Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
  • C01B15/01—Hydrogen peroxide
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
  • C01B15/01—Hydrogen peroxide
  • C01B15/037—Stabilisation by additives

Definitions

• the present invention heats and evaporates an aqueous hydrogen peroxide solution, contacts the mist and / or gas with an object, and determines the number of bacteria attached to the object and / or floating in the vicinity of the object.
• the present invention relates to an aqueous hydrogen peroxide solution used for the reduction, a production method thereof, and a sterilization method using the same.
• the technology to reduce the number of bacteria adhering to the object by contacting the object with high temperature mist or hydrogen peroxide vapor of hydrogen peroxide solution is the sterilization of clean room for electronic industry and pet before filling beverage Applied to bottle sterilization.
• high-performance hydrogen peroxide aqueous solutions used for aseptic filling have been demanded. That is, there are demands for a material that has little residue when hydrogen peroxide and water are evaporated, and a material that has high stability in high temperature or metal storage containers.
• a small amount of metal is eluted from a metal tank by a chelating agent such as phosphoric acid added as a stabilizer to an aqueous hydrogen peroxide solution, and the stability of hydrogen peroxide decreases.
• a chelating agent such as phosphoric acid added as a stabilizer to an aqueous hydrogen peroxide solution
• the stability of hydrogen peroxide decreases.
• a stabilizer is used in a large amount, a decrease in stability can be avoided, but it is not preferable in the application because operation obstruction such as nozzle clogging is likely to occur.
• JP 11-47242 A JP 2006-240969 A Special table 2009-507878
• An object of the present invention is to solve the above-mentioned problems in the prior art, and to provide a hydrogen peroxide aqueous solution to be used for so-called steam sterilization, a production method thereof, and a sterilization method using the same.
• the present invention is as follows.
• aqueous hydrogen peroxide solution used for reducing the number of bacteria, wherein the aqueous hydrogen peroxide solution contains hydrogen peroxide, a phosphate and an aluminum salt as essential components.
• the phosphate is tripotassium phosphate, trimagnesium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, phosphoric acid
• the aqueous hydrogen peroxide solution according to ⁇ 1> which is at least one selected from the group consisting of sodium dihydrogen, trisodium phosphate, and bis (hydrogen hydrogen phosphate) calcium.
• ⁇ 3> The aqueous hydrogen peroxide solution according to ⁇ 1>, wherein the phosphate is a hydrogen phosphate.
• ⁇ 4> The aqueous hydrogen peroxide solution according to any one of ⁇ 1> to ⁇ 3>, wherein the addition concentration of the phosphate is 1 to 18 mg / kg.
• ⁇ 5> The hydrogen peroxide solution according to any one of ⁇ 1> to ⁇ 4>, wherein the aluminum salt is potassium aluminum sulfate.
• ⁇ 6> The hydrogen peroxide solution according to any one of ⁇ 1> to ⁇ 5>, wherein the addition concentration of the aluminum salt is 1 to 4 mg / kg.
• ⁇ 7> L-ascorbic acid and its salt, ethylenediaminetetraacetate, citric acid and its salt, gluconic acid and its salt, L-glutamic acid and its salt, silicate, nitrate, carbonate, pyrophosphate, and sulfuric acid
• ⁇ 8> The aqueous hydrogen peroxide solution according to ⁇ 7>, wherein the addition concentration of the acid and / or salt is 2 to 12 mg / kg.
• ⁇ 9> The aqueous hydrogen peroxide solution according to any one of ⁇ 1> to ⁇ 8>, wherein the concentration of the hydrogen peroxide is 30% by weight to 40% by weight.
• ⁇ 11> The method for producing an aqueous hydrogen peroxide solution according to any one of ⁇ 1> to ⁇ 9>, wherein a phosphate and an aluminum salt are added to the aqueous hydrogen peroxide solution as a raw material.
• a sterilization method comprising mixing air and a mist and / or gas of the hydrogen peroxide aqueous solution according to any one of ⁇ 1> to ⁇ 9>, and then bringing the mixture into contact with an object.
• the sterilization method according to ⁇ 12> wherein when bringing the aqueous hydrogen peroxide solution into contact with the object, the air is heated to accompany the mist and / or gas of the aqueous hydrogen peroxide solution.
• ⁇ 15> The sterilization method according to any one of ⁇ 12> to ⁇ 14>, wherein the object is a packaging container, a food machine, a plastic bottle, or a plastic bottle preform.
• ⁇ 16> The sterilization method according to any one of ⁇ 12> to ⁇ 14>, wherein the object is a closed space.
• ⁇ 17> The sterilization method according to ⁇ 16>, wherein the closed space is an automobile, a clean room for electronic industry, a living space, a medical space, a kitchen, a kitchen, a vehicle, or an aircraft.
• ⁇ 18> Reduce the number of bacteria in the facility by bringing a hydrogen peroxide solution mist and / or hydrogen peroxide vapor generator into the facility to generate a hydrogen peroxide solution mist and / or hydrogen peroxide vapor.
• ⁇ 19> The sterilization method according to ⁇ 18>, wherein the facility is a toiletry facility, a waste disposal facility, or a barn.
• the stability of hydrogen peroxide is improved, the deposits derived from the stabilizer of the aqueous hydrogen peroxide solution remaining on the spray nozzle or the evaporator are reduced, and the residue can be easily removed by washing with water. .
• the aqueous hydrogen peroxide solution of the present invention contains a phosphate and an aluminum salt as active ingredients for stabilizing hydrogen peroxide. Furthermore, other acid and / or salt may be included as an additive for facilitating water washing of the evaporation residue adhering to the nozzle or the evaporator.
• a chelating agent such as phosphoric acid that has been added as a stabilizer to an aqueous hydrogen peroxide solution causes a trace amount of metal to elute from the metal tank, resulting in a decrease in the stability of hydrogen peroxide. This problem can be solved by using salt.
• the phosphate used in the present invention include tripotassium phosphate, trimagnesium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, dipotassium hydrogen phosphate, and potassium dihydrogen phosphate.
• Disodium hydrogen phosphate, sodium dihydrogen phosphate, trisodium phosphate, and bis (hydrogen hydrogen phosphate) calcium are preferable, and disodium hydrogen phosphate is particularly preferable.
• the phosphate used by this invention is a hydrogen phosphate.
• the aluminum salt used in the present invention can be used without any problem as long as it is a food additive containing aluminum.
• potassium aluminum sulfate is preferred.
• acids and / or salts that improve the water-washing property of evaporation residue adhering to a nozzle or an evaporator can also be selected from designated additives of the Food Sanitation Law.
• the concentration of phosphate added is preferably 1 to 18 mg / kg, more preferably 1 to 12 mg / kg.
• the concentration of aluminum salt added is preferably 1 to 4 mg / kg, and more preferably 1 to 3 mg / kg.
• the concentration of hydrogen peroxide is preferably 30 to 40% by weight, more preferably 33 to 37% by weight. It is preferable that the concentration of hydrogen peroxide is 30 to 40% by weight because the bactericidal power is appropriate.
• the concentration of other acids and / or salts preferably used in the aqueous hydrogen peroxide solution of the present invention is preferably 2 to 12 mg / kg, more preferably 3 to 10 mg / kg.
• the concentration of the other acid and / or salt added is 2 to 12 mg / kg, the evaporative residue detergency becomes high, which is preferable.
• the addition concentration of phosphate is 2 to 4 mg / kg
• the addition concentration of aluminum salt is 2 to 3 mg / kg
• the addition concentration of other acids and / or salts is 3 to 5 mg / kg. is there.
• Heavy metals are known as hydrogen peroxide decomposition components, but the decomposition components contained in an aqueous hydrogen peroxide solution produced industrially are almost limited to Fe, Cr, Ni, and Pd. In the present invention, it is desirable to use an aqueous hydrogen peroxide solution in which the Ni and Pd concentrations are each 0.1 ppb or less and the Fe and Cr concentrations are each 5 ppb or less.
• the aqueous hydrogen peroxide solution of the present invention can be produced by directly adding a phosphate and an aluminum salt and other accompanying acids and / or salts to the hydrogen peroxide aqueous solution as a raw material.
• the method for producing mist and / or gaseous hydrogen peroxide is not particularly limited. Examples include a method using ultrasonic waves and a method using heating. It is preferable to heat and vaporize the aqueous hydrogen peroxide solution above the boiling point with an evaporator and spray the hydrogen peroxide gas together with air.
• the apparatus for heating and evaporating the aqueous hydrogen peroxide solution of the present invention is not particularly limited, and a known apparatus can be used.
• the temperature for vaporization by heating is more preferably 100 to 150 ° C.
• Examples of the object include a packaging container, a food machine, a plastic bottle and / or a plastic bottle preform, and a closed space.
• closed spaces examples include automobiles, electronic industry clean rooms, living spaces, medical spaces, kitchens, kitchens, vehicles, and aircraft.
• a hydrogen peroxide aqueous solution mist and / or hydrogen peroxide vapor generator is brought into the facility to generate a hydrogen peroxide aqueous solution mist and / or hydrogen peroxide vapor to reduce the number of bacteria in the facility. You can also.
• this facility examples include toiletries, waste disposal facilities, and barns.
• Example preparation method> The stability of hydrogen peroxide was examined at the stage assuming (1) immediately after compounding, (2) post-storage after storage of aluminum tank, and (3) storage of stainless steel tank after storage of aluminum tank. After using a predetermined aqueous hydrogen peroxide solution and adding a desired amount of additives, the hydrogen peroxide concentration was set to 35% by weight. The amount of the additive is as shown in Tables 1 to 3. Explanation of (2): Two test pieces (30 mm ⁇ 30 mm ⁇ 2 mm) made of aluminum were placed in 300 ml of the hydrogen peroxide solution in the present invention, and allowed to stand at 45 ° C. for 24 hours.
• ⁇ Sample measurement method> The stability of hydrogen peroxide was evaluated by the JIS stability, and the physical properties of the evaporation residue were evaluated by the adhering water washing property.
• the JIS stability was measured by the method specified in JIS-1463.
• the evaluation of the ability to wash the adhering matter was made by placing a SUS304 test piece (30 mm x 30 mm x 2 mm) on a hot plate heated to 150 ° C, dropping 3 ml of an aqueous hydrogen peroxide solution onto the test piece, and evaporating the water. And deposits were deposited.
• the test piece was washed with running water, the state of the deposit residue before and after washing was observed by SEM, and the remaining amount was evaluated.
• ⁇ Remaining amount is 40% or less of the area in the photo
• ⁇ Remaining amount is more than 40 to less than 70% of the area in the photo
• X Remaining amount is 70% or more of the area in the photo.
• Table 1 shows the results when the essential components of the present invention are lacking.
• no aluminum salt potential alum
• no phosphate was added as in Comparative Examples 5, 7 and 12, or as in Comparative Example 13, It can be seen that when phosphoric acid is added instead of JIS, the JIS stability is not satisfactory, and the residue cleaning property is not satisfactory.
• Table 2 shows the results when the essential components of the present invention are satisfied. Compared with the results shown in Table 1, the JIS stability was improved and the residue washes were also improved. In particular, Example 14 shows a remarkable effect on the residue cleaning property.
• Example 3 shows the results when the amounts of potassium alum, sodium dihydrogen phosphate, and sodium sulfate were changed.
• Example 4 is a reproduction from Table 2. Examples 20 and 21 have high JIS stability and remarkably good residue cleaning properties.
• the stability of hydrogen peroxide is improved, the deposits derived from the stabilizer of the aqueous hydrogen peroxide solution remaining on the spray nozzle and the evaporator are reduced, and the residue can be easily removed by washing with water. For this reason, the aseptic filling apparatus can be stably operated without blocking a thin pipe portion such as a nozzle.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
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• Apparatus For Disinfection Or Sterilisation (AREA)
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• 2014
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