酸組成物を得た。得られた過酢酸組成物については、調合してから６３日後に全過酸化物濃度を測定し、安定度を算出した。 (Example 5)
The test piece of SUS304 was not inserted, 35% by mass of Mitsubishi Gas Chemical Co., Ltd. instead of 35% by mass of hydrogen peroxide aqueous solution (product name: Diamond Power HP, containing a small amount of aluminum) manufactured by Mitsubishi Gas Chemical Co., Ltd. Aqueous solution of hydrogen peroxide (product name: 35% hydrogen peroxide), 1-hydroxyethylidene-1,1-diphosphonic acid (product name: Dayquest 2010) manufactured by Italmatch Japan Ltd. The same procedure as in Example 1 was repeated except that 1-hydroxyethylidene-1,1-diphosphonic acid (product name: PH-210) manufactured by Co., Ltd. was used, and 5.5% by mass of hydrogen peroxide, acetic acid 48. Used as a food additive containing 0% by mass, 14.0% by mass of peracetic acid, and 0.8% by mass of 1-hydroxyethylidene-1,1-diphosphonic acid To obtain a peracetic acid composition. For the obtained peracetic acid composition, the total peroxide concentration was measured 63 days after preparation, and the stability was calculated.
（実施例６）
　純水３．４ｇと６０質量％の１－ヒドロキシエチリデン－１，１－ジホスホン酸（イタルマッチジャパン株式会社製、製品名：デイクエスト２０１０）を０．６ｇ、氷酢酸を２６．６ｇ（昭和電工株式会社製、製品名：９９％純良酢酸）、３５質量％の過酸化水素水溶液（三菱ガス化学株式会社製、製品名：35％過酸化水素）を１９．４ｇ、ポリエチレン容器内で混合した。調合時の全過酸化物濃度は１３．７％であった。混合後、２５℃で１０日間静置することで過酸化水素７．４質量％、酢酸４２．３質量％、過酢酸１３．７質量％、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸０．８質量％を含有する食品添加物として使用される過酢酸組成物を得た。得られた過酢酸組成物については、調合してから３５日後に全過酸化物濃度を測定し、安定度を算出した。 (Example 6)
0.6 g of pure water 3.4 g and 60% by mass 1-hydroxyethylidene-1,1-diphosphonic acid (Italmatch Japan Ltd., product name: Dayquest 2010), 26.6 g glacial acetic acid (Showa Denko Product name: 99% pure acetic acid), 35% by mass of hydrogen peroxide aqueous solution (Mitsubishi Gas Chemical Co., Ltd., product name: 35% hydrogen peroxide) 19.4 g were mixed in a polyethylene container. The total peroxide concentration at the time of preparation was 13.7%. After mixing, the mixture is allowed to stand at 25 ° C. for 10 days, whereby hydrogen peroxide 7.4% by mass, acetic acid 42.3% by mass, peracetic acid 13.7% by mass, and 1-hydroxyethylidene-1,1-diphosphonic acid 0 A peracetic acid composition used as a food additive containing 8% by mass was obtained. For the obtained peracetic acid composition, the total peroxide concentration was measured 35 days after preparation, and the stability was calculated.
（実施例７）
　３５質量％の過酸化水素水溶液（三菱ガス化学株式会社製、製品名：35％過酸化水素）の代わりに３５質量％の過酸化水素水溶液（三菱ガス化学株式会社製、製品名：ダイヤパワーＨＰ、アルミニウム微量含有）を使用したこと以外は実施例６と同様に操作し、過酸化水素７．５質量％、酢酸４２．１質量％、過酢酸１４．１質量％、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸０．８質量％を含有する食品添加物として使用される過酢酸組成物を得た。得られた過酢酸組成物については、調合してから３５日後に全過酸化物濃度を測定し、安定度を算出した。 (Example 7)
35% by mass hydrogen peroxide aqueous solution (manufactured by Mitsubishi Gas Chemical Co., Ltd., product name: Diapower HP) instead of 35% by mass hydrogen peroxide aqueous solution (manufactured by Mitsubishi Gas Chemical Co., Ltd., product name: 35% hydrogen peroxide) Operating in the same manner as in Example 6 except that a slight amount of aluminum was used), 7.5% by mass of hydrogen peroxide, 42.1% by mass of acetic acid, 14.1% by mass of peracetic acid, and 1-hydroxyethylidene A peracetic acid composition used as a food additive containing 0.8% by mass of 1,1-diphosphonic acid was obtained. For the obtained peracetic acid composition, the total peroxide concentration was measured 35 days after preparation, and the stability was calculated.
（実施例８）
　３５質量％の過酸化水素水溶液（三菱ガス化学株式会社製、製品名：35％過酸化水素）に鉄標準液（和光純薬工業株式会社製、Ｆｅ１０００）、リン酸二水素ナトリウム二水和物（和光純薬工業株式会社製、試薬特級）を添加し、添加後の３５質量％の過酸化水素水溶液中の鉄含有量を１００μｇ／ｋｇ、ＰＯ４ ３－含有量を５２．９ｍｇ／ｋｇとしたこと以外は実施例６と同様に操作し、過酸化水素７．３質量％、酢酸４２．２質量％、過酢酸１３．９質量％、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸０．８質量％を含有する食品添加物として使用される過酢酸組成物を得た。得られた過酢酸組成物については、調合してから３５日後に全過酸化物濃度を測定し、安定度を算出した。 (Example 8)
Iron standard solution (Wako Pure Chemical Industries, Ltd., Fe 1000) in 35% by mass hydrogen peroxide aqueous solution (Mitsubishi Gas Chemical Co., Ltd., product name: 35% hydrogen peroxide), sodium dihydrogen phosphate dihydrate (Wako Pure Chemical Industries, Ltd., reagent special grade) is added, iron content in 35% by mass of hydrogen peroxide aqueous solution after addition is 100 μg / kg, and PO 4 3- content is 52.9 mg / kg The same procedures as in Example 6 were carried out except that 7.3% by mass of hydrogen peroxide, 42.2% by mass of acetic acid, 13.9% by mass of peracetic acid, and 0-hydroxyethylidene-1,1-diphosphonic acid were used. A peracetic acid composition used as a food additive containing 8% by mass was obtained. For the obtained peracetic acid composition, the total peroxide concentration was measured 35 days after preparation, and the stability was calculated.
（実施例９）
　３５質量％の過酸化水素水溶液（三菱ガス化学株式会社製、製品名：35％過酸化水素）に鉄標準液（和光純薬工業株式会社製、Ｆｅ１０００）、リン酸二水素ナトリウム二水和物（和光純薬工業株式会社製、試薬特級）を添加し、添加後の３５質量％の過酸化水素水溶液中の鉄含有量を５１０μｇ／ｋｇ、ＰＯ４ ３－含有量を５２．９ｍｇ／ｋｇとしたこと以外は実施例６と同様に操作し、過酸化水素７．３質量％、酢酸４２．４質量％、過酢酸１３．７質量％、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸０．８質量％を含有する食品添加物として使用される過酢酸組成物を得た。得られた過酢酸組成物については、調合してから３５日後に全過酸化物濃度を測定し、安定度を算出した。 (Example 9)
Iron standard solution (Wako Pure Chemical Industries, Ltd., Fe 1000) in 35% by mass hydrogen peroxide aqueous solution (Mitsubishi Gas Chemical Co., Ltd., product name: 35% hydrogen peroxide), sodium dihydrogen phosphate dihydrate (Wako Pure Chemical Industries, Ltd., reagent special grade) is added, iron content in 35% by mass hydrogen peroxide aqueous solution after addition is 510 μg / kg, and PO 4 3- content is 52.9 mg / kg The same procedures as in Example 6 were carried out except that 7.3% by mass of hydrogen peroxide, 42.4% by mass of acetic acid, 13.7% by mass of peracetic acid and 0-hydroxyethylidene-1,1-diphosphonic acid were used. A peracetic acid composition used as a food additive containing 8% by mass was obtained. For the obtained peracetic acid composition, the total peroxide concentration was measured 35 days after preparation, and the stability was calculated.
（実施例１０）
　純水５５．０ｇと６０質量％の１－ヒドロキシエチリデン－１，１－ジホスホン酸（イタルマッチジャパン株式会社製、製品名：デイクエスト２０１０）を１２．８ｇ、氷酢酸を６５１．０ｇ（昭和電工株式会社製、製品名：９９％純良酢酸）、３５質量％の過酸化水素水溶液（三菱ガス化学株式会社製、製品名：35％過酸化水素）を３８１．１ｇ、ポリエチレン容器内で混合した後、２５℃で１０日間静置することで過酸化水素５．８質量％、酢酸４７．７質量％、過酢酸１４．５質量％、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸０．７質量％を含有する食品添加物として使用される過酢酸組成物を得た。平衡定数は２．４であった。得られた過酢酸組成物を純水で１．２倍希釈し、２５℃で１０日間静置することで過酸化水素６．０質量％、酢酸４２．４質量％、過酢酸９．４質量％、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸０．６質量％を含有する食品添加物として使用される過酢酸組成物を得た。得られた過酢酸組成物については、平衡定数を算出し、引火点を測定した。 (Example 10)
Pure water 55.0 g and 60 mass% 1-hydroxyethylidene-1,1-diphosphonic acid (Italmatch Japan Ltd. make, product name: DIGEST 2010) 12.8 g, glacial acetic acid 651.0 g (Showa Denko Product name: 99% pure good acetic acid), after mixing 381.1 g of 35% by mass hydrogen peroxide aqueous solution (Mitsubishi Gas Chemical Co., Ltd. product name: 35% hydrogen peroxide) in a polyethylene container By standing at 25 ° C. for 10 days, 5.8 mass% hydrogen peroxide, 47.7 mass% acetic acid, 14.5 mass% peracetic acid, and 1-hydroxyethylidene-1,1-diphosphonic acid 0.7 The peracetic acid composition used as a food additive containing mass% was obtained. The equilibrium constant was 2.4. The obtained peracetic acid composition is diluted 1.2 times with pure water and allowed to stand at 25 ° C. for 10 days, whereby 6.0 mass% of hydrogen peroxide, 42.4 mass% of acetic acid, 9.4 mass of peracetic acid A peracetic acid composition was obtained which was used as a food additive containing%, and 0.6% by weight of 1-hydroxyethylidene-1,1-diphosphonic acid. The equilibrium constant was calculated for the obtained peracetic acid composition, and the flash point was measured.
（実施例１１）
　得られた過酢酸組成物を純水で１．３倍希釈した以外は実施例１０と同様に操作し、過酸化水素６．０質量％、酢酸３９．９質量％、過酢酸７．９質量％、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸０．５質量％を含有する食品添加物として使用される過酢酸組成物を得た。得られた過酢酸組成物については、平衡定数を算出し、引火点を測定した。 (Example 11)
The same operation as in Example 10 is carried out except that the obtained peracetic acid composition is diluted 1.3 times with pure water, and 6.0 mass% of hydrogen peroxide, 39.9 mass% of acetic acid, 7.9 mass of peracetic acid A peracetic acid composition used as a food additive containing 5% by weight of 1-hydroxyethylidene-1,1-diphosphonic acid was obtained. The equilibrium constant was calculated for the obtained peracetic acid composition, and the flash point was measured.
（実施例１２）
　得られた過酢酸組成物を純水で１．４倍希釈した以外は実施例１０と同様に操作し、過酸化水素５．９質量％、酢酸３７．７質量％、過酢酸６．２質量％、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸０．５質量％を含有する食品添加物として使用される過酢酸組成物を得た。得られた過酢酸組成物については、平衡定数を算出し、引火点を測定した。 (Example 12)
The same operation as in Example 10 is carried out except that the obtained peracetic acid composition is diluted 1.4 times with pure water, and 5.9 mass% of hydrogen peroxide, 37.7 mass% of acetic acid, 6.2 mass of peracetic acid A peracetic acid composition used as a food additive containing 5% by weight of 1-hydroxyethylidene-1,1-diphosphonic acid was obtained. The equilibrium constant was calculated for the obtained peracetic acid composition, and the flash point was measured.
（比較例１）
　３５質量％の過酸化水素水溶液（三菱ガス化学株式会社製、製品名：ダイヤパワーＨＰ、アルミニウム微量含有）の代わりに３５質量％の過酸化水素水溶液（三菱ガス化学株式会社製、製品名：UELM35）を使用したこと以外は実施例１と同様に操作し、過酸化水素５．５質量％、酢酸４８．７質量％、過酢酸１３．５質量％、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸０．８質量％を含有する食品添加物として使用される過酢酸組成物を得た。得られた過酢酸組成物については、調合してから２１日後に全過酸化物濃度を測定し、安定度を算出した。 (Comparative example 1)
35% by mass aqueous hydrogen peroxide solution (manufactured by Mitsubishi Gas Chemical Co., Ltd., product name: UELM 35) instead of 35% by mass aqueous hydrogen peroxide solution (manufactured by Mitsubishi Gas Chemical Co., Ltd., product name: Diapower HP, containing a small amount of aluminum) The same procedure as in Example 1 was repeated except that 5.5% by mass of hydrogen peroxide, 48.7% by mass of acetic acid, 13.5% by mass of peracetic acid, and 1-hydroxyethylidene-1,1- were obtained. A peracetic acid composition used as a food additive containing 0.8% by mass of diphosphonic acid was obtained. About the obtained peracetic acid composition, the total peroxide concentration was measured 21 days after preparation, and stability was computed.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
  
Figure JPOXMLDOC01-appb-T000006
  

Claims (14)

  1. 　過酸化水素水溶液、酢酸溶液、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸を含む物質を混合する工程を含む、食品添加物として使用される過酢酸組成物の製造方法であって、
    　前記過酸化水素水溶液が、アルミニウムを１０μｇ／ｋｇ以上含有し、かつ、過酸化水素を３０～４０質量％含有する、前記製造方法。     A method for producing a peracetic acid composition used as a food additive, comprising the step of mixing a substance containing hydrogen peroxide aqueous solution, acetic acid solution, and 1-hydroxyethylidene-1,1-diphosphonic acid,
    The method according to the above, wherein the aqueous solution of hydrogen peroxide contains 10 μg / kg or more of aluminum and 30 to 40% by mass of hydrogen peroxide.
  2. 　さらに、前記過酸化水素水溶液が、鉄を５０μｇ／ｋｇ以下含有し、かつ、ＰＯ４ ３－を５０ｍｇ／ｋｇ以下含有する、請求項１に記載の製造方法。 The method according to claim 1, wherein the aqueous hydrogen peroxide solution further contains 50 μg / kg or less of iron and 50 mg / kg or less of PO 4 3- .
  3. 　前記酢酸溶液が、アルミニウムを１０μｇ／ｋｇ以上含有し、鉄を５０μｇ／ｋｇ以下含有し、ＰＯ４ ３－を５０ｍｇ／ｋｇ以下含有し、かつ、酢酸を９０～９９．９９質量％含有する、請求項１又は２に記載の製造方法。 The acetic acid solution contains aluminum at 10 μg / kg or more, iron at 50 μg / kg or less, PO 4 3- at 50 mg / kg or less, and acetic acid at 90 to 99.99% by mass. Item 3. The method according to item 1 or 2.
  4. 　前記１－ヒドロキシエチリデン－１，１－ジホスホン酸を含む物質が、アルミニウムを１０μｇ／ｋｇ以上含有し、鉄を７ｍｇ／ｋｇ以下含有し、ＰＯ４ ３－を５０ｍｇ／ｋｇ以下含有し、かつ、１－ヒドロキシエチリデン－１，１－ジホスホン酸を５５～６５質量％含有する、請求項１～３のいずれか一項に記載の製造方法。 The substance containing 1-hydroxyethylidene-1,1-diphosphonic acid contains 10 μg / kg or more of aluminum, 7 mg / kg or less of iron, 50 mg / kg or less of PO 4 3- and 1 The production method according to any one of claims 1 to 3, which comprises 55 to 65% by mass of -hydroxyethylidene-1,1-diphosphonic acid.
  5. 　前記混合工程において混合する温度が、２５～３５℃である、請求項１～４のいずれか一項に記載の製造方法。 The method according to any one of claims 1 to 4, wherein the temperature to be mixed in the mixing step is 25 to 35 属 C.
  6. 　前記混合工程において混合する時間が、６０分以下である、請求項１～５のいずれか一項に記載の製造方法。 The production method according to any one of claims 1 to 5, wherein the mixing time in the mixing step is 60 minutes or less.
  7. 　前記混合工程において混合をした後に、１日以上静置する、請求項１～６のいずれか一項に記載の製造方法。 The method according to any one of claims 1 to 6, wherein the mixture is allowed to stand for one day or more after being mixed in the mixing step.
  8. 　さらに、得られた過酢酸組成物を水で希釈する工程を含む、請求項１～７のいずれか一項に記載の製造方法。 The production method according to any one of claims 1 to 7, further comprising the step of diluting the obtained peracetic acid composition with water.
  9. 　請求項１～８のいずれか一項に記載の食品添加物として使用される過酢酸組成物の製造方法に用いられる製造装置であって、
    　過酸化水素溶液、酢酸溶液、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸を含む物質を混合し、攪拌して溶解するための混合釜、過酸化水素水溶液投入装置、溶解した氷酢酸投入装置、及び１－ヒドロキシエチリデン－１，１－ジホスホン酸投入装置を有する、食品添加物として使用される過酢酸組成物を製造する製造装置。     A manufacturing apparatus used for a method of manufacturing a peracetic acid composition used as a food additive according to any one of claims 1 to 8,
    Mixing pot for mixing, stirring and dissolving substances containing hydrogen peroxide solution, acetic acid solution and 1-hydroxyethylidene-1,1-diphosphonic acid, hydrogen peroxide aqueous solution feeder, dissolved glacial acetic acid feeder And a production device for producing a peracetic acid composition used as a food additive, having a 1-hydroxyethylidene-1,1-diphosphonic acid feeding device.
  10. 　アルミニウムを５０μｇ／ｋｇ以上含み、鉄を３００μｇ／ｋｇ以下含み、ＰＯ４ ３－を２００ｍｇ／ｋｇ以下含み、かつ、過酸化水素換算で全過酸化物濃度が１０～１８質量％である、食品添加物として使用される過酢酸組成物。 Food additives containing 50 μg / kg or more of aluminum, 300 μg / kg or less of iron, 200 mg / kg or less of PO 4 3- and having a total peroxide concentration of 10 to 18% by mass in terms of hydrogen peroxide Peracetic acid composition used as a product.
  11. 　アルミニウムを２５μｇ／ｋｇ以上含み、鉄を２０μｇ／ｋｇ以下含み、ＰＯ４ ３－を１５ｍｇ／ｋｇ以下含み、かつ、過酸化水素換算で全過酸化物濃度が５～１２質量％である、食品添加物として使用される過酢酸組成物。 Food additives containing 25 μg / kg or more of aluminum, 20 μg / kg or less of iron, 15 mg / kg or less of PO 4 3- and a total peroxide concentration of 5 to 12% by mass in terms of hydrogen peroxide Peracetic acid composition used as a product.
  12. 　平衡定数が２以上である、請求項１１に記載の過酢酸組成物。 The peracetic acid composition according to claim 11, wherein the equilibrium constant is 2 or more.
  13. 　引火点を有さない、請求項１１又は１２に記載の過酢酸組成物。 The peracetic acid composition according to claim 11 or 12, which has no flash point.
  14. 　請求項１０～１３のいずれか一項に記載の過酢酸組成物と、食品とを接触させる、食品の殺菌方法。
     
     
          A method of sterilizing a food, comprising bringing the peracetic acid composition according to any one of claims 10 to 13 into contact with the food.


PCT/JP2018/038232 2017-11-27 2018-10-15 Method for producing peracetic acid composition to be used as food additive WO2019102742A1 (en)

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JP2010537970A (en) * 2007-08-30 2010-12-09 イーコラブ インコーポレイティド Storage stable low corrosive ready-to-use peroxycarboxylic acid antibacterial composition
US20140256811A1 (en) * 2013-03-05 2014-09-11 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids

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