Patent Publication Number: US-2023141766-A1

Title: Sterilizing method and sterilizer

Description:
TECHNICAL FIELD 
     The present disclosure relates to a sterilizing method and a sterilizer. 
     BACKGROUND ART 
     Reusable medical instruments used for surgical operations and medical cares in hospitals are subjected to treatment of sterilization after sufficient cleaning in order to remove adhesive matter such as blood and protein. 
     A sterilizing method is known that uses hydrogen peroxide as main sterilization gas and further uses additional gas for executing such sterilization treatment in order to improve the sterilization efficiency. Patent Literature 1 discloses sterilizing method and apparatus that execute a series of steps of reducing a pressure in a chamber housing an object to be sterilized, injecting vapor of an aqueous solution of hydrogen peroxide for sterilization to keep the state, and further injecting ozone gas for sterilization to keep the state. 
     CITATION LIST 
     Patent Literature 
     
         
         Patent Literature 1: Japanese Patent No. 5480975 
       
    
     SUMMARY OF THE INVENTION 
     The object to be sterilized, when subjected to the sterilization by use of the sterilizing apparatus as disclosed in Patent Literature 1, is housed in the chamber of the sterilizing apparatus in a state of being preliminarily wrapped with a wrapping member, such as a sterilization bag, in order to prevent re-contamination after the sterilization. The component in the sterilization gas, however, may be adsorbed to the wrapping member during the step of actually sterilizing the object to be sterilized wrapped with the wrapping member. Such an adsorbed object could prevent the sterilization gas sequentially supplied from reaching the object to be sterilized. 
     An object of the present disclosure is to provide a sterilizing method and a sterilizer capable of improving a sterilization efficiency in the entire sterilizing treatment. 
     Solution to Problem 
     A first aspect of the present disclosure provides a sterilizing method including a preliminary decompression step of decompressing an inside of a chamber with respect to an atmospheric pressure after an object to be sterilized wrapped with a wrapping member made from a material that absorbs ozone gas and hydrogen peroxide is housed in the chamber, an ozone adsorption step of injecting ozone gas to the inside of the chamber under a decompressed state achieved in the preliminary decompression step to cause the ozone gas to be adsorbed to the wrapping member, and a sterilization step of sterilizing the sterilization object using the zone gas and hydrogen peroxide after the ozone adsorption step. 
     A second aspect of the present disclosure provides a sterilizer configured to sterilize a sterilization object, including a chamber configured to house a sterilization object wrapped with a wrapping member made from a material that absorbs ozone gas and hydrogen peroxide, an evaporator configured to communicate with the chamber and evaporate an aqueous solution of hydrogen peroxide, water in which pyrogen is removed or inactivated, water in which bacteria or microbes are removed or inactivated, pure water, water from which scale is removed, tap water, or a solution containing a volatile component so as to be filled with vapor thus produced, an ozone generator configured to communicate with the chamber and produce ozone gas, and a controller configured to control an operation of injecting, to an inside of the chamber, the vapor produced by the evaporator or the ozone gas produced by the ozone generator, wherein the controller is configured to decompress the inside of the chamber and inject the ozone gas to the inside of the chamber under a decompressed state, and then sterilize the sterilization object by use of the ozone gas and the hydrogen peroxide. 
    
    
     
       BRIEF DESCRIPTION OF DRAWINGS 
         FIG.  1    is a schematic diagram showing a configuration of a sterilizer according to an embodiment. 
         FIG.  2    is a flowchart showing a process of sterilizing method according to the embodiment. 
         FIG.  3    is a graph showing a change in pressure inside a chamber according to the embodiment. 
         FIG.  4    is a table showing plural processing modes executed by the sterilizer according to the embodiment. 
         FIG.  5    is a flowchart showing a process of sterilization steps according to the embodiment. 
     
    
    
     DESCRIPTION OF EMBODIMENTS 
     An embodiment of the present disclosure will be described in detail below with reference to the drawings. The following dimensions, materials, and specific numerical values in the embodiment are described for illustration purposes, and the present disclosure is not intended to be limited thereto unless otherwise specified. The elements having substantially the same functions and structures illustrated below are designated by the same reference numerals, and overlapping explanations are not made below. The elements described below but not related directly to the present disclosure are not shown in the drawings. 
       FIG.  1    is a schematic diagram showing a configuration of a sterilizer  100  according to the present embodiment. The sterilizer  100  sterilizes an object to be sterilized by use of sterilization gas. Materials mainly included in the sterilization gas used in the present embodiment are hydrogen peroxide (H 2 O 2 ) and ozone (O 3 ). 
     The object to be sterilized is herein presumed to be a medical instrument used in a hospital for surgical operations and medical cares and brought into contact with a blood circulatory system or aseptic tissues. Examples of medical instruments include a heat-resistant steel product such as a pair of forceps, a surgical tweezer, and surgical scissors, a hard endoscope made from stainless steel used for laparoscopic surgery or a soft endoscope used for bronchial or urinary surgery, and a non-heat resistant resin product such as a power supply cable as an attachment for these endoscopes. The object to be sterilized is also presumed to be housed in a chamber  11  of the sterilizer  100  in a state of being preliminarily wrapped with a wrapping member in order to prevent re-contamination after the sterilization. The wrapping member is, for example, made of nonwoven fabric of fine mesh, which passes the sterilization gas but barely allows bacteria to pass therethrough. The nonwoven fabric may mainly include resin material such as polyethylene. The wrapping member of this type is sometimes referred to also as a sterilization bag or sterilization wrap. 
     The sterilizer  100  includes a chamber unit  10 , a hydrogen peroxide supply unit  20 , an ozone supply unit  30 , an exhaustion unit  40 , an air introduction unit  50 , and a control unit  60 . 
     The chamber unit  10  includes the chamber  11  for housing the object to be sterilized, and peripheral components. The chamber unit  10  includes the chamber  11  having a door  12 , a first heater  13 , and a first manometer  14 . 
     The chamber  11  is a holder for housing and placing the object to be sterilized therein. The chamber  11  is also referred to as a sterilization container. The chamber  11  is made from stainless steel or an aluminum alloy, and has a structure resistant to a vacuum and decompression. The present embodiment is illustrated below with a case in which a capacity of the chamber  11  is 100 liters (L), for example. The door  12  is arranged on the chamber  11  in an openable/closable manner. The chamber  11  is tightly sealed to prevent vacuum leakage or leakage of the sterilization gas when the door  12  is closed so that the inside of the chamber  11  is decompressed. 
     The first heater  13  is installed at a circumference of the chamber  11  together with a thermal member to keep the internal temperature of the chamber  11  constant during the sterilization treatment. The temperature in the chamber  11  is measured by a thermometer (not illustrated) installed in the chamber  11 . 
     The first manometer  14  is a vacuum gauge installed in the chamber  11  to measure the pressure inside the chamber  11 . 
     The hydrogen peroxide supply unit  20  supplies vapor of hydrogen peroxide to the chamber  11  during the sterilization treatment. The hydrogen peroxide supply unit  20  according to the present embodiment can independently supply the vapor separately produced from two aqueous solutions of hydrogen peroxide. One of the aqueous solutions of hydrogen peroxide is referred to below as a “first aqueous solution”, and the other aqueous solution of hydrogen peroxide is referred to below as a “second aqueous solution”. A concentration of the hydrogen peroxide contained in the first aqueous solution or the second aqueous solution, or a total amount of the hydrogen peroxide contained in the first aqueous solution or the second aqueous solution is determined according to the presence or absence of a duct part in the object to be sterilized or the material used for the object to be sterilized, as described in detail below. The hydrogen peroxide supply unit  20  includes a bottle  21 , an extraction pipe  22 , a tube pump  23 , a storage part  24 , an evaporator  26 , and a second heater  29 . 
     The bottle  21  stores the aqueous solution of the hydrogen peroxide. The bottle  21 , when exposable, is referred to also as a cartridge. The present embodiment uses the two aqueous solutions of the hydrogen peroxide, and uses a first bottle  21   a  for storing the first aqueous solution and a second bottle  21   b  for storing the second aqueous solution. 
     The extraction pipe  22  extracts the aqueous solutions of the hydrogen peroxide from the respective bottles  21 , and supplies the extracted aqueous solutions to the storage part  24 . The present embodiment uses a first extraction pipe  22   a  that extracts the first aqueous solution from the first bottle  21   a , and a second extraction pipe  22   b  that extracts the second aqueous solution from the second bottle  21   b.    
     The tube pump  23  is arranged in the middle of the respective extraction pipes  22  to suck a necessary amount of the aqueous solutions of the hydrogen peroxide every time out of the respective bottles  21 . The present embodiment uses a first tube pump  23   a  arranged in the middle of the first extraction pipe  22   a , and a second tube pump  23   b  arranged in the middle of the second extraction pipe  22   b . The respective extraction pipes  22  may be provided with an optical liquid-level sensor (not illustrated), for example. The respective tube pumps  23  suck up the aqueous solutions of the hydrogen peroxide until the liquid-level sensor reacts, and temporarily stop in response to the reaction of the liquid-level sensor and then rotate with a predetermined number of times, so as to supply the predetermined amount of the respective aqueous solutions to the storage part  24 . 
     The storage part  24  is connected to the respective extraction pipes  22  to temporarily store the predetermined amount of the respective aqueous solutions of the hydrogen peroxide sucked out of the bottles  21  before the supply to the evaporator  26 . The storage part  24  used may be a semi-transparent fluororesin tube through which the amount of the solution stored inside can be visually confirmed. Since the respective tube pumps  23  can stably supply the constant amount of the solution when driven under an atmospheric pressure, the storage part  24  may be supplied with the air via a first filter  25  so as to be under the atmospheric pressure. The first filter  25  is a high-efficiency particulate air (HEPA) filter, for example. 
     The evaporator  26  communicates with the storage part  24  via a first supply pipe  27 , and evaporates the aqueous solution of the hydrogen peroxide introduced through the storage part  24 . The evaporator  26  is, for example, made from stainless steel so as to have resistance to corrosion caused by the hydrogen peroxide, and has a structure resistant to a vacuum and decompression since the evaporator  26  is decompressed simultaneously with the chamber  11 . 
     The first supply pipe  27  is provided with a first electromagnetic valve  70 . When the first electromagnetic valve  70  is open, the aqueous solution of the hydrogen peroxide stored in the storage part  24  is sucked and introduced toward the decompressed evaporator  26 . Since the storage part  24  is under the atmospheric pressure after being supplied with the air via the first filter  25 , the air is also sucked together with the aqueous solution of the hydrogen peroxide. The aqueous solution of the hydrogen peroxide remaining in the storage part  24  and the first supply pipe  27  is also sucked and introduced toward the evaporator  26 , so that the constant amount of the vapor of the hydrogen peroxide is stably supplied to the inside of the chamber  11 . 
     The evaporator  26  communicates with the chamber  11  via a plurality of injection pipes  28 . The present embodiment uses a first injection pipe  28   a  and a second injection pipe  28   b  arranged on a ceiling at two positions in the diagonal line. The first injection pipe  28   a  is provided with a second electromagnetic valve  71 , and the second injection pipe  28   b  is provided with a third electromagnetic valve  72 . When the aqueous solution of the hydrogen peroxide is evaporated in the evaporator  26  to increase the pressure inside the evaporator  26 , the second electromagnetic valve  71  or the third electromagnetic valve  72  is opened for a predetermined period of time, so that the vapor of the aqueous solution of the hydrogen peroxide is injected to the inside of the chamber  11 . The arrangement of the plural injection pipes  28  as described above can further enhance the uniform diffusion of the vapor inside the chamber  11 . The evaporator  26  may be provided with a pressure sensor  39  for determining whether the pressure inside the evaporator  26  is increased to a level within a predetermined range after the injection of the vapor so as to determine whether the predetermined amount of the vapor is supplied from the storage part  24 . 
     The second heater  29  is arranged at a circumference of the evaporator  26  to keep the internal temperature of the evaporator  26  constant. The inside of the evaporator  26  is constantly kept at a predetermined temperature in a range of 65° C. to 120° C., for example. 
     The ozone supply unit  30  supplies the ozone gas to the chamber  11  during the sterilization treatment. The ozone gas used in the present embodiment is produced inside the ozone supply unit  30 . The ozone supply unit  30  includes an oxygen generation device  31 , an ozone generator  32 , an ozone densitometer  33 , a buffer tank  34 , and a second manometer  35 . 
     The oxygen generation device  31  produces oxygen (O 2 ) serving as raw material of ozone. The oxygen generation device  31  can adopt a pressure swing adsorption (PSA) mode that causes nitrogen in the air to be adsorbed to an adsorbent such as zeolite to produce oxygen with a high concentration. In particular, the oxygen generation device  31  may be a PSA device having a discharge pressure in a range of about 0.03 to 0.08 MPa as a gauge pressure, and a flowing amount in a range of about 1 to 4 L/min A pipe connecting the oxygen generation device  31  and the ozone generator  32  is provided with a fourth electromagnetic valve  73 . Controlling the open and closed states of the fourth electromagnetic valve  73  as necessary can regulate the supply amount of the oxygen to the ozone generator  32 . 
     The ozone generator  32  produces the ozone gas from the oxygen produced by the oxygen generation device  31 . The ozone generator  32  can adopt a silent discharge mode that applies a high voltage with a high frequency to the oxygen to be discharged and decomposed so as to produce the ozone. The present embodiment is illustrated with a case in which the ozone supply unit  30  includes two ozone generators  32 . A production ability of the ozone generators  32  is given by 2 g/hr×two ozone generators=4 g/hr, for example. The ozone generators  32  in this case operate for 1.5 minutes while receiving 1 L/min of the oxygen, so as to produce the ozone with the amount given by 4 g×1.5 minutes/60 minutes=0.1 g. The ozone generators  32  communicate with the buffer tank  34  via a second supply pipe  36 . 
     The ozone densitometer  33  measures a concentration of the ozone gas produced by the ozone generators  32  in the second supply pipe  36 . For example, a case is presumed below in which a measurement value obtained by the ozone densitometer  33  is 70 g/m 3  when the ozone gas is allowed to flow through the second supply pipe  36  for 1.5 minutes with the flowing amount of 1 L/min. The amount of the ozone produced in this case corresponds to the amount given by 1 L/min×1.5 minutes×70 g/1000 L=0.105 g. In addition, a case is presumed in which 0.105 g of the ozone gas is injected to the inside of the chamber  11  with the capacity of 100 L, and the air is further introduced thereto so as to be under the atmospheric pressure. The concentration of the ozone in the chamber  11  in this case corresponds to a volume concentration given by 0.105 g/48 g×22.4 L/100 L×1,000,000=490 ppm, where 48 g is a molecular amount of the ozone, and 22.4 L is the amount of reference gas. 
     The second supply pipe  36  is provided with a fifth electromagnetic valve  74  between the ozone densitometer  33  and the buffer tank  34 . The second supply pipe  36  between the ozone densitometer  33  and the fifth electromagnetic valve  74  may communicate with the exhaustion unit  40  via a piping system X including a sixth electromagnetic valve  75 . When the fifth electromagnetic valve  74  is closed and the sixth electromagnetic valve  75  is open, the ozone gas flowing from the respective ozone generators  32  is supplied toward the exhaustion unit  40 . 
     The buffer tank  34  temporarily stores the ozone gas produced by the respective ozone generators  32  before the supply to the evaporator  26 . The buffer tank  34  is, for example, made from stainless steel so as to have resistance to corrosion caused by the hydrogen peroxide, and has a structure resistant to decompression. The present embodiment is illustrated below with a case in which a capacity of the buffer tank  34  is two liters (L). The buffer tank  34  communicates with the evaporator  26  via a third supply pipe  37 . The third supply pipe  37  is provided with a seventh electromagnetic valve  76 . When the ozone gas is injected to the buffer tank  34  while the seventh electromagnetic valve  76  is closed, the pressure inside the buffer tank  34  is transiently increased. 
     The second manometer  35  is a vacuum gauge installed at the buffer tank  34  to measure the pressure inside the buffer tank  34 . A controller  61  monitors the pressure inside the buffer tank  34  by use of the second manometer  35 , so as to confirm whether the ozone injected is increased to a predetermined pressure in the buffer tank  34 , or confirm whether leakage or stoppage of the ozone is caused in the second supply pipe  36  or the like. 
     According to the present embodiment, the ozone gas supplied from the buffer tank  34  is not directly but indirectly injected to the chamber  11  via the evaporator  26 . An introduction port of the sterilization gas toward the chamber  11  is shared with the hydrogen peroxide and the ozone gas. 
     As another embodiment, the ozone gas may be directly injected to the chamber  11  from the buffer tank  34  without bypassing the evaporator  26 . The direct injection of the ozone gas to the chamber  11  without bypassing the evaporator  26  has the advantage of increasing the speed of diffusion of the ozone gas inside the chamber  11 . This case also has the advantage of increasing the ozone concentration in the chamber  11  when the second electromagnetic valve  71  and the third electric valve  72  arranged between the evaporator  26  and the chamber  11  are closed. 
     The exhaustion unit  40  vents the atmosphere inside the chamber  11  so as to decompress the inside of the chamber  11  or discharge the gas present inside the chamber  11  to the outside. In particular, the exhaustion unit  40  removes excessive gas from the chamber  11  or the object to be sterilized itself to decompress the inside of the chamber  11  to a medium vacuum level of 100 Pa or below, for example, before the sterilization treatment in order to improve the sterilization effect during the sterilization treatment. The exhaustion unit  40  also eliminates the sterilization gas remaining in the chamber  11  or the object to be sterilized after the sterilization treatment. The exhaustion unit  40  includes a vacuum pump  41 , a catalyst tank, and a heater. 
     The vacuum pump  41  used herein can be a dry pump such as a scroll pump for medium vacuum, or a hydraulic rotating pump such as a rotary pump. The vacuum pump  41  in the present embodiment is a hydraulic rotating pump. The vacuum pump  41  and the chamber  11  communicate with each other via an exhaustion pipe  38 . The exhaustion pipe  38  is provided with an eighth electromagnetic valve  77 . When the pressure inside the chamber  11  reaches a predetermined value during the decompression, for example, the controller  61  closes the eighth electromagnetic valve  77  to stop the operation of the vacuum pump  41 . 
     The catalyst tank is made from stainless steel, for example, and includes a catalyst such as a pellet type and a honeycomb type. The catalyst mainly includes manganese dioxide, for example, and decomposes the hydrogen peroxide and the ozone. The catalyst tank in the present embodiment is arranged at two positions on the upstream side and the downstream side of the vacuum pump  41  in view of decomposing gas having a risk of corroding the vacuum pump, and also in view of keeping the exhaustion speed as appropriate. A first catalyst tank  42  is a catalyst tank arranged on the upstream side of the vacuum pump  41 . A second catalyst tank  43  is a catalyst tank arranged on the downstream side of the vacuum pump  41 . 
     As described above, the ozone supply unit  30  can supply the ozone gas to the exhaustion unit  40  via the piping system X such that the ozone generators  32 , the fifth electromagnetic valve  74 , and the sixth electromagnetic valve  75  are controlled as appropriate. 
     The heater keeps the respective catalyst tanks at a temperature in a range of 60° C. to 90° C., for example. A third heater  44  keeps the temperature of the first catalyst tank  42 . A fourth heater  45  keeps the temperature of the second catalyst tank  43 . 
     The air introduction unit  50  introduces the air into the inside of the chamber  11 . The air introduction unit  50  includes a second filter  51  and a plurality of introduction ports. 
     The second filter  51  prevents dust in the air from entering the inside of the chamber  11  upon the introduction of the air. The second filter  51  used herein may be a HEPA filter which is a nonwoven filter of fine mesh, for example. 
     The respective introduction ports introduce the air through the second filter  51  to the inside of the chamber  11 . The introduction ports are preferably arranged at different positions in the chamber  11  in order to equalize the gas concentration inside the chamber  11  simultaneously with the introduction of the air. The present embodiment uses two introduction ports, a first introduction port  52  and a second introduction port  53 , for example, arranged on the ceiling at two positions in the diagonal line. The first introduction port  52  is provided with a ninth electromagnetic valve  78 . The second introduction port  53  is provided with a tenth electromagnetic valve  79 . The controller  61  independently controls the open and closed states of the ninth electromagnetic valve  78  and the tenth electromagnetic valve  79 , so as to introduce the air into the inside of the chamber  11  from the different positions at each appropriate timing. 
     The introduction ports are not limited to those directly arranged at the chamber  11 . Another embodiment may employ the introduction ports that are connected to the chamber  11  via the evaporator  26 , or may employ the introduction ports that are connected to the chamber  11  via the buffer tank  34 . The introduction ports may also be connected to the chamber  11  via both the evaporator  26  and the buffer tank  34 , for example. 
     The control unit  60  controls the operations of driving power system elements in the respective units included in the sterilizer  100  in accordance with various kinds of operational commands. The control unit  60  includes the controller  61  and a touch panel  62 . The controller  61  is electrically connected to several types of power system elements and measurement system elements. The controller  61  controls the operations of the respective power system elements in accordance with a command input via the touch panel  62 , a sequence of control operations preliminarily stored, or detection signals acquired from several types of sensors, for example. The touch panel  62  is electrically connected to the controller  61 , and is used by the operator to input the information or command and to visually recognize the information provided from the sterilizer side. 
     Next, a process of a sterilizing method according to the present embodiment by use of the sterilizer  100  is described below. 
       FIG.  2    is a flowchart showing the process of the sterilizing method according to the present embodiment.  FIG.  3    is a graph showing a change in pressure inside the chamber  11  with a lapse of time through the process of the sterilizing method according to the present embodiment. 
     The sterilizing method according to the present embodiment includes a treatment mode selection step S 100 , a preliminary decompression step S 200 , an ozone adsorption step S 300 , a sterilization decompression step S 400 , a sterilization step S 500 , and an aeration step S 700 . 
     Before starting the treatment mode selection step S 100 , the operator such as a nurse in a hospital places the object to be sterilized wrapped with a wrapping member in the chamber  11 , and closes the door  12  to make the inside of the chamber  11  airtight. At this point, the power of the sterilizer  100  is presumed to be already turned on so as to complete a warming-up. 
     In the sterilization treatment in the present embodiment, the operator can choose a treatment mode depending on the type of the object to be sterilized. The type of the object to be sterilized is classified according to the shape and the material of the object to be sterilized, for example. In particular, the shape of the object to be sterilized may be classified in accordance with the presence or absence of a duct part. The treatment mode selection step S 100  is a step of inputting the treatment mode chosen by the operator to the sterilizer  100 . 
       FIG.  4    is a table showing the respective treatment modes executable by the sterilizer  100 . The treatment modes may include the following three modes, for example. A short mode is applied to a case in which the object to be sterilized is a medical instrument having no duct part. The medical instrument of this type is a steel product such as a pair of forceps, for example, and is mainly subjected to surface sterilization. A normal mode is applied to a case in which the object to be sterilized is a medical instrument made from resin having a duct part. A long mode is applied to a case in which the object to be sterilized is a medical instrument made from stainless steel having a duct part. The medical instrument of this type is a hard endoscope having a thin tube with an inner diameter of about 1 mm, for example. 
     The treatment modes differ from each other in the treatment time, the injected amount of the aqueous solution of the hydrogen peroxide, or the number of exposure times in the subsequent steps. The column of the injected amount of the aqueous solution of the hydrogen peroxide in the table shown in  FIG.  4    indicates a range of possible values per pulse corresponding to one operation of the sterilization step S 500  described below. In particular, the upper row in the column indicates the algebra regarding the injected amount of the first aqueous solution, and the lower row indicates the algebra regarding the injected amount of the second aqueous solution. 
     The preliminary decompression step S 200  is a step executed preliminary to the subsequent ozone adsorption step S 300  to decompress the inside of the chamber  11  with respect to the atmospheric pressure.  FIG.  3    indicates a period in which the preliminary decompression step S 200  is executed by H11. The preliminary decompression step S 200  decompresses the inside of the chamber  11  to a level of 100 Pa, for example. 
     The ozone adsorption step S 300  is a step of injecting the ozone gas to the inside of the chamber  11  under the decompressed state obtained in the preliminary decompression step S 200  to cause the ozone gas to be adsorbed to the wrapping member wrapping the object to be sterilized. The present embodiment executes an ozone injection step S 505  separately from the ozone adsorption step S 300 . If the ozone adsorption step S 300  would not be executed, the ozone gas injected to the inside of the chamber  11  would be adsorbed to the wrapping member wrapping the object to be sterilized in the ozone injection step S 505 . The ozone as an adsorbed object may prevent the ozone gas sequentially supplied from reaching the object to be sterilized. The present embodiment thus causes the ozone gas to be adsorbed to the wrapping member in the ozone adsorption step S 300  before executing the ozone injection step S 505  so as to lead the wrapping member to a saturated state or a state approximate to the saturated state. Preliminarily leading the wrapping member to the saturated state or the state approximate to the saturated state can avoid or decrease the adsorption of the ozone gas to the wrapping member when injecting the ozone gas to the inside of the chamber  11  in the ozone injection step S 505 , so as to allow the ozone gas to easily reach the object to be sterilized accordingly. Some of the ozone gas injected in the ozone adsorption step S 300  reaches the object to be sterilized to contribute to the sterilization, in addition to the ozone gas being adsorbed to the wrapping member. 
     The execution of the subsequent ozone injection step S 505  might be eliminated when the concentration of the ozone gas in the gas supplied to the inside of the chamber  11  is increased in the ozone adsorption step S 300 . The execution of the ozone adsorption step S 300  might be eliminated instead when the concentration of the ozone gas in the gas supplied to the inside of the chamber  11  is increased in the ozone injection step S 505 . However, the increase in the concentration of the ozone gas as described above might have an unintended influence that would cause deformation of the object to be sterilized, for example, depending on the material used for the object to be sterilized. To deal with this, the series of the process in the sterilizing method according to the present embodiment includes the several steps for injecting the ozone gas to the inside of the chamber  11 , so as to further avoid or decrease the influence of the ozone gas on the shape or composition of the object to be sterilized. In view of the decrease in the influence of the ozone gas as described above, the gas to be supplied to the inside of the chamber  11  in the ozone adsorption step S 300  is defined to contain the ozone gas with the concentration of about 1%. When the ozone gas is presumed to be produced in the ozone supply unit  30  as described in the present embodiment, the gas to be supplied to the inside of the chamber  11  contains 99% of oxygen other than the ozone gas. If the concentration of the ozone gas is defined to be higher, the constituent members such as the ozone generators  32  that produce the ozone gas may need to implement higher performance. Defining the concentration of the ozone gas to about 1% has the advantage of facilitating the ozone generation by the ozone generators  32 . Defining the concentration of the ozone gas to about 1% also has the advantage of avoiding an unintended influence on the object to be sterilized, since the concentration of the ozone gas after being injected to the inside of the chamber  11  can be decreased to 500 ppm or lower. 
       FIG.  3    indicates the timing of starting the ozone adsorption step S 300  by T11. The internal state of the chamber  11  may be kept during a period H12 after the ozone gas is injected to the inside of the chamber  11  in the ozone adsorption step S 300 , as shown in  FIG.  3   . For example, when the treatment mode is the short mode, the concentration of the ozone gas in the ozone adsorption step S 300  may be about 400 ppm, while the retention time corresponding to the period H12 may be three minutes. An exposure condition for the ozone gas in this case is approximately given by 400 (ppm)×3 (minutes)=1200 (ppm/min). The control by the controller  61  upon the injection of the ozone gas is the same as the control in the ozone injection step S 505  described below. In addition, a preparation step similar to an ozone preparation step S 504  described below may be executed before the ozone adsorption step S 300 . 
     As illustrated above, the gas supplied to the inside of the chamber  11  in the ozone adsorption step S 300  contains a great amount of the oxygen, as compared with the ozone gas. The present embodiment then injects the vapor of the first aqueous solution of the hydrogen peroxide to the inside of the chamber  11  in a first vapor injection step S 502 . The hydrogen peroxide does not easily reach the surface of the object to be sterilized when the vapor of the first aqueous solution is injected to the inside of the chamber  11  in the first vapor injection step S 502  if a large amount of the oxygen remains inside the chamber  11 . The sterilization decompression step S 400  is a step executed in view of such a problem to remove the oxygen remaining inside the chamber  11  before the first vapor injection step S 502 . In addition, decompressing the inside of the chamber  11  in the sterilization decompression step S 400  can enhance the performance of leading the hydrogen peroxide to reach the object to be sterilized. 
     In the sterilization decompression step S 400 , the controller  61  opens the eighth electromagnetic valve  77  after starting up the vacuum pump  41  so as to decompress the inside of the chamber  11  during a period H13 shown in  FIG.  3   . The controller  61  then further opens the second electromagnetic value  71 , the third electromagnetic value  72 , and the seventh electromagnetic value  76 , so as to decompress the inside of each of the evaporator  26  and the buffer tank  34 , in addition to the chamber  11 . The treatment time indicated in the table shown in  FIG.  4    is measured from the point of starting the decompression in this case. 
     A target pressure achieved in the sterilization decompression step S 400  is set to a pressure sufficient to remove the oxygen and lead the vapor of the first aqueous solution of the hydrogen peroxide to reach the object to be sterilized reliably in the subsequent first vapor injection step S 502 . For example, the target pressure in this case is set to 50 Pa or lower, and particularly preferably set in a range of 25 to 35 Pa. 
     The controller  61 , when having achieved the target pressure, closes the second electromagnetic valve  71 , the third electromagnetic valve  72 , the seventh electromagnetic valve  76 , and the eighth electromagnetic valve  77  to stop the vacuum pump  41 . The controller  61  then leads the process to proceed to the sterilization step S 500  after the sterilization decompression step S 400 . The internal state of the chamber  11  may be kept during a period H14 after the execution of the sterilization decompression step S 400 , as shown in  FIG.  3   . 
     When the treatment mode is the long mode, the object to be sterilized is a thin tube made of stainless steel, for example. Upon the choice of the long mode, the temperature of the object to be sterilized may be preliminarily increased and kept for a predetermined period of time such as about two minutes while keeping the pressure achieved, so as to reduce an influence of water condensation inside the duct part as much as possible. 
       FIG.  5    is a flowchart showing a process of the sterilization step S 500 . The sterilization step S 500  is a step mainly contributing to the sterilization of the object to be sterilized. The sterilization step S 500  includes a first vapor preparation step S 501 , the first vapor injection step S 502 , and a first state keeping step S 503 . 
     The first vapor preparation step S 501  is a step of producing the vapor of the first aqueous solution to be injected in the subsequent first vapor injection step S 502 . The controller  61  first rotates the first tube pump  23   a  to suck the first aqueous solution out of the first bottle  21   a , and then injects an equally-divided amount of the defined amount of the first aqueous solution to the storage part  24 . The defined amount in this case is a total injected amount per pulse, and varies depending on the respective treatment modes as shown in  FIG.  3   . For example, when the treatment mode is the short mode, the concentration of the hydrogen peroxide contained in the first aqueous solution is set to a predetermined concentration (x1) in a range of 30% to 60%, and the defined amount is a predetermined amount (y1) in a range of 1 to 4 ml. When the defined amount is divided by two and is then injected, for example, the equally-divided amount of the defined amount is half of y1, which is a predetermined amount (y1/2) in a range of 0.5 to 2 ml. The controller  61  then opens the first electromagnetic valve  70  for a predetermined period of time such as five seconds. Since the inside of the evaporator  26  has been already decompressed, the first aqueous solution is immediately sucked up to the evaporator  26 . The air then enters the storage part  24 , which communicates with the atmosphere via the first filter  25 , so that the first aqueous solution remaining in the storage part  24  or the first supply pipe  27  is also sent to the evaporator  26 . The controller  61  then closes the first electromagnetic valve  70  to evaporate the first aqueous solution in the evaporator  26  for a predetermined period of time such as five seconds. The evaporator  26  is constantly warmed up at a predetermined temperature in a range of 65° C. to 120° C., for example. When a regulated amount of the first aqueous solution is injected so as to be substantially completely evaporated inside the evaporator  26  having a capacity of a predetermined value in a range of 0.5 to 2 L under a pressure of 50 Pa, for example, the pressure is presumed to be increased to a level of about a saturated vapor pressure. The controller  61  then leads the process to proceed to the first vapor injection step S 502  after the first vapor preparation step S 501 . 
     The first vapor injection step S 502  is a step of injecting the vapor of the first aqueous solution produced in the evaporator  26  to the inside of the chamber  11 .  FIG.  3    indicates the timing of starting the first vapor injection step S 502  by T12. The controller  61  first opens the second electromagnetic valve  71  and the third electromagnetic valve  72  for a predetermined period of time such as ten seconds. The vapor of the first aqueous solution is then strongly injected to the inside of the chamber  11  due to the difference in pressure. When the object to be sterilized particularly has a duct part, the vapor penetrates to the inside of the duct part more easily as the difference in the pressure is higher. In addition, the vapor is easily equalized inside the chamber  11  as described above. The controller  61  then closes the second electromagnetic valve  71  and the third electromagnetic valve  72 . The controller  61  repeats the injection of the vapor of the first aqueous solution in the same process depending on the treatment mode to be chosen. For example, when the treatment mode is the short mode, the vapor of the first aqueous solution is to be injected to the evaporator  26  per pulse with an amount obtained such that the predetermined concentration (x1) in the range of 30% to 60% is multiplied by the predetermined amount (y1) in the range of 1 to 4 ml. If an excessively large amount of the first aqueous solution is injected at once, the inside of the evaporator  26  reaches the saturated vapor pressure, which may impede the sufficient evaporation to cause the first aqueous solution to remain in the evaporator  26 . In view of this, the controller  61  may divide the amount of the first aqueous solution half-and-half so as to sequentially evaporate each divided amount of the first aqueous solution to inject the vapor to the chamber  11  two times. The controller  61  may divide the amount of the first aqueous solution into more than two so as to sequentially inject the vapor of the first aqueous solution to the chamber  11 . The controller  61  then leads the process to proceed to the first state keeping step S 503  after the first vapor injection step S 502 . 
     The first state keeping step S 503  is a step of keeping the vapor of the first aqueous solution in the chamber  11  for a predetermined period of time to sterilize the object to be sterilized.  FIG.  3    indicates the predetermined retention time by H15. The retention time at this point varies depending on the respective treatment modes. The retention time in the short mode is three minutes, for example. The retention time in the normal mode is four minutes, for example. The retention time in the long mode is six minutes, for example. The retention time thus gradually increases in the order of the short mode, the normal mode, and the long mode. 
     The sterilization step S 500  includes the ozone preparation step S 504  and the ozone injection step S 505 . 
     The ozone preparation step S 504  is a step of producing the ozone gas to be injected in the subsequent ozone injection step S 505 . The ozone preparation step S 504  is not necessarily executed after the completion of the first state keeping step S 503 , but is only required to be executed before the start of the ozone injection step S 505  so as to prepare the ozone gas. The controller  61  first opens the fourth electromagnetic valve  73  to supply the oxygen with a high concentration to the ozone generators  32 . The controller  61  may close the fifth electromagnetic valve  74  and open the sixth electromagnetic valve  75  for several tens of seconds from the start of driving the ozone generators  32 , so as to lead the ozone gas to flow through the piping system of the first catalyst tank  42  without supplying the ozone gas to the buffer tank  23  until the concentrations of the oxygen and the ozone are stabilized. The controller  61  then closes the sixth electromagnetic valve  75  and opens the fifth electromagnetic valve  74 , so as to fill the buffer tank  34  with the ozone gas until reaching a predetermined flowing amount, a predetermined concentration, and a predetermined period of time. The controller  61  after finishing filling the buffer tank  34  with the ozone gas closes the fifth electromagnetic valve  74  to stop driving the ozone generators  32 . 
     The ozone injection step S 505  is a step of injecting the ozone gas produced in the ozone preparation step S 504  to the chamber  11 .  FIG.  3    indicates the timing of starting the ozone injection step S 505  by T13. The ozone injection step S 505  is executed after the completion of the first state keeping step S 503 . The controller  61  opens the seventh electromagnetic valve  76  and further opens the second electromagnetic valve  71  and the third electromagnetic valve  72  for a predetermined period of time such as five seconds to inject the ozone gas to the chamber  11 . The pressure inside the buffer tank  34  is set to a predetermined pressure in a range of about 0.03 to 0.08 MPa to the maximum as a gauge pressure, or a predetermined pressure in a range of about 0.13 to 0.18 MPa as an absolute pressure. The injection of the ozone gas to the inside of the chamber  11  under the decompression of 3000 Pa or less as an absolute pressure is presumed to be completed within about several seconds due to the pressure difference. 
     As described above, the sterilizer  100  uses the buffer tank  34  so as to inject the ozone gas to the inside of the chamber  11  when the pressure of the ozone gas is increased in the buffer tank  34 . The injection of the ozone gas as described above further facilitates the equalization of diffusion of the ozone gas inside the chamber  11 . In addition, the ozone gas is allowed to easily enter the inside of a tube of the object to be sterilized having a duct part. The sterilizer  100  thus can further decrease the used amount of the ozone while keeping the sterilization efficiency. 
     The ozone injection step S 505  injects the ozone gas to the inside of the chamber  11  through the inside of the evaporator  26 , so as to use the ozone gas to push the hydrogen peroxide remaining in the evaporator  26  into the chamber  11  to further improve the sterilization effect. The sterilizer  100  can share the introduction port provided in the chamber  11  to be used as a port to which the hydrogen peroxide is introduced and as a port to which the ozone gas is introduced, so as to simplify the circumferential configuration of the chamber  11 . 
     The sterilization step S 500  further includes a second vapor preparation step S 506 , a second vapor injection step S 507 , an outside air injection step S 508 , and a second state keeping step S 509 . 
     The second vapor preparation step S 506  is a step of producing the vapor of the second aqueous solution to be injected in the subsequent second vapor injection step S 507 . The second vapor preparation step S 506  is not necessarily executed after the completion of the ozone injection step S 505 , but is only required to be executed before the start of the second vapor injection step S 507  so as to prepare the vapor of the second aqueous solution. The generation of the vapor of the second aqueous solution may be executed through a process similar to the generation of the vapor of the first aqueous solution in the first vapor preparation step S 501 . 
     The controller  61  first rotates the second tube pump  23   b  to suck the second aqueous solution out of the second bottle  21   b , and then injects an equally-divided amount of the defined amount to the storage part  24 . For example, when the treatment mode is the short mode, the concentration of the hydrogen peroxide contained in the second aqueous solution is set to a predetermined concentration (x2) in a range of 0.1% to 10%, and the defined amount is a predetermined amount (y2) in a range of 2 to 8 ml. When the defined amount is divided by two and is then injected, for example, the equally-divided amount of the defined amount is half of y2, which is a predetermined amount (y2/2) in a range of 1 to 4 ml. The controller  61  then opens the first electromagnetic valve  70  for a predetermined period of time such as five seconds. Since the inside of the evaporator  26  has been already decompressed, the second aqueous solution is immediately sucked up to the evaporator  26 . The air then enters the storage part  24 , which communicates with the atmosphere via the first filter  25 , so that the second aqueous solution remaining in the storage part  24  or the first supply pipe  27  is also sent to the evaporator  26 . The controller  61  then closes the first electromagnetic valve  70  to evaporate the second aqueous solution in the evaporator  26  for a predetermined period of time such as five seconds. The evaporator  26  is constantly warmed up at a predetermined temperature in a range of 65° C. to 120° C., for example. When a regulated amount of the second aqueous solution is injected so as to be substantially completely evaporated inside the evaporator  26  having a capacity of a predetermined value in a range of 0.5 to 2 L under a pressure of 50 Pa, for example, the pressure is presumed to be increased to a level of about a saturated vapor pressure. The controller  61  then leads the process to proceed to the second vapor injection step S 507  after the second vapor preparation step S 506 . 
     The second vapor injection step S 507  is a step of injecting the vapor of the second aqueous solution produced by the evaporator  26  to the chamber  11 .  FIG.  3    indicates the timing of starting the second vapor injection step S 507  by T14. The ozone itself cannot contribute to the sterilization well, but increases the reactivity when moisture is added thereto. The reason for this is presumed that a OH radical or the like is produced when the ozone reacts with moisture or the hydrogen peroxide remaining on surfaces of bacteria so as to effectively destroy cell walls of the bacteria. In view of this, the present embodiment injects the vapor of the second aqueous solution to the inside of the chamber  11  immediately after the completion of the injection of the ozone gas. The hydrogen peroxide contained in the vapor injected to the inside of the chamber  11  is presumed to penetrate cells of the bacteria through the cell walls destroyed by the ozone to attack cell nuclei, so as to improve the sterilization effect. 
     With regard to the relationship between the first aqueous solution and the second aqueous solution, the concentration of the hydrogen peroxide contained in the second aqueous solution may be lower than or equal to the concentration of the hydrogen peroxide contained in the first aqueous solution. 
     The injection of the vapor of the first aqueous solution is defined as a main sterilization treatment using the hydrogen peroxide as a material for the sterilization gas. The injection of the vapor of the second aqueous solution is defined as an auxiliary treatment for improving the sterilization efficiency of the sterilization treatment due to the injection of the ozone gas. When the vapor of the second aqueous solution is injected in the second vapor injection step S 507 , the concentration of the hydrogen peroxide contained in the aqueous solution can be set to be lower for the second aqueous solution than for the first aqueous solution, or set to be equal to each other. This can decrease the used amount of the hydrogen peroxide in the entire sterilization treatment when the sterilizing method according to the present embodiment uses both the first aqueous solution and the second aqueous solution. In addition, the amount of the hydrogen peroxide that might remain on the surface of the object to be sterilized or inside the chamber  11  can be decreased in proportion to the decrease in the used amount of the hydrogen peroxide. 
     Alternatively, with regard to the relationship between the first aqueous solution and the second aqueous solution, the total amount of the hydrogen peroxide contained in the second aqueous solution may be smaller than or equal to the total amount of the hydrogen peroxide contained in the first aqueous solution. 
     Setting the total amount of the hydrogen peroxide contained in the second aqueous solution to be smaller than or equal to the total amount of the hydrogen peroxide contained in the first aqueous solution can decrease the used amount of the hydrogen peroxide in the entire sterilization treatment regardless of whether the concentration of the hydrogen peroxide contained in the second aqueous solution is higher than the concentration of the hydrogen peroxide contained in the first aqueous solution. 
     The concentration of the hydrogen peroxide contained in the first aqueous solution or the second aqueous solution, or the total amount of the hydrogen peroxide contained in the first aqueous solution or the second aqueous solution may be defined in accordance with the presence or absence of a duct part in the object to be sterilized or the material used for the object to be sterilized. 
     The present embodiment illustrates the three treatment modes that differ from each other in the presence or absence of a duct part in the object to be sterilized or the material used for the object to be sterilized. For example, the object to be sterilized to which the sterilization treatment in the normal mode can be subjected is a thin tube made from resin. The object to be sterilized to which the sterilization treatment in the long mode can be subjected is a thin tube made from stainless steel. With regard to the comparison between the thin tube of resin and the thin tube of stainless steel, the thin tube of stainless steel is typically harder to sterilize than the thin tube of resin. The reason for this is presumed that the reactivity between a transition element such as Fe, Mo, or Cr contained in stainless steel and the hydrogen peroxide is high, and the hydrogen peroxide is thus decomposed in the middle of the treatment to impede the sufficient supply of the hydrogen peroxide to the inside of the thin tube. Another reason for this is presumed that the thin tube of stainless steel has higher thermal conductivity than the thin tube of resin, and is cooled more quickly under a decompressed environment to easily cause water condensation of the hydrogen peroxide inside the thin tube, which impedes the sufficient supply of the hydrogen peroxide to the inside of the thin tube. 
     When the thin tube of stainless steel is sterilized, for example, the present embodiment can deal with the above-described problem such that the concentration of the hydrogen peroxide contained in the second aqueous solution is set to be higher than the concentration of the hydrogen peroxide contained in the second aqueous solution used in the other treatment modes. The concentration of the hydrogen peroxide contained in the second aqueous solution in this case still does not exceed the concentration of the hydrogen peroxide contained in the first aqueous solution. When the concentration of the hydrogen peroxide contained in the second aqueous solution is equal to the concentration of the hydrogen peroxide contained in the first aqueous solution, the injected amount of the second aqueous solution can be decreased. In other words, the present embodiment, when sterilizing the thin tube of stainless steel, can particularly decrease the entire used amount of the hydrogen peroxide (the concentration of the hydrogen peroxide in the first aqueous solution and the second aqueous solution×the sum of the injected amount of the hydrogen peroxide), as compared with conventional sterilizing methods. The same is also applied to the case in which the total amount of the hydrogen peroxide contained in the second aqueous solution is smaller than or equal to the total amount of the hydrogen peroxide contained in the first aqueous solution, so as to accurately decrease the entire used amount of the hydrogen peroxide (the sum of the total amount of the hydrogen peroxide in the first aqueous solution and the total amount of the hydrogen peroxide in the second aqueous solution). 
     The sterilization effect is increased as the concentration of the hydrogen peroxide contained in the second aqueous solution is further increased. The increase in the concentration of the hydrogen peroxide contained in the second aqueous solution can be presumed to lead to a reduction in the treatment time. The present embodiment is illustrated with a case, when the treatment mode is the long mode, for example, in which the concentration of the hydrogen peroxide contained in the second aqueous solution is set to the predetermined concentration (x1) in the range of 30% to 60% that is equal to the concentration of the hydrogen peroxide contained in the first aqueous solution. While the injected amount per pulse in the short mode or the normal mode is set to the predetermined value (y2) in the range of 2 to 8 ml, the injected amount in the long mode can be set to a smaller predetermined amount (y3) in a range of 1 to 5 ml. 
     As described above, the second vapor injection step S 507  is executed immediately after the completion of the ozone injection step S 505 . The injection of the vapor of the second aqueous solution may be executed through a process similar to the injection of the vapor of the first aqueous solution in the first vapor injection step S 502 . 
     The controller  61  first opens the second electromagnetic valve  71  and the third electromagnetic valve  72  for a predetermined period of time such as ten seconds, and injects the vapor of the second aqueous solution to the chamber  11 . The controller  61  then closes the second electromagnetic valve  71  and the third electromagnetic valve  72 . The controller  61  repeats the injection of the vapor of the second aqueous solution through the same process depending on the respective treatment modes. When the treatment mode is the short mode, the controller  61  may also divide the amount of the second aqueous solution of y2 (2 to 8 ml) by two so as to evaporate and sequentially inject the second aqueous solution half-and-half to the chamber  11 , for example. The controller  61  may divide the amount of the second aqueous solution into more than two so as to sequentially inject the vapor of the second aqueous solution to the chamber  11 . The controller  61  then leads the process to proceed to the outside air injection step S 508  after the second vapor injection step S 507 . 
     While the present embodiment is illustrated above with the case of injecting the vapor of the second aqueous solution of the hydrogen peroxide in the second vapor injection step S 507 , the method may inject vapor produced from water or a solution containing a volatile component described below, instead of the second aqueous solution. The water used for producing the vapor may be water in which pyrogen is removed or inactivated, or water in which bacteria or microbes are removed or inactivated. The use of the water in which pyrogen is removed or inactivated or the water in which bacteria or microbes are removed or inactivated can preliminarily prevent contamination of the object to be sterilized caused by pyrogen and the like. The water as used herein may be pure water or ultrapure water such as purified water to which sterilization or disinfection treatment is subjected. The water as used herein may also be pure water, water from which scale is removed, or tap water. The use of the pure water or the water from which scale is removed can eliminate an adverse effect (such as clogging) caused by scale in the evaporator  26 , so as to produce the vapor efficiently. Examples of the water from which scale is removed include filtered water from which scale crystals are removed and soft water from which positive ions that can be a cause of scale are removed. The tap water is available more readily than the pure water or the water from which scale is removed, and does not need to be subjected to pretreatment. The volatile component may be sodium hypochlorite or alcohols. An example of alcohols may be ethanol. Since the sodium hypochlorite or alcohols have a bactericidal action, the injection of the vapor of the solution containing the volatile component as described above can further improve the sterilization efficiency. 
     The following is an example of injecting the vapor of the pure water in the second vapor injection step S 507 , instead of the second aqueous solution, in which the pure water is presumed to be stored in the second bottle  21   b . The pure water is evaporated by the evaporator  26 . The use of the pure water instead of the second aqueous solution can also have the advantage of improving the reactivity of the ozone gas, as in the case described above. The table shown in  FIG.  3    illustrates the case in which the concentration of the hydrogen peroxide contained in the second aqueous solution in the short mode and the normal mode (x2: a predetermined value in a range of 0.1% to 10%) is greatly lower than the concentration of the hydrogen peroxide contained in the first aqueous solution (x1: a predetermined value in a range of 30% to 60%). In the case in which one of these two treatment modes can be chosen and the sterilization effect is not strictly required for the object to be sterilized, for example, the pure water can be used instead of the second aqueous solution. This can decrease the used amount of the hydrogen peroxide in the entire sterilization treatment. 
     The outside air injection step S 508  is a step of injecting the outside air that is the atmosphere or dry nitrogen gas to the inside of the chamber  11 .  FIG.  3    indicates the timing of starting the outside air injection step S 508  by T15. The present embodiment is illustrated below with a case in which the outside air is the atmosphere. The outside air injection step S 508  is executed immediately after the completion of the second vapor injection step S 507 . The injection of the air to the inside of the chamber  11  pushes the hydrogen peroxide or the ozone gas congested particularly in the middle of the duct part in the object to be sterilized, so as to further promote the sterilization. The injection of the air to the inside of the chamber  11  also equalizes the distribution of the concentration of the gas present inside the chamber  11  so as to ensure the uniform sterilization. The injection of the air to the inside of the chamber  11  further increases the internal pressure to lead the hydrogen peroxide in the vapor to be slightly condensed on the surface of the object to be sterilized, so as to improve the sterilization effect. The condensation as used herein is referred to also as micro-condensation. Particularly when the outside air is the atmosphere, the cost for the raw material for the gas to be injected can be decreased, and the configuration for injecting the air to the inside of the chamber  11  can be simplified, so as to reduce the manufacturing costs for the sterilizer  100  accordingly. 
     The controller  61  injects the air into the inside of the chamber  11  via the air introduction unit  50 . In particular, the controller  61  controls the open and closed states of the ninth electromagnetic valve  78  and the tenth electromagnetic valve  79  as necessary, so as to regulate the injected amount of the air introduced through the second filter  51 . The air is continuously introduced until reaching a predetermined pressure. In the present embodiment, the controller  61  closes the ninth electromagnetic valve  78  and the tenth electromagnetic valve  79  after injecting the air until the pressure inside the chamber  11  reaches about 90 kPa that is about 90% of the atmospheric pressure. The reason for this is that the gas may leak out of the door  12  through the sealing part if the internal pressure of the chamber  11  is equal to the external pressure. The controller  61  then leads the process to proceed to the second state keeping step S 509  after the outside air injection step S 508 . 
     As described above, the outside air injection step S 508  is effective particularly upon choosing the normal mode or the long mode that is applied to the case in which the object to be sterilized has a duct part. In the case of the short mode for mainly executing the surface sterilization on the object to be sterilized not having a duct part, the outside air injection step S 508  is not necessarily executed in view of the simplification of the process when the short mode can ensure the preferable sterilization effect. 
     The second state keeping step S 509  is a step of keeping the state of the inside of the chamber  11  for a predetermined period of time after the completion of the outside air injection step S 508 .  FIG.  3    indicates the predetermined retention time by H15. Keeping the state of the inside of the chamber  11  for the predetermined period of time can further promote the sterilization action as described in the outside air injection step S 508 . The retention time at this point varies depending on the respective treatment modes. The retention time in the short mode is two minutes, for example. The retention time in the normal mode is three minutes, for example. The retention time in the long mode is five minutes, for example. 
     The series of the operations of the sterilization step S 500  as described above may be repeated several times as necessary depending on the object to be sterilized. The controller  61  then determines whether the operations of the sterilization step S 500  need to be repeated (step S 600 ), as shown in  FIG.  2   , after the completion of the second state keeping step S 509 . The first series of the operations of the sterilization step S 500  is counted as one corresponding to a single exposure, and the number of times of the exposure in the following steps is indicated by the pulse number. The controller  61 , when determining that the sterilization step S 500  needs to be repeated (YES), leads the process to proceed to the sterilization decompression step S 400  to execute the decompression operation so as to execute the sterilization step for the second pulse. When determining that no more sterilization step is needed (NO), the controller  61  leads the process to proceed to the following aeration step S 700 . 
     The number of pulses required is defined so as to ensure a sterilization security standard of 10 −6  or lower (SAL&lt;10 −6 ). To achieve the standard, the sterilization step in a half cycle corresponding to one pulse needs to annihilate 10 −6  or greater of indicator bacteria. The present embodiment defines two pulses as a full cycle in all of the three treatment modes. The series of the operations of the sterilization step S 500  may be repeated for the predetermined number of times without the execution of determination of whether the repetition of the operations in the sterilization step S 500  is required. 
     The aeration step S 700  is a step of decompressing the inside of the chamber  11  to a predetermined vacuum degree to remove the hydrogen peroxide and the ozone as the sterilization gas, and then injecting the air to reach a level of about the atmospheric pressure so as to dilute the sterilization gas. In the present embodiment, the treatment operation in the aeration step S 700  in the short mode differs from the other treatment modes. 
     First, the aeration step S 700  in the case in which the treatment mode is the short mode is described below. The time for the contact between the sterilization gas and the object to be sterilized is shorter for the short mode than for the other modes. The aeration step S 700  in this case includes the following treatment step, for example, so as to decrease the treatment time. 
     The controller  61  first starts up the vacuum pump  41  and opens the eighth electromagnetic valve  77  to start the decompression of the inside of the chamber  11  immediately after the completion of the second state keeping step S 509  as quickly as possible. Simultaneously, the controller  61  opens the second electromagnetic valve  71 , the third electromagnetic valve  72 , and the seventh electromagnetic valve  76 , so as to discharge the remaining gas inside the evaporator  26  and the buffer tank  34 . The short mode keeps decompressing the inside of the chamber  11  until the internal pressure reaches 100 Pa, for example. The sterilization gas discharged passes through the first catalyst tank  42  and the second catalyst tank  43 , so as to lead the hydrogen peroxide to be decomposed to be harmless water and oxygen and lead the ozone to be decomposed to be harmless oxygen to be discharged to the outside of the sterilizer  100  with a concentration of a safety management value or lower. The controller  61  then closes the eighth electromagnetic valve  77  when the pressure inside the chamber  11  reaches a predetermined decompressed pressure. 
     The controller  61  then opens the ninth electromagnetic valve  78  and the tenth electromagnetic valve  79  to inject the air to the inside of the chamber  11  through the second filter  51 . Simultaneously, the controller  61  opens the second electromagnetic valve  71 , the third electromagnetic valve  72 , and the seventh electromagnetic valve  76  to inject the air also to the inside of each of the evaporator  26  and the buffer tank  34 . The injected air diffuses and dilutes the gas remaining inside the chamber  11 , and removes the sterilization gas adhering to the object to be sterilized or the inner surface of the chamber  11 . The controller  61  keeps injecting the air until the pressure inside the chamber  11  reaches about 90 kPa that is about 90% of the atmospheric pressure, and then closes the ninth electromagnetic valve  78  and the tenth electromagnetic valve  79 . 
     The controller  61  repeats the decompression and the air injection as described above for the prescribed number of times. In the short mode, the total repeated number of times can be three, for example. When the time required for the decompression is presumed to be about three minutes and the time required for the air injection is presumed to be about 0.5 minutes, the aeration step S 700  is to take the time given by 3.5 minutes×three times=10.5 minutes. The controller  61  returns the pressure inside the chamber  11  to the atmospheric pressure by the air injection after repeating the decompression and the air injection for the prescribed number of times, and finishes the aeration step S 700 . The controller  61  ends the sterilization treatment after the aeration step S 700 . 
     Second, the aeration step S 700  in the case in which the treatment mode is the other modes other than the short mode is described below. The time for the contact between the sterilization gas and the object to be sterilized, and the amount of the hydrogen peroxide adhering to the object to be sterilized or the amount of the hydrogen peroxide remaining inside the chamber  11  are greater for the other modes than for the short mode. The aeration step S 700  in this case includes the following treatment step, for example. 
     The fundamental operations of the decompression and the air injection are the same as those in the case in which the treatment mode is the short mode. The pressure presumed to reach upon the decompression, which is set to 100 Pa or lower in the short mode, is set to 50 Pa or lower in the other modes, for example, which is stricter than the case of the short mode, since the object to be sterilized can have a duct part in the other modes. 
     The controller  61  keeps executing the decompression while injecting the air after the completion of the first decompression and air injection. In particular, the controller  61  starts up the vacuum pump  41  and opens the eighth electromagnetic valve  77  to start the decompression, and then opens the ninth electromagnetic valve  78  and the tenth electromagnetic valve  79  after a delay of about two seconds, for example, so as to inject the air through the second filter  51 . A timing of stopping the air injection at the time of injecting the air after the decompression is assumed to be a point at which the pressure inside the chamber  11  is led to about 90 kPa or greater. A timing of stopping the air injection at the time of decompressing while injecting the air may be set to a point at which the pressure inside the chamber  11  is led to about 90 kPa or lower. The exhaustion during the air injection enhances the flow of the air, so as to actively remove the sterilization gas adhering to the object to be sterilized or the inner surface of the chamber  11 . Since the object to be sterilized is wrapped with the wrapping member particularly upon the normal sterilization treatment, the sterilization gas adsorbed to the wrapping member can be effectively removed. The time for decompressing while injecting the air is set to about five minutes, for example. The time required for each treatment for the exhaustion during the air injection is shorter than the time required for each treatment for the air injection after the decompression, so as to reduce the entire time necessary for the aeration step S 700  accordingly. 
     The controller  61  further repeats the operations similar to the decompression and the air injection executed for the first time. The repeating number of times in this case may be two, for example. 
     The aeration step S 700  in this case takes about 15.5 minutes in total, in which the time required for the first decompression and air injection is 3.5 minutes, the time required for decompressing while injecting the air is 5 minutes, and the time required for the second decompression and air injection is 3.5 minutes×2=7 minutes. The controller  61  then returns the pressure inside the chamber  11  to the atmospheric pressure by the air injection, and finishes the aeration step S 700 . The controller  61  ends the sterilization treatment after the aeration step S 700 . 
     While the aeration step S 700  repeats the decompression and the air injection several times as described above, which is effective in the elimination of the remaining sterilization gas, the treatment time is increased as the repeating number of times is increased. When the decompression and the air injection are repeated five times, for example, the time (five minutes) shorter than the time (six minutes) taken for repeating two times (three minutes×two times) may be substituted for the next repeating time. This can discharge the sterilization gas remaining inside the chamber  11  more efficiently, and further reduce the time required for the aeration step S 700 . 
     The treatment time taken for the sterilization treatment according to the present embodiment described above in each treatment mode is substantially the same as indicated in the table shown in  FIG.  3   . The operator removes the object to be sterilized from the chamber  11  after the completion of the series of the steps for the sterilization treatment. 
     The effects achieved by the sterilizing method and the sterilizer  100  that can execute the sterilizing method according to the present embodiment are described below. 
     The sterilizing method according to the present embodiment includes the preliminary decompression step S 200  of decompressing the inside of the chamber  11  with respect to the atmospheric pressure after the object to be sterilized wrapped with the wrapping member made from a material that absorbs the ozone gas and the hydrogen peroxide is housed in the chamber  11 . The sterilizing method further includes the ozone adsorption step S 300  of injecting the ozone gas to the inside of the chamber  11  under the decompressed state achieved in the preliminary decompression step S 200  to cause the ozone gas to be adsorbed to the wrapping member. The sterilizing method further includes the sterilization step S 500  of sterilizing the object to be sterilized by use of the ozone gas and the hydrogen peroxide after the ozone adsorption step S 300 . 
     The sterilizer  100  according to the present embodiment includes the chamber  11  that houses the object to be sterilized wrapped with the wrapping member made from a material that absorbs the ozone gas and the hydrogen peroxide. The sterilizer  100  further includes the evaporator  26  that communicates with the chamber  11  and evaporates the aqueous solution of the hydrogen peroxide, water in which pyrogen is removed or inactivated, water in which bacteria or microbes are removed or inactivated, pure water, water from which scale is removed, tap water, or the solution containing the volatile component so as to be filled with the vapor thus obtained. The sterilizer  100  further includes the ozone generators  32  that communicates with the chamber  11  and produces the ozone gas. The sterilizer  100  further includes the controller  61  that controls the operation of injecting, to the inside of the chamber  11 , the vapor produced by the evaporator  26  or the ozone gas produced by the ozone generators  32 . The controller  61  decompresses the inside of the chamber  11  and injects the ozone gas to the inside of the chamber  11  under the decompressed state, and then sterilizes the object to be sterilized by use of the ozone gas and the hydrogen peroxide. 
     As described above, the present embodiment includes the sterilization step S 500  that sterilizes the object to be sterilized by use of the ozone gas and the hydrogen peroxide, so as to have a higher sterilization efficiency than a case of sterilizing the object to be sterilized only by use of the hydrogen peroxide, for example. The present embodiment also includes the ozone adsorption step S 300 , before the sterilization step S 500 , that injects the ozone gas to the inside of the chamber  11  under the decompressed state to cause the ozone gas to be adsorbed to the wrapping member wrapping the object to be sterilized. Namely, the present embodiment causes the ozone gas to be adsorbed to the wrapping member so as to lead the wrapping member to a saturated state before the injection of the ozone gas in the sterilization step S 500 . When the ozone gas is injected to the inside of the chamber  11  in the sterilization step S 500 , the ozone gas barely reacts on the wrapping member, so as to easily reach the object to be sterilized through the wrapping member. The present embodiment thus can preliminarily avoid a decrease in the sterilization efficiency derived from the adsorption of the ozone gas in the sterilization step S 500 , so as to enhance the sterilization efficiency in the entire sterilization treatment accordingly, as compared with the case of sterilizing the object to be sterilized only through the sterilization step S 500 . 
     The sterilizing method and the sterilizer according to the present embodiment thus can improve the sterilization efficiency in the entire sterilization treatment. 
     The sterilizing method according to the present embodiment may further include the sterilization decompression step S 400  of decompressing the inside of the chamber  11  after the ozone adsorption step S 300 . The sterilization step S 500  in this case may be executed under the decompressed state achieved in the sterilization decompression step S 400 . 
     When the ozone gas is injected to the inside of the chamber  11  in the ozone adsorption step S 300 , the gas to be supplied to the inside of the chamber  11  also contains gas other than the ozone gas. The gas other than the ozone gas is typically oxygen. If oxygen remains inside the chamber  11  when the subsequent sterilization step S 500  is executed, the progress of the sterilization treatment could be impeded. The sterilizing method including the sterilization decompression step S 400  can preliminarily remove the remaining gas before the sterilization step S 500 . 
     The sterilization step in the sterilizing method according to the present embodiment may include the first vapor injection step S 502  of injecting, to the inside of the chamber  11 , the vapor produced from the first aqueous solution of the hydrogen peroxide. The sterilization step may further include the ozone injection step S 505  of injecting the ozone gas to the inside of the chamber  11  after the first vapor injection step S 502 . The sterilization step may further include the second vapor injection step S 507  of injecting, to the inside of the chamber  11 , the vapor produced from the second aqueous solution of the hydrogen peroxide. The vapor injected in the second vapor injection step S 507  may be produced from water in which pyrogen is removed or inactivated, water in which bacteria or microbes are removed or inactivated, pure water, water from which scale is removed, tap water, or the solution containing the volatile component, instead of the vapor produced from the second aqueous solution. 
     The sterilizing method as described above subjects the object to be sterilized to the sterilization treatment by use of the vapor of the first aqueous solution and then to the sterilization treatment by use of the ozone gas. The sterilizing method according to the present embodiment injects the vapor produced from the second aqueous solution after injecting the ozone gas to the inside of the chamber  11 . The sterilization treatment by use of the ozone gas as described above can improve the reactivity of the ozone gas, so as to ensure the higher sterilization efficiency than the case of executing the sterilization treatment only by use of the ozone gas. The sterilizing method according to the present embodiment can also achieve the similar effects when using, instead of the vapor produced from the second aqueous solution, the vapor produced from water in which pyrogen is removed or inactivated, water in which bacteria or microbes are removed or inactivated, pure water, water from which scale is removed, tap water, or the solution containing the volatile component. Using the water in which pyrogen is removed or inactivated or the water in which bacteria or microbes are removed or inactivated, for example, can preliminarily prevent contamination of the object to be sterilized caused by pyrogen, bacteria, or microbes. 
     The sterilizing method according to the present embodiment may produce the ozone gas to be used in the ozone adsorption step S 300  by the ozone generator  32  that produces the ozone gas in the ozone injection step S 505 . 
     The sterilizing method as described above can use the same gas as the ozone gas used in the ozone adsorption step S 300  and as the ozone gas used in the ozone injection step S 505  having the same concentration, for example. This can simplify the setting of the conditions for the sterilizing method, and also simplify the configuration of the sterilizer  100  that executes the sterilizing method. 
     The sterilizing method according to the present embodiment may set the pressure inside the chamber  11  when injecting the ozone gas in the ozone adsorption step S 300  to be higher than the pressure inside the chamber  11  when injecting the vapor produced from the first aqueous solution in the first vapor injection step S 502 . 
     The sterilizing method as described above can further reduce the time by the point of achieving the pressure inside the chamber  11  upon the injection of the ozone gas in the ozone adsorption step S 300 . This further reduce the working time of the sterilizer  100  that executes the sterilizing method. 
     The sterilizing method according to the present embodiment may use oxygen-rich gas containing ozone gas and oxygen that is supplied to the inside of the chamber  11  in the ozone adsorption step S 300 . 
     The sterilizing method as described above can avoid unnecessary production or usage of the ozone gas while achieving the improvement in the sterilization efficiency in the entire sterilization treatment. 
     It should be understood that the present disclosure includes various embodiments not described herein. 
     REFERENCE SIGNS LIST 
     
         
         
           
               10  CHAMBER UNIT 
               11  CHAMBER 
               12  DOOR 
               13  FIRST HEATER 
               14  FIRST MANOMETER 
               20  HYDROGEN PEROXIDE SUPPLY UNIT 
               21  BOTTLE 
               22  EXTRACTION PIPE 
               22   a  FIRST EXTRACTION PIPE 
               22  SECOND EXTRACTION PIPE 
               23  TUBE PUMP 
               23   a  FIRST TUBE PUMP 
               23   b  SECOND TUBE PUMP 
               24  STORAGE PART 
               25  FIRST FILTER 
               26  EVAPORATOR 
               27  FIRST SUPPLY PIPE 
               28  INJECTION PIPE 
               28   a  FIRST INJECTION PIPE 
               28   b  SECOND INJECTION PIPE 
               29  SECOND HEATER 
               30  OZONE SUPPLY UNIT 
               31  OXYGEN GENERATION DEVICE 
               32  OZONE GENERATOR 
               33  OZONE DENSITOMETER 
               34  BUFFER TANK 
               35  SECOND MANOMETER 
               36  SECOND SUPPLY PIPE 
               37  THIRD SUPPLY PIPE 
               38  EXHAUSTION PIPE 
               39  PRESSURE SENSOR 
               40  EXHAUSTION UNIT 
               41  VACUUM PUMP 
               42  FIRST CATALYST TANK 
               43  SECOND CATALYST TANK 
               44  THIRD HEATER 
               45  FOURTH HEATER 
               50  AIR INTRODUCTION UNIT 
               51  SECOND FILTER 
               52  FIRST INTRODUCTION PORT 
               53  SECOND INTRODUCTION PORT 
               60  CONTROL UNIT 
               61  CONTROLLER 
               62  TOUCH PANEL 
               70  FIRST ELECTROMAGNETIC VALVE 
               71  SECOND ELECTROMAGNETIC VALVE 
               72  THIRD ELECTROMAGNETIC VALVE 
               73  FOURTH ELECTROMAGNETIC VALVE 
               74  FIFTH ELECTROMAGNETIC VALVE 
               75  SIXTH ELECTROMAGNETIC VALVE 
               76  SEVENTH ELECTROMAGNETIC VALVE 
               77  EIGHTH ELECTROMAGNETIC VALVE 
               78  NINTH ELECTROMAGNETIC VALVE 
               79  TENTH ELECTROMAGNETIC VALVE 
               100  STERILIZER