KR20160032015A - Aqueous hydrogen peroxide solution for disinfection applications, method for producing same, and disinfection method using same - Google Patents

Abstract

According to the present invention, it is possible to provide an aqueous hydrogen peroxide solution which contains hydrogen peroxide, a phosphate and an aluminum salt as essential components as an aqueous hydrogen peroxide solution used for reducing the number of bacteria. Further, according to the present invention, it is possible to provide a sterilization method characterized by mixing air and a mist of the aqueous hydrogen peroxide solution and / or gas and then bringing the object into contact with the object.

Description

TECHNICAL FIELD The present invention relates to an aqueous hydrogen peroxide solution for sterilization, a method for producing the aqueous hydrogen peroxide solution, a sterilization method using the aqueous hydrogen peroxide solution, a disinfection method,

An object of the present invention is to provide an aqueous hydrogen peroxide solution and an aqueous hydrogen peroxide solution used for heating the aqueous hydrogen peroxide solution to evaporate and bringing the mist and / or gas into contact with the object to reduce the number of microorganisms floating in the vicinity of the object and / A production method thereof, and a sterilization method using the same.

A technique of reducing the number of microorganisms attached to an object by bringing a high-temperature mist or hydrogen peroxide vapor of an aqueous hydrogen peroxide solution into contact with the object has been applied to sterilization of clean rooms for electronic industries and sterilization of PET bottles before beverage filling. Particularly in recent years, along with the spread of PET bottles, high performance aqueous hydrogen peroxide solution used for aseptic filling has been demanded. That is, it is demanded that there are few residues when hydrogen peroxide and water are evaporated, and that they are highly stable in high temperature or metal storage containers. In the case of using an aqueous hydrogen peroxide solution for aseptic filling, there is known a method in which an aqueous hydrogen peroxide solution is heated to a boiling point or more by an evaporator, and a gas of hydrogen peroxide is sprayed with air to sterilize the container (see Patent Document 1). However, there is a problem that a part of the stabilizer added to the aqueous hydrogen peroxide solution adheres to the spray nozzle and the evaporator to obstruct the piping and the like, thereby hindering stable operation of the sterilizing device. In addition, although not so far described, when the aqueous hydrogen peroxide solution is stored in a tank made of aluminum or stainless steel, there is a problem that the stability is gradually lowered although the concentration is not changed.

As a means for solving the above-mentioned obstruction problem, it has been proposed to reduce the addition amount of the stabilizer added to the aqueous hydrogen peroxide solution. In this case, since the amount of the stabilizer added is determined according to the amount of the decomposing active material contained in the aqueous hydrogen peroxide solution, it is necessary to use an aqueous hydrogen peroxide solution having a low concentration of the decomposing active material.

For example, it is known that when sodium pyrophosphate and orthophosphoric acid are used as stabilizers at a level at which the decomposition active substance concentration is 5 ppb or less, the stability of hydrogen peroxide can be secured even when the total added amount is 40 mg / kg or less (See Patent Document 2).

It has also been reported that the stability of hydrogen peroxide can be secured even when the amount of the aminotrismethylenephosphonic acid added is 50 mg / kg or less by adjusting the evaporation (dry) residue to 10 mg / kg or less (see Patent Document 3).

As mentioned above, although some means for solving the problem of clogging have been proposed, a means for solving the problem of lowering the stability of hydrogen peroxide in storage of a tank, which has not been presently known, has not been found. Recent studies by the present inventors have revealed that a trace amount of metal is eluted from a metal tank by a chelating agent such as phosphoric acid which is added as a stabilizer in an aqueous hydrogen peroxide solution to lower the stability of hydrogen peroxide. When a stabilizer is used in a large amount, a decrease in stability can be avoided, but it is not preferable in this application because the inhibition of the operation such as the nozzle clogging described above tends to occur.

In addition, as a countermeasure against the occlusion problem, even if the addition amount of the stabilizer to the aqueous hydrogen peroxide solution is reduced, the remaining part of the adhering matter to the spray nozzle and the evaporator can not be completely removed and the piping part is closed , The problem of hindering the stable operation of the sterile filling device could not be completely solved.

Japanese Patent Application Laid-Open No. 11-47242 Japanese Laid-Open Patent Publication No. 2006-240969 Japanese Published Patent Publication No. 2009-507887

It is an object of the present invention to solve the above problems in the prior art, and to provide an aqueous hydrogen peroxide solution, a method of producing the same, and a sterilization method using the aqueous hydrogen peroxide solution.

The inventors of the present invention have made intensive studies on the amount of stabilizer added to the aqueous hydrogen peroxide solution, the stabilizer component, the evaporation residue and its water-waxy property, the impurity contained therein, the storage stability and the safety of use. As a result, The use of the aqueous hydrogen peroxide solution reduces the adherence of the aqueous hydrogen peroxide solution remaining in the spray nozzle and the evaporator due to the stabilizer and allows the residues to be easily removed by washing with water so that an aqueous hydrogen peroxide solution The present invention has been accomplished.

That is, the present invention is as follows.

≪ 1 > An aqueous hydrogen peroxide solution used for reducing the number of bacteria, which comprises hydrogen peroxide, a phosphate and an aluminum salt as essential components.

≪ 2 > The method according to claim 1, wherein the phosphate is selected from the group consisting of tripotassium phosphate, 3 magnesium phosphate, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, (Hydrogen phosphate) calcium, and the aqueous hydrogen peroxide solution according to < 1 >, wherein the hydrogen peroxide solution is at least one selected from the group consisting of hydrogen peroxide (hydrogen phosphate) and calcium.

<3> The hydrogen peroxide solution according to <1>, wherein the phosphate is a hydrogen phosphate salt.

<4> The aqueous hydrogen peroxide solution according to any one of <1> to <3>, wherein the concentration of the phosphate is 1 to 18 mg / kg.

<5> The aqueous hydrogen peroxide solution according to any one of <1> to <4>, wherein the aluminum salt is aluminum potassium sulfate.

<6> The aqueous hydrogen peroxide solution according to any one of <1> to <5>, wherein the aluminum salt has an added concentration of 1 to 4 mg / kg.

<7> A pharmaceutical composition according to any one of <7> to <7>, wherein the group consisting of 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, The aqueous hydrogen peroxide solution according to any one of &lt; 1 &gt; to &lt; 6 &gt;, which contains at least one acid and / or a salt selected.

<8> The hydrogen peroxide solution according to <7>, wherein the 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 wt% to 40 wt%.

&Lt; 10 &gt; A sterilizing agent using the aqueous hydrogen peroxide solution according to any one of &lt; 1 &gt; to &lt; 9 &gt;.

<11> A process 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 an aqueous hydrogen peroxide solution serving as a raw material.

<12> A sterilization method, comprising mixing air and a mist of hydrogen peroxide solution described in any one of <1> to <9> and / or a gas, and then contacting the object.

<13> The sterilization method according to <12>, wherein the aqueous hydrogen peroxide solution is brought into contact with a subject by heating the air to cause the mist and / or gas of the aqueous hydrogen peroxide solution to accompany the object.

<14> A method for sterilization according to <12> or <13>, wherein the aqueous hydrogen peroxide solution is heated to 100 ° C. to 150 ° C. to be brought into contact with an object.

<15> The sterilization method according to any one of <12> to <14>, wherein the object is a packaging container, a food machine, a PET bottle, or a PET 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 a clean room for an automobile, an electronic industry, a residence space, a medical space, a kitchen, a kitchen, a vehicle, or an aircraft.

<12> The method according to any one of <12> to <14>, wherein the apparatus for generating mist and / or hydrogen peroxide vapor of an aqueous hydrogen peroxide solution is brought into the facility to generate a mist of hydrogen peroxide solution and / or hydrogen peroxide vapor, And the sterilization method described in any one of &lt; 1 &gt;

<19> The sterilization method according to <18>, wherein the facility is a toilette facility, a waste treatment facility, or a barn.

According to the present invention, the stability of the hydrogen peroxide is improved, the adherence of the aqueous hydrogen peroxide solution remaining in the spray nozzle, the evaporator, etc. from the stabilizer is reduced, and the residue can be easily removed by washing with water.

Hereinafter, the present invention will be described in detail.

The aqueous hydrogen peroxide solution of the present invention contains a phosphate salt and an aluminum salt as effective components for stabilizing hydrogen peroxide. Further, other acid and / or salt may be contained as an additive for facilitating the washing property of the evaporation residue adhered to the nozzle or the evaporator.

There has been a problem that a trace amount of metal is eluted from a metal tank by a chelating agent such as phosphoric acid which has been added as a stabilizer in a conventional aqueous hydrogen peroxide solution to lower the stability of hydrogen peroxide. However, this problem can be solved by using a phosphate.

Examples of the phosphate used in the present invention include, for example, tripotassium phosphate, 3 magnesium phosphate, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, dihydrogen phosphate Sodium phosphate, trisodium phosphate and bis (hydrogenphosphate) calcium are preferable, and disodium hydrogen phosphate is particularly preferable. In addition, the phosphate used in the present invention is preferably a hydrogen phosphate.

The aluminum salt used in the present invention can be used without particular problems if it is a food additive containing aluminum, for example, aluminum potassium sulfate is preferable.

In the present invention, the acid and / or salt may be selected from the specified additives of the food hygiene law which improves the washing property of the evaporation residue attached to the nozzle, the evaporator, and the like. Concretely, there can be mentioned, for example, L-ascorbic acid and / or its salt, ethylenediaminetetraacetate, citric acid and / or its salt, gluconic acid and / or its salt, L- glutamic acid and / or its salt, silicate, Pyrophosphate, and sulfate are preferable, and sulfate is particularly preferable.

In the aqueous hydrogen peroxide solution of the present invention, the concentration of the phosphate added is preferably 1 to 18 mg / kg, more preferably 1 to 12 mg / kg. If the added concentration of phosphate is 1 to 18 mg / kg, a stabilizing effect is obtained, and the amount of evaporation residue attached to the evaporator or nozzle is suppressed.

In the aqueous hydrogen peroxide solution of the present invention, the addition concentration of the aluminum salt is preferably 1 to 4 mg / kg, more preferably 1 to 3 mg / kg. When the added concentration of the aluminum salt is 1 to 4 mg / kg, a stabilizing effect is obtained, and the amount of the evaporation residue attached to the evaporator or the nozzle is suppressed.

In the aqueous hydrogen peroxide solution of the present invention, the concentration of hydrogen peroxide is preferably 30 to 40 wt%, and more preferably 33 to 37 wt%. If the concentration of hydrogen peroxide is 30 to 40% by weight, the sterilizing power is preferable because the strength becomes appropriate.

The addition concentration of other acid and / or salt 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. If the addition concentration of the other acid and / or salt is 2 to 12 mg / kg, the detergency of the evaporated residue becomes high, which is preferable.

Particularly preferably, the concentration of the phosphate is 2 to 4 mg / kg, the concentration of the aluminum salt is 2 to 3 mg / kg, and the concentration of the other acid and / or salt is 3 to 5 mg / kg.

As a decomposition component of hydrogen peroxide, heavy metals are known, but decomposition components contained in industrially produced aqueous hydrogen peroxide solution are almost limited to Fe, Cr, Ni and Pd. In the present invention, it is preferable to use an aqueous hydrogen peroxide solution having Ni and Pd concentrations of 0.1 ppb or less and Fe and Cr concentrations of 5 ppb or less, respectively.

The aqueous hydrogen peroxide solution of the present invention can be prepared by directly adding a phosphate and an aluminum salt and an additional acid and / or salt to an aqueous hydrogen peroxide solution as a raw material.

The method of producing hydrogen peroxide in the form of mist and / or gas is not particularly limited. An ultrasonic wave method, and a heating method. It is preferable to spray the hydrogen peroxide gas with air by heating the aqueous hydrogen peroxide solution to a boiling point or more with an evaporator.

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 the vaporization is more preferably 100 deg. C to 150 deg.

It is more preferable that the hydrogen peroxide solution is brought into contact with the object by heating the air to accompany the mist and / or gas of the aqueous hydrogen peroxide solution.

Examples of objects include packaging containers, food machines, PET bottles and / or PET bottle preforms, closed spaces, and the like.

The closed space includes, for example, a clean room for a car, an electronic industry, a residence space, a medical space, a kitchen, a kitchen, a vehicle, and an aircraft.

In the present invention, an apparatus for generating a mist of hydrogen peroxide solution and / or hydrogen peroxide vapor may be brought into the facility to generate a mist of hydrogen peroxide solution and / or hydrogen peroxide vapor to reduce the number of bacteria in the facility.

As this facility, a toilette facility, a waste disposal facility, and a house are exemplified.

Example

Next, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited by the following examples.

&Lt; Preparation method of sample &gt;

The stability of hydrogen peroxide was investigated in the following steps: (1) immediately after combination, (2) assumption after storage of an aluminum tank, and (3) storage of a stainless steel tank after storage of an aluminum tank.

After adding a desired amount of an additive using a predetermined hydrogen peroxide aqueous solution, the hydrogen peroxide concentration was made 35 wt%. The amounts of additives are shown in Tables 1 to 3.

(2): Two aluminum test pieces (30 mm x 30 mm x 2 mm) were put into 300 ml of the aqueous hydrogen peroxide solution of the present invention and allowed to stand at 45 캜 for 24 hours.

(3): After (2), a test piece made of aluminum was taken out, and two test pieces (30 mm x 30 mm x 2 mm) made of SUS304 were put in place, .

Further, 3 Na of citric acid represents trisodium citrate, and similarly, sodium gluconate represents sodium gluconate. In addition, the potassium alum represents aluminum potassium sulfate (AlK (SO ₄ ) ₂ .12H ₂ O).

&Lt; Measurement method of sample &gt;

The stability of hydrogen peroxide was evaluated by the stability of JIS, and the physical properties of the evaporation residue were evaluated by the water resistance of the adherend. The JIS stability was measured by the method specified in JIS-1463. The evaluation of water resistance of the adherend was carried out by placing a test piece (30 mm x 30 mm x 2 mm) made of SUS304 on a hot plate heated to 150 DEG C, dropping 3 milliliters of an aqueous hydrogen peroxide solution onto the test piece, Deposits were deposited. The test piece was rinsed with running water, and the state of the residue of the adhered substance before and after the rinsing was observed by SEM, and it was evaluated that the remaining amount of the rubbing residue was small and small. ◯ = less than 40% of the area in the photograph, Δ = less than 40% to less than 70% of the area in the photograph, × = more than 70%

Table 1 shows the results when the essential components of the present invention are omitted.

When no aluminum salt (potassium alum) was added as in Comparative Examples 1 to 11, no phosphate was added as in Comparative Examples 5, 7, and 12, or when phosphoric acid was added instead of phosphate as in Comparative Example 13, The JIS stability is not satisfied and the residue cleaning property is not satisfied.

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 cleaning property was also improved.

Particularly in Example 14, a remarkable effect was observed in the residue cleaning property.

Table 3 shows the results in the case where the addition amount of potassium alum, sodium dihydrogenphosphate and sodium sulfate was varied.

The fourth embodiment is a re-publication from Table 2.

In Examples 20 and 21, the JIS stability is high and the residue cleaning property is also remarkably good.

Industrial availability

According to the present invention, the stability of hydrogen peroxide is improved, the adherence of the aqueous hydrogen peroxide solution remaining in the spray nozzle, the evaporator, etc. from the stabilizer is reduced, and the residue can be easily removed by washing with water, Stable operation of the sterilizing device can be achieved without closing the piping.

Claims (19)

An aqueous hydrogen peroxide solution used for reducing the number of bacteria, comprising hydrogen peroxide, a phosphate and an aluminum salt as essential components. The method according to claim 1,
Wherein the phosphate is selected from the group consisting of tripotassium phosphate, 3 magnesium phosphate, 2 ammonium ammonium phosphate, ammonium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, ) Calcium. &Lt; / RTI &gt; The method according to claim 1,
Wherein said phosphate is hydrogenphosphate. 4. The method according to any one of claims 1 to 3,
An aqueous solution of hydrogen peroxide having an added concentration of the phosphate of 1 to 18 mg / kg. 5. The method according to any one of claims 1 to 4,
Wherein the aluminum salt is aluminum potassium sulfate. 6. The method according to any one of claims 1 to 5,
And an aqueous solution of hydrogen peroxide in which the aluminum salt is added at a concentration of 1 to 4 mg / kg. 7. The method according to any one of claims 1 to 6,
At least one selected from the group consisting of L-ascorbic acid and its salt, ethylenediamine tetraacetate, citric acid and its salt, gluconic acid and its salt, L-glutamic acid and its salt, silicate, nitrate, carbonate, pyrophosphate, An aqueous hydrogen peroxide solution containing one acid and / or a salt. 8. The method of claim 7,
Wherein the concentration of the acid and / or salt added is 2 to 12 mg / kg. 9. The method according to any one of claims 1 to 8,
Wherein the hydrogen peroxide concentration is 30 wt% to 40 wt%. A disinfectant using the aqueous hydrogen peroxide solution according to any one of claims 1 to 9. The method for producing an aqueous hydrogen peroxide solution according to any one of claims 1 to 9, wherein a phosphate and an aluminum salt are added to an aqueous hydrogen peroxide solution as a raw material. Air and a mist of an aqueous hydrogen peroxide solution according to any one of claims 1 to 9 and / or a gas are mixed and then contacted with an object. 13. The method of claim 12,
A method of sterilization in which a mist of hydrogen peroxide solution and / or gas is accompanied by heating air when bringing an aqueous hydrogen peroxide solution into contact with an object. The method according to claim 12 or 13,
Wherein the hydrogen peroxide solution is heated to 100 占 폚 to 150 占 폚 to contact the object. 15. The method according to any one of claims 12 to 14,
Wherein the object is a packaging container, a food machine, a PET bottle, or a PET bottle preform. 15. The method according to any one of claims 12 to 14,
Wherein the object is a closed space. 17. The method of claim 16,
Wherein said closed space is a clean room for an automobile, an electronic industry, a living space, a medical space, a kitchen, a kitchen, a vehicle, or an aircraft. 15. The method according to any one of claims 12 to 14,
A device for generating mist and / or hydrogen peroxide vapor of an aqueous hydrogen peroxide solution is brought into the facility to generate a mist of hydrogen peroxide solution and / or hydrogen peroxide vapor to reduce the number of bacteria in the facility. 19. The method of claim 18,
Wherein the facility is a toilette facility, a waste treatment facility, or a housing.