JP6382712B2 - Sterilization method - Google Patents

Description

  The present invention relates to a sterilization method suitable for sterilizing a container filled with a liquid such as drinking water.

A rotary filling device is known as a system for filling a container such as a PET (Polyethylene terephthalate) bottle, a glass bottle, or a bottle can with a liquid such as drinking water. This rotary filling device is provided with a plurality of filling valves on the outer periphery of the rotating body, and the filling from the filling valve into the container is carried out while the rotating body rotates almost once and the container is conveyed in the circumferential direction. I do. Then, after filling the container, the lid is attached to the container by a capper or a stopper.
Inside the container, the PET bottle is formed by blowing air into a test tubular precursor called a preform. For this molding, a biaxial stretch blow molding method is mainly used. The biaxial stretch blow molding method is a molding method in which a heated preform is inserted into a mold and then expanded in the circumferential direction by blowing pressurized air while being stretched in a vertical direction with a rod called a stretch rod.
A beverage filling system for PET bottles has a PET bottle molding device on the upstream side, and there is a form in which the molded PET bottle is supplied to the filling device. There is also a form of supplying to

By the way, when filling liquids such as drinking water, it is necessary to prevent contamination of bacteria in the container as much as possible. For this reason, in a clean room, container sterilization / rinsing, cap sterilization, liquid filling and cap attachment A so-called aseptic filling method that performs such a series of processes is employed. In the case of a beverage filling system equipped with a PET bottle molding device on the upstream side, it may be required to sterilize the PET bottle molded by this molding device and supply it to the filling device.
As sterilization in the aseptic filling method, it is mainstream to use a peracetic acid-based disinfectant composed of an aqueous solution containing a drug, for example, peracetic acid (PAA) or hydrogen peroxide (H ₂ O ₂ ) (for example, Patent Document 1). , 2).
However, when peracetic acid is used as a bactericidal agent, the problem is that resistant bacteria against peracetic acid are created. In addition, with hydrogen peroxide, although there are few problems with resistant bacteria, there is a problem that when PET bottles are targeted, they are absorbed by PET and remain in the container.

Sterilization using ozone (O ₃ ) is known as a technique that does not have a problem of resistant bacteria and does not have a problem of remaining on an object to be sterilized (for example, Patent Documents 3 and 4).

JP 2014-181039 A JP 2014-080207 A Japanese Patent Laid-Open No. 63-59961 JP-A-4-33658

The sterilization method using ozone does not have the problems of the sterilization method using a peracetic acid-based disinfectant composed of an aqueous solution. Here, assuming application to a rotary filling device premised on mass production, it is required to suppress the supply amount of ozone from the viewpoint of production cost. However, in the conventional sterilization method using ozone, it is necessary to supply ozone over a relatively long time in order to obtain a desired sterilization performance.
Therefore, an object of the present invention is to provide a sterilization method capable of obtaining a desired sterilization performance even if the amount of ozone supplied toward an object to be sterilized is suppressed.

When the present inventors supply ozone gas containing humidity (hereinafter referred to as “wet ozone gas”) in the same amount toward the object to be sterilized, rather than continuously supplying ozone gas to the object to be sterilized, It has been found that a higher sterilization ability can be obtained by resuming the supply of wet ozone gas after drying the resulting condensed water in the middle. This means that by removing the dew condensation water, it is possible to suppress the supply amount of wet ozone gas necessary to obtain the desired sterilization performance.
The sterilization method of the present invention based on the above is a sterilization method for supplying wet ozone gas, which is ozone gas containing humidity, toward the inside of a beverage container which is an object to be sterilized, and a first supply step for supplying wet ozone gas; A condensation removal processing step for stopping the supply of the wet ozone gas toward the inside of the container and removing the dew condensation water based on the wet ozone gas supplied in the first supply step from the inner peripheral surface of the container; And a second supply step for restarting the supply of the wet ozone gas toward the inside of the container after the treatment step.

In the sterilization method of the present invention, as a process for removing condensed water from the inner peripheral surface of the container, it is preferable to supply a dry gas toward the inside of the container .

To shorten the time of condensation removal processing steps, that higher than the container temperature of the gas supplied dry, you facilitate evaporation of condensed water. In addition to supplying a dry gas, the surface temperature of the object to be sterilized can be increased by, for example, radiant heating using an infrared lamp, and evaporation of condensed water can be promoted.

In the sterilization method of the present invention, the wet ozone gas supplied toward the inside of the container preferably has a higher temperature than the container .
In the sterilization method of the present invention, it is preferable that the humidity of the wet ozone gas supplied toward the inside of the container is adjusted according to the temperature of the sterilization target.
In the sterilization method of the present invention, the temperature of the container is preferably adjusted according to the humidity of the supplied wet ozone gas.
In the sterilization method of the present invention, it is preferable that wet ozone gas is supplied into a container housed in a chamber capable of forming a sealed space. This chamber is preferably maintained at a higher temperature than the container. It is preferable that the wet ozone gas is supplied toward the outside of the container in addition to the inside of the container accommodated in the chamber.

  ADVANTAGE OF THE INVENTION According to this invention, when sterilizing using ozone, desired sterilization performance can be obtained, suppressing the supply amount of the wet ozone gas toward the sterilization target object.

It is a figure which shows typically the mechanism of sterilization by this embodiment. It is a figure which shows the example of a combination of the supply step by this embodiment, and a dew condensation removal step. It is a figure which shows the process example in the case of applying this invention to disinfection of a PET bottle. It is a figure which shows the other example of a process in the case of applying this invention to disinfection of a PET bottle. It is a table | surface which shows the result of the experiment example (bacterial species: Bacillus atrophaeus) which evaluated bactericidal performance.

Hereinafter, the present invention will be described based on embodiments.
[Mechanism of sterilization]
The present invention is premised on supplying wet ozone gas (hereinafter referred to as wet ozone gas), which is ozone gas containing humidity, toward an object to be sterilized. For example, when the object to be sterilized is a beverage container, wet ozone gas is supplied into the container. As shown in FIG. 1A, this sterilization is performed by reacting ozone (O ₃ ) and water (H ₂ O) contained in the wet ozone gas with hydroxyl radical (hereinafter referred to as OH radical). Is attacked by bacteria B and is made by the oxidation action. The OH radical has the strongest oxidizing power among molecular species called so-called active oxygen. In order to promote the attack of OH radicals on the bacteria B, the present invention is directed to condensation of wet ozone gas on the sterilization target T.
Here, bacterial cells have a chromosome that controls the function of genetic information in the central core, a soft cell membrane composed of proteins and lipids on the outside, and a cell wall composed of proteins, polysaccharides, and lipids on the outside. Yes. The sterilization mechanism of bacteria by OH radicals starts from oxidative destruction of this cell wall with a strong oxidizing power. Thus, sterilization using ozone is understood to be different from a mechanism in which, for example, chlorine passes through cell walls and cell membranes to destroy enzymes.

According to the study by the present inventors, even if wet ozone gas is continuously supplied to the sterilization object, the desired sterilization performance corresponding to the supplied amount cannot be obtained. This is clear from experimental examples described later. The reason will be described with reference to FIG. When the wet ozone gas is supplied, moisture contained in the wet ozone gas is condensed on the surface of the sterilization target T. This is a premise for obtaining the effect of the present invention. However, when the supply of wet ozone gas is continued, dew condensation accumulates on the surface of the sterilization target one after another, and a considerable area of the surface of the sterilization target becomes condensed water W As a result, bacteria B adhering to the surface of the sterilization target T are also covered with the dew condensation water E. For the sterilization B covered with the dew condensation water W, even if OH radicals are generated in the vicinity of the sterilization target T by the supply of the wet ozone gas, the opportunity for the OH radicals to come into contact with the bacteria B is lost. As a result, even if the wet ozone gas is continuously supplied, the desired sterilization performance cannot be obtained.
Therefore, as shown in FIG. 1 (c), the present invention exposes the bacteria B by removing the condensed water W adhering to the sterilization target T, thereby creating an opportunity to contact OH radicals. is there.

  In addition, the dew condensation removal process in the present invention is not intended to remove all the dew condensation water adhering to the sterilization target, and it is sufficient that a considerable number of bacteria B covered with the dew condensation water can be exposed. That is, by performing an experiment on a specific sterilization target, it is only necessary to set the conditions for the condensation removal process that can obtain the desired sterilization performance.

  The present invention includes a first supply step for supplying wet ozone gas, a condensation removal processing step for removing condensed water based on the wet ozone gas from the object to be sterilized, and a second supply for restarting the supply of wet ozone gas toward the object to be sterilized. And steps. The settings of the first supply step, the condensation removal processing step, and the second supply step are arbitrary as long as the object of the present invention can be achieved. Hereinafter, some examples will be described with reference to FIG. In FIG. 2, the horizontal axis intends the time for supplying the wet ozone gas, and the vertical axis intends the flow rate per unit time for supplying the wet ozone gas (hereinafter simply referred to as flow rate).

As shown to Fig.2 (a), the supply time and supply flow rate of wet ozone gas in each of a 1st supply step and a 2nd supply step can be made the same. In this case, the total amount of wet ozone gas supplied in each of the first supply step and the second supply step (hereinafter referred to as supply amount) is the same.
Moreover, as shown in FIG.2 (b), although the flow volume in each of a 1st supply step and a 2nd supply step is made the same, the supply time of a 1st supply step can be made shorter than a 2nd supply step. Although not shown, conversely, the supply time of the first supply step can be made longer than that of the second supply step.
Further, as shown in FIG. 2C, the supply time in each of the first supply step and the second supply step is the same, but the flow rate of the first supply step can be made smaller than that of the second supply step. Although not shown, conversely, the flow rate of the first supply step can be made larger than that of the second supply step.
Furthermore, as shown in FIG. 2 (d), the supply of wet ozone gas is divided into a first supply step, a second supply step, and a third supply step, and between the first supply step and the second supply step, A dew condensation removal process step can be performed between the second supply step and the third supply step. That is, the two steps of the first supply step and the second supply step defined in the present invention are the minimum units for dividing the supply of the wet ozone gas, and the present invention can be provided with the third supply step and the subsequent steps.
Any one of the above may be selected according to the embodiment of the sterilization target, the specification of the wet ozone gas to be supplied (concentration of ozone, supply flow rate, temperature, etc.), or a pattern other than the above may be selected. For example, when the time that can be spent on the sterilization process is determined, the first supply step and the condensation removal step are performed on the assumption that the condensed water generated in the first supply step is sufficiently removed in the condensation removal processing step. The time required for each can be set. FIGS. 2B and 2C show that the amount of wet ozone gas supplied before the decondensation removal processing step is less than that after the decondensation removal processing step, and the time required for the decondensation removal processing step is shortened and the dew condensation is performed. There is an advantage that water can be sufficiently removed.

[Wet ozone gas]
Next, the wet ozone gas used in the present invention will be described.
The wet ozone gas can be obtained by generating dry ozone gas (hereinafter referred to as dry ozone gas) and applying humidity to the generated dry ozone gas. The dry ozone gas is typically generated as a mixed gas of ozone (O ₃ ) and oxygen (O ₂ ) using oxygen (O ₂ ) gas as a raw material. In the present invention, the ozone concentration in the dry ozone gas is selected from the range of 5 to 20% by volume, preferably 10 to 15% by volume. In addition, as a raw material which produces | generates dry ozone gas, not only pure oxygen but the gas containing oxygen as a raw material, for example, air, can also be used. Also in this case, the dry ozone gas is still a mixed gas of ozone (O ₃ ) and oxygen (O ₂ ). The dry state is a relative expression with respect to the wet state, and does not mean that no humidity is provided, but means that no humidity is intentionally provided.

As a method for generating dry ozone gas, there are a silent discharge method, an electrolysis method, an ultraviolet lamp method, and the like. The silent discharge method is used for industrial use, and it is preferable to apply the silent discharge method in the present invention, but it does not prevent other methods from being adopted. Here, silent discharge is a discharge phenomenon observed when a dielectric is provided between parallel electrodes, oxygen gas is supplied therebetween, and an alternating high voltage is applied between the two electrodes. . Electrons e are emitted into the gas by this silent discharge. A first step of causing the electrons e to collide with stable oxygen molecules O ₂ to dissociate the oxygen molecules O ₂ into oxygen atoms O; an oxygen atom O, an oxygen molecule O _2, and a third substance M (for example, a nitrogen molecule) Ozone is generated by the second step in which a three-body collision including) occurs. Therefore, the ozone gas in the present invention may contain this third substance M.
First step: O ₂ + e → 2O + e
Second step: O + O ₂ + M → O ₃ + M

  In order to obtain wet ozone gas, humidity is given to dry ozone gas. In the present invention, the method of applying humidity is arbitrary, the bubble dissolution method, the mixing method of mixing each of the generated wet gases such as wet oxygen and ozone gas, and supplying dry ozone gas to the water sprayed in a shower form A shower method or the like can be employed. Moreover, after producing | generating ozone water by arbitrary methods, this can be vaporized and wet ozone gas can also be produced | generated, water vapor | steam can be produced | generated by arbitrary methods, and dry ozone gas can also be made to contact this.

The wet ozone gas preferably has a relative humidity of 45 to 100% at the temperature of the object to be sterilized. This is because sufficient sterilization ability can be obtained when the relative humidity of the wet ozone gas is 45% or more. A more preferable relative humidity is 80 to 100%, and a more preferable relative humidity is 95 to 100%.
The relative humidity here is the relative humidity at the temperature of the sterilization object, and is different from the relative humidity at the time when the wet ozone gas is generated. In other words, it is preferable that the relative humidity of the generated wet ozone gas is adjusted in consideration of the temperature of the sterilization target.

[Condensation removal treatment]
In the dew condensation removing process of the present invention, one method can be selected from the following (a) to (d), and at least two methods (a) to (d) can be combined. .
(A) Supplying dried gas Continuously supplying air (air, dry air) in a dry state toward an object to be sterilized with condensed water attached, thereby absorbing moisture with air and evaporating the condensed water. Can do. The gas to be supplied is not limited to air, and various gases such as oxygen (O ₂ ), inert gas (for example, nitrogen gas), and dry ozone gas can be used.
The form of supplying the dried gas requires a supply source of the gas and a piping system that sends the gas from the supply source, but is advantageous in that the burden on equipment is less than other methods. In particular, if the piping system for supplying the wet ozone gas is also used as the piping system for supplying the gas for drying, the burden on the facility is remarkably reduced.
(B) Depressurization (vacuum drying) in an enclosed space
A method called vacuum drying is adopted in which the object to be sterilized is housed in a sealed space, and by depressurizing the sealed space, the water vapor partial pressure difference between the sealed space and the surface of the object to be sterilized is increased to evaporate the condensed water. can do. In order to reduce the pressure, a vacuum pump may be used. In this case, the evaporated water is discharged together with the exhaust to the outside of the sealed space.
When this method is employed, sterilization can be performed inside a chamber that can form a sealed space, and the chamber can be sealed before being subjected to vacuum drying.
(C) Heating The condensed water is evaporated by heating the object to be sterilized. The dried gas mentioned above can be heated to evaporate the condensed water.
The heating can directly heat the object to be sterilized or can indirectly heat it. As direct heating, for example, heating by bringing a heater into contact with the object to be sterilized is mentioned, and as indirect heating, supplying heated dry gas to the object to be sterilized is mentioned.
(D) Applying acceleration While (a) to (c) remove condensed water by evaporation, condensing water is given by applying physical force to the sterilization target, specifically acceleration. It can be separated from the object to be sterilized. An example of imparting acceleration is to vibrate the sterilization object at a high frequency. In the case where the sterilization target is a container such as a PET bottle, the condensed water can be discharged out of the container by turning the container with the mouth portion directed to the outer periphery and the bottom of the container as the center of rotation.

[Application example to beverage containers]
Hereinafter, a specific example of application of the present invention to a beverage container, for example, a PET bottle 1 will be described with reference to FIG.
This example is based on the premise that the inner peripheral surface and the outer peripheral surface of the PET bottle 1 continuously conveyed from the upstream process are sterilized, and the PET bottle 1 is delivered to the downstream process. The process described here includes a sterilization process for performing sterilization itself, and a rinsing process for rinsing the sterilized PET bottle 1. The sterilization process is divided into a first supply step, a condensation removal processing step, and a second supply step. In addition, it is preferable to accommodate the PET bottle 1 in the chamber 10 through the sterilization process and the rinse process.

As a first supply step, wet ozone gas is supplied from the opening of the mouth portion 2 of the upright PET bottle 1 toward the inner space of the body portion 3, and the inside of the chamber 10 is from the PET bottle 1. Also feed outside.
By supplying the wet ozone gas, the OH radicals generated inside the PET bottle 1 sterilize the inner peripheral surface and the outer peripheral surface of the PET bottle 1.
If the wet ozone gas is supplied for a predetermined time, the supply of the wet ozone gas is stopped and the first supply step is terminated, and the process proceeds to the dew condensation removal processing step.
In the condensation removal processing step, dry air is supplied to the internal space of the PET bottle 1 and the outside of the PET bottle 1. By supplying this dry air, the condensed water generated on the inner and outer peripheral surfaces of the PET bottle 1 is dried and removed. Dry air may be at normal temperature or may be heated. The same applies to dry air used in the rinsing process.
If the dry air is supplied for a predetermined time, the supply of the dry air is stopped, the dew condensation removing process step is finished, and the process proceeds to the second supply step. In the second supply step, wet ozone gas is supplied to the inside and outside of the PET bottle 1 in the same manner as in the first supply step. If the wet ozone gas is supplied only for the yard time, the supply of the wet ozone gas is stopped and the sterilization process is terminated.

When the sterilization process ends, the process proceeds to the rinsing process.
In the rinsing process, in order to discharge wet ozone gas remaining inside the PET bottle 1 to the outside, dry air is supplied to the inside and outside of the PET bottle 1 in order to remove the residue adhering to the inside and outside of the PET bottle 1. In the rinsing step, water may be used instead of dry air, or dry air and water may be used in combination. Also, depending on the type of product liquid filled in the PET bottle 1, the rinsing step can be omitted.

  The present embodiment is based on the premise that the supplied wet ozone gas is condensed on the inner peripheral surface and the outer peripheral surface of the PET bottle 1. Therefore, in order to ensure this dew condensation, it is preferable that the wet ozone gas has a higher temperature than the PET bottle which is a sterilization target.

In addition, as described above, the sterilization performance by the wet ozone gas depends on the relative humidity of the wet ozone gas with respect to the sterilization target. Therefore, it is preferable to adjust so that the relative humidity of wet ozone gas may become the preferable range with respect to the temperature of PET bottle 1 which is a sterilization object. This adjustment may be performed by adjusting the relative humidity of the wet ozone gas or by adjusting the temperature of the PET bottle 1.
In the former case, the temperature of the PET bottle 1 is measured, and the humidity of the generated wet ozone gas is varied according to the measured temperature.
In the latter case, the temperature of the PET bottle 1 supplied to the region to be sterilized is measured in advance, and the PET bottle 1 may be cooled or heated so that the necessary relative humidity can be obtained.

As an example to which the present invention is applied in a beverage filling system, for example, there is a case in which a PET bottle 1 that has just been molded and placed in a downstream process of a PET bottle 1 molding apparatus is sterilized. The molding of the PET bottle 1 involves heating the preform, and the molded PET bottle 1 has a temperature of about 70 ° C., for example, and the PET bottle 1 is cooled depending on the temperature of the wet ozone gas and the relative humidity. There is a need.
Moreover, as another example to which the present invention is applied in a beverage filling system, there is a case where a PET bottle 1 that has already been formed and stored is sterilized. In this case, the temperature of the PET bottle 1 is about room temperature (for example, 25 ° C.), but the PET bottle 1 needs to be heated depending on the temperature of the wet ozone gas and the relative humidity.
In order to cool or heat the PET bottle 1, for example, cold air or warm air may be blown into the PET bottle 1 or blown outside before the sterilization step.

  Further, when the PET bottle 1 accommodated in the chamber 10 is sterilized, in order to effectively consume the wet ozone gas for sterilization of the PET bottle 1, it is necessary to avoid the condensation of the wet ozone gas in the chamber 10. preferable. Therefore, it is preferable to measure the temperature of the PET bottle 1 and adjust the temperature by providing a heater so that the chamber 10 is maintained at a higher temperature than the PET bottle 1 being conveyed.

[Experimental example]
Using Bacillus atrophaeus as a bacterial species, an experiment for evaluating the bactericidal performance of a 500 mL PET bottle (specimen) was performed as follows. The evaluation results are shown in FIG.
As the sterilization process, the present invention example in which the condensation removal treatment step is performed between the first supply step and the second supply step, and Comparative Examples 1 to 3 in which the wet ozone gas is continuously supplied without performing the condensation removal treatment step. Went.

The specifications of wet ozone gas and dry air used for sterilization are as follows.
Wet ozone gas: temperature; 80 ° C., ozone concentration; 10 vol. %,
Flow rate: 20 mL / min. (No.1, 2)
30 mL / min. (No. 3, 4)
Dry air: room temperature, flow rate; 20 mL / min.

In FIG. 5, when the present invention example (No. 1) and the comparative example 1 (No. 2) are compared, even if the supply amount of wet ozone gas is the same, the sterilization performance is remarkably improved by performing the condensation removal treatment step. I understand that
In addition, when the present invention example (No. 1) and the comparative examples 2 and 3 (No. 3 and 4) are compared, high sterilization performance can be achieved even if the supply amount of wet ozone gas is small by performing the condensation removal treatment step. It can be seen that

[Effect]
As described above, according to the present invention, a desired sterilization performance can be obtained by performing the condensation removal processing step even if the amount of ozone supplied to the sterilization target is suppressed.

The preferred embodiments of the present invention have been described above. However, the configurations described in the above embodiments can be selected or changed to other configurations as appropriate without departing from the gist of the present invention. is there.
For example, although PET bottle 1 was shown as an object to be sterilized in the embodiment, the object to be sterilized in the present invention is arbitrary, and can be widely applied to containers and manufacturing equipment in the food field including beverages, instruments and equipment in the medical field, etc. Can do.

  In the description with reference to FIG. 3, wet ozone gas is blown into the PET bottle 1, but the present invention is not limited to this. That is, in the present invention, as shown in FIG. 4, by reducing the pressure inside the PET bottle 1, the wet ozone gas supplied around the PET bottle 1 is sucked into the PET bottle 1, and the wet ozone gas is contained inside. It can be made to act on a peripheral surface and an outer peripheral surface. In the sterilization treatment by suction, since the wet ozone gas is drawn into the PET bottle 1 after the air inside the PET bottle 1 is discharged, the wet ozone gas can be efficiently applied to the PET bottle 1.

1 PET Bottle 2 Mouth 3 Body 10 Chamber

Claims (9)

A sterilization method for supplying wet ozone gas, which is ozone gas containing humidity, toward the inside of a beverage container that is a sterilization target,
A first supply step for supplying the wet ozone gas;
Condensation removal processing step of stopping the supply of the wet ozone gas toward the inside of the container and removing the condensed water based on the wet ozone gas supplied in the first supply step from the inner peripheral surface of the container When,
A second supply step for restarting the supply of the wet ozone gas toward the inside of the container after the dew condensation removing treatment step ;
The wet ozone gas supplied toward the inside of the container is
The temperature is higher than the container,
The sterilization method characterized by the above-mentioned. The process of removing the condensed water from the inner peripheral surface of the container,
A process of supplying a dry gas toward the inside of the container,
The sterilization method according to claim 1. Supplying the dry gas at a higher temperature than the container to promote evaporation of the condensed water;
The sterilization method according to claim 2. While supplying the gas in the dry state, directly heating the container with a heating element, and raising the temperature, promote evaporation of the condensed water,
The sterilization method according to claim 2. The wet ozone gas supplied toward the inside of the container is
The humidity is adjusted according to the temperature of the container,
The sterilization method as described in any one of Claims 1-4 . The container is
The temperature is adjusted according to the humidity of the supplied wet ozone gas.
The sterilization method as described in any one of Claims 1-4 . The wet ozone gas is supplied to the inside of the container housed in a chamber that can form a sealed space.
The sterilization method according to any one of claims 1 to 6 . The chamber is
Maintained at a higher temperature than the vessel,
The sterilization method according to claim 7 . In addition to the inside of the container housed in the chamber, the wet ozone gas is supplied toward the outside of the container,
The sterilization method according to claim 7 or claim 8 .

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