JP6980272B2 - Sterilization method and its equipment - Google Patents

Description

The present invention relates to a sterilization method and an apparatus for sterilizing an object to be sterilized such as fungi and molds, and more particularly to a sterilization method and an apparatus thereof capable of sterilizing an object to be sterilized with a simple structure and efficiently.

Currently, in a wide range of industrial fields such as food, medical care, and housing, as consumers' needs for safety and comfort increase, there is a growing need for reliable sterilization of various viruses, bacteria, fungi, and other bacteria. It is getting higher.

For example, the current sterilization needs are diverse, such as sterilization of washing water once used for cleaning treatment and purification of contaminated spaces in various factories and workplaces (space sterilization).

In the conventional sterilizing device, the sterilizing object is sterilized by using a chemical (treatment solution) that sterilizes the sterilized object such as bacteria and mold.

Conventional sterilization methods include, for example, water, hypochlorous acid, thickeners, lubricants and water retention agents, and include the water, the hypochlorous acid, the thickener, and the lubricant. It is known that a semi-fluid composition used for lubrication, moisturizing, disinfection and sterilization, which is characterized by being mixed with the water-retaining agent and stirred to form a hydrogel body or a viscous body, is used (Patent Document 1). reference).

Further, as a conventional sterilizing method, for example, a bactericidal agent prepared by mixing an acetate buffer solution and sodium hypochlorite, the final pH of which is in the range of 5.0 to 6.0. There is also known a sterilization method in which a non-heated food is immersed and the temperature of the non-heated food is maintained in the range of 40 ° C. to 70 ° C. for 3 minutes or longer (see Patent Document 2).

Further, as conventional sterilization methods, for example, (a) 0.1 to 5% by mass of a hypochlorite alkali metal salt, (b) 0.01 to 1% by mass of a quaternary ammonium type surfactant, and (C) There is also known one using a composition for removing mold stains containing 0.01 to 1% by mass of a polyether-modified silicone having HLB 11 or higher (see Patent Document 3).

Further, as a conventional sterilization method, for example, hypochlorite, a caustic alkali, a hydrotropic agent, and an alkyldimethylamine oxide having a linear alkyl group having 14 or more carbon atoms are used in an amount of 1% by weight or more and 8% by weight. It is also known to use an antifungal / antifungal agent characterized by blending the following (see Patent Document 4).

In addition, conventional sterilization methods include, for example, clay minerals such as laponite, hypochlorites such as sodium hypochlorite, chlorine dioxide precursors such as sodium chlorite, water, and, if necessary,. It is also known that a surfactant such as polyoxyethylene hydrogenated castor oil and a fragrance or herb component are mixed to use a thixotropic composition (see Patent Document 5).

Further, as a conventional sterilization method, a sterilization method of spraying an aqueous solution of hypochlorous acid into a space is also known (see, for example, Patent Document 6 and Patent Document 7).

As another conventional sterilization method, unlike the sterilization method in which a liquid substance is brought into direct contact as described above, a sterilization effect is exhibited even in a portion not in direct contact, for example, R-SO ₂ NXM (R is fragrance). A solid halogen composition containing a solid halogen agent represented by a cyclic group, X being chlorine or bromine, and M being an alkali or alkaline earth metal) and an acidic substance is known (Patent Document 8). reference).

Japanese Unexamined Patent Publication No. 2015-178497 Japanese Unexamined Patent Publication No. 2016-0861815 Japanese Unexamined Patent Publication No. 2011-178941 Japanese Unexamined Patent Publication No. 2015-189702 Japanese Unexamined Patent Publication No. 2016-132655 Japanese Unexamined Patent Publication No. 2011-201838 International Bulletin WO2016 / 170827 Japanese Unexamined Patent Publication No. 2002-265308

However, in the conventional sterilization method, for example, as in Patent Documents 1 to 5, in the case of sterilizing an object to be sterilized by immersing it in a treatment solution, a step of further treating the waste liquid produced as a by-product after the sterilization treatment is performed. It is additionally necessary, and as a result, the work process is increased and complicated, and the work is troublesome. In addition, since the object to be sterilized is sterilized by immersing it in a treatment solution, a large-scale device is required for the needs for large-scale sterilization treatment, that is, an increase in cost is inevitable. It is difficult in reality because it invites people.

Furthermore, since the conventional sterilization method uses a liquid chemical (chemical solution), it is necessary to surely remove the used chemical after sterilization, especially when sterilizing food, and as a result. In addition to requiring many work processes and increasing costs, it is undeniable that chemicals may remain in food after sterilization, and there is a problem in ensuring safety. In addition, since a liquid chemical (chemical solution) is used, there is also a problem that it cannot be applied to an application for sterilizing an internal space such as a factory.

Further, for example, as in Patent Document 6 and Patent Document 7, there is a sterilization method in which an aqueous solution of hypochlorous acid is sprayed into a space, but it is essentially the same as using a liquid drug, especially for foods. When sterilizing, it is necessary to surely remove the used chemicals after sterilization as described above, and it is undeniable that the chemicals may remain in the food after the sterilization treatment, so that safety is ensured. There is also a problem in.

In addition, some of them show a bactericidal effect even in a part that does not come into direct contact with each other. For example, as shown in Patent Document 8, an aromatic compound is used, and there is a concern about its safety and disposal after use. There is a problem that processing and handling itself are difficult

As described above, a sterilization method and an apparatus thereof that have a simple structure, are easy to scale up, and can sterilize a sterilized object safely and efficiently have not yet been found.

INDUSTRIAL APPLICABILITY The present invention has been made to solve the above problems, and provides a sterilization method and an apparatus thereof that can sterilize an object to be sterilized safely and efficiently with a simpler configuration than the conventional one and can be easily scaled up. The purpose is to do.

As a result of diligent research, the present inventors have found a new sterilization method that does not require the chemical solution used in the conventional sterilization treatment by using a certain substance for the sterilization treatment without making it into a liquid state. We have derived a new type of sterilization method and equipment that can sterilize objects to be sterilized efficiently with a simpler structure than before and easy to scale up.
That is, the present invention is a sterilization method for sterilizing an object to be sterilized, in which a treated gas containing a sterilizing component, which is produced by contacting the hypochlorite of needle-like crystals with the raw material gas, is sterilized. It is a sterilization method characterized by contacting with.
Further, the present invention is a sterilizer for sterilizing an object to be sterilized, and a processed gas containing a sterilizing component, which is produced by bringing the raw material gas into contact with hypochlorite of needle-like crystals, is the object to be sterilized. It is a sterilizer characterized by being brought into contact with.
Specifically, the present invention is as follows.
[1] A sterilization method for sterilizing an object to be sterilized.
A sterilization method, characterized in that a raw material gas is brought into contact with hypochlorite of needle-like crystals to generate a treated gas, and the treated gas is brought into contact with an object to be sterilized.
[2] The sterilization method according to [1], wherein the hypochlorite has an apparent density of crystal aggregates of 0.4 to 1.4 g / mL.
[3] In the sterilization method according to [1] or [2],
A sterilization method, wherein the needle-like crystals constituting the hypochlorite have a needle-like body having a width of 40 to 850 μm and a length of 150 to 3000 μm.
[4] In the sterilization method according to any one of [1] to [3],
A sterilization method, wherein the hypochlorite is sodium hypochlorite pentahydrate.
[5] In the sterilization method according to any one of [1] to [4],
A sterilization method comprising contacting the raw material gas with chloride in a pre-stage and / or a post-stage of contacting the raw material gas with the hypochlorite to generate the treated gas.
[6] In the sterilization method described in [5],
A sterilization method, wherein the chloride is sodium chloride.
[7] In the sterilization method according to any one of [1] to [6],
A sterilization method comprising introducing the raw material gas at a space velocity (SV) of 1000 to 125000 h- ¹ and bringing it into contact with the hypochlorite.
[8] In the sterilization method according to any one of [1] to [7],
A sterilization method, characterized in that the raw material gas is air.
[9] In the sterilization method according to any one of [1] to [8],
A sterilization method comprising accumulating the generated treated gas and bringing the accumulated treated gas into contact with an object to be sterilized.
[10] In the sterilization method according to any one of [1] to [9],
A sterilization method comprising blowing the treated gas into a liquid sterilization object.
[11] In the sterilization method according to any one of [1] to [9],
A sterilization method comprising spraying the treated gas onto a gaseous or solid object to be sterilized.
[12] In the sterilization method according to any one of [1] to [11],
A sterilization method, wherein the sterilization target is at least one selected from the group consisting of Escherichia coli, Staphylococcus aureus, Bacillus subtilis, red mold, and black jiuqu.
[13] A sterilizer that sterilizes an object to be sterilized.
A crystal laminate containing hypochlorite of acicular crystals and
A raw material gas supply unit that supplies the raw material gas to the crystal laminated portion, and a raw material gas supply unit.
A processing gas supply unit for supplying a processing gas generated by contacting the raw material gas with the crystal laminated portion to the sterilization target is provided.
A sterilization apparatus, characterized in that the object to be sterilized comes into contact with the treated gas supplied by the treated gas supply unit and is sterilized.
[14] In the sterilizer according to [13],
A sterilizing apparatus, wherein the hypochlorite is sodium hypochlorite pentahydrate.
[15] In the sterilizer according to [13] or [14],
A sterilizer comprising a filter portion made of chloride as a chloride layer in the front stage and / or the rear stage of the crystal laminated portion.
[16] In the sterilizer according to [15],
A sterilizer, characterized in that the chloride is sodium chloride.
[17] In the sterilizer according to any one of [13] to [16],
The sterilization apparatus, wherein the treated gas supply unit includes a gas storage unit that stores the generated treated gas in a container, and brings the treated gas accumulated by the gas storage unit into contact with an object to be sterilized. ..

According to the sterilization method and the sterilization apparatus of the present invention, it is possible to sterilize the object to be sterilized efficiently with a simpler structure than before, easy to increase the scale, and so on.

Explanatory drawings (a) of needle-like crystals of hypochlorite used in the sterilization method according to the first embodiment of the present invention and the apparatus thereof, and explanatory views (b) and (c) showing an example of the sterilization apparatus. show. An explanatory diagram showing an example of a sterilizer according to the first embodiment of the present invention is shown. An explanatory diagram showing an example of a sterilizer according to a second embodiment of the present invention is shown. An explanatory diagram showing an example of a sterilizer according to a third embodiment of the present invention is shown. The photograph of the result before and after the sterilization of Escherichia coli by the sterilization method which concerns on Example 1 of this invention is shown. Photographs (n = 2) of the results of sterilizing Staphylococcus aureus by the sterilization method according to Example 2 of the present invention are shown. The photograph of the result of immersing Escherichia coli by the sterilization method according to the comparative example in liquid sodium hypochlorite is shown. A photograph of the result of releasing untreated air against Escherichia coli by the sterilization method according to the reference example is shown. The photograph of the result of sterilizing the bacterial solution containing Staphylococcus aureus by the sterilization method according to Example 3 of the present invention is shown. The photograph of the result of sterilizing the bacterial solution containing Bacillus subtilis by the sterilization method according to Example 4 of the present invention is shown. The photograph of the result of sterilizing the bacterial solution containing red mold by the sterilization method according to Example 5 of the present invention is shown. The photograph of the result of sterilizing the bacterial solution containing black jiuqu by the sterilization method according to Example 6 of the present invention is shown.

Embodiments of the present invention will be described below. The following embodiments are examples of carrying out the present invention, and the present invention is not limited to these embodiments.

(First Embodiment)
The sterilization method according to the first embodiment of the present invention is a sterilization method for sterilizing an object to be sterilized, in which a raw material gas is brought into contact with hypochlorite of needle-like crystals to generate a treated gas, and the treatment is performed. It brings the gas into contact with the object to be sterilized.

As shown in FIG. 1 (a), the hypochlorite used in the present invention is an elongated needle-like body having a width a and a length b (that is, a high aspect ratio (length b / width a)). The hypochlorite 1 as a crystal aggregate composed of needle-like crystals 1a, which are crystals, is not particularly limited.
The individual size of the needle-shaped body constituting the needle-shaped crystal is not particularly limited, but the width a is preferably 40 to 850 μm and the length b is preferably 150 to 3000 μm, and higher sterilization efficiency can be obtained. It will be a thing.

Since the hypochlorite of needle-shaped crystals is configured as an aggregate of needle-shaped bodies, it exists as a crystal aggregate having a large specific surface area (small apparent density), and the contact area with the raw material gas is large. It increases, the sterilizing component contained in the treated gas increases, and the sterilizing object can be sterilized with high efficiency. The apparent density of the crystal aggregate is not particularly limited, but it is more preferable to have an apparent density of 0.4 to 1.4 g / mL.

Hypochlorite is not particularly limited as long as it is composed of compound include hypochlorous acid (ClO), more preferably a hydrate containing water component (H 2 _O), for example, It is preferable to use sodium hypochlorite pentahydrate (NaClO ・ 5H _{2 O).} As such sodium hypochlorite pentahydrate (NaClO 5H ₂ O), for example, Kaneka crystalline hypochlorite sodium can be used and is easily available.

The object to be sterilized is not particularly limited, but can be a general fungus or mold, and can be sterilized regardless of whether it is liquid, gaseous or solid. be able to. A more preferred target can be at least one selected from the group consisting of Escherichia coli, Staphylococcus aureus, Bacillus subtilis, red mold, and black jiuqu.

The raw material gas is not particularly limited as long as it is a gas, but it is preferable to use air from the viewpoint of easy handling, but in addition to this, nitrogen gas or the like can also be used from the viewpoint of easy handling. ..

Contacting the raw material gas with hypochlorite includes bringing the raw material gas into contact with the surface of the hypochlorite, and the raw material gas is a packed layer filled with hypochlorite (hereinafter referred to as). , It may also be referred to as a "crystal laminated portion"), and it is also included to be passed through and distributed.

The treated gas is a gas obtained by contacting the raw material gas with hypochlorite, and is a gas containing a bactericidal component derived from hypochlorite by contacting with hypochlorite. be.

When the treated gas is brought into contact with the object to be sterilized, it may be brought into contact with the surface of the object to be sterilized or may be brought into contact with the whole.
When the object to be sterilized is a gas, the treated gas can be brought into contact with the object to be sterilized in a closed container. In the case of directly adding a drug as in the past, there is a problem that the risk of residual drug remains, especially in food applications, but in the present embodiment, such a problem is obtained only by bringing the treated gas into contact with the sterilized object. It is possible to perform an excellent sterilization treatment that is less likely to cause risk.
In addition to this, the generated processing gas can be sprayed on the internal space such as in a factory, and the internal space can be sterilized.

As described above, it has been confirmed that the sterilized object is sterilized by the hypochlorite-derived sterilizing component contained in the treated gas by bringing the treated gas into contact with the sterilized object (implementation described later). See example).

Although the mechanism for exerting the excellent bactericidal effect of the present invention has not been elucidated in detail yet, the hypochlorite of needle-like crystals is present as the above-mentioned crystal aggregate having a large specific surface area, so that it can be used as a raw material gas. Hypochlorite is increased in contact area, the contact reaction with the raw material gas occurs efficiently in a short time, and the bactericidal component derived from hypochlorite is efficiently contained in the raw material gas. It is presumed that a treated gas containing a bactericidal component derived from an acid salt has been obtained.

In the sterilization apparatus using hypochlorite in the present invention, a crystal laminated portion containing hypochlorite of needle-like crystals, a raw material gas supply portion that supplies a raw material gas to the crystal laminated portion, and a raw material gas crystallize. The configuration may include a processing gas supply unit that supplies the processing gas generated in contact with the unit to the object to be sterilized.

As an example of the sterilizer, as shown in FIG. 1 (b), a hypochlorite crystal 1 (crystal laminated portion), a chamber 10 accommodating the hypochlorite crystal 1 (crystal laminated portion), and a chamber 10 are used. A holding portion 3 having a plurality of through holes for holding the hypochlorite crystal 1 in the chamber 10, a flow meter 20 for measuring the flow rate of the raw material gas A to be introduced into the chamber 10, and a raw material to be introduced into the chamber 10. It can be configured to include a gas cylinder 30 (raw material gas supply unit) for storing the gas A. From the chamber 10, the processing gas B generated by the contact of the raw material gas A with the hypochlorite crystal 1 (crystal laminated portion) is released. That is, the chamber 10 functions as a processing gas supply unit that supplies the processing gas B, and the object to be sterilized is sterilized by coming into contact with the processing gas B supplied from the processing gas supply unit.
In FIGS. 2 and 3 described later, a configuration including at least a gas cylinder 30 (raw material gas supply unit) and a chamber 10 (processed gas supply unit) for storing the raw material gas A is referred to as a sterilizer 100.

In the present invention, the flow rate when the raw material gas is brought into contact with the hypochlorite crystal 1 (crystal laminated portion) needs to be appropriately adjusted for the concentration of the bactericidal component, and therefore the space velocity (SV) is particularly limited. However, 1000 to 125000 h- ¹ is preferable. The packing density of hypochlorite is preferably 0.3 to 1.4 g / mL.
Here, the space velocity (SV) is the aeration amount (m ^{3 / h) / (volume (m 3} ) of the packed layer (crystal laminated portion) of the hypochlorous acid crystal), that is, the aeration amount (m ³ /). h) × packing density of hypochlorous acid crystals (g / m ³ ) / a numerical value defined by the weight (g) of hypochlorous acid crystals. The space velocity (SV) can be calculated by measuring the numerical value of each requirement included in the above definition and calculating according to the definition.

The pressure condition for introducing the raw material gas A into the chamber 10 is not particularly limited and may be normal pressure.

As described above, in addition to sterilizing the treated gas B by contacting it with the sterilizing object X immediately after it is generated, the generated treated gas B is temporarily stored (stored) and the accumulated treated gas is stored. It is also possible to sterilize B by contacting it with an object to be sterilized. As a sterilizer in this case, for example, as shown in FIG. 1 (c), the processing gas supply unit has a gas storage unit that stores (stores) the generated processed gas B in a container (sealed container 12). It is also possible to bring the processed gas B stored (stored) in the closed container 12 into contact with the sterilizing object X by the gas storage unit. The means for connecting the chamber 10 in which the processing gas B is generated and the closed container 12 is not particularly limited, but for example, a tube 11 as shown in FIG. 1C can be used.

The closed container 12 is not particularly limited, but for example, a cylinder capable of being completely sealed can be used. When the treated gas B is discharged from the closed container 12, it is preferable to apply pressure to release the treated gas B. The contact is surely made, and more efficient sterilization can be performed.

In another embodiment of the sterilization method according to the present embodiment, as shown in FIG. 2, the processed gas B generated by the sterilizer 100 is discharged into the container 200 containing the sterilization object X. Thereby, the processing gas B can be brought into contact with the sterilizing object X to sterilize the sterilizing object X.

Further, in another embodiment of the sterilization method according to the present embodiment, even when the sterilization object X is a gas (or is contained in the gas) in the configuration of FIG. 2, the sterilization object is similarly sterilized. By discharging (spraying) the processed gas B generated by the sterilizer 100 into the container 200 containing the gas containing the object X, the processed gas B is brought into contact with the sterilized object X to be sterilized. X can be sterilized. The container 200 is not always essential, and for example, by spraying the generated processing gas B on the entire internal space such as in a factory, sterilization can be performed over the entire internal space.

As described above, in the past, when a chemical is directly added to a sterilized object to sterilize it, there remains a risk of residual chemicals, especially in food applications, and there is a problem in ensuring safety. However, in the present embodiment, the treated gas B is used. Can be sterilized only by bringing it into contact with the object X to be sterilized, and an extremely clean and excellent sterilization treatment can be performed, which is unlikely to cause a drug residue risk as in the past.

Further, in the case of sterilizing by immersing the object to be sterilized in the treatment solution as in the conventional case, an additional step (waste liquid treatment) of further treating the waste liquid produced as a by-product after the sterilization treatment is required. In the embodiment, since the treated gas B is sterilized only by contacting it with the object X to be sterilized, it is possible to perform an extremely simple and excellent sterilization treatment that does not require the conventional waste liquid treatment.

(Second embodiment)
The sterilization method and the apparatus thereof according to the second embodiment of the present invention will be described with reference to FIG.

In the sterilization method according to the second embodiment of the present invention, the processing gas B generated by the sterilization apparatus 100 is blown into a liquid sterilization object.

As an example of the apparatus according to the second sterilization method, as shown in FIG. 3, the processing gas B supplied from the processing gas supply unit is circulated to the sterilization apparatus 100 according to the first embodiment to the outside. A tube 40 is provided, and the tube 40 is immersed in a storage container 300 for storing a solution containing a sterilizing object.

The processing gas B released from the tube 40 by the apparatus shown in FIG. 3 is bubbled into a solution containing a sterilizing object (for example, water containing germs) and moves as bubbles B'in the solution. The object to be sterilized can be easily sterilized.

(Third embodiment)
The sterilization method and the apparatus thereof according to the third embodiment of the present invention will be described with reference to FIG.

The sterilization method according to the third embodiment of the present invention is the sterilization method according to each of the first or second embodiments, wherein the hypochlorite crystal is in the chamber 10 in FIG. / Or a chloride layer is provided in the subsequent stage.

In the sterilizing apparatus according to the third embodiment of the present invention, in the chamber 10 of FIG. 1 (b), a filter made of chloride is placed in the front stage and / or the rear stage of the hypochlorite crystal 1 (crystal laminated portion). The part 2 can be provided as a chloride layer.
For example, as shown in FIG. 4A, a filter portion 2 made of chloride can be provided as a chloride layer in the subsequent stage of the hypochlorite crystal 1 (crystal laminated portion), and FIG. 4B can be provided. As shown in the above, a filter portion 2 made of chloride may be provided as a chloride layer in front of the hypochlorite crystal 1 (crystal laminated portion). In any case, the filter portion 2 made of chloride is used in contact with the hypochlorite crystal 1 (crystal laminated portion).

The chloride constituting the filter portion 2 is not particularly limited, but sodium chloride is preferable from the viewpoint of ease of handling.
With such a configuration including the filter portion 2, chloride acts as a protective film for protecting the hypochlorite crystal 1 (crystal laminated portion) and also plays a role of removing water, so that the hypochlorite crystal It is possible to suppress the dissolution of 1 (crystal laminated portion) due to moisture, and the performance of hypochlorite crystal 1 (crystal laminated portion) (ability to generate treated gas B containing a high concentration of bactericidal component) is longer. The bactericidal ability can be further improved by stably producing the treated gas B which is maintained and has high bactericidal properties.

Further, more preferably, as shown in FIG. 4C, a filter portion 2 made of chloride is provided as a chloride layer in the front and rear stages of the hypochlorite crystal 1 (crystal laminated portion). It is to be. In this way, due to the sandwich configuration in which chloride sandwiches the hypochlorite crystal 1 (crystal laminated portion) above and below, the performance of the hypochlorite crystal 1 (crystal laminated portion) can be further extended for a longer period of time. It can be maintained and the bactericidal capacity can be further improved.

The field that can be used in the present invention is not particularly limited as long as it is used for sterilization, and can be applied to a wide range of uses. For example, in a wide range of industrial fields such as food, medical care, and housing, various viruses and bacteria. , Fungi and other bacteria can be sterilized safely and reliably. In addition, it cleans objects to be sterilized in various states regardless of gas, liquid, or solid, such as sterilization of pre-purified water after being used for cleaning once and purification of contaminated spaces in various factories and workplaces (space sterilization). Can be sterilized.

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.

(Example 1)
The space sterilization test is performed using the device shown in FIG. 1 (b) described above. Specifically, the inner diameter of the chamber 10 (cylinder) in the sterilizer 100 is 3 cm, the height is 8 cm, and the internal volume is 56. The container 200 is a cylinder with a height of 12.5 cm and an inner diameter of 13 cm, and discharges the processing gas into the container 200 through a hole provided in the center of the bottom surface of the container 200.
As the needle-shaped crystal hypochlorite sodium pentahydrate, Kaneka Crystal Hypochlorite Soda (manufactured by Kaneka Corporation; width 150 to 350 μm, length 600 to 1000 μm, effective chlorine concentration 40%) is used. Using. 1.0 g of the above crystalline hypochlorite soda was filled as uniformly as possible from the upper part of the cylinder onto the holding portion 3.
The height of the crystal laminated portion is 0.14 cm, and the packed density of the packed layer (crystal laminated portion) is 1.01 g / cm ³ .

Air, which is the raw material gas, is subjected to a hypochlorite of needle-like crystals at a ^{flow rate of 0.75 L / min <space velocity SV is 45500 h -1} > in the chamber 10 under atmospheric pressure (under a pressure of about 0.1 MPa). Contact with sodium chlorite / pentahydrate to obtain a treated gas.

E. coli sterilized, the liquid (hereinafter sometimes abbreviated as "E. coli solution".) Containing 10 ⁶ cells / mL of E. coli in, Sanai / bio Checker TTC <San-Ai Oil Co.> culture medium cap after immersing the medium portion in, after placed in a container, sealed, and allowed to stand for 24 hours at a temperature 37 ° C., is obtained by culturing, by comparison table bio checker TTC annex, there are 10 ⁶ E. coli Confirmed to do.
10 ⁶ cells / mL of the vessel 200 in which the media cap and allowed to stand for Sanai / bio checker TTC with the medium cultured Escherichia coli, the resulting treated gas was introduced for 5 minutes (release).

<Measurement of E. coli number in space sterilization>
To a medium contacted with treated gas or untreated gas, 5 mL of ultrapure water was added and allowed to stand for 30 minutes, then transferred to a beaker, and ultrapure water was added to prepare a 50 mL bacterial solution.
A dip slide in a medium cap of San-Ai / Biochecker TTC <manufactured by San-Ai Oil Co., Ltd.> was immersed in the prepared bacterial solution for 5 seconds. The excess bacterial solution on the dip slide was cut off, and the medium cap was placed in the container. The biochecker TTC was kept at 37 ° C. for 24 hours to culture E. coli attached to the dip slide.
The dip slide after culturing was taken out from the container, and the number of colonies (number / mL) of E. coli was determined using the control table described in the instruction manual of Checker TTC.

<Measurement of residual chlorine in space sterilization>
The gas after space sterilization was introduced (bubbling) into 200 mL of physiological saline in a 250 mL bottle made of polyethylene through a tube (made of polyethylene, length 50 cm, inner diameter 6 mm) from the upper part of the container 200.
^{Immersion method detector tube for detecting free residual chlorine (ClO −} ) based on the residual chlorine concentration in physiological saline after introduction (bubbling) <Gastec Co., Ltd., Free Residual Chlorine (ClO ⁻ ) liquid detector tube, No. It was measured using 222> and used as the amount of residual chlorine in space sterilization.

The results before and after the introduction of the treated gas (before and after the space sterilization) are shown in the table below together with the photographs of the biochecker before and after the treatment in FIG. As is clear from the obtained results (number measurement by comparison with the comparison table described in the biochecker TTC instruction manual), it was confirmed that the number of E. coli was reduced to 0 by the treated gas, and the E. coli was surely sterilized. It was confirmed that it was done.

(Comparative Example 1)
Against E. coli solution 15mL containing 10 ⁶ cells / mL of E. coli, was charged with sodium hypochlorite aqueous solution prepared by dissolving the crystalline sodium hypochlorite 0.5g of ultrapure water 40 mL.
After reacting for 10 minutes, the bactericidal effect was confirmed and the number of bacteria was counted. FIG. 7 shows the photographic results of the obtained biochecker before and after the treatment. From the obtained results, although E. coli was killed, the chlorine concentration remained very high.

The number of Escherichia coli in the sodium hypochlorite aqueous solution after the treatment was measured by the following method.
The dip slide in the medium cap of San-Ai / Biochecker TTC <manufactured by San-Ai Oil Co., Ltd.> was immersed in the bacterial solution treated with the sodium hypochlorite aqueous solution for 5 seconds. The biochecker TTC was kept at 37 ° C. for 24 hours to culture E. coli attached to the dip slide.
The dip slide after culturing was taken out from the container, and the number of E. coli colonies (number / mL) was determined using the control table described in the instruction manual of the biochecker TTC.
The residual chlorine concentration in the treated sodium hypochlorite aqueous solution is determined by diluting the treated sodium hypochlorite aqueous solution 100-fold with ultrapure water and then dipping to detect ^{free residual chlorine (ClO −).} Law detector tube <Gastec Co., Ltd., free residual chlorine (ClO ⁻ ) liquid detector tube, No. It was measured using 222>.

(Reference Example 1)
Since Escherichia coli is an anaerobic bacterium, it is known that the bactericidal effect differs depending on the presence of air (oxygen). In order to confirm this, the result of introducing only the untreated gas A (air) into the container 200 for 5 minutes using the apparatus of FIG. 2 is shown in FIG. 8 (photograph of the biochecker before and after the introduction of air). .. From the obtained results (no change was observed in red color only by air introduction), Escherichia coli did not die and remained as it was. Therefore, the bactericidal effect of the treated gas in contact with sodium hypochlorite pentahydrate Was confirmed.

(Example 2)
Staphylococcus aureus to be sterilized, the cell count (the number of colonies) was prepared the media aligned to 10 ⁷ cells / mL (purchased at the National Institute of Technology and Evaluation Center for Biotechnology).

The results of an experiment in which the release time of the treated gas was 0 minutes, 10 minutes, and 20 minutes for Staphylococcus aureus under the same conditions as in Example 1 are shown in the table below together with the photograph of FIG. .. In Comparative Example 1, since it is the result of using the liquid sodium hypochlorite, the gas introduction time shows the contact time with the liquid sodium hypochlorite. From the obtained results, the bactericidal effect was confirmed even in aerobic Staphylococcus aureus.

(Example 3)
For the bacterial solution containing Staphylococcus aureus to be sterilized, add 5 mL of physiological saline to Staphylococcus aureus on the medium (purchased at the Biotechnology Center, Product Evaluation Technology Infrastructure Organization) and let stand for 30 minutes. After that, the operation of transferring to a beaker was performed 5 times, and then 250 mL of the bacterial solution was prepared by adding physiological saline.

The number of bacteria in the bacterial solution was measured by measuring the absorptiometric intensity of the bacterial solution.
Absorptiometry was performed by using an absorptiometer <Spectrophotometer V-560 manufactured by JASCO Corporation> to measure the intensity at a wavelength of 198 nm.
Regarding the number of bacteria in the bacterial solution, the number of bacterial bacteria (number of colonies) was also determined using San-Ai / Biochecker TTC <manufactured by San-Ai Oil Co., Ltd.>. The culture conditions were the same as in Example 1.

The submerged bubbling test is performed using the apparatus shown in FIG. 3 described above. Specifically, the configurations of the sterilizer 100 and the container 200 and the conditions for producing the treated gas are the same as those of the first embodiment, and the container 200 is used. The treated gas was introduced into 100 L of Staphylococcus aureus solution contained in a tube 40 <polyethylene, length 50 cm, inner diameter 6 mm> storage container 300 <polyethylene, 250 mL> connected to the upper part for 30 minutes (bubbling). did.
The photographs of the biochecker before and after the in-liquid bubbling test are shown in FIG.

Table 3 shows the number of bacteria and the amount of residual chlorine after the treatment measured by the following method. Incidentally, when the treated gas was bubbled in 250 mL of physiological saline for 30 minutes, the amount of residual chlorine in the physiological saline was 28 ppm.
In addition, the results of introducing only air instead of the treated gas are also shown in FIGS. 9 and 3.

<Measurement of bacterial count during liquid bubbling>
The number of bacteria (number of colonies) was determined using San-Ai / Biochecker TTC <manufactured by San-Ai Oil Co., Ltd.> for the bacterial solution treated by submerged bubbling. The culture conditions of the checker were the same as in Example 1.

<Measurement of residual chlorine during liquid bubbling>
The residual chlorine concentration of the bacterial solution after treatment by ^{submerged bubbling is the immersion method detector tube that detects free residual chlorine (ClO −} ) <manufactured by Gastec Co., Ltd., No. It was measured using 222>.

(Comparative Example 2)
An aqueous sodium hypochlorite solution was prepared by dissolving 3 g of crystalline sodium hypochlorite in 100 mL of ultrapure water in a 250 mL container.
In the apparatus used in Example 3, instead of the sterilizing apparatus 100, an apparatus for supplying the aqueous solution-treated gas obtained by bubbling air at a flow rate of 0.75 mL / min in the aqueous solution is installed. , The obtained aqueous solution-treated gas was introduced (bubbling) for 30 minutes.
As a result, cell number in the case of liquid bubbling treated with aqueous sodium hypochlorite solution treatment gas is 10 ⁷ / mL, sterilization effect was not confirmed.

(Example 4)
<Treatment gas bubbling into bacterial fluid containing Bacillus subtilis>
The bacterial solution containing Staphylococcus aureus to be sterilized (purchased from the Biotechnology Center, Product Evaluation Technology Infrastructure Organization) was prepared by the same operation as Staphylococcus aureus. Against bacteria solution containing Bacillus subtilis ⁽¹⁰⁵ cells / mL), except for changing the introduction time of the processing gas to 60 minutes, in the same manner as in Example 3 was conducted bubbling test liquid.
The photographs of the biochecker before and after the in-liquid bubbling test are shown in FIG.
Table 3 shows the number of bacteria and the residual chlorine concentration after treatment for the bacterial solution containing Bacillus subtilis.
In addition, the results of introducing only air instead of the treated gas are also shown in FIGS. 10 and 3.

(Example 5)
<Treatment gas bubbling for bacterial solution containing red mold>
The bacterial solution containing red mold to be sterilized (purchased from the Biotechnology Center, Product Evaluation Technology Infrastructure Organization) was prepared by the same operation as Staphylococcus aureus. An in-liquid bubbling test was carried out by the same operation as in Example 3 except that the introduction time of the treated gas was changed to 45 minutes for the bacterial solution containing red mold (5 × 10 ^{6 cells / mL).} The photographs of the biochecker before and after the in-liquid bubbling test are shown in FIG.
Table 3 shows the number of bacteria and the residual chlorine concentration after treatment for the bacterial solution containing Bacillus subtilis.
In addition, the results of introducing only air instead of the treated gas are also shown in FIGS. 11 and 3.

(Example 6)
<Treatment gas bubbling into bacterial solution containing black jiuqu>
The bacterial solution containing black jiuqu to be sterilized (purchased from the Biotechnology Center, Product Evaluation Technology Infrastructure Organization) was prepared by the same operation as Staphylococcus aureus. Against bacteria solution containing black koji ⁽¹⁰⁶ / mL), except for changing the introduction time of the processing gas to 90 minutes, in the same manner as in Example 3 was conducted bubbling test liquid.
The photographs of the biochecker before and after the in-liquid bubbling test are shown in FIG.
Table 3 shows the number of bacteria and the residual chlorine concentration after treatment for the bacterial solution containing Bacillus subtilis.
In addition, the results of introducing only air instead of the treated gas are also shown in FIGS. 12 and 3.

Primary chlorite crystal (crystal laminated part)
1a Needle-shaped crystal 2 Filter part 3 Holding part 10 Chamber 11 Tube 12 Closed container 20 Flow meter 30 Gas cylinder 40 Tube 100 Sterilizer 200 Container 300 Storage container A Raw material gas B Processed gas B'Bubbling of treated gas B bubbles X sterilization Object

Claims (17)

It is a sterilization method that sterilizes the object to be sterilized.
A sterilization method, characterized in that a raw material gas is brought into contact with hypochlorite of needle-like crystals to generate a treated gas, and the treated gas is brought into contact with an object to be sterilized. The sterilization method according to claim 1, wherein the hypochlorite has an apparent density of crystal aggregates of 0.4 to 1.4 g / mL. In the sterilization method according to claim 1 or 2,
A sterilization method, wherein the needle-like crystals constituting the hypochlorite have a needle-like body having a width of 40 to 850 μm and a length of 150 to 3000 μm. In the sterilization method according to any one of claims 1 to 3.
A sterilization method, wherein the hypochlorite is sodium hypochlorite pentahydrate. In the sterilization method according to any one of claims 1 to 4,
A sterilization method comprising contacting the raw material gas with chloride in a pre-stage and / or a post-stage of contacting the raw material gas with the hypochlorite to generate the treated gas. In the sterilization method according to claim 5,
A sterilization method, wherein the chloride is sodium chloride. In the sterilization method according to any one of claims 1 to 6,
A sterilization method comprising introducing the raw material gas at a space velocity (SV) of 1000 to 125000 h- ¹ and bringing it into contact with the hypochlorite. In the sterilization method according to any one of claims 1 to 7.
A sterilization method, characterized in that the raw material gas is air. In the sterilization method according to any one of claims 1 to 8,
A sterilization method comprising accumulating the generated treated gas and bringing the accumulated treated gas into contact with an object to be sterilized. In the sterilization method according to any one of claims 1 to 9,
A sterilization method, characterized in that the treated gas is blown into a liquid sterilization object. In the sterilization method according to any one of claims 1 to 9,
A sterilization method comprising spraying the treated gas onto a gaseous or solid object to be sterilized. In the sterilization method according to any one of claims 1 to 11.
A sterilization method, wherein the sterilization target is at least one selected from the group consisting of Escherichia coli, Staphylococcus aureus, Bacillus subtilis, red mold, and black jiuqu. A sterilizer that sterilizes objects to be sterilized.
A crystal laminate containing hypochlorite of acicular crystals and
A raw material gas supply unit that supplies the raw material gas to the crystal laminated portion, and a raw material gas supply unit.
A processing gas supply unit for supplying a processing gas generated by contacting the raw material gas with the crystal laminated portion to the sterilization target is provided.
A sterilization apparatus, characterized in that the object to be sterilized comes into contact with the treated gas supplied by the treated gas supply unit and is sterilized. In the sterilizer according to claim 13,
A sterilizing apparatus, wherein the hypochlorite is sodium hypochlorite pentahydrate. In the sterilizer according to claim 13 or 14.
A sterilizer comprising a filter portion made of chloride as a chloride layer in the front stage and / or the rear stage of the crystal laminated portion. In the sterilizer according to claim 15,
A sterilizer, characterized in that the chloride is sodium chloride. In the sterilizer according to any one of claims 13 to 16,
The sterilization apparatus, wherein the treated gas supply unit includes a gas storage unit that stores the generated treated gas in a container, and brings the treated gas accumulated by the gas storage unit into contact with an object to be sterilized. ..

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