Liquid-filled combination container, inspection method, and method for manufacturing a liquid-filled combination container

Abstract

To inspect the oxygen concentration in a container storing liquid without opening the container.SOLUTION: A liquid-containing combination container comprises: a container which stores liquid in a storage part and has oxygen permeability; a barrier container which houses the container and has oxygen barrier properties; at least one oxygen reaction agent capable of reacting with oxygen in the barrier container; and a fluorescent material which differs in fluorescence time or fluorescence intensity according to ambient oxygen concentration. The oxygen reaction agent is fixed on one of the outer surface of the container and the inner surface of the barrier container. The fluorescent material is provided on the inner surface at a fluorescent material installation position distant from the storage part of the container.SELECTED DRAWING: Figure 8

Description

[Technical Field]

[0001] This disclosure relates to a liquid-filled combination container, an inspection method, and a method for manufacturing a liquid-filled combination container. [Background technology]

[0002] Containers for holding liquids are known (for example, Patent Document 1). Depending on the type of liquid, the liquid may decompose due to oxygen within the container. To address this problem, it is conceivable to perform a process to reduce the oxygen concentration of the liquid inside the container. For example, the oxygen concentration inside the container and the oxygen concentration of the liquid contained within the container can be reduced by nitrogen bubbling. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2011-212366 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] There is a need to inspect the oxygen concentration inside a container containing a liquid, for purposes such as confirming that the oxygen concentration inside the container and the oxygen concentration of the liquid contained within the container are sufficiently low. In particular, if the container is opened by breaking it in order to inspect its oxygen concentration, the oxygen concentration inside the container will change, and the container will need to be resealed. Therefore, there is a need to inspect the oxygen concentration of a container containing a liquid without opening the container. This disclosure aims to inspect the oxygen concentration of a container containing a liquid without opening the container. [Means for solving the problem]

[0005] A first liquid-filled combination container according to one embodiment of the present disclosure is A container that holds liquid in its compartment and is oxygen-permeable, A barrier container that houses the container and has oxygen barrier properties, At least one oxygen reactant that can react with oxygen inside the barrier container, A fluorescent material whose fluorescence time or fluorescence intensity varies according to the ambient oxygen concentration, The oxygen reactant is fixed to at least one of the outer surface of the container and the inner surface of the barrier container, The fluorescent material is provided on the inner surface of the container at a position for installing the fluorescent material that is separated from the contact region of the accommodating portion of the container that contacts the liquid, The container has light transmissibility at least at the position for installing the fluorescent material, The barrier container has a light transmissive position having light transmissibility, By passing through the light transmissive position of the barrier container and the position for installing the fluorescent material of the container, light can be irradiated onto the fluorescent material from outside the barrier container.

[0006] A second liquid-containing combined container according to an embodiment of the present disclosure, [[ID=*20]]A container that houses a liquid in an accommodating portion and has oxygen permeability, A barrier container that houses the container and has oxygen barrier properties, At least one oxygen reactant that can react with oxygen inside the barrier container, <* A fluorescent material whose fluorescence time or fluorescence intensity varies according to the ambient oxygen concentration, The fluorescent material is provided on the inner surface of the container at a position for installing the fluorescent material that is separated from the contact region of the accommodating portion of the container that contacts the liquid, The container has light transmissibility at least at the position for installing the fluorescent material, The barrier container has a light transmissive position having light transmissibility, An oxygen reactant accommodating portion for accommodating the oxygen reactant is partitioned in a part of the barrier container, By being accommodated in the oxygen reactant accommodating portion, the oxygen reactant is arranged at a position that is not sandwiched between the position for installing the fluorescent material and the light transmissive position.

[0007] Note: In the translation, the text marked with '*' is the corrected text according to the context. In the original text, there is an unclear reference in item

[20] , and the corrected text makes the description more complete and logical. If there are specific requirements not to modify the original text, please let me know and I will adjust accordingly.In the first and second liquid-containing combined containers according to an embodiment of the present disclosure, the barrier container may contact the outer surface of the container at the position where the fluorescent material is installed.

[0008] In the first and second liquid-containing combined containers according to an embodiment of the present disclosure, the container may have a coating layer that constitutes the inner surface of the container and suppresses the adhesion of the liquid to the inner surface of the container.

[0009] In the first and second liquid-containing combined containers according to an embodiment of the present disclosure, the container may contain at least one of the materials of glass and cyclic olefin polymer.

[0010] The first and second liquid-containing combined containers according to an embodiment of the present disclosure adhere the fluorescent material to the inner surface of the container at the position where the fluorescent material is installed, and further include an adhesive layer having light permeability. The adhesive layer may contain at least one resin selected from the group consisting of a photocurable acrylic resin, a photocurable silicone resin, and an epoxy resin.

[0011] In the first and second liquid-containing combined containers according to an embodiment of the present disclosure, the barrier container may contain at least one of acrylic resin and polyethylene terephthalate resin.

[0012] In the first and second liquid-containing combined containers according to an embodiment of the present disclosure, the barrier container may have flexibility that can be deformed so as to contact the outer surface of the container at the position where the fluorescent material is installed.

[0013] The third liquid-containing combined container according to an embodiment of the present disclosure includes a container that stores a liquid and has oxygen permeability, a barrier container that houses the container and has oxygen barrier properties, and at least one oxygen reactant that can react with oxygen in the barrier container. The oxygen reagent is fixed to at least one of the outer surface of the container and the inner surface of the barrier container. The container has a first position and a second position of the containment portion that are away from the contact area that comes into contact with the liquid, The oxygen reagent is spaced apart from the straight line connecting the first position and the second position. The container has light transmittance at least at the first and second positions, The barrier container is light-transmitting at least at positions that intersect the straight line connecting the first position and the second position.

[0014] A fourth liquid-filled combination container according to one embodiment of the present disclosure is A container that holds liquid in its compartment and is oxygen-permeable, A barrier container that houses the aforementioned container and has oxygen barrier properties, The barrier container comprises at least one oxygen reagent capable of reacting with oxygen in the barrier container, The container has a first position and a second position of the containment portion that are away from the contact area that comes into contact with the liquid, The oxygen reagent is spaced apart from the straight line connecting the first position and the second position. The container has light transmittance at least at the first and second positions, The barrier container has light transmittance at least at a position intersecting the straight line connecting the first position and the second position. A portion of the barrier container is partitioned to contain the oxygen reagent, The oxygen reagent is housed in the oxygen reagent housing, thereby positioning itself at a location separated from the straight line connecting the first position and the second position.

[0015] In a third and fourth liquid-filled combination container according to one embodiment of the present disclosure, the barrier container may be in contact with the outer surfaces of the first and second positions of the container.

[0016] A third and fourth liquid-filled combination container according to one embodiment of the present disclosure further comprises an outer container for housing the barrier container, The outer container may have a light-transmitting portion that intersects the straight line connecting the first position and the second position and allows light to pass through.

[0017] In a first to fourth liquid-containing combination container according to one embodiment of the present disclosure, the container may be fixed to the barrier container.

[0018] In one embodiment of the present disclosure, the positional relationship between the container and the oxygen reagent may be defined in the first to fourth liquid-containing combination containers.

[0019] In a first to fourth liquid-filled combination container according to one embodiment of the present disclosure, the container comprises a container body having an opening and a stopper for closing the opening, The stopper has oxygen permeability. The stopper includes a first surface facing the container body and a second surface located on the opposite side of the first surface. The oxygen reactant may be located on the second side of the stopper.

[0020] A fifth liquid-filled combination container according to one embodiment of the present disclosure is A container that holds liquid in its compartment and is oxygen-permeable, A barrier container that houses the aforementioned container and has oxygen barrier properties, At least one oxygen reagent capable of reacting with oxygen in the barrier container, A fluorescent material having different fluorescence duration or fluorescence intensity depending on the ambient oxygen concentration, The fluorescent material is provided on the inner surface of the container's housing portion at a location where the fluorescent material is installed, away from the contact area that comes into contact with the liquid. The container has light transmittance at least at the location where the fluorescent material is installed. The barrier container has light-transmitting positions that are light-transmitting, The oxygen reagent is held in a holding space formed between a part of the outer surface of the container and a part of the inner surface of the barrier container. The holding space is not located between the fluorescent material installation position and the light transmission position.

[0021] A sixth liquid-filled combination container according to one embodiment of the present disclosure is: A container that holds liquid in its compartment and is oxygen-permeable, A barrier container that houses the aforementioned container and has oxygen barrier properties, The barrier container comprises at least one oxygen reagent capable of reacting with oxygen in the barrier container, The container has a first position and a second position of the containment portion that are away from the contact area that comes into contact with the liquid, The container has light transmittance at least at the first and second positions, The barrier container has light transmittance at least at a position intersecting the straight line connecting the first position and the second position. The oxygen reagent is held in a holding space formed between a part of the outer surface of the container and a part of the inner surface of the barrier container. The straight line connecting the first position and the second position does not pass through the holding space.

[0022] A sixth liquid-containing combination container according to one embodiment of the present disclosure, the container comprises a container body having an opening and a lid portion including a stopper for closing the opening, The container body comprises a head that forms the opening, a neck connected to the head, a body having a greater width than the neck in a direction perpendicular to the axial direction in which the axis of the container extends, and shoulders connecting the neck and the body. The first position and the second position may be located on the neck portion.

[0023] A sixth liquid-filled combination container according to one embodiment of the present disclosure, wherein the container has a third and fourth position that is separate from the contact area in contact with the liquid and is different from the first and second positions of the containment portion, The container has light transmittance at least at the third and fourth positions, The barrier container may be light-transmitting at least at positions that intersect the straight line connecting the third position and the fourth position.

[0024] In a sixth liquid-filled combination container according to one embodiment of the present disclosure, the length of the line segment located within the container on the straight line connecting the first position and the second position is equal to the length of the line segment located within the container on the straight line connecting the third position and the fourth position. The sum of the lengths of the line segments located in the space between the container and the barrier container on the straight line connecting the first position and the second position may be equal to the sum of the lengths of the line segments located in the space between the container and the barrier container on the straight line connecting the third position and the fourth position.

[0025] In a sixth liquid-filled combination container according to one embodiment of the present disclosure, the barrier container is in contact with the container in a first contact region that is continuous in the circumferential direction and encircles the axis of the container, and in a second contact region that is continuous in the circumferential direction and faces the first contact region across the axis. The first position and the third position are located on the first contact area, The second and fourth positions may be located on the second contact area.

[0026] In a sixth liquid-filled combination container according to one embodiment of the present disclosure, on a virtual plane perpendicular to the axis and passing through the first contact region and the second contact region, The angle formed by the straight line connecting one end of the first contact region in the circumferential direction to the axis and the straight line connecting the other end of the first contact region in the circumferential direction to the axis is 120° or more. The angle between the straight line connecting one end of the second contact region in the circumferential direction to the axis and the straight line connecting the other end of the second contact region in the circumferential direction to the axis may be 120° or more.

[0027] A sixth liquid-containing combination container according to one embodiment of the present disclosure, the container comprises a container body having an opening and a lid portion including a stopper for closing the opening, The barrier container may be a bag that houses the container between the first film and the second film, comprising a first film constituting the first surface of the barrier container, a second film constituting the second surface of the barrier container facing the first surface, and a sealing portion that joins the first film and the second film in at least a portion of the first film and the second film.

[0028] In a sixth liquid-filled combination container according to one embodiment of the present disclosure, the sealing portion may join the first film and the second film over the entire circumference in the in-plane direction of the first film and the second film.

[0029] In a sixth liquid-filled combination container according to one embodiment of the present disclosure, the sealing portion has a first lateral sealing portion and a second lateral sealing portion that face each other in a direction perpendicular to the axial direction in which the axis of the container extends, The length obtained by subtracting 1 / 4 of the total circumference of the container in the circumferential direction around the axis from the distance between the first lateral seal portion and the second lateral seal portion, and then multiplying by 0.8, may be smaller than the maximum width in the direction perpendicular to the thickness direction of the oxygen reagent.

[0030] In a sixth liquid-containing combination container according to one embodiment of the present disclosure, the distance between the first film and the lid and the distance between the second film and the lid may be smaller than the width of the oxygen reagent in the thickness direction.

[0031] A sixth liquid-filled combination container according to one embodiment of the present disclosure, the container body comprises a head that forms the opening, a neck connected to the head, a body having a width greater than the neck in a direction perpendicular to the axial direction in which the axis of the container extends, and a shoulder connecting the neck and the body, The distance between the first film and the shoulder portion and the distance between the second film and the shoulder portion may be smaller than the width of the oxygen reactant in the thickness direction.

[0032] In a sixth liquid-filled combination container according to one embodiment of the present disclosure, the barrier container has a first contact region and a second contact region in which portions not joined by the sealing portion joining the first film and the second film are in close contact with each other. The first contact region and the second contact region may be formed at positions that sandwich the container in a direction perpendicular to the axial direction in which the container's axis extends.

[0033] In a sixth liquid-filled combination container according to one embodiment of the present disclosure, at least a portion of the first and second contact regions may overlap with a portion of the oxygen reagent in the axial direction.

[0034] In the first to sixth liquid-filled combination containers according to one embodiment of the present disclosure, the oxygen reactant may be an oxygen absorber that absorbs oxygen in the barrier container, or an oxygen sensing material that detects the oxygen state in the barrier container.

[0035] A first inspection method according to one embodiment of the present disclosure is: A method for testing the oxygen concentration inside a liquid-containing combination container as described above, A fluorescence measurement step involves irradiating the fluorescent material with light that causes the fluorescent material to fluoresce, passing it through the light transmission position of the barrier container and the fluorescent material installation position of the container, and measuring the fluorescence time or fluorescence intensity of the fluorescent material. The method includes a measurement step of measuring the oxygen concentration in the container based on the fluorescence time or fluorescence intensity of the fluorescent material measured in the fluorescence measurement step.

[0036] In a first inspection method according to one embodiment of the present disclosure, the barrier container is in contact with the outer surface of the fluorescent material placement position of the container, In the fluorescence measurement step, the fluorescence time or fluorescence intensity of the fluorescent material may be measured by irradiating the fluorescent material with light that causes the fluorescent material to fluoresce, passing through the portion of the container that is in contact with the fluorescent material installation position and the portion of the barrier container that is in contact with the fluorescent material installation position.

[0037] In a first inspection method according to one embodiment of the present disclosure, in the fluorescence measurement step, a detection device having an illumination unit that emits light to cause the fluorescent material to fluoresce and a sensor unit that measures the fluorescence time or fluorescence intensity of the fluorescent material may be brought into contact with a portion of the barrier container that contacts the fluorescent material installation position, the fluorescent material may be irradiated with light to cause the fluorescent material to fluoresce using the illumination unit, and the fluorescence time or fluorescence intensity of the fluorescent material may be measured using the sensor unit.

[0038] In a first inspection method according to one embodiment of the present disclosure, the barrier container has flexibility that allows it to be deformed to contact the outer surface of the container where the fluorescent material is installed. The method may further include the step of bringing the detection device into contact with the barrier container and pressing the barrier container with the detection device to bring it into contact with the outer surface of the container where the fluorescent material is installed.

[0039] A second inspection method according to one embodiment of the present disclosure is: A method for testing the oxygen concentration inside a liquid-containing combination container as described above, A step of measuring the attenuation rate of the laser light or LED light, which has a wavelength attenuated according to the oxygen concentration in the optical path, is irradiated onto the liquid-filled combination container so as to pass through the light-transmitting position of the barrier container and the first and second positions of the container, and the attenuation rate of the laser light or LED light is measured. The method includes a measurement step of measuring the oxygen concentration inside the container based on the attenuation rate measured in the attenuation rate measurement step.

[0040] In a second inspection method according to one embodiment of the present disclosure, in the attenuation rate measurement step, the laser light or LED light may be irradiated onto the liquid-filled combination container so as to penetrate the first and second positions of the container, while the barrier container is in contact with the outer surfaces of the first and second positions of the container.

[0041] A second inspection method according to one embodiment of the present disclosure may further comprise the step of bringing the barrier container into contact with the outer surfaces of the first and second positions of the container.

[0042] In a second inspection method according to one embodiment of the present disclosure, the wavelength of the laser light or the LED light may include a wavelength of 760 nm.

[0043] A second inspection method according to one embodiment of the present disclosure comprises a first standard sample measurement step of irradiating a first standard sample, which includes a container containing air inside and a barrier container containing the container, with laser light or LED light so as to pass through the inside of the container, and measuring the attenuation rate of the laser light or LED light; The second standard sample comprises a container in which the internal oxygen concentration is lower than that of air and the internal oxygen concentration is specified, and a barrier container containing the container, and the laser light or LED light is irradiated onto the container so as to pass through the inside of the container, and the attenuation rate of the laser light or LED light is measured. The measurement step includes a step of calculating the oxygen concentration inside the liquid-filled combination container from the decay rate measured in the decay rate measurement step, based on the relationship between the decay rate measured in the first standard sample measurement step and the oxygen concentration inside the container in the first standard sample, and the relationship between the decay rate measured in the second standard sample measurement step and the oxygen concentration inside the container in the second standard sample.

[0044] In a second inspection method according to one embodiment of the present disclosure, in the first standard sample measurement step, the barrier container, the light source for irradiating the liquid-containing combination container with the laser light or the LED light, and the measuring instrument for measuring the attenuation rate of the laser light or the LED light are arranged relative to the container of the first standard sample, similar to the arrangement of the barrier container, the light source for irradiating the laser light or the LED light relative to the container in the attenuation rate measurement step, and the first standard sample is irradiated with the laser light or the LED light. In the second standard sample measurement step, the barrier container, light source, and measuring instrument of the second standard sample may be positioned relative to the container of the second standard sample in the same manner as when the laser light or LED light is irradiated onto the liquid-containing combination container in the attenuation rate measurement step, and the laser light or LED light may be irradiated onto the second standard sample.

[0045] A third inspection method according to one embodiment of the present disclosure is a method for inspecting a liquid-filled combination container comprising: a container having oxygen permeability and containing a liquid in its containment section; a barrier container having oxygen barrier properties and containing the said container; at least one oxygen reagent capable of reacting with oxygen in the barrier container; and a fluorescent material having different fluorescence time or fluorescence intensity depending on the ambient oxygen concentration. The fluorescent material is provided on the inner surface of the container's housing portion at a location where the fluorescent material is installed, away from the contact area that comes into contact with the liquid. The container has light transmittance at least at the location where the fluorescent material is installed. The barrier container has light-transmitting positions that are light-transmitting, The arrangement step involves arranging the oxygen reagent so that it is not located between the fluorescent material installation position and the light transmission position. A fluorescence measurement step involves irradiating the fluorescent material with light that causes the fluorescent material to fluoresce, passing it through the light transmission position of the barrier container and the fluorescent material installation position of the container, and measuring the fluorescence time or fluorescence intensity of the fluorescent material. The method includes a measurement step of measuring the oxygen concentration in the container based on the fluorescence time or fluorescence intensity of the fluorescent material measured in the fluorescence measurement step.

[0046] A fourth inspection method according to one embodiment of the present disclosure is a method for inspecting a liquid-containing combination container comprising: a container having an oxygen permeable capacity for containing a liquid in its containment section; a barrier container having oxygen barrier properties for containing the container; and at least one oxygen reagent capable of reacting with oxygen in the barrier container, The container has a first position and a second position of the containment portion that are away from the contact area that comes into contact with the liquid, The container has light transmittance at least at the first and second positions, The barrier container has light transmittance at least at a position intersecting the straight line connecting the first position and the second position. The arrangement step involves arranging the oxygen reactant at a position spaced apart from the straight line connecting the first position and the second position, A step of measuring the attenuation rate of the laser light or LED light, which has a wavelength attenuated according to the oxygen concentration in the optical path, is irradiated onto the liquid-filled combination container so as to pass through the light-transmitting position of the barrier container and the first and second positions of the container, and the attenuation rate of the laser light or LED light is measured. The method includes a measurement step of measuring the oxygen concentration inside the container based on the attenuation rate measured in the attenuation rate measurement step.

[0047] In a fourth inspection method according to one embodiment of the present disclosure, the container has a third and fourth position that is separate from the contact area in contact with the liquid and is different from the first and second positions of the containment portion, The container has light transmittance at least at the third and fourth positions, The barrier container has light transmittance at least at a position intersecting the straight line connecting the third position and the fourth position, An additional placement step is to place the oxygen reactant at a position spaced apart from the straight line connecting the third position and the fourth position, An additional attenuation rate measurement step is performed by irradiating the liquid-filled combination container with laser light or LED light of a wavelength attenuated according to the oxygen concentration in the optical path, such that the light passes through the light-transmitting position of the barrier container and the third and fourth positions of the container, and measuring the attenuation rate of the laser light or LED light. An additional measurement step, which measures the oxygen concentration in the container based on the decay rate measured in the additional decay rate measurement step, The system may also include an average value calculation step, which calculates the average value of the oxygen concentration in the container from a plurality of measured oxygen concentrations, including at least the oxygen concentration measured in the measurement step and the oxygen concentration measured in the additional measurement step.

[0048] In a fourth inspection method according to one embodiment of the present disclosure, the length of the line segment located within the container on the straight line connecting the first position and the second position is equal to the length of the line segment located within the container on the straight line connecting the third position and the fourth position. The sum of the lengths of the line segments located in the space between the container and the barrier container on the straight line connecting the first position and the second position may be equal to the sum of the lengths of the line segments located in the space between the container and the barrier container on the straight line connecting the third position and the fourth position.

[0049] A fourth inspection method according to one embodiment of the present disclosure further comprises a contact step of bringing the barrier container into contact with the outer surface of the container, In the contact step, the barrier container is brought into contact with the container in a first contact region that is continuous in the circumferential direction and encircles the axis of the container, and a second contact region that is continuous in the circumferential direction and faces the first contact region across the axis. The first position and the third position are located on the first contact area, The second and fourth positions may be located on the second contact area.

[0050] In a fourth inspection method according to one embodiment of the present disclosure, on a virtual plane perpendicular to the axis and passing through the first contact region and the second contact region, The angle formed by the straight line connecting one end of the first contact region in the circumferential direction to the axis and the straight line connecting the other end of the first contact region in the circumferential direction to the axis is 120° or more. The angle between the straight line connecting one end of the second contact region in the circumferential direction to the axis and the straight line connecting the other end of the second contact region in the circumferential direction to the axis may be 120° or more.

[0051] In a fourth inspection method according to one embodiment of the present disclosure, the barrier container is a bag that houses the container between the first film and the second film, comprising: a first film constituting a first surface of the barrier container; a second film constituting a second surface of the barrier container facing the first surface; and a sealing portion that joins the first film and the second film in at least a portion of the first film and the second film. The process further comprises a contact step of bringing the barrier container into contact with the outer surfaces of the first and second positions of the container, In the contact step, the barrier container may be brought into contact with the outer surfaces of the first and second positions of the container by pulling the first tensile region of the barrier container, which does not overlap with the container in a plan view from the thickness direction of the first film, and the second tensile region, which faces the first tensile region with the container in between in a plan view from the thickness direction of the first film, so as to move away from each other.

[0052] A fourth inspection method according to one embodiment of the present disclosure further comprises a contact step of bringing the barrier container into contact with the outer surfaces of the first and second positions of the container, In the contact step, the barrier container may be brought into contact with the outer surfaces of the first and second positions of the container by a pressing member that pushes the barrier container from the outside and brings it into contact with the outer surface of the container.

[0053] In a fourth inspection method according to one embodiment of the present disclosure, the container comprises a container body having an opening and a lid portion including a stopper for closing the opening, The container body comprises a head that forms the opening, a neck connected to the head, a body having a greater width than the neck in a direction perpendicular to the axial direction in which the axis of the container extends, and shoulders connecting the neck and the body. The first position and the second position may be located on the neck portion.

[0054] A fourth inspection method according to one embodiment of the present disclosure, comprising an acquisition step of measuring the oxygen concentration in the container by the inspection method described above at a first time and a second time after the first time, to obtain a first oxygen concentration which is the oxygen concentration in the container at the first time and a second oxygen concentration which is the oxygen concentration in the container at the second time, The method may include a step of determining the oxygen saturation solubility in the liquid contained in the container based on the second oxygen concentration, and determining the amount of oxygen dissolved in the liquid based on the determined oxygen saturation solubility, when the second oxygen concentration is 100 times or more the detection limit and 0.99 times or more and 1.01 times or less the first oxygen concentration, when the second oxygen concentration is above the detection limit and less than 100 times the detection limit and 0.9 times or more and 1.1 times or less the first oxygen concentration, or when the second oxygen concentration is below the detection limit and the first oxygen concentration is below the detection limit.

[0055] In a fourth inspection method according to one embodiment of the present disclosure, the acquisition step may include a step of vibrating the container at a time between the first time and the second time.

[0056] In a fourth inspection method according to one embodiment of the present disclosure, the acquisition step may include a step of determining whether the oxygen concentration in the barrier container is below a target value.

[0057] A fourth inspection method according to one embodiment of the present disclosure, comprising the steps of measuring the oxygen concentration in the container by the inspection method described above at a first measurement time and a second measurement time after the first measurement time, and obtaining the oxygen concentration in the container at the first measurement time and the oxygen concentration in the container at the second measurement time, A step of determining the oxygen saturation solubility in the liquid contained in the container at the first measurement time based on the oxygen concentration in the container at the first measurement time, and determining a first oxygen solubility amount, which is the amount of oxygen dissolved in the liquid at the first measurement time, based on the determined oxygen saturation solubility. A step of determining the oxygen saturation solubility in the liquid contained in the container at the second measurement time based on the oxygen concentration in the container at the second measurement time, and determining the second oxygen solubility amount, which is the amount of oxygen dissolved in the liquid at the second measurement time, based on the determined oxygen saturation solubility. A step of calculating the rate of decrease in the amount of oxygen dissolved in the liquid based on the first oxygen dissolution amount and the second oxygen dissolution amount, and determining whether the rate of decrease is equal to or greater than a target value, The method may also include a step of determining whether the oxygen concentration inside the barrier container is below a target value.

[0058] A method for manufacturing a first liquid-filled combination container according to one embodiment of the present disclosure is: The system includes an inspection step for inspecting combination containers containing liquids using the inspection method described above.

[0059] A seventh liquid-filled combination container according to one embodiment of the present disclosure is: A container that holds liquid in its compartment and is oxygen-permeable, A barrier container that houses the aforementioned container and has oxygen barrier properties, At least one oxygen reagent capable of reacting with oxygen in the barrier container, A fluorescent material having different fluorescence duration or fluorescence intensity depending on the ambient oxygen concentration, The oxygen reagent is fixed to at least one of the outer surface of the container and the inner surface of the barrier container. The fluorescent material is provided on the inner surface of the barrier container where the fluorescent material is installed in the barrier container. The barrier container has light transmittance at least at the location where the fluorescent material is installed in the barrier container, By allowing light to pass through the fluorescent material installation position in the barrier container, it is possible to irradiate the fluorescent material from outside the barrier container.

[0060] A fifth inspection method according to one embodiment of the present disclosure is: A method for testing the oxygen concentration of the barrier container in the liquid-containing combination container described above, A barrier container fluorescence measurement step involves irradiating the fluorescent material with light that causes the fluorescent material to fluoresce, passing it through the fluorescent material installation position in the barrier container of the barrier container, and measuring the fluorescence time or fluorescence intensity of the fluorescent material. The barrier container measurement step includes measuring the oxygen concentration inside the barrier container based on the fluorescence time or fluorescence intensity of the fluorescent material measured in the barrier container fluorescence measurement step.

[0061] An eighth liquid-filled combination container according to one embodiment of the present disclosure is A container that holds liquid in its compartment and is oxygen-permeable, A barrier container that houses the aforementioned container and has oxygen barrier properties, The barrier container comprises at least one oxygen reagent capable of reacting with oxygen in the barrier container, The oxygen reagent is fixed to at least one of the outer surface of the container and the inner surface of the barrier container. The barrier container has a first barrier container position and a second barrier container position, The oxygen reagent and the container are spaced apart from the straight line connecting the first barrier container position and the second barrier container position. The barrier container is light-transmitting at least the first and second positions of the barrier container.

[0062] A sixth inspection method according to one embodiment of the present disclosure is: A method for testing the oxygen concentration inside the barrier container of the liquid-containing combination container described above, A barrier container attenuation rate measurement step involves irradiating the liquid-filled combination container with laser light or LED light of a wavelength attenuated according to the oxygen concentration in the optical path, such that the light passes through the first and second positions of the barrier container, and measuring the attenuation rate of the laser light or LED light. The system includes a barrier container measurement step, which measures the oxygen concentration inside the barrier container based on the attenuation rate measured in the barrier container attenuation rate measurement step. [Effects of the Invention]

[0063] According to the present invention, the oxygen concentration of a container holding a liquid can be tested without opening the container. [Brief explanation of the drawing]

[0064] [Figure 1] Figure 1 is a diagram illustrating a first embodiment of the present disclosure, and is a perspective view showing an example of a liquid-filled combination container. [Figure 2] Figure 2 is a longitudinal cross-sectional view showing liquid-containing containers that may be included in the liquid-containing combination container shown in Figure 1. [Figure 3] Figure 3 is a longitudinal cross-sectional view showing a method for measuring the oxygen permeability in a portion of the container shown in Figure 2. [Figure 4] Figure 4 is a perspective view showing another example of a barrier container. [Figure 5] Figure 5 is a perspective view showing yet another example of a barrier container. [Figure 6] Figure 6 is a perspective view showing yet another example of a barrier container. [Figure 7] Figure 7 is a perspective view showing yet another example of a barrier container. [Figure 8] Figure 8 is a cross-sectional view showing the deformation of the barrier container in the liquid-filled combination container shown in Figure 1. [Figure 9] Figure 9 is a cross-sectional view showing an example of an oxygen absorber. [Figure 10] Figure 10 is a cross-sectional view showing an example of an oxygen-absorbing film containing an oxygen absorber. [Figure 11] Figure 11 illustrates an example of a manufacturing method for the liquid-filled combination container shown in Figure 1 and the liquid-filled container shown in Figure 2. [Figure 12] Figure 12 is a perspective view showing how to use the liquid-filled container shown in Figure 2. [Figure 13] Figure 13 shows an example of a method for inspecting a combination container containing liquid, as shown in Modification Example 1. [Figure 14] Figure 14 shows another example of the inspection method for liquid-containing combination containers in Modification Example 1. [Figure 15] Figure 15 is a cross-sectional view showing a modified example 2 of a combination container containing liquid. [Figure 16] Figure 16 is a cross-sectional view showing a liquid-filled combination container of Modification 3. [Figure 17] Figure 17 is a cross-sectional view showing an example of a liquid-filled combination container according to a second embodiment of the present disclosure. [Figure 18] Figure 18 is a cross-sectional view showing another example of a liquid-filled combination container according to a second embodiment of the present disclosure. [Figure 19] Figure 19 is a cross-sectional view showing a liquid-filled combination container of Modification 4. [Figure 20] Figure 20 shows an example of a method for inspecting a combination container containing liquid, as shown in Modification 5. [Figure 21] Figure 21 shows another example of the inspection method for liquid-filled combination containers in Modification Example 5. [Figure 22A] Figure 22A shows an example of a liquid-filled combination container according to Modification 6. [Figure 22B] Figure 22B shows an example of a liquid-filled combination container according to Modification 7. [Figure 22C] Figure 22C shows an example of a liquid-filled combination container according to Modification 8. [Figure 23A] Figure 23A shows an example of a barrier container according to Modification 9. [Figure 23B]Figure 23B shows an example of a liquid-filled combination container according to Modification 10. [Figure 23C] Figure 23C shows an example of a liquid-filled combination container according to Modification 10. [Figure 24] Figure 24 shows an example of a method for inspecting a combination container containing liquid according to a third embodiment of the present disclosure. [Figure 25] Figure 25 shows another example of a method for inspecting liquid-filled combination containers according to a third embodiment of the present disclosure. [Figure 26] Figure 26 is a front view showing a liquid-filled combination container according to a fourth embodiment of the present disclosure. [Figure 27] Figure 27 is a cross-sectional view showing a liquid-filled combination container according to a fourth embodiment of the present disclosure. [Figure 28] Figure 28 is a cross-sectional view showing a liquid-filled combination container according to a fourth embodiment of the present disclosure. [Figure 29] Figure 29 is a cross-sectional view showing a liquid-filled combination container according to a fourth embodiment of the present disclosure. [Figure 30] Figure 30 is a cross-sectional view showing the movement of the liquid-filled combination container shown in Figure 29 within the barrier container. [Figure 31] Figure 31 is a front view showing an example of a liquid-filled combination container according to Modification 12. [Figure 32] Figure 32 is a cross-sectional view showing another example of the liquid-filled combination container of Modification 12. [Figure 33] Figure 33 is a cross-sectional view showing an example of a liquid-filled combination container according to Modification 13. [Figure 34] Figure 34 is a cross-sectional view showing another example of the liquid-filled combination container of Modification 13. [Figure 35] Figure 35 is a cross-sectional view showing a liquid-filled combination container according to a fifth embodiment of the present disclosure. [Figure 36] Figure 36 shows an example of the contact process in the inspection method of Modification 14. [Figure 37] Figure 37 shows an example of the contact process in the inspection method of Modified Example 15. [Modes for carrying out the invention]

[0065] [First Embodiment] A first embodiment of the present invention will be described below with reference to the drawings. Note that, for the sake of illustration and ease of understanding, the scale and aspect ratios of the drawings attached to this specification have been appropriately altered and exaggerated from those of the actual objects.

[0066] Figures 1 to 12 illustrate a first embodiment of the present disclosure. The liquid-filled container 30L includes a container 30 and a liquid L contained in the container 30. The container 30 is oxygen permeable. The container 30 includes at least a portion that is oxygen permeable. The container 30 has an inner surface 30a, which is the side of the container 30 that contains the liquid L, and an outer surface 30b, which is the side opposite to the inner surface 30a. The liquid-filled combination container 10L includes the liquid-filled container 30L and a barrier container 40. The barrier container 40 has oxygen barrier properties. The barrier container 40 is capable of containing the liquid-filled container 30L. In the liquid-filled combination container 10L, the liquid-filled container 30L is contained in the barrier container 40. With this liquid-filled combination container 10L, the amount of oxygen in the barrier container 40 can be adjusted by an oxygen absorber 21 that absorbs oxygen in the barrier container 40, thereby sufficiently reducing the oxygen concentration in the container 30 in a short period of time.

[0067] Furthermore, the liquid-filled container 30L of the first embodiment is equipped with a fluorescent material 27. The fluorescent material 27 provided in the liquid-filled container 30L exhibits different fluorescence times or fluorescence intensity depending on the ambient oxygen concentration. Fluorescence time is the time from when the fluorescent material 27 begins to fluoresce upon irradiation with light until the fluorescent material 27 is extinguished. Fluorescence intensity is the intensity of fluorescence of the fluorescent material 27 when it is irradiated with light. In particular, the fluorescence intensity at the wavelength in which the fluorescent material 27 exhibits the strongest fluorescence intensity may be used as the fluorescence intensity. Specifically, the fluorescence time of the fluorescent material 27 is shorter when the ambient oxygen concentration is high, and longer when the ambient oxygen concentration is low. Also, the fluorescence intensity of the fluorescent material 27 is lower when the ambient oxygen concentration is high, and higher when the ambient oxygen concentration is low. The fluorescent material 27 is provided on the inner surface 30a of the container 30. The oxygen concentration inside the container 30 can be checked by irradiating the fluorescent material 27 with light that causes it to fluoresce and measuring the fluorescence time or fluorescence intensity of the fluorescent material 27.

[0068] Each component will be described in more detail by referring to the illustrated example. First, we will explain the 30L liquid container.

[0069] The liquid-filled container 30L includes the container 30 and the liquid L contained within the container 30. The container 30 is oxygen permeable. The container 30 can seal the liquid L. The container 30 is permeable to oxygen but impermeable to liquid L. The oxygen-permeable container 30 is an airtight container.

[0070] An airtight container is defined as a container in which no gas leakage is detected by the immersion method specified in JIS Z 2330:2012. More specifically, a container that prevents the leakage of air bubbles when immersed in water containing a gas is considered airtight. Furthermore, an airtight container is considered airtight when no air bubble leakage is observed from the container when immersed in water containing a gas. In the immersion test, the container under test is immersed to a depth of 10 cm to 30 cm below the water surface. The presence or absence of air bubbles is determined by visual observation over a 10-minute period.

[0071] The liquid L contained in container 30 is not particularly limited. Liquid L may be a solution containing a solvent and a solute dissolved in the solvent. The solvent is not particularly limited. The solvent may be water or alcohol. Liquid L is not limited to a liquid in the strict sense. Liquid L may be a suspension in which solid particles are dispersed. Liquid L as a food may be tea, coffee, black tea, soup, broth, stock, or a concentrated liquid obtained by concentrating one or more of these. Liquid L as a medicine may be an oral medicine, a topical medicine, or an injectable medicine. As something other than food or medicine, liquid L may be blood or body fluids.

[0072] Liquid L is contained in container 30. The portion of container 30 that contains liquid L is referred to as the containment section 31. The volume of liquid L contained in container 30 is smaller than the volume of container 30. Therefore, liquid L comes into contact with a portion of the containment section 31. When container 30 is in a stationary state, the area of ​​the containment section 31 that comes into contact with liquid L is referred to as the contact area 31a. The state in which container 30 is stationary includes the state in which container 30 is positioned so that the liquid level of liquid L remains stable for a predetermined time. For example, container 30 is pre-designed so that the liquid level of liquid L remains stable for a predetermined time when positioned in a specific orientation. In this case, the state in which container 30 is stationary includes the state in which container 30 is positioned in that specific orientation. For example, in Figure 1, the contact area 31a is the area of ​​the containment section 31 that comes into contact with liquid L when container 30 is in an upright position. The upright position of the container 30 refers to, for example, a state in which the container 30 is stably placed on a horizontal surface. As will be described later, if the container 30 includes a container body 32 having an opening 33, the upright position of the container 30 may also refer to a state in which the opening 33 side of the container body 32 is facing upward. The stationary position of the container 30 includes the upright position of the container 30, and also includes other positions in which the container 30 is positioned so that the liquid level of the liquid L contained in the storage section 31 is stable. For example, the stationary position of the container 30 may include a state in which the opening 33 side of the container body 32 is facing sideways, and a state in which the opening 33 side of the container body 32 is facing diagonally upward. The stationary position of the container 30 also includes a state in which the liquid level of the liquid L is stabilized by supporting the container 30 with the barrier container 40. The state in which the container 30 is left standing includes a state in which the liquid L surface is stabilized by supporting the container 30 with a component other than the barrier container 40. Specifically, the state in which the container 30 is left standing includes a state in which the liquid L surface is stabilized by supporting the container 30 with an intermediate container 50, which will be described later, and which houses the container 30 and is also housed in the barrier container 40. The state in which the container 30 is left standing includes a state in which the liquid L surface is stabilized by supporting the container 30 with an outer container 55, which will be described later, and which houses the container 30 and the barrier container 40. The state in which the container 30 is left standing includes a state in which the liquid L surface is stabilized by suspending the container 30.The space above the contact area 31a in the container 30 that comes into contact with the liquid L, and in which gas can be contained, is referred to as the headspace HS.

[0073] The inside of container 30 may be sterile. Liquid L may be a liquid that should be kept sterile. Liquid L that should be kept sterile includes highly sensitive liquids such as food and pharmaceuticals. Highly sensitive liquids L are easily degraded by post-sterilization (also called final sterilization) performed after manufacturing. Post-sterilization cannot be applied to highly sensitive liquids. Examples of post-sterilization include high-pressure steam sterilization, dry heat sterilization, radiation sterilization, ethylene oxide gas sterilization, and hydrogen peroxide gas plasma sterilization. In this specification, highly sensitive liquid L means a liquid in which 5% or more of the total weight percentage of the active ingredients contained in the liquid decomposes by post-sterilization, and one or more of the weight percentage of one or more of the active ingredients contained in the liquid decomposes by post-sterilization. Highly sensitive liquids L to which post-sterilization cannot be applied can be manufactured using a manufacturing line set up in a sterile environment. That is, highly sensitive liquids L can be manufactured by aseptic operation. Examples of highly sensitive liquids L include anticancer drugs, antiviral drugs, vaccines, and antipsychotics.

[0074] The oxygen content of liquid L produced by aseptic techniques can be adjusted by replacing the entire space where the liquid L production line is located with an inert gas. However, creating an inert gas atmosphere throughout the entire space where the liquid L production line is located would require enormous capital investment. Therefore, the oxygen content in containers containing highly sensitive liquids has been left to methods such as replacing the atmosphere inside the container with an inert gas or bubbling liquid L with an inert gas.

[0075] In contrast, according to the invention described below, by placing the liquid-filled container 30L inside the barrier container 40 and using an oxygen absorber 21 that absorbs oxygen inside the barrier container 40, the oxygen concentration inside the barrier container 40 can be sufficiently reduced. Moreover, the oxygen concentration (%) inside the container 30 can be sufficiently reduced in a short period of time, and furthermore, the amount of dissolved oxygen (mg / L) in the liquid L can be sufficiently reduced. For example, the amount of dissolved oxygen in the liquid L can be reduced to less than 0.15 mg / L, 0.04 mg / L or less, 0.03 mg / L or less, 0.02 mg / L or less, and even less than 0.015 mg / L.

[0076] Furthermore, products (liquid L) labeled as "sterilized" or "aseptic," and the inside of the containers containing such products, as well as pharmaceutical products (liquid L) and the inside of the containers containing such products, where sterility is a requirement for commercialization, fall under the definition of "aseptic state" as used herein. The sterility assurance level (SAL) specified in JIS T0806:2014 is 10. -6 The product (liquid L) that meets the criteria and the inside of the container containing the product also qualify as "sterile" as used herein. A product in which no bacteria grow after being stored at room temperature (e.g., 20°C) or higher for 4 weeks also qualify as "sterile" as used herein. A product in which no bacteria grow after being stored in a refrigerated state (e.g., 8°C or lower) for 8 weeks or more also qualify as "sterile" as used herein. A chemical in which no bacteria grow after being stored at a temperature of 28°C to 32°C for 2 weeks also qualify as "sterile" as used herein.

[0077] The container 30 is oxygen permeable. A container being oxygen permeable means that, in an atmosphere of 23°C and 40% RH humidity, oxygen can pass through the container at a predetermined oxygen permeability rate or higher, allowing it to move between the inside and outside of the container. The predetermined oxygen permeability rate is 1 × 10⁻⁶. -1It is above a certain oxygen permeation rate. The predetermined oxygen permeation rate may be 1 (mL / (day×atm)) or more, 1.2 (mL / (day×atm)) or more, or 5 (mL / (day×atm)) or more. According to the container 30 having oxygen permeability, the amount of oxygen in the container 30 can be adjusted by the oxygen permeation of the container 30.

[0078] An upper limit may be set for the oxygen permeation rate through the container 30. By setting the upper limit, leakage of water vapor and the like from the container 30 can be suppressed. By setting the upper limit, the influence on the liquid L in the container 30 due to the high gas permeation rate after the barrier container 40 is opened can be suppressed. The oxygen permeation rate through the container 30 may be 100 (mL / (day×atm)) or less, 50 (mL / (day×atm)) or less, or 10 (mL / (day×atm)) or less.

[0079] The above-mentioned arbitrary lower limit of the oxygen permeation rate may be combined with the above-mentioned arbitrary upper limit of the oxygen permeation rate to define the range of the oxygen permeation rate.

[0080] The oxygen permeation coefficient of the material constituting the oxygen-permeable part of the container 30 is 1×10 -12 (cm 3 (STP)·cm / (cm 2 ·sec·Pa)) or more, 5×10 -12 (cm 3 (STP)·cm / (cm 2 ·sec·Pa)) or more, 1×10 -11 (cm 3 (STP)·cm / (cm 2 ·sec·Pa)) or more. By providing a lower limit for the oxygen permeation coefficient, the oxygen permeation of the container 30 is promoted, and the oxygen concentration in the container 30 can be adjusted quickly. When the oxygen-permeable part includes a plurality of layers, the material constituting at least one layer may have the above-mentioned oxygen permeation coefficient, or the materials constituting all the layers may have the above-mentioned oxygen permeation coefficient.

[0081] When the object being measured is a resin film or resin sheet, the oxygen permeability coefficient is the value measured in accordance with JIS K7126-1. When the object being measured is rubber, the oxygen permeability coefficient is the value measured in accordance with JIS K6275-1. The oxygen permeability coefficient is the value measured using an OXTRAN (2 / 61) permeability meter manufactured by MOCON, Inc. of the United States, under conditions of 23°C and 40% RH.

[0082] All gases may be permeable to container 30. Only some gases, including oxygen, may be permeable to container 30. Only oxygen may be permeable to container 30.

[0083] The container 30 may have oxygen permeability if the entire container 30 is permeable to oxygen. Alternatively, the container 30 may have oxygen permeability if only a portion of it is permeable to oxygen.

[0084] As shown in Figure 2, the container 30 may include a container body 32 and a stopper 34. The container body 32 has an opening 33. The stopper 34 is held in the opening 33. As shown in Figure 2, the stopper 34 includes a first surface 34e facing the container body 32 and a second surface 34f located on the opposite side of the first surface 34e. The stopper 34 contacts the opening 33 at the first surface 34e. The stopper 34 closes the opening 33. In this way, the stopper 34 prevents leakage of liquid L from the opening 33. In this example, the stopper 34 may be oxygen permeable. If the oxygen permeable portion of the container 30 is not in contact with the liquid L, oxygen permeation through that portion can be promoted. In the normal state (with the container 30 upright), the stopper 34 of the container 30 including the container body 32 and the stopper 34 is separated from the liquid L contained in the container body 32. In other words, under normal storage conditions for the container 30, oxygen permeation through the stopper 34 of the container 30 can be promoted. In this respect, by imparting oxygen permeability to the stopper 34, the amount of oxygen inside the container 30 can be quickly adjusted.

[0085] The oxygen-permeable stopper 34 has the above-mentioned oxygen permeability coefficient (cm 3 (STP)·cm / (cm2 It may be formed from a material having an oxygen permeability coefficient of 0.5 sec·Pa. The oxygen permeability coefficient of the material constituting the stopper 34 may be greater than that of the material constituting the container body 32. A portion of the stopper 34 may be oxygen permeable. A portion of the stopper 34 may be oxygen permeable throughout its entire thickness. The stopper 34 may be oxygen permeable throughout its entire thickness in the central portion away from the periphery, and have oxygen barrier properties in the peripheral portion surrounding the central portion.

[0086] For example, the configuration of the oxygen-permeable portion of the container 30 may be determined such that storing a container 30 containing a liquid with an oxygen solubility of 8 mg / L in a barrier container 40 for four weeks can reduce the oxygen concentration (%) inside the container 30 by 5% or more.

[0087] In the illustrated example, the area of ​​the opening 33, i.e., the opening area of ​​the container body 32, is 1 mm². 2 Anything above that is also acceptable, 10mm 2 Anything above that is also acceptable, 30mm 2 The above is also acceptable. The thickness of the stopper 34 may be 3 mm or less, or 1 mm or less. These allow for increased oxygen permeability in the container 30, enabling rapid adjustment of the oxygen concentration inside the container 30. The syringe needle can be punctured into the stopper 34. Furthermore, from the viewpoint of enabling puncture of a straw, the thickness of the stopper, for example, the thickness of a film-like stopper, may be 0.something mm or less.

[0088] The area of ​​opening 33 is 5000 mm². 2 The following are also acceptable. The thickness of the stopper 34 may be 0.01 mm or more. These measures can suppress leakage of water vapor and the like, and suppress the impact on the liquid inside the container 30 after opening the barrier container 40, which is caused by the high oxygen permeability rate. The range of the opening area may be defined by combining the upper limit of the opening area with any lower limit of the opening area as described above. The range of the thickness of the stopper 34 may be defined by combining the lower limit of the thickness of the stopper 34 with any upper limit of the thickness of the stopper 34 as described above.

[0089] The oxygen-permeable stopper 34 is not particularly limited and may have various configurations. In the example shown in Figure 2, the stopper 34 is inserted into the opening 33 of the container body 32 to close the opening 33. The stopper 34 shown in Figure 2 includes a plate-shaped plate portion 34a and a cylindrical portion 34b extending from the plate-shaped portion 34a. The cylindrical portion 34b is, for example, cylindrical. The cylindrical portion 34b is inserted into the opening 33. The plate-shaped portion 34a includes a flange portion extending radially outward from the cylindrical portion 34b. The flange portion of the plate-shaped portion 34a rests on the head 32d of the container body 32. As another example, the stopper 34 may have an external or internal helix. The stopper 34 may be attached to the container body 32 by the interlocking of the helices.

[0090] The stopper 34 may contain silicone. The stopper 34 may be formed solely of silicone. A portion of the stopper 34 may be formed of silicone. The silicone contained in the stopper 34 is solid under the conditions in which the container 30 is intended to be used. The silicone contained in the stopper 34 does not need to contain silicone that is liquid at room temperature, such as silicone oil. Silicone is a substance whose main chain consists of siloxane bonds. The stopper 34 may be formed of a silicone elastomer. The stopper 34 may be formed of silicone rubber.

[0091] Silicone rubber refers to a rubber-like substance made of silicone. It is a synthetic resin primarily composed of silicone, and is a rubber-like substance. Silicone rubber is a rubber-like substance with siloxane bonds as its main chain. Silicone rubber may also be a thermosetting compound containing siloxane bonds. Examples of silicone rubber include methyl silicone rubber, vinyl-methyl silicone rubber, phenyl-methyl silicone rubber, dimethyl silicone rubber, and fluorosilicone rubber.

[0092] The oxygen permeability coefficient of silicone and the oxygen permeability coefficient of silicone rubber are 1 × 10⁻⁶. -12 (cm 3 (STP)·cm / (cm 2 It is also acceptable if it is greater than 1 × 10 -11 (cm3 (STP)·cm / (cm 2 It is also acceptable if it is greater than (·sec·Pa). The oxygen permeability coefficient of silicone and the oxygen permeability coefficient of silicone rubber are 1 × 10 -9 (cm 3 (STP)·cm / (cm 2 It may also be less than (·sec·Pa). Silicone and silicone rubber have a hydrogen permeability coefficient about 10 times higher, an oxygen permeability coefficient about 20 times higher, and a nitrogen permeability coefficient about 30 times higher than natural rubber. Silicone and silicone rubber have a hydrogen permeability coefficient of 70 times or more higher, an oxygen permeability coefficient of 40 times or more higher, and a nitrogen permeability coefficient of 650 times or more higher than butyl rubber.

[0093] The stopper 34 may be made of silicone in at least a portion of it. That is, the whole or a portion of the stopper 34 may be made of silicone or silicone rubber. For example, a portion of the stopper 34 may be made of silicone or silicone rubber over its entire thickness. This portion may be the central part of the stopper 34, or a part or all of the peripheral portion surrounding the central part.

[0094] As shown in Figure 2, the container body 32 may include a bottom 32a, a body 32b, a neck 32c, and a head 32d in that order. The bottom 32a and body 32b may form a liquid L storage section 31. The head 32d forms the tip of the container body 32. The head 32d is thicker than the other parts. The neck 32c is located between the body 32b and the head 32d. The neck 32c is narrower in width, and especially narrower in diameter, than the body 32b and the head 32d.

[0095] The container body 32 may be transparent so that the contained liquid L can be observed from the outside. In other words, the container body 32 may be light-transmitting. Here, being transparent and having light transmittance means that the transmittance at a specific wavelength is 10% or more, preferably 20% or more, and more preferably 50% or more. In the first embodiment, the above-mentioned specific wavelength is the wavelength of light that excites the fluorescent material 27 and the wavelength of fluorescence emitted by the fluorescent material 27. For example, when the fluorescent material 27 is excited by blue LED light and emits fluorescence at a wavelength of 500 nm to 600 nm, the above-mentioned specific wavelength is a wavelength around 450 nm and a wavelength of 500 nm to 600 nm. Furthermore, as in the inspection method for the liquid-filled combination container 10L described in the second embodiment later, when laser light or LED light of a wavelength attenuated according to the oxygen concentration in the optical path is irradiated through the container 30 so as to pass through it, the attenuation rate of the laser light or LED light is measured, and the oxygen concentration in the container 30 is measured based on the measured attenuation rate, the above-mentioned specific wavelength is the wavelength attenuated according to the oxygen concentration. The wavelength attenuated according to the oxygen concentration is, for example, 760 nm. Note that the inspection method for the liquid-filled combination container 10L described in the second embodiment later can also be adapted to measure the concentration of other gases such as carbon dioxide and water vapor in the container 30. In addition, the transparent members and parts of the members, and the light-transmitting members and parts of the members referred to herein, may have a haze (JIS K7136:2000) of 50% or less, preferably 30% or less, more preferably 10% or less, and even more preferably 5% or less.

[0096] As shown in Figure 2, the container 30 may further include a fastener 36. The fastener 36 prevents the stopper 34 from coming off the container body 32. The fastener 36 is attached to the head 32d of the container body 32. As shown in Figures 1 and 2, the fastener 36 covers the periphery of the plate-shaped portion 34a of the stopper 34. The fastener 36 presses the flange portion of the plate-shaped portion 34a against the head 32d. The fastener 36 prevents the stopper 34 from coming off the container body 32 while partially exposing the stopper 34. The fastener 36 makes the space between the stopper 34 and the container body 32 liquid-tight and airtight. The fastener 36 makes the container 30 airtight. The fastener 36 may be a sheet of metal that can be fixed to the head 32d. The fastener 36 may be a cap that is screwed onto the head 32d.

[0097] In the illustrated example, the oxygen permeability coefficient of the material constituting the container body 32 may be smaller than that of the material constituting the stopper 34. The container body 32 may have oxygen barrier properties. That is, the container 30 may have oxygen permeability in only a part of it. The oxygen permeability coefficient of the material constituting the oxygen barrier portion is 1 × 10⁻⁶. -13 (cm 3 (STP)·cm / (cm 2 It is also acceptable to have values ​​less than or equal to 1 × 10⁻⁶ sec·Pa. -17 (cm 3 (STP)·cm / (cm 2 It is also acceptable to use values ​​below (sec·Pa).

[0098] Here, the container 30 may contain at least one of the materials of glass and cyclic olefin polymer. For example, the container body 32 of the container 30 may contain at least one of the materials of glass and cyclic olefin polymer. The cyclic olefin polymer contained in the container 30 may be a cyclic olefin copolymer. An example of a container body 32 that has oxygen barrier properties and contains glass is a glass bottle. An example of a container body 32 that has oxygen barrier properties and contains cyclic olefin polymer is a container body 32 made using a resin sheet or resin plate containing cyclic olefin polymer. In this example, the resin sheet or resin plate may consist of a layer having cyclic olefin polymer. The container body 32 may also contain a laminate containing a metal vapor-deposited film. A container body 32 using a laminate or glass can be given transparency as well as oxygen barrier properties. When the container 30 or container body 32 is transparent, the liquid L contained inside can be seen from the outside of the container 30.

[0099] The container 30 may have a coating layer 38 that constitutes the inner surface 30a of the container 30. In the example shown in Figure 2, the container body 32 of the container 30 has a base layer 37 and a coating layer 38. The coating layer 38 constitutes the inner surface 30a of the container 30 and suppresses the adhesion of liquid L to the inner surface 30a of the container 30. In the first embodiment, the coating layer 38 constitutes the inner surface 30a of the container 30, at least the fluorescent material installation position 39 which will be described later. As an example, the coating layer 38 constitutes the portion of the inner surface 30a of the container 30 that is made up of the container body 32 and that partitions the headspace HS. In the example shown in Figure 2, the coating layer 38 constitutes the entire portion of the inner surface 30a of the container 30 that is made up of the container body 32.

[0100] A portion of a container being oxygen-permeable means that, in an atmosphere of 23°C and 40% RH humidity, oxygen can pass through that portion of the container at a predetermined oxygen permeability rate or higher, allowing it to move between the inside and outside of the container. The predetermined oxygen permeability rate is 1 × 10⁻⁶. -1The oxygen permeability is (mL / (day×atm)) or higher. The predetermined oxygen permeability may be 1 (mL / (day×atm)) or higher, 1.2 (mL / (day×atm)) or higher, or 3 (mL / (day×atm)) or higher. The amount of oxygen in the container 30 can also be adjusted by making a portion of the container 30 oxygen permeable.

[0101] The predetermined oxygen permeability may be 100 mL / (day × atm) or less, 50 mL / (day × atm) or less, or 10 mL / (day × atm) or less. By setting an upper limit on the oxygen permeability, leakage of water vapor, etc., can be suppressed, and the impact on the liquid inside the container 30 after opening the barrier container 40, which is caused by a high oxygen permeability rate, can be suppressed. The range of oxygen permeability may be determined by combining the above-mentioned arbitrary lower limit of oxygen permeability with the above-mentioned arbitrary upper limit of oxygen permeability.

[0102] The oxygen permeability (mL / (day×atm)) through a portion of a container can be measured using a test container 70 containing that portion, as shown in Figure 3. The test container 70 includes a partition wall 71. The test container 70 has an internal space partitioned by the partition wall 71. The partition wall 71 includes a portion of the container and a main wall 72 that has oxygen barrier properties. The permeability through the portion of the container is specified as the oxygen permeability (mL / (day×atm)) of the test container 70.

[0103] The oxygen concentration in the test container 70 is maintained at, for example, 0.05% or less. The test container 70 is connected to a first channel 76 and a second channel 77. The second channel 77 is connected to an oxygen meter 79 that measures the amount of oxygen. The oxygen meter 79 can measure the amount of oxygen (mL) flowing through the second channel 77. The oxygen meter 79 can be the oxygen meter used in OXTRAN (2 / 61) manufactured by MOCON, Inc. of the United States. The first channel 76 supplies gas into the test container 70. The first channel 76 may supply an oxygen-free gas. The first channel 76 may supply an inert gas. The first channel 76 may supply nitrogen. The second channel 77 discharges the gas from the test container 70. The first channel 76 and the second channel 77 maintain a state in which the test container 70 is substantially free of oxygen. The oxygen concentration in the test container 70 may be maintained at 0.05% or less, at less than 0.03%, or at 0%.

[0104] The test container 70 is placed in a test atmosphere with a temperature of 23°C and a humidity of 40%RH. The oxygen concentration in the atmosphere in which the test container 70 is placed is higher than the oxygen concentration inside the test container 70. The test atmosphere may also be an air atmosphere. The oxygen concentration in an air atmosphere is 20.95%. When the test container 70 is placed in the test atmosphere, oxygen moves from the test atmosphere into the test container 70 by permeating a portion 30X of the container. The gas inside the test container 70 is discharged from the second channel 77. By measuring the amount of oxygen flowing through the second channel 77 with an oxygen meter 79, the daily oxygen permeation rate (mL / (day×atm)) permeating a portion 30X in an atmosphere with a temperature of 23°C and a humidity of 40%RH can be measured.

[0105] In the illustrated example, the test container 70 is placed inside the test chamber 78. The atmosphere inside the test chamber 78 is maintained at a temperature of 23°C and a humidity of 40%RH. Air is supplied into the test chamber 78 from a supply channel 78A. The gas inside the test chamber 78 is discharged from a discharge channel 78B. The supply channel 78A and the discharge channel 78B circulate the air, maintaining the oxygen concentration inside the test chamber 78 at 20.95%.

[0106] In the example shown in Figure 3, a pump for circulating air may be provided in either the supply passage 78A or the discharge passage 78B. In the example shown in Figure 3, the supply passage 78A and the discharge passage 78B may be open to an air atmosphere at atmospheric pressure. Furthermore, the test container 70 does not have to be placed inside the test chamber 78. The test chamber 78 may be omitted, and the test container 70 may be placed in an air atmosphere at atmospheric pressure.

[0107] Figure 3 shows a method for measuring oxygen permeability, using an oxygen-permeable portion 30X of a container 30 as an example. In the example shown in Figure 3, the partition wall 71 is composed of the oxygen-permeable portion 30X of the container 30 and a main wall 72 having oxygen barrier properties. For example, the partition wall 71 may be composed of the portion 30X cut out from the container 30 and a main wall 72 connected to the peripheral edge of the portion 30X. This main wall 72 has a through hole 72A that exposes the portion 30X. The portion around the through hole 72A and the portion 30Y adjacent to the portion 30X may be airtightly joined. In the illustrated example, the portion 30Y adjacent to the portion 30X is airtightly joined to the portion around the through hole 72A of the main wall 72 via a barrier bonding material 73. In the example shown in Figure 3, the portion of the container 30 near the stopper 34 shown in Figure 2 has been cut off. In this example, the stopper 34 is an oxygen-permeable portion 30X. The portions 32c and 32d that form the opening 33 of the container body 32 and the fastener 36 are airtightly connected to the main wall portion 72 via a barrier bonding material 73 as portions 30Y adjacent to the oxygen-permeable portion 30X.

[0108] In the example shown in Figure 3, the container body 32 is cut at the neck portion 32c. The stopper 34 is compressed and held within the opening 33 formed by the head portion 32d of the container body 32. The container body 32 and the stopper 34 are airtight due to the fastener 36. The fastener 36, which has oxygen barrier properties such as aluminum, partially covers the stopper 34. The oxygen barrier properties of the container body 32 and the fastener 36 are connected to the main wall portion 72 via a barrier bonding material 73. The stopper 34 is maintained in a state similar to that when the container 30 is closed during actual use, due to compression within the opening 33 and tightening by the fastener 36. Therefore, the amount of oxygen permeation through the stopper 34 can be measured under the same conditions as during actual use.

[0109] The above describes a method for measuring the oxygen permeability (mL / (day×atm)) through a portion of a container. The oxygen permeability (mL / (day×atm)) through the entire container can be determined by dividing the container into two or more parts and adding up the oxygen permeability measured for each part. For example, the oxygen permeability of the container 30 shown in Figure 2 can be determined by measuring the oxygen permeability of the container body 32 and adding up the oxygen permeability of the container body 32 with the oxygen permeability of a portion 30X measured by the method shown in Figure 3. The oxygen permeability (mL / (day×atm)) of the container body 32 can be measured using a test container 70 made by combining the container body 32 with the main wall portion 72.

[0110] The volume of container 30 may be, for example, 1 mL or more and 1100 mL or less, 3 mL or more and 700 mL or less, or 5 mL or more and 200 mL or less.

[0111] In the illustrated example, the container body 32 is a glass bottle. That is, the base layer 37 of the container body 32 is made of glass. The base layer 37 of the container body 32 is formed of, for example, borosilicate glass. This container 30 may also be a vial bottle. A vial bottle is a container 30 that includes a container body 32, a stopper 34 inserted into the opening 33 of the container body 32, and a seal as a fastener to secure the stopper 34. In a vial bottle container 30, the seal is crimped to the top of the container body together with the stopper using a hand gripper or the like. The volume of the vial bottle container 30 may be 1 mL or more, or 3 mL or more. The volume of the vial bottle container 30 may be 500 mL or less, or 200 mL or less.

[0112] If the container 30 is a vial, the oxygen permeability coefficient of the material constituting the stopper 34 may be greater than that of the glass constituting the container body 32. By separating the oxygen-permeable portion of the container 30 from the liquid L, the movement of oxygen from inside to outside the container 30 can be promoted. A vial container 30 can be stably placed on a mounting surface by bringing the bottom 32a of the container body 32 into contact with the mounting surface. That is, in the case of a vial container 30, the state in which the bottom 32a of the container body 32 is in contact with the mounting surface is the upright state of the container 30 described above. In this case, the stopper 34 is separated from the liquid L. The stopper 34 does not come into contact with the liquid L. Therefore, under normal storage conditions for the container 30, oxygen permeation through the stopper 34 of the container 30 can be promoted.

[0113] The illustrated container 30 can maintain a negative internal pressure under atmospheric pressure. The container 30 can contain a gas while maintaining a negative pressure under atmospheric pressure. The container 30 may also contain a gas while maintaining a positive pressure under atmospheric pressure. In these examples, the container 30 may have sufficient rigidity to maintain its shape. However, the container 30 may deform somewhat under atmospheric pressure when maintaining a negative or positive internal pressure. Examples of a container 30 that can maintain a negative or positive internal pressure include the illustrated specific examples described above and metal cans.

[0114] Being able to contain a gas while maintaining a negative pressure under atmospheric pressure means that the gas can be contained without damage while maintaining an internal pressure of 0.80 atm or higher. A container 30 capable of containing a gas while maintaining a negative pressure under atmospheric pressure may be an airtight container even when the internal pressure is 0.80 atm. In a container capable of containing a gas while maintaining a negative pressure under atmospheric pressure, the volume when the internal pressure is 0.80 atm can be maintained at 95% or more of the volume when the internal pressure is 1.0 atm.

[0115] As an example of container 30, we have described a container having a container body 32 and a stopper 34, where the stopper 34 is oxygen permeable. However, the form of container 30 is not limited to this. Container 30 may have a container body 32 in which at least a part is oxygen permeable and a stopper 34 that has oxygen barrier properties.

[0116] The barrier container 40 has a volume capable of containing the container 30. The barrier container 40 can be closed by welding, such as heat sealing or ultrasonic bonding, or by joining with a bonding material such as an adhesive or bonding agent. The barrier container 40 may be an airtight container. The volume of the barrier container 40 may be, for example, 5 mL or more and 1200 mL or less. If the container 30 is a small container such as a vial, for example a container with a volume of 1 mL or more and 20 mL or less, the volume of the barrier container 40 may be 1.5 mL or more and 500 mL or less.

[0117] The barrier container 40 has oxygen barrier properties. A container has oxygen barrier properties if its oxygen permeability (mL / (m³) is low. 2 This means that the oxygen permeability (mL / (m)) of an oxygen barrier container is 1 or less. 2The value of ×day × atm) may be 0.5 or less, or 0.1 or less. Oxygen permeability is measured in accordance with JIS K7126-1. Oxygen permeability is measured in an environment of 23°C and 40% RH using an OXTRAN (2 / 61) permeability meter manufactured by MOCON, Inc. of the United States. For containers to which JIS K7126-1 does not apply, the oxygen permeability may be determined by measuring the above-mentioned oxygen permeability and dividing the obtained oxygen permeability by the surface area.

[0118] The oxygen permeability coefficient of the material constituting the barrier container 40 having oxygen barrier properties is 1 × 10⁻⁶ -13 (cm 3 (STP)·cm / (cm 2 It is also acceptable to have values ​​less than or equal to 1 × 10⁻⁶ sec·Pa. -17 (cm 3 (STP)·cm / (cm 2 It is also acceptable to use values ​​below (sec·Pa).

[0119] Examples of barrier containers 40 having oxygen barrier properties include containers having a metal layer formed by vapor deposition or transfer, and glass bottles. The barrier container 40 may include a laminate containing a layer having oxygen barrier properties. The laminate may include a resin layer or a metal vapor-deposited film. In this case, the resin layer or metal vapor-deposited film may have oxygen barrier properties. The barrier container 40 includes a transparent portion. In other words, the barrier container 40 has a light-transmitting position 40b that is light-transmitting. Part of the barrier container 40 may be transparent. The entire barrier container 40 may be transparent. Barrier containers 40 using laminates, and barrier containers 40 using glass or resin, can be given transparency along with oxygen barrier properties. By giving the barrier container 40 transparency, the liquid-filled container 30L contained inside can be seen from the outside of the barrier container 40.

[0120] The barrier container 40 may contain at least one of either acrylic resin or polyethylene terephthalate resin. For example, if the barrier container 40 includes a laminate containing a resin layer, the resin layer may contain either or both of either acrylic resin or polyethylene terephthalate resin.

[0121] In the example shown in Figure 1, the barrier container 40 is made of a resin film having oxygen barrier properties. The barrier container 40 is a so-called pouch. The barrier container 40 shown in Figure 1 is a so-called gusset bag. This barrier container 40 includes a first main film 41a, a second main film 41b, a first gusset film 41c, and a second gusset film 41d. The films 41a to 41d are airtightly joined together, for example, by welding such as heat sealing or ultrasonic bonding, or by joining using adhesives such as glues or bonding agents.

[0122] In the barrier container 40 shown in Figure 1, instead of joining separate films, a single folded film may constitute two or more adjacent films 41a to 41d. As shown in Figure 1, the gusset bag can form a rectangular bottom surface on the barrier container 40. By placing the container 30 on the bottom surface, the container 30 can be stably stored inside the barrier container 40. However, as shown in Figure 4, the barrier container 40 may include a bottom film 41e along with the first main film 41a and the second main film 41b instead of a gusset bag. This pouch is also called a standing pouch. This pouch can also form a bottom surface, and the container 30 can be stably stored inside the barrier container 40.

[0123] As shown in Figures 5 to 7, a barrier container 40 that can be unfolded into a planar shape may be used. All of the barrier containers 40 shown in Figures 5 to 7 can be manufactured by joining resin films at a sealing portion 43. The barrier container 40 shown in Figure 5 can be manufactured by joining a first main film 41a and a second main film 41b at a sealing portion 43 provided around its circumference.

[0124] The barrier container 40 shown in Figure 6 has a film 41 that is folded over at the folded portion 41x. The barrier container 40 can be manufactured by joining the opposing portions of the folded film 41 at the seal portion 43. In the barrier container 40 shown in Figure 6, a storage space is formed in the portion surrounded by the folded portion 41x and the three-sided seal portion 43.

[0125] The barrier container 40 shown in Figure 7 is also called a pillow-type container. The barrier container 40 is obtained by joining two ends of a single film 41 together as sealing portions 43, forming a tubular shape, and then joining both ends of the tubular shape together as sealing portions 43.

[0126] When the container 30 is housed in the barrier container 40 shown in Figures 5 to 7, the barrier container 40 shown in Figures 5 to 7 may be supported by a stand member or the like so that the container 30 can stand still. In particular, the barrier container 40 shown in Figures 5 to 7 may be supported by a stand member or the like so that the container 30 can stand upright. For example, the barrier container 40 may be supported so that the opening 33 side of the container body 32 faces upward.

[0127] In the various examples described above, the film forming the barrier container 40 may be transparent.

[0128] As an example, the barrier container 40 contacts the outer surface 30b of the container 30 at the fluorescent material installation position 39, which will be described later. As an example, the barrier container 40 contacts the outer surface 30b of the fluorescent material installation position 39 when the fluorescent material 27 is irradiated with light by the inspection method described later to measure the fluorescence time or fluorescence intensity of the fluorescent material 27. The barrier container 40 contacts the outer surface 30b of the fluorescent material installation position 39 at the light transmission position 40b. The barrier container 40 does not need to contact the outer surface 30b of the fluorescent material installation position 39 when the fluorescent material 27 is irradiated with light by the inspection method described later to measure the fluorescence time or fluorescence intensity of the fluorescent material 27. Hereinafter, unless otherwise specified, the liquid-filled combination container 10L of the first embodiment will be described, which includes a barrier container 40 that contacts the outer surface 30b of the container 30 at the fluorescent material installation position 39. The barrier container 40 shown in Figures 1, 4 to 7 has the flexibility to be deformable to contact the outer surface 30b of the fluorescent material installation position 39 of the container 30. In particular, the barrier container 40 has the flexibility to be deformable to contact the outer surface 30b of the fluorescent material installation position 39 of the container 30 at the light transmission position 40b. Figure 8 is a cross-sectional view showing the barrier container 40 deformed to contact the outer surface 30b of the fluorescent material installation position 39 of the container 30 in the liquid-filled combination container 10L shown in Figure 1. Note that in Figure 8, the layer structure of the container body 32 is not shown, and the cross-sectional shape of the container body 32 is shown. In Figure 8, for the convenience of illustration, the position in which the oxygen absorber 21 and oxygen detection material 25, which will be described later, are fixed to the inner surface of the barrier container 40 has been changed from the position in Figure 1.

[0129] The specific configuration of the barrier container 40 described above is merely illustrative, and various modifications are possible.

[0130] As shown in Figure 1, the liquid-filled combination container 10L further comprises at least one oxygen reagent 20 that can react with oxygen in the barrier container 40. The oxygen reagent 20 is either an oxygen absorber 21 that absorbs oxygen in the barrier container 40, or an oxygen sensing material 25 that detects the oxygen state in the barrier container 40. The liquid-filled combination container 10L may comprise a plurality of oxygen reagents 20. In the example shown in Figure 1, the liquid-filled combination container 10L comprises two oxygen reagents 20. In the example shown in Figure 1, the liquid-filled combination container 10L comprises an oxygen absorber 21 as the first oxygen reagent 20. The liquid-filled combination container 10L comprises an oxygen sensing material 25 as the second oxygen reagent 20.

[0131] The oxygen reagent 20 is fixed to at least one of the outer surface 30b of the container 30 and the inner surface of the barrier container 40. In the example shown in Figure 1, the two oxygen reagents 20 are fixed to the inner surface of the barrier container 40.

[0132] The oxygen reagent 20 is fixed in a position that does not obstruct the irradiation of light that fluoresces the fluorescent material 27 when inspecting the oxygen concentration inside the container 30 in the inspection method for the liquid-containing combination container 10L described later. For example, when the oxygen reagent 20 is fixed to the outer surface 30b of the container 30, the oxygen reagent 20 is fixed in a position on the outer surface 30b of the container 30 that does not overlap with the fluorescent material installation position 39. For example, when the oxygen reagent 20 is fixed to the inner surface of the barrier container 40, the oxygen reagent 20 is fixed in a position on the inner surface of the barrier container 40 that does not overlap with the fluorescent material installation position 39 in a direction perpendicular to the inner surface of the barrier container 40. For example, the oxygen reagent 20 is fixed so that it is not located between the light transmission position 40b of the barrier container 40 and the fluorescent material installation position 39 of the container 30. This prevents the light transmitted through the light transmission position 40b of the barrier container 40 and the fluorescent material installation position 39 of the container 30 from being blocked by the oxygen reagent 20. Therefore, by allowing light to pass through the light transmission position 40b of the barrier container 40 and the fluorescent material installation position 39 of the container 30, it becomes possible to irradiate the fluorescent material 27 with light from outside the barrier container 40.

[0133] The method for fixing the oxygen reagent 20 to at least one of the outer surface 30b of the container 30 and the inner surface of the barrier container 40 is not particularly limited. The oxygen reagent 20 may be fixed to at least one of the outer surface 30b of the container 30 and the inner surface of the barrier container 40 by bonding with an adhesive or the like. The oxygen reagent 20 may be fixed to the outer surface 30b of the container 30 and the inner surface of the barrier container 40 by being sandwiched between the outer surface 30b of the container 30 and the inner surface of the barrier container 40. The oxygen reagent 20 may be fixed to at least one of the outer surface 30b of the container 30 and the inner surface of the barrier container 40 by a member (not shown) that is positioned inside the barrier container 40 and outside the container 30. The oxygen absorber 21 and oxygen detection material 25 shown in Figure 1 are bonded to the inner surface of the barrier container 40 with an adhesive (not shown).

[0134] The oxygen reagent 20 may be fixed to the outer surface 30b of the container 30 so that its position relative to the outer surface 30b of the container 30 does not change even when the orientation of the liquid-filled combination container 10L is changed. The oxygen reagent 20 can be fixed to the outer surface 30b of the container 30 so that its position relative to the outer surface 30b of the container 30 does not change even when the orientation of the liquid-filled combination container 10L is changed, for example by using an adhesive. The oxygen reagent 20 may be fixed to the inner surface of the barrier container 40 so that its position relative to the inner surface of the barrier container 40 does not change even when the orientation of the liquid-filled combination container 10L is changed. The oxygen reagent 20 can be fixed to the inner surface of the barrier container 40 so that its position relative to the inner surface of the barrier container 40 does not change even when the orientation of the liquid-filled combination container 10L is changed, for example by using an adhesive.

[0135] The oxygen reagent 20 may be fixed to at least one of the outer surface 30b of the container 30 and the inner surface of the barrier container 40 by the action of gravity when the container 30 of the liquid-filled combination container 10L is in a stationary state, particularly when the container 30 is upright. For example, the oxygen reagent 20 may be sandwiched between the outer surface 30b of the container 30 and the inner surface of the barrier container 40, thereby suppressing horizontal movement and vertical movement by the action of gravity. In this case, the oxygen reagent 20 is considered to be fixed to the outer surface 30b of the container 30 and the inner surface of the barrier container 40. Alternatively, the oxygen reagent 20 may be sandwiched between a member (not shown) located inside the barrier container 40 and outside the container 30, thereby suppressing horizontal movement and vertical movement by the action of gravity. In this case, the oxygen reagent 20 is considered to be fixed to the outer surface 30b of the container 30. Furthermore, the oxygen reagent 20 may be sandwiched between a member (not shown) located inside the barrier container 40 and outside the container 30, thereby suppressing its horizontal movement and also suppressing its vertical movement due to gravity. In this case, the oxygen reagent 20 is considered to be fixed to the inner surface of the barrier container 40. Even in the aforementioned fixing configuration utilizing gravity, the position of the oxygen reagent 20 in the liquid-filled combination container 10L is stably determined. Even in the aforementioned fixing configuration utilizing gravity, movement of the oxygen reagent 20 due to shaking of the liquid-filled combination container 10L is suppressed.

[0136] The oxygen absorber 21 is not particularly limited as long as it contains a composition that can absorb oxygen. Iron-based oxygen absorbers and non-ferrous oxygen absorbers can be used as the oxygen absorber 21. The oxygen absorber 21 includes, for example, an oxygen absorber composition in which metal powders such as iron powder, reducing inorganic substances such as iron compounds, polyhydric phenols, polyhydric alcohols, reducing organic substances such as ascorbic acid or its salts, or metal complexes are the main components of the oxygen absorption reaction. The oxygen absorber 21 includes, for example, iron oxide. The oxygen absorber 21 is, for example, an oxygen absorber available from Mitsubishi Gas Chemical Co., Ltd. under the trade name "Ageless". The above-described composition is included in the oxygen absorber 21 as, for example, the oxygen absorber body 22 shown in Figure 9.

[0137] As shown in Figure 1, the liquid-filled combination container 10L includes an oxygen absorber 21 housed in a barrier container 40 together with the liquid-filled container 30L. The oxygen absorber 21 may also include an oxygen absorber body 22. In the example shown in Figure 9, the oxygen absorber 21 includes an oxygen-permeable packaging 22a and an oxygen absorber body 22 housed in the packaging 22a. As the oxygen absorber 21 containing the oxygen absorber body 22, you may use iron-based moisture-dependent FX type, iron-based self-reacting S type, SPE type, ZP type, ZI-PT type, ZJ-PK type, E type, organic self-reacting GLS type, GL-M type, GE type, etc., which are available from Mitsubishi Gas Chemical Company, Inc. As the oxygen absorber 21 containing the oxygen absorber body 22, you may use ZH type, Z-PK type, Z-PR type, Z-PKR type, ZM type, etc., which are available from Mitsubishi Gas Chemical Company, Inc., for use in pharmaceuticals.

[0138] The oxygen absorber 21 may be included in the oxygen absorber film 23. Figure 10 shows an example of a laminate 46 including the oxygen absorber film 23. The laminate 46 including the oxygen absorber film 23 may constitute at least a part of the barrier container 40. For example, the laminate 46 including the oxygen absorber film 23 may constitute the films 41a to 41e of the barrier container 40 shown in Figures 1 and 4 to 7. The laminate 46 shown in Figure 10 includes a first layer 46a, a second layer 46b, and a third layer 46c. The first layer 46a may be the outermost layer made of polyethylene terephthalate or nylon, etc. The second layer 46b may be an oxygen barrier layer made of aluminum foil, an inorganic vapor-deposited film, a metal vapor-deposited film, etc. The third layer 46c may be the innermost layer forming a heat seal layer. The illustrated third layer 46c includes a base material made of thermoplastic resin and an oxygen absorber 21 dispersed in the base material. As shown in the example in Figure 10, the barrier container 40 may include an oxygen-absorbing film 23 containing an oxygen absorber 21 as part of the laminate 46. The oxygen absorber 21 is not limited to the heat-seal layer or the innermost layer 46c, but may also be included in the adhesive layer or the intermediate layer of the laminate. As another example, the container 30 may include an oxygen-absorbing film 23 containing an oxygen absorber 21. The oxygen absorber 21 may be provided separately from the container 30 or barrier container 40, as shown in the examples in Figures 1 and 8, or it may be provided as part of the container 30 or barrier container 40, as shown in Figure 10. As shown in Figure 10, if the laminate 46 including the oxygen-absorbing film 23 containing the oxygen absorber 21 constitutes at least a part of the barrier container 40, the oxygen absorber 21 is considered to be fixed to the inner surface of the barrier container 40. If the container 30 includes an oxygen-absorbing film 23 containing an oxygen absorber 21, the oxygen absorber 21 is considered to be fixed to the outer surface 30b of the container 30.

[0139] The oxygen-absorbing film 23, which does not constitute at least a part of the barrier container 40, may be fixed to at least one of the outer surface 30b of the container 30 and the inner surface of the barrier container 40. If the oxygen-absorbing film 23, which does not constitute at least a part of the barrier container 40, is fixed to the outer surface 30b of the container 30, the oxygen absorber 21 is deemed to be fixed to the outer surface 30b of the container 30. If the oxygen-absorbing film 23, which does not constitute at least a part of the barrier container 40, is fixed to the inner surface of the barrier container 40, the oxygen absorber 21 is deemed to be fixed to the inner surface of the barrier container 40.

[0140] As the oxygen absorber 21 absorbs oxygen, the oxygen concentration in the barrier container 40 decreases, and oxygen in the container 30 moves into the barrier container 40. By using the oxygen absorber 21, the oxygen concentration in the barrier container 40 and the oxygen concentration in the container 30 can be reduced more effectively. The inventors have confirmed that by using a sufficient amount of the oxygen absorber 21, the oxygen concentration in the barrier container 40 and the oxygen concentration in the container 30 can be kept low, for example, below 0.3%, 0.1%, 0.05%, below 0.03%, and even 0%. Furthermore, as the oxygen concentration in the container 30 decreases, the amount of oxygen dissolved in the liquid L contained in the container 30 also decreases. The inventors of this case have confirmed that by using a sufficient amount of oxygen scavenger 21, the amount of oxygen dissolved in liquid L can be significantly reduced and maintained at, for example, less than 0.15 mg / L, less than 0.04 mg / L, 0.03 mg / L or less, 0.02 mg / L or less, less than 0.015 mg / L, and more preferably 0 mg / L.

[0141] The amount of oxygen absorber 21 is set to an amount that can absorb the total amount of oxygen present in container 30 and barrier container 40.

[0142] The oxygen concentration (%) in container 30 can be determined by the same method as the method for determining the oxygen concentration in container 30 in the inspection method for the liquid-filled combination container 10L described later in the first or second embodiment. The oxygen concentration (%) in barrier container 40 can be determined by the same method as the method for determining the oxygen concentration in barrier container 40 in the inspection method for the liquid-filled combination container 10L described later in the third embodiment. From the determined oxygen concentration (%) and temperature of the headspace HS, the saturation solubility of oxygen in liquid L can be determined. Based on the determined saturation solubility, the amount of oxygen dissolved in liquid L (mg / L) can be determined.

[0143] The oxygen detection material 25 may display the detected oxygen state. The oxygen detection material 25 may detect the oxygen concentration. The oxygen detection material 25 may display the detected oxygen concentration value. The oxygen detection material 25 may display the detected oxygen concentration value by color.

[0144] The oxygen detection material 25 may contain a variable organic dye that changes color reversibly through oxidation and reduction. For example, the oxygen reducing agent may contain an organic dye such as a thiazine dye, azine dye, or oxazine dye, and a reducing agent, and may be in solid form. The oxygen reducing agent may also contain an oxygen indicator ink composition. The oxygen indicator ink composition may contain a resin solution, a thiazine dye, etc., reducing sugars, and an alkaline substance. The thiazine dye, etc., reducing sugars, and alkaline substance may be dissolved or dispersed in the resin solution. The substances contained in the oxygen detection material 25 may change reversibly through oxidation and reduction. By using an oxygen detection material 25 containing a reversible substance, the oxygen detection material 25 contained in the container changes its display color in accordance with the deoxygenation of the container before deoxygenation is completed, allowing the amount of oxygen in the container to be observed from outside the transparent container, and the oxygen-related state inside the container to be understood. Furthermore, the oxygen detection material 25 contained within the container can indicate an increase in oxygen concentration after deoxygenation is complete, or a state in which oxygen has entered the container due to the formation of a pinhole or the like during distribution, by changing its display color. For example, the oxygen detection material 25 includes tablets. For example, the oxygen detection material 25 turns pink when the surrounding oxygen concentration is sufficiently low, and turns blue when the surrounding oxygen concentration is high.

[0145] More specifically, a commercially available tablet-type oxygen indicator, such as the oxygen indicator 25 available from Mitsubishi Gas Chemical Co., Ltd. under the trade name "Ageless Eye," may be used. Alternatively, an oxygen indicator 25 coated with an ink composition having an oxygen detection function, such as the oxygen indicator 25 available from Mitsubishi Gas Chemical Co., Ltd. under the trade name "Paper Eye," may be used. "Ageless Eye" and "Paper Eye" are functional products that can easily indicate, by color change, that the oxygen concentration in a transparent container is less than 0.1% by volume, indicating an oxygen-free state. As the oxygen indicator 25, one that can be used together with an oxygen absorber for maintaining the freshness of food and the quality of medical pharmaceuticals may be used. For example, as the oxygen indicator 25, one that can be used together with an oxygen absorber available from Mitsubishi Gas Chemical Co., Ltd. under the trade name "Ageless," for maintaining the freshness of food and the quality of medical pharmaceuticals may be used.

[0146] As shown in Figure 1, the oxygen detection material 25 may have a display section 26 that can be observed from outside the transparent barrier container 40. In the example shown in Figure 1, the oxygen detection material 25 is housed in the barrier container 40, similar to the oxygen absorber 21. The oxygen detection material 25 may be joined to the inner surface of the barrier container 40 or the outer surface of the container 30 via welding or a bonding material. The oxygen detection material 25 may be positioned so that its display section 26 is not obscured by the oxygen absorber 21. Furthermore, if the container 30 has a label, it is preferable that the oxygen absorber 21 and the oxygen detection material 25 are positioned so as not to cover the label.

[0147] Furthermore, the oxygen sensing material 25 may detect the oxygen state inside the container 30. The oxygen sensing material 25 may be housed inside the container 30. The oxygen sensing material 25 may display the detected oxygen state inside the container 30. The oxygen sensing material 25 may detect the oxygen concentration inside the container 30. The oxygen sensing material 25 may display the detected oxygen concentration value inside the container 30. The oxygen sensing material 25 may display the detected oxygen concentration value inside the container 30 using color.

[0148] The fluorescent material 27 is provided on the inner surface 30a of the container 30 at the fluorescent material installation position 39. The fluorescent material installation position 39 is away from the contact area 31a. In other words, the fluorescent material installation position 39 where the fluorescent material 27 is provided on the inner surface 30a is a position that is in contact with the headspace HS of the container 30. In the liquid-filled container 30L shown in Figure 1, the fluorescent material installation position 39 is located on the container body 32. That is, the fluorescent material 27 is provided on the portion of the inner surface 30a of the container 30 that is made up of the container body 32. Although not shown, the fluorescent material installation position 39 may also be located on the stopper 34. That is, the fluorescent material 27 is provided on the portion of the inner surface 30a of the container 30 that is made up of the stopper 34. The container 30 is light-transmitting at least at the fluorescent material installation position 39.

[0149] The fluorescent material 27 is a material whose fluorescence time or fluorescence intensity varies depending on the ambient oxygen concentration. The excitation wavelength of the fluorescent material 27 is, for example, between 498 nm and 600 nm. Fluorescent materials include, for example, those manufactured by Funakoshi Co., Ltd., such as FITC, HyLyte Flour 488, ATTO 488, MFP488, Oyster 500, ATTO 520, ATTO532, DY-500XL, Alexa Fluor 555, HiLyte Plus 555, Cy3, DyLight547, Rhodamine, TRITC, DY-548, DY-554, DY-555, Alexa Fluor 546, DY-556, NorthernLights557, Oyster 550, 5-TAMRA, DY-505-X5, DY-547, Oyster 556, DY-549, ATTO 550, B-PE, R-PE, DY-560, TAMRA, MFP555, Spectrum Orange, DY-510XL, ATTO These are 565, CY3.5, ROX (X-Rhodamine, Rhodamine Red X), DY-590, 5-ROX, Spectrum Red, Texas Red, DyLight 594, Alexa Fluor 594, HiLyte Fluor TR, ATTO 590, MFP590, DY-480XL, DY-481XL, DY-520XL, or DY-521XL. The fluorescent material 27 has a size such that the fluorescence time or fluorescence intensity of the fluorescent material 27 can be measured by the measurement method described later.

[0150] In the example shown in Figure 2, the liquid-filled container 30L further comprises an adhesive layer 28 that adheres the fluorescent material 27 to the inner surface 30a of the fluorescent material placement position 39 of the container 30. The adhesive layer 28 is light-transmitting. The adhesive layer 28 contains a non-fluorescent resin. As an example, the adhesive layer 28 contains at least one resin selected from the group consisting of non-fluorescent acrylic resins, silicone resins, and epoxy resins. The adhesive layer 28 may also contain at least one resin selected from the group consisting of non-fluorescent photocurable acrylic resins, photocurable silicone resins, and epoxy resins. Here, "non-fluorescent photocurable acrylic resin" means a photocurable acrylic resin that has not been processed to fluoresce upon light irradiation, such as by containing a fluorescent agent. "Non-fluorescent photocurable acrylic resin" includes photocurable acrylic resins that have not been processed to fluoresce upon light irradiation, but emit fluorescence of the material itself, i.e., autofluorescence, when irradiated with light. Whether an acrylic resin is a photocurable acrylic resin or not, and whether a silicone resin is a photocurable silicone resin or not, can be determined by analyzing the composition of the resin, particularly the monomers it contains.

[0151] Specifically, the fluorescent material 27 may be bonded to the inner surface 30a of the fluorescent material installation position 39 of the container 30 by the following methods. First, a non-fluorescent photocurable acrylic resin is placed between the inner surface 30a of the fluorescent material installation position 39 of the container 30 and the fluorescent material 27. Next, the photocurable acrylic resin is cured by irradiation with light to form an adhesive layer 28. Alternatively, the fluorescent material 27 may be bonded by placing a photocurable silicone resin between the inner surface 30a of the fluorescent material installation position 39 of the container 30 and the fluorescent material 27 and curing it by irradiation with light. Alternatively, the fluorescent material 27 may be bonded by placing an epoxy resin between the inner surface 30a of the fluorescent material installation position 39 of the container 30 and the fluorescent material 27 and curing it.

[0152] As described later, in the liquid-filled combination container 10L, light can be irradiated onto the fluorescent material 27 from outside the barrier container 40 by allowing light to pass through the light transmission position 40b of the barrier container 40 and the fluorescent material installation position 39 of the container 30.

[0153] A method for testing the oxygen concentration inside a 10L liquid-filled combination container 30 is described below. The method for testing the oxygen concentration inside a 10L liquid-filled combination container 30 comprises a fluorescence measurement step and a measurement step. Furthermore, the method for testing the oxygen concentration inside a 30L liquid-filled combination container 30 comprises a fluorescence measurement step and a measurement step. The method for testing the oxygen concentration inside a 10L liquid-filled combination container 30 further comprises a step of bringing a barrier container 40 into contact with the outer surface 30b of the fluorescent material installation position 39 of the container 30.

[0154] In a testing method for testing the oxygen concentration inside a 10L liquid-filled combination container 30, the first step is to bring a barrier container 40 into contact with the outer surface 30b of the fluorescent material placement position 39 of the container 30. In the step of bringing the barrier container 40 into contact with the outer surface 30b of the fluorescent material placement position 39 of the container 30, as shown in Figure 8, the detection device 80 is brought into contact with the barrier container 40, and the barrier container 40 is pressed by the detection device 80 to bring the barrier container 40 into contact with the outer surface 30b of the fluorescent material placement position 39 of the container 30. In particular, the barrier container 40 is brought into contact with the outer surface 30b of the fluorescent material placement position 39 of the container 30 at the light transmission position 40b. As described above, the barrier container 40 is flexible. Therefore, by pressing the barrier container 40 with the detection device 80, the barrier container 40 can be brought into contact with the outer surface 30b of the fluorescent material placement position 39 of the container 30.

[0155] The detection device 80 is a device for measuring the fluorescence time or fluorescence intensity of a fluorescent material. In the example shown in Figure 8, the detection device 80 has a rod-like shape. The detection device 80 has an illumination unit 81 and a sensor unit 82. In the example shown in Figure 8, the illumination unit 81 and the sensor unit 82 are provided at one end 80a of the rod-shaped detection device 80.

[0156] The illumination unit 81 is the part that emits light to cause the fluorescent material 27 to fluoresce. The illumination used as the illumination unit 81 is not particularly limited as long as it emits light of a wavelength that causes the fluorescent material 27 to fluoresce. For example, an LED light can be used as the illumination unit 81. For example, if the fluorescent material 27 is FITC manufactured by Funakoshi Co., Ltd., a light source that emits light with a wavelength of approximately 500 nm is used as the illumination unit 81. If the fluorescent material 27 is ATTO 520 manufactured by Funakoshi Co., Ltd., an illumination unit that emits light with a wavelength of approximately 520 nm is used as the illumination unit 81. If the fluorescent material 27 is Alexa Fluor 555 manufactured by Funakoshi Co., Ltd., an illumination unit that emits light with a wavelength of approximately 550 nm is used as the illumination unit 81. The illumination unit 81 may also be an LED light that emits green light with a wavelength of 525 nm.

[0157] The sensor unit 82 is the part that measures the fluorescence time or fluorescence intensity of the fluorescent material 27. The sensor unit 82 is not particularly limited as long as it is a sensor capable of measuring the fluorescence time or fluorescence intensity of the fluorescent material 27. The sensor used as the sensor unit 82 is, for example, the detector attached to the XY-1 SMA trace manufactured by PreSens. The detection part of the sensor is, for example, a CCD array.

[0158] In the example shown in Figure 8, one end 80a of the detection device 80, which is equipped with the illumination unit 81 and the sensor unit 82, is brought into contact with the barrier container 40, and the barrier container 40 is pressed by the detection device 80. As a result, the barrier container 40 is in contact with the outer surface 30b of the fluorescent material installation position 39 of the container 30.

[0159] After bringing the barrier container 40 into contact with the outer surface 30b of the container 30 at the fluorescent material installation position 39, a fluorescence measurement process is performed. In the fluorescence measurement process, the fluorescent material 27 is irradiated with light that causes it to fluoresce, and the fluorescence time or fluorescence intensity of the fluorescent material 27 is measured. The irradiation of the fluorescent material 27 with light that causes it to fluoresce is performed using the illumination unit 81. The fluorescence time or fluorescence intensity of the fluorescent material 27 is measured using the sensor unit 82.

[0160] In the fluorescence measurement process, light that causes the fluorescent material 27 to fluoresce is transmitted through the light transmission position 40b of the barrier container 40 and the fluorescent material installation position 39 of the container 30, and irradiated onto the fluorescent material 27. The fluorescence measurement process is performed with the barrier container 40 in contact with the outer surface 30b of the fluorescent material installation position 39 of the container 30. In the fluorescence measurement process, light that causes the fluorescent material 27 to fluoresce is transmitted through the barrier container 40 and the fluorescent material installation position 39 of the container 30, and irradiated onto the fluorescent material 27. In the example shown in Figure 8, the barrier container 40 is pressed by the detection device 80, causing it to be in contact with the outer surface 30b of the fluorescent material installation position 39 of the container 30.

[0161] In the example shown in Figure 8, the detection device 80 is brought into contact with the portion of the barrier container 40 that contacts the fluorescent material installation position 39, and the illumination unit 81 is used to irradiate the fluorescent material 27 with light. As a result, the light from the illumination unit 81 passes through the portion of the container 30 that contacts the fluorescent material installation position 39 and the portion of the barrier container 40 that contacts the fluorescent material installation position 39, and irradiates the fluorescent material 27. The light generated by the fluorescence of the fluorescent material 27 passes through the portion of the container 30 that contacts the fluorescent material installation position 39 and the portion of the barrier container 40 that contacts the fluorescent material installation position 39, and reaches the sensor unit 82. Therefore, the fluorescence time or fluorescence intensity of the fluorescent material 27 can be measured using the sensor unit 82. If the illumination unit 81 is an LED light that emits green light with a wavelength of 525 nm, the fluorescent material 27 will emit light with a wavelength longer than 525 nm, for example, red light.

[0162] In the measurement process, the oxygen concentration inside the container 30 is checked based on the fluorescence time or fluorescence intensity of the fluorescent material 27 measured in the fluorescence measurement process. As described above, the fluorescence time or fluorescence intensity of the fluorescent material 27 varies depending on the ambient oxygen concentration. In the measurement process, the oxygen concentration (%) inside the container 30 is measured based on the correspondence between the ambient oxygen concentration and the fluorescence time or fluorescence intensity of the fluorescent material 27. The oxygen concentration (%) inside the container 30 measured in the measurement process is the oxygen concentration (%) in the gas contained in the headspace HS of the container 30.

[0163] Furthermore, in the case of a liquid-filled combination container 10L in which the barrier container 40 does not come into contact with the outer surface 30b of the fluorescent material installation position 39 of the container 30, the step of bringing the barrier container 40 into contact with the outer surface 30b of the fluorescent material installation position 39 of the container 30 is not performed when inspecting the oxygen concentration inside the container 30. Even in this case, the oxygen concentration inside the container 30 can be inspected in the fluorescence measurement step by irradiating the fluorescent material 27 with light that causes the fluorescent material 27, passing through the fluorescent material installation position 39 of the container 30.

[0164] According to the inspection method described above, the condition of the liquid-filled container 30L or the liquid-filled combination container 10L can be inspected by inspecting the oxygen concentration (%) inside the container 30 measured in the measurement process. For example, the measured oxygen concentration (%) inside the container 30 can be used to inspect whether the oxygen concentration inside the container 30 has been sufficiently reduced by the oxygen absorber 21 or the like. For example, if the oxygen concentration (%) inside the container 30 measured in the measurement process is less than 0.3%, it can be determined that the oxygen concentration inside the container 30 has been sufficiently reduced. Alternatively, it may be determined that the oxygen concentration inside the container 30 has been sufficiently reduced when the measured oxygen concentration (%) inside the container 30 is 0.1% or less, 0.05% or less, or less than 0.03%.

[0165] Furthermore, in the inspection method described above, it is also possible to inspect whether the amount of dissolved oxygen (mg / L) in the liquid L of the liquid-filled container 30L has been sufficiently reduced by the oxygen scavenger 21 or the like, based on the oxygen concentration (%) inside the container 30 measured in the measurement step. For example, it is possible to inspect whether the amount of dissolved oxygen (mg / L) in the liquid L has been sufficiently reduced based on the change in oxygen concentration (%) inside the container 30 over time. If a sufficiently long time has elapsed since the liquid-filled combination container 10L was manufactured, the movement of oxygen between the headspace HS of the container 30 and the liquid L will reach an equilibrium state. As an example, if the oxygen concentration (%) inside the container 30 has been sufficiently reduced in such an equilibrium state, it can be determined that the amount of dissolved oxygen (mg / L) in the liquid L has been sufficiently reduced. The change in oxygen concentration (%) inside the container 30 over time can be obtained by measuring the oxygen concentration (%) inside the container 30 at multiple points in time at different intervals since the liquid-filled combination container 10L was manufactured, using the method described above. In this case, the measurement of the oxygen concentration (%) inside the container 30 is performed, for example, every day.

[0166] This section describes a specific method for testing whether the amount of dissolved oxygen (mg / L) in liquid L has been sufficiently reduced based on the change in oxygen concentration (%) within container 30 over time. First, identify the point in time when the oxygen concentration (%) within container 30 falls below the standard value. Then, observe the change in oxygen concentration (%) within container 30 for 14 days or more from the point in time when it falls below the standard value. If the oxygen concentration (%) within container 30 does not rise above the standard value, it can be determined that the amount of dissolved oxygen (mg / L) in liquid L has been sufficiently reduced. In this case, the standard value for oxygen concentration (%) within container 30 is, for example, 0.3%. The standard value for oxygen concentration (%) within container 30 may also be 0.1%, 0.05%, or 0.03%.

[0167] Alternatively, the rate of decrease in the oxygen concentration (%) inside the container 30 can be calculated based on the change in the oxygen concentration (%) inside the container 30 over time, obtained by measuring the oxygen concentration (%) inside the container 30 using the method described above, and it may be checked whether the rate of decrease is sufficiently high.

[0168] The "decrease rate" used for oxygen concentration (%) refers to the percentage of the decrease in oxygen concentration value (%) over the 24 hours from the day before the target day to the target day, relative to the oxygen concentration value (%) on the day before the target day. That is, "decrease rate = (oxygen concentration on the day before the target day - oxygen concentration on the target day) / oxygen concentration on the day before the target day) × 100 (%)". The unit of the "decrease rate" is (% / day). The decrease rate (% / day) can be adjusted by the amount of oxygen absorber 21, the volume of container 30, the volume of barrier container 40, the amount of liquid L, the oxygen permeability performance of container 30, etc.

[0169] For example, if a decrease rate of 15% / day or more is maintained from the time the barrier container 40 containing container 30 is closed until the oxygen concentration inside container 30 falls to 0.1% or less, then it can be judged that the decrease rate of oxygen concentration (%) inside container 30 is sufficiently high. The standard value for the decrease rate until the oxygen concentration inside container 30 falls to 0.1% or less, which is judged to be sufficiently high, may be 20% / day or more, 25% / day or more, 30% / day or more, 35% / day or more, or 40% / day or more.

[0170] In the measurement process, the oxygen concentration and oxygen partial pressure inside the container 30 may be measured, and the condition of the liquid-filled container 30L or the liquid-filled combination container 10L may be inspected based on the oxygen partial pressure inside the container 30L.

[0171] A method for manufacturing a 10L liquid-filled combination container is described below. By manufacturing the 10L liquid-filled combination container, a 30L liquid-filled container with adjusted oxygen concentration is obtained. The method for manufacturing the 10L liquid-filled combination container may include an inspection step in which the 10L liquid-filled combination container is inspected using the inspection method described above.

[0172] First, a 30L liquid container and a barrier container 40 before sealing are prepared. The 30L liquid container is produced by filling the container 30 with liquid L. For example, liquid L such as food or medicine is produced using a production line set up in a sterile environment maintained under positive pressure. The sterile environment is maintained under positive pressure from the viewpoint of suppressing the intrusion of foreign substances such as bacteria. As a result, the internal pressure of the resulting 30L liquid container becomes positive pressure, similar to the production environment.

[0173] The partial volume of container 30 (headspace HS), obtained by subtracting the volume of liquid L from the volume of container 30, may be 50 mL or less, 30 mL, 10 mL, or 5 mL or less. By adjusting the partial volume of container 30 in this way, when the barrier container 40 containing container 30 is closed in the process described later, the time from closing the barrier container 40 until oxygen permeation through container 30 reaches equilibrium can be shortened.

[0174] The volume of liquid L contained in container 30 may be 20 mL or less, or 10 mL or less. By adjusting the volume of liquid L in this way, the time from closing the barrier container 40 containing container 30 until oxygen permeation through container 30 reaches equilibrium can be shortened.

[0175] Upper and lower limits may be set for the ratio (%) of the partial volume of container 30 (headspace HS volume) (mL), obtained by subtracting the volume of liquid L from the volume of container 30, to the partial volume of barrier container 40 (mL), obtained by subtracting the volume occupied by container 30 from the volume of barrier container 40. This ratio may be 50% or less, or 20% or less. By setting such an upper limit, the oxygen concentration in container 30 can be reduced sufficiently and quickly. In addition, space for container 30 can be secured within the barrier container 40, and container 30 can be easily housed within the barrier container 40. Furthermore, the time from closing the barrier container 40 containing container 30 until oxygen permeation through container 30 reaches equilibrium can be shortened. This suppresses the decomposition of liquid L by oxygen. This ratio may be 5% or more, or 10% or more. By setting a lower limit in this way, the barrier container 40 does not become too large relative to container 30, and the handling of the liquid-filled combination container 10L can be improved.

[0176] Next, as shown in Figure 11, the resulting liquid-filled container 30L is placed in the barrier container 40. As shown in Figure 11, the barrier container 40 before closure has an opening 40a for accommodating the liquid-filled container 30L. In the barrier container 40 shown in Figure 1, for example, the upper edges of the films 41a to 41d are not joined to each other, thus forming the opening 40a. Then, as shown in Figure 11, the liquid-filled container 30L is placed in the barrier container 40 through the opening 40a.

[0177] At least one oxygen reagent 20 capable of reacting with oxygen in the barrier container 40 is provided. As an example, an oxygen absorber 21 that absorbs oxygen in the barrier container 40 is provided. For example, if at least one of the container 30 and the barrier container 40 includes an oxygen absorber film 23 (see Figure 10), no special work is required to provide the oxygen absorber 21. When using the oxygen absorber 21 shown in Figures 1 and 8, the oxygen absorber 21 is contained in the barrier container 40. The placement of the oxygen reagent 20, such as the oxygen absorber 21, in the barrier container 40 and the placement of the liquid-filled container 30L in the barrier container 40 may be performed either first or in parallel.

[0178] The amount of oxygen absorber 21 is set to an amount that can absorb the total amount of oxygen present in container 30 and barrier container 40.

[0179] Before closing the barrier container 40, as described later, the inside of the barrier container 40 may be replaced with an inert gas. By replacing it with an inert gas, the oxygen concentration (%) inside the barrier container 40 can be sufficiently reduced to below atmospheric pressure. This causes oxygen to move from container 30 to the barrier container 40, and the amount of oxygen inside container 30 can be rapidly reduced. By rapidly reducing the amount of oxygen inside container 30, the decomposition of liquid L by oxygen can be suppressed more effectively. An inert gas is a stable gas with low reactivity. Examples of inert gases include noble gases such as nitrogen, helium, neon, and argon.

[0180] Replacement with an inert gas can be achieved, for example, by blowing an inert gas into the barrier container 40 or by closing the barrier container 40 in a chamber where the atmosphere has been replaced with an inert gas. These methods can reduce the oxygen concentration inside the barrier container 40 to between 0.5% and 1.0%. Since the barrier container 40 does not directly contain liquid, replacement with an inert gas can be carried out smoothly.

[0181] Subsequently, as shown in Figures 1 and 8, the barrier container 40 containing the liquid container 30L is closed. In the barrier container 40 shown in Figure 1, the barrier container 40 is closed by joining the upper edges of the films 41a to 41d to each other to close the opening 40a. The joining may be carried out using a joining material such as an adhesive or bonding agent, or by welding such as heat sealing or ultrasonic bonding. The barrier container 40 becomes airtight when closed.

[0182] In the process of closing a barrier container 40 containing a liquid container 30L, a volume of gas smaller than the volume obtained by subtracting the volume of the liquid container 30L from the maximum volume that the inside of the barrier container 40 can hold may be sealed inside. For example, in the process of closing a barrier container 40 containing a liquid container 30L, the gas is discharged from inside the barrier container 40 before the barrier container 40 is closed. This allows the barrier container 40 to be closed with a volume of gas smaller than the volume obtained by subtracting the volume of the liquid container 30L from the maximum volume that the inside of the barrier container 40 can hold sealed inside. In this case, it is preferable to discharge a volume of gas equal to 5% or more of the maximum volume that the inside of the barrier container 40 can hold from inside the barrier container 40 before closing the barrier container 40. It is more preferable to discharge a volume of gas equal to 10% or more of the maximum volume that the inside of the barrier container 40 can hold from inside the barrier container 40, and even more preferable to discharge a volume of gas equal to 20% or more.

[0183] By sealing a volume of gas smaller than the volume obtained by subtracting the volume of the liquid-filled container 30L from the maximum volume that the inside of the barrier container 40 can hold, the following effects can be obtained: When the combined liquid-filled container 10L reduces the oxygen concentration in the headspace HS of container 30 and reduces the amount of oxygen dissolved in liquid L, the rate of decrease in the oxygen concentration in the headspace HS and the rate of decrease in the amount of oxygen dissolved in liquid L can be accelerated. In addition, the volume of the space formed between the barrier container 40 and container 30 is reduced. As a result, when the oxygen reagent 20 is held in the space formed between the barrier container 40 and container 30, as in the fourth and fifth embodiments described later, the oxygen reagent 20 can be held more stably in the space formed between the barrier container 40 and container 30.

[0184] The process up to closing the barrier container 40 may be carried out in a sterile environment. That is, the liquid container 30L manufactured in a sterile state, the sterilized or sterile barrier container 40, and the oxygen reactant 20 such as the oxygen absorber 21 are brought into a sterile environment, such as a sterile chamber. In the sterile environment, the barrier container 40 containing the liquid container 30L is closed. The inside of the barrier container 40 containing the liquid container 30L also becomes sterile. That is, the liquid container 30L can be stored in the barrier container 40 in a sterile state.

[0185] Subsequently, the liquid-filled container 30L is stored in the barrier container 40. The barrier container 40 has oxygen barrier properties. The movement of oxygen from the environment in which the barrier container 40 is placed into the barrier container 40 is suppressed. The oxygen absorber 21 absorbs the oxygen inside the barrier container 40. Therefore, the oxygen concentration (%) inside the barrier container 40, which is outside the container 30, is reduced by the oxygen absorption of the oxygen absorber 21 and becomes lower than the oxygen concentration (%) inside the container 30. The container 30 is oxygen permeable. Therefore, the oxygen inside the container 30 permeates through the container 30 and moves into the barrier container 40. As oxygen moves from the container 30 to the barrier container 40, the oxygen concentration inside the container 30 decreases. In this way, by storing the liquid-filled container 30L in the barrier container 40, the amount of oxygen in the container 30 contained within the barrier container 40 can be adjusted. In the final equilibrium state where oxygen permeation through container 30 is in equilibrium, the oxygen concentration in container 30 may be equal to the oxygen concentration in barrier container 40.

[0186] In addition, as the oxygen concentration in container 30 decreases, the partial pressure of oxygen in container 30 also decreases. When the partial pressure of oxygen in container 30 decreases, the saturation solubility of oxygen in liquid L in container 30 (mg / L) also decreases. As a result, the amount of oxygen dissolved in liquid L (mg / L) can be reduced.

[0187] The oxygen content of container 30 within the barrier container 40 may be adjusted until the oxygen permeation through container 30 reaches equilibrium. The oxygen content of container 30 within the barrier container 40 may be adjusted until the oxygen concentration (%) in container 30 decreases to a predetermined value. The oxygen content of container 30 within the barrier container 40 may be adjusted until the amount of dissolved oxygen (mg / L) in liquid L in container 30 decreases to a predetermined value. The oxygen content of container 30 within the barrier container 40 may be adjusted until the liquid L of the liquid-filled combination container 10 L is used. In addition, the liquid-filled combination container 10 L may be circulated while the oxygen content of container 30 is being adjusted within the barrier container 40.

[0188] Whether oxygen permeation through container 30 is in equilibrium can be determined based on the oxygen concentration inside container 30 measured in the inspection process described later. This determination is made if the difference between the oxygen concentration value (%) inside container 30 at a certain point in time and the oxygen concentration value (%) inside container 30 24 hours prior to that point in time is ±5% or less of the oxygen concentration value (%) inside container 30 at that point in time, then equilibrium is considered to have been reached.

[0189] By separating the oxygen-permeable portion of the container 30 from the barrier container 40 at least partially, the movement of oxygen from the container 30 to the barrier container 40 can be promoted. In the example shown in Figure 1, a gap G is formed between the oxygen-permeable stopper 34 of the container 30 housed in the barrier container 40 and the barrier container 40. In this example, it is possible to prevent the oxygen-barrier barrier container 40 from covering the oxygen-permeable stopper 34. This prevents the oxygen permeability of the container 30 from being hindered by the barrier container 40. Therefore, by providing a gap G, it is possible to promote a reduction in the amount of oxygen in the container 30.

[0190] The gap G can be secured by making the storage space of the barrier container 40 larger than the outer shape of the container 30. If the barrier container 40 is made of a flexible material such as a resin film, the gap G between the stopper 34 and the barrier container 40 can be formed by adjusting the shape of the barrier container 40.

[0191] As described above, the method for manufacturing the liquid-filled combination container 10L may include an inspection step in which the liquid-filled combination container 10L is inspected by the inspection method described above. In other words, after placing the liquid-filled container 30L inside the barrier container 40, an inspection step may be performed in which the oxygen concentration inside the container 30 is inspected by the inspection method described above, thereby completing the manufacturing of the liquid-filled combination container 10L.

[0192] Specifically, after placing a liquid-filled container 30L into a barrier container 40, the oxygen concentration (%) inside the container 30 may be measured using the inspection method described above to check whether the oxygen concentration (%) inside the container 30 has been sufficiently reduced. Alternatively, the change in oxygen concentration (%) inside the container 30 over time may be obtained, and based on the change in oxygen concentration (%) inside the container 30 over time, it may be checked whether the amount of dissolved oxygen (mg / L) in the liquid has been sufficiently reduced. Furthermore, based on the change in oxygen concentration (%) inside the container 30 over time, the rate of decrease in oxygen concentration (%) inside the container 30 may be calculated, and it may be checked whether the rate of decrease is sufficiently high.

[0193] In this way, a 30L liquid-filled container and a 10L liquid-filled combination container can be obtained, with the oxygen concentration and oxygen dissolution rate adjusted accordingly.

[0194] A method for manufacturing a liquid-filled combination container 10L includes the steps of closing a barrier container 40 containing a container 30, and adjusting the amount of oxygen in the container 30 contained within the barrier container 40. At least one oxygen reagent 20 capable of reacting with the oxygen in the barrier container 40 is provided. As an example, an oxygen scavenger 21 that absorbs oxygen in the barrier container 40 is provided. In the step of adjusting the amount of oxygen, the oxygen in the container 30 permeates through the container 30, thereby reducing the oxygen concentration in the container 30 and reducing the amount of dissolved oxygen in the liquid L. According to this embodiment, the oxygen concentration in the container 30 can be reduced to, for example, less than 0.3%, 0.1% or less, 0.05% or less, less than 0.03%, and even 0%. According to this embodiment, the oxygen concentration in the barrier container 40 and the oxygen concentration in the container 30 can be sufficiently reduced, for example, to less than 0.3%, 0.1% or less, 0.05% or less, less than 0.03%, and even 0%. Furthermore, the amount of oxygen dissolved in the liquid L inside the container 30 can be sufficiently reduced, for example, to less than 0.15 mg / L, 0.04 mg / L or less, preferably 0.03 mg / L or less, more preferably 0.02 mg / L or less, more preferably less than 0.015 mg / L, and even more preferably 0 mg / L. This suppresses the decomposition of the liquid L in the container 30 by oxygen. Since the oxygen absorber 21 can be placed outside the container 30, the oxygen absorber 21 does not impair the sterile condition inside the container 30.

[0195] The effects of a 30L liquid container and a 10L liquid combination container are described below. Liquid L can be decomposed by oxygen. The solvent in liquid L as an aqueous solution can be decomposed by oxygen. Solid matter such as particles contained in liquid L as a suspension can be decomposed by oxygen. Decomposition by oxygen is a more significant problem in liquid L such as food and pharmaceuticals. Highly sensitive liquid L is easily decomposed by oxygen.

[0196] As described above, the oxygen concentration in container 30 can be sufficiently reduced using the 30L liquid-filled container and the 10L liquid-filled combination container. This allows for a sufficient reduction in the amount of dissolved oxygen in the liquid L contained in container 30. The total amount of oxygen in container 30, i.e., the oxygen in the headspace HS and the dissolved oxygen in the liquid L, can be reduced. This suppresses the decomposition of the liquid L by oxygen.

[0197] Furthermore, the oxygen concentration in the headspace HS of container 30, which is not occupied by the liquid L, as shown in Figures 1 and 2, can be reduced to approximately 1.5% or less by replacing the headspace HS with an inert gas or by bubbling the liquid L with an inert gas before attaching the stopper 34 to the container body 32. For example, the oxygen concentration in the headspace HS can be reduced to between 0.5% and 1%. In addition, it is thought that the amount of oxygen dissolved in the liquid contained in the container can be reduced by manufacturing the liquid in an atmosphere replaced with an inert gas and storing the liquid in a container with oxygen barrier properties. However, installing the entire liquid manufacturing line in an atmosphere replaced with an inert gas requires extensive modifications to the manufacturing equipment and enormous capital investment. Also, in the field of expensive chemicals, in order to ensure stability against temperature, oxygen, moisture, light, etc., the chemicals are sometimes freeze-dried and stored in powder form. However, powdering liquid chemicals for storage and converting powdered chemicals back into liquid when used has significant disadvantages in terms of effort, time, and cost.

[0198] In contrast, according to this embodiment, a container 30 containing liquid L can be manufactured using existing equipment without significantly changing conventional methods. Therefore, equipment modifications and capital investments can be avoided. Particularly when applied to liquids such as pharmaceuticals, it is useful in that it eliminates the need to apply for approval from public institutions regarding changes to manufacturing equipment and manufacturing processes. Furthermore, it eliminates the need for freeze-drying liquid L or converting powder back into liquid. Moreover, there are no special constraints on the container 30. Therefore, materials such as glass and resin, which have low elution rates and are widely used as containers for food and pharmaceuticals, can be used. If the container body 32 has barrier properties, the material of the container body 32 is, for example, glass. If the container body 32 does not have barrier properties, the material of the container body 32 is polyethylene, polypropylene, etc.

[0199] Next, we will explain how to use the 10L liquid-filled combination container.

[0200] To use the liquid L contained in the combination container 10, first, the barrier container 40 is opened. Next, the liquid container 30L is removed from the opened barrier container 40. After that, the liquid L can be taken out of the liquid container 30L and used. In the illustrated container 30, the container 30 can be opened by removing the fixing device 36 from the container body 32 and then removing the stopper 34 from the container body 32. This allows the liquid L inside the container 30 to be used.

[0201] As shown in Figure 12, the liquid L may be a drug injected into the syringe 60. The liquid L may also be a liquid contained in a vial container 30. The liquid L may be an injectable drug. Examples of injectable drugs include anticancer drugs, antiviral drugs, vaccines, and antipsychotics. The syringe 60 includes a cylinder 62 and a piston 66. The cylinder 62 has a cylinder body 63 and a needle 64 protruding from the cylinder body 63. The tubular needle 64 allows access to the space in the cylinder body 63 for containing the liquid L. The piston 66 has a piston body 67 and a gasket 68 held in the piston body 67. The gasket 68 may be made of rubber or the like. The gasket 68 is inserted into the cylinder body 63 and partitions the space for containing the liquid L within the cylinder body 63. The liquid L injected into this syringe 60 may be transferred from the syringe 60 to another syringe or container before being administered to a patient or the like. In this example, the drug may be administered to the patient from a different syringe or container.

[0202] Incidentally, the pressure inside the 30L liquid container may be adjusted. For example, the pressure inside the 30L liquid container may be kept low. The pressure inside the 30L liquid container may also be kept negative. According to this example, unintended leakage of the liquid during storage of the 30L liquid container and splashing of the liquid when the container 30 is opened can be effectively suppressed. The problem of leakage and splashing becomes more serious with toxic liquids, such as highly pharmacologically active drugs.

[0203] For example, highly sensitive liquids that deteriorate after manufacturing using gas, heat, gamma rays, etc., such as food and pharmaceuticals, and more specifically anticancer drugs, antiviral drugs, vaccines, and antipsychotics, are manufactured in a sterile environment and sealed in containers. In other words, liquids to which final sterilization methods cannot be applied are manufactured using aseptic techniques. The sterile environment created by aseptic techniques is usually maintained at positive pressure to suppress bacterial invasion. Therefore, the pressure inside the container containing the liquid L becomes a predetermined positive pressure corresponding to the sterile environment.

[0204] According to this embodiment, such problems can also be addressed. As described above, the liquid-containing container 30L is stored within the barrier container 40. During this storage, oxygen within the container 30 permeates through the container 30 and moves into the barrier container 40. Due to the oxygen permeation, the pressure within the container 30 can be decreased. That is, the pressure of the container 30 containing the liquid L can be adjusted after closing the container 30 and enclosing the liquid L.

[0205] Next, the effects of the inspection method for the liquid-containing container 30L and the inspection method for the liquid-containing combined container 10L according to the first embodiment will be described. The inspection method according to the first embodiment includes a fluorescence measurement step of irradiating light onto the fluorescent material 27 provided on the inner surface 30a of the container 30 and measuring the fluorescence time or fluorescence intensity of the fluorescent material 27. Further, it includes a measurement step of measuring the oxygen concentration within the container 30 based on the fluorescence time or fluorescence intensity of the fluorescent material 27 measured in the fluorescence measurement step. Thereby, the oxygen concentration within the container 30 can be measured and inspected without opening the container 30.

[0206] In addition, in the inspection method of the first embodiment, a detection device 80 having an illumination unit 81 and a sensor unit 82 is brought into contact with the portion of the barrier container 40 that contacts the fluorescent material installation position 39, and light is irradiated onto the fluorescent material 27 using the illumination unit 81, and the fluorescence time or fluorescence intensity of the fluorescent material 27 is measured using the sensor unit 82. Because the detection device 80 is in contact with the portion of the barrier container 40 that contacts the fluorescent material installation position 39, the positional relationship of the fluorescent material 27, the illumination unit 81, and the sensor unit 82 is determined. Therefore, when measuring the oxygen concentration in the container 30 of the same liquid-filled combination container 10L at multiple time points, the positional relationship of the fluorescent material 27, the illumination unit 81, and the sensor unit 82 can be aligned at the time of measurement. Also, when measuring the oxygen concentration in the containers 30 of multiple liquid-filled combination containers 10L each, the positional relationship of the fluorescent material 27, the illumination unit 81, and the sensor unit 82 can be aligned at the time of measurement. This allows for consistent measurement conditions when measuring the oxygen concentration in a 10L container 30 containing the same liquid at multiple points in time, or when measuring the oxygen concentration in multiple 10L containers 30 containing the same liquid. This improves the accuracy of oxygen concentration measurement. Furthermore, because the detection device 80 is in contact with the portion of the barrier container 40 that contacts the fluorescent material installation position 39, the oxygen concentration can be measured with a sufficiently small distance between the illumination unit 81 and the sensor unit 82 and the fluorescent material 27. This improves the accuracy of oxygen concentration measurement.

[0207] In addition, the inspection method of the first embodiment further includes the step of bringing the detection device 80 into contact with the deformable barrier container 40, and pressing the barrier container 40 with the detection device 80 to bring it into contact with the outer surface 30b of the fluorescent material installation position 39 of the container 30. This brings the barrier container 40 into contact with the fluorescent material installation position 39 of the container 30. The detection device 80 is also brought into contact with the portion of the barrier container 40 that contacts the fluorescent material installation position 39. This allows the positional relationship between the fluorescent material 27, the illumination unit 81, and the sensor unit 82 to be determined as described above.

[0208] Moreover, the manufacturing method of the liquid-containing combined container 10L of the first embodiment inspects the liquid-containing combined container 10L by the inspection method described above. As a result, the oxygen concentration in the container 30 can be measured and inspected without opening the container 30, and then the liquid-containing combined container 10L can be manufactured.

[0209] Next, the effects of the liquid-containing container 30L and the liquid-containing combined container 10L of the first embodiment in performing the above-described inspection method will be described. The liquid-containing container 30L and the liquid-containing combined container 10L of the first embodiment include a fluorescent material 27 provided on the inner surface 30a of the container 30. Therefore, by the inspection method described above, the oxygen concentration in the container 30 can be measured and inspected without opening the container 30. Also, the oxygen concentration in the container 30 can be measured and inspected without opening the barrier container 40.

[0210] In addition, the oxygen reactant 20 is fixed to at least one of the outer surface 30b of the container 30 and the inner surface of the barrier container 40. The effect of this will be explained. Consider the case where the oxygen reactant 20 is not fixed to either the outer surface 30b of the container 30 or the inner surface of the barrier container 40. In this case, even if the oxygen reactant 20 is arranged at a position that does not prevent the irradiation of the fluorescent material 27 with the light that causes the fluorescent material 27 to fluoresce, the oxygen reactant 20 can move to a position that prevents the irradiation of the fluorescent material 27 with the light that causes the fluorescent material 27 to fluoresce. In particular, after the barrier container 40 is closed, if the oxygen reactant 20 moves to a position that prevents the irradiation of the fluorescent material 27 with light, it is difficult to correct the position of the oxygen reactant 20 without opening the barrier container 40. In contrast, the oxygen reactant 20 of the first embodiment is fixed to at least one of the outer surface 30b of the container 30 and the inner surface of the barrier container 40. Thereby, it is possible to suppress the oxygen reactant 20 from moving to a position that prevents the irradiation of the fluorescent material 27 with light. In particular, by fixing the oxygen reactant 20 at a position that does not prevent the irradiation of the fluorescent material 27 with the light that causes the fluorescent material 27 to fluoresce, the fluorescent material 27 can be irradiated with light without being blocked by the oxygen reactant 20.

[0211] In addition, the fluorescent material 27 is placed on the inner surface 30a of the fluorescent material installation position 39, which is away from the contact area 31a of the housing section 31 of the container 30. Therefore, the presence of the liquid L contained in the housing section 31 around the fluorescent material 27 suppresses a decrease in the measurement accuracy of the oxygen concentration in the gas contained in the headspace HS of the container 30.

[0212] In addition, the container 30 has a coating layer 38 that constitutes the inner surface 30a of the container 30 and suppresses the adhesion of liquid L to the inner surface 30a of the container 30. This suppresses the adhesion of liquid L to the inner surface 30a around the fluorescent material installation position 39 of the container 30, and prevents the liquid L adhering to the inner surface 30a from further migrating to the fluorescent material 27. Therefore, the reduction in the measurement accuracy of the oxygen concentration in the gas contained in the headspace HS of the container 30 due to the adhesion of liquid L to the fluorescent material 27 is suppressed.

[0213] In addition, the container 30 includes at least one of the materials glass and a cyclic olefin polymer. The above-mentioned materials have low autofluorescence intensity, i.e., the fluorescence of the material itself produced when irradiated with light. In particular, the autofluorescence intensity produced when irradiated with green light at a wavelength of 525 nm is low. Therefore, by using the above-mentioned materials as the material of the container 30, it is possible to suppress the decrease in the accuracy of measuring the fluorescence time or fluorescence intensity of the fluorescent material 27 due to the influence of the autofluorescence of the material of the container 30. This improves the accuracy of oxygen concentration measurement. Glass has particularly low autofluorescence intensity. For this reason, it is especially preferable for the container 30 to include glass. By including glass in the container 30, it is possible to more effectively suppress the decrease in the accuracy of measuring the fluorescence time or fluorescence intensity of the fluorescent material 27.

[0214] In addition, the barrier container 40 contains at least one of acrylic resin or polyethylene terephthalate resin. By using the above-mentioned materials as the material for the barrier container 40, the oxygen barrier properties of the barrier container 40 can be ensured. Furthermore, by using the above-mentioned materials as the material for the barrier container 40, the thickness of the wall surface of the barrier container 40 can be reduced. This makes it easier to ensure the transparency of the barrier container 40. As a result, light can be efficiently irradiated onto the fluorescent material 27 from the outside of the barrier container 40. Furthermore, the fluorescence time or fluorescence intensity of the fluorescent material 27 can be accurately measured from the outside of the barrier container 40. In addition, it becomes easy to provide the barrier container 40 with the flexibility to be deformable so as to contact the outer surface 30b of the fluorescent material installation position 39 of the container 30. Furthermore, the above-mentioned materials have low autofluorescence intensity. In particular, the autofluorescence intensity produced when irradiated with green light at a wavelength of 525 nm is low. Therefore, by using the above-mentioned material as the material for the barrier container 40, it is possible to suppress the reduction in the accuracy of measuring the fluorescence time or fluorescence intensity of the fluorescent material 27 due to the influence of autofluorescence of the barrier container 40 material. This improves the accuracy of oxygen concentration measurement.

[0215] In addition, the adhesive layer 28 that adheres the fluorescent material 27 to the inner surface 30a of the container 30 contains at least one resin selected from the group consisting of non-fluorescent photocurable acrylic resins, photocurable silicone resins, and epoxy resins. By using the above-mentioned materials as the material for the adhesive layer 28, the transparency of the adhesive layer 28 can be ensured. Therefore, light can be efficiently irradiated onto the fluorescent material 27 through the adhesive layer 28. Furthermore, the fluorescence time or fluorescence intensity of the fluorescent material 27 can be accurately measured through the adhesive layer 28.

[0216] Furthermore, by using the above-mentioned material as the material for the adhesive layer 28, it is possible to suppress the dissolution of the adhesive layer 28 material into the liquid L when it comes into contact with the liquid L. For example, when the adhesive layer 28 is subjected to the elution test of the plastic pharmaceutical container test method specified in the 18th edition of the Japanese Pharmacopoeia, it meets the standards for elutions of polyethylene or polypropylene aqueous injection containers. That is, when the elution test of the plastic pharmaceutical container test method specified in the Japanese Pharmacopoeia is performed, in the foaming test, the foam generated almost disappears within 3 minutes. Also, in the pH test, the difference between the test solution and the blank solution is 1.5 or less. Also, in the potassium manganate reducing substance test, the difference in the amount of 0.002 mol / L potassium permanganate solution consumed is 1.0 ml or less. Also, in the ultraviolet absorption spectrum test, the absorbance at wavelengths of 220 nm to less than 241 nm is 0.08 or less, and the absorbance at wavelengths of 241 nm to 350 nm is 0.05 or less. Furthermore, in the evaporation residue test, the mass of the evaporation residue is 1.0 mg or less.

[0217] Furthermore, the materials described above are medical adhesives that can be used in living organisms such as humans. In particular, the materials described above are materials that are used as adhesives in living organisms such as humans and are considered to have little effect on living organisms even if they dissolve into the liquids of the body. For this reason, by using the materials described above as the material for the adhesive layer 28, even if the material of the adhesive layer 28 dissolves into the liquid L, the impact of the dissolution of the adhesive layer 28 on the liquid L and on living organisms that ingest the liquid L can be reduced. In particular, when the liquid L is a liquid L that is ingested by living organisms such as food or medicine, the impact of the dissolution of the adhesive layer 28 on the liquid L and on living organisms that ingest the liquid L can be reduced. Non-fluorescent photocurable acrylic resins are considered to have particularly little effect on living organisms. For this reason, it is particularly preferable that the adhesive layer 28 contains a non-fluorescent photocurable acrylic resin. By containing a non-fluorescent photocurable acrylic resin in the container 30, the impact of the dissolution of the adhesive layer 28 on the liquid L and on living organisms that ingest the liquid L can be reduced more effectively. In addition, the materials described above have low fluorescence intensity of the material itself, such as autofluorescence of the resin contained in the material. In particular, the fluorescence intensity of the material itself, which is produced when irradiated with green light at a wavelength of 525 nm, is low. Therefore, by using the above-mentioned material as the material for the adhesive layer 28, it is possible to suppress the decrease in the accuracy of measuring the fluorescence time or fluorescence intensity of the fluorescent material 27 due to the influence of autofluorescence of the adhesive layer 28 material.

[0218] For example, the container 30 is transparent at least at the fluorescent material placement position 39. The barrier container 40 is also transparent at least in the portion that contacts the outer surface 30b of the fluorescent material placement position 39. This allows light to be efficiently irradiated onto the fluorescent material 27 through the container 30 and the barrier container 40.

[0219] It is possible to make various modifications to the first embodiment described above. Hereinafter, modifications of the first embodiment will be described with reference to the drawings as necessary. In the following description and the drawings used therein, parts that can be configured in the same way as in the first embodiment will be given the same reference numerals as those used for the corresponding parts in the first embodiment, and redundant explanations may be omitted. Also, if it is clear that the effects and advantages obtained in the first embodiment can be obtained in the modifications, the explanation may be omitted.

[0220] (Variation 1) In the first embodiment described above, a method for inspecting a liquid-filled combination container 10L was shown, which includes the step of bringing the barrier container 40 into contact with the outer surface 30b of the fluorescent material placement position 39 of the container 30 by pressing the barrier container 40 with the detection device 80. However, the method of bringing the barrier container 40 into contact with the outer surface 30b of the fluorescent material placement position 39 of the container 30 is not limited to this.

[0221] Figure 13 shows an example of the inspection method for a liquid-filled combination container 10L according to Modification 1, in which the barrier container 40 is in contact with the outer surface 30b of the fluorescent material placement position 39 of the container 30. Figure 14 shows another example of the inspection method for a liquid-filled combination container 10L according to Modification 1, in which the barrier container 40 is in contact with the outer surface 30b of the fluorescent material placement position 39 of the container 30. The liquid-filled combination container 10L shown in Figures 13 and 14 comprises the liquid-filled container 30L shown in Figures 1 and 2, and the barrier container 40 shown in Figure 4 that contains the liquid-filled container 30L. Figures 13 and 14 correspond to cross-sectional views of the liquid-filled combination container 10L in which the barrier container 40 is in contact with the outer surface 30b of the fluorescent material placement position 39 of the container 30. In the example shown in Figures 13 and 14, the liquid-filled combination container 10L comprises one oxygen reagent 20. In the examples shown in Figures 13 and 14, the oxygen reagent 20 is the oxygen scavenger 21. In the example shown in Figure 13, the oxygen reagent 20 is fixed to the inner surface of the barrier container 40. In the example shown in Figure 14, the oxygen reagent 20 is fixed to the outer surface 30b of the container 30. In the example shown in Figure 14, the oxygen reagent 20 is fixed to the stopper 34 of the container 30.

[0222] In the example shown in Figure 13, the liquid-filled combination container 10L further comprises a shrink film 91 wrapped around the outer circumference of the barrier container 40 so as to cover the fluorescent material placement position 39 of the container 30. The shrink film 91 is a heat-shrinkable resin film. The material of the shrink film 91 is, for example, polystyrene, polypropylene, polyethylene terephthalate, or polyvinyl chloride. In the example shown in Figure 13, heat is applied to the shrink film 91 wrapped around the outer circumference of the barrier container 40, causing the shrink film 91 to shrink, thereby bringing the barrier container 40 into contact with the outer surface 30b of the fluorescent material placement position 39 of the container 30. In the liquid-filled combination container 10L shown in Figure 13, the barrier container 40 is fixed to the container 30 by the shrink film 91. In the liquid-filled combination container 10L shown in Figure 13, the positional relationship between the fluorescent material 27, the illumination unit 81, and the sensor unit 82 can be determined by bringing the detection device 80 into contact with the portion of the shrink film 91 that overlaps with the fluorescent material installation position 39.

[0223] In the example shown in Figure 14, the barrier container 40 is brought into contact with the outer surface 30b of the fluorescent material placement position 39 on the container 30 by degassing the inside of the barrier container 40 to create a vacuum. In the liquid-filled combination container 10L shown in Figure 14, the barrier container 40 is fixed to the container 30 by degassing the inside of the barrier container 40.

[0224] It is preferable that no wrinkles are formed in the portion of the barrier container 40 that comes into contact with the outer surface 30b of the container 30 where the fluorescent material is installed. By preventing wrinkle formation, a decrease in the accuracy of oxygen concentration measurement due to wrinkles can be suppressed. For example, wrinkles in that portion can cause diffuse reflection of light irradiated onto the fluorescent material 27 or the fluorescence of the fluorescent material 27, thereby suppressing a decrease in the accuracy of oxygen concentration measurement.

[0225] In the embodiment shown in Figure 13 or Figure 14, when the barrier container 40 is brought into contact with the outer surface 30b of the fluorescent material placement position 39 of the container 30, the operation of bringing the barrier container 40 into contact with the outer surface 30b of the fluorescent material placement position 39 of the container 30 may be performed after the step of adjusting the oxygen amount in the manufacturing of the liquid-filled combination container 10L, and before the inspection method for the liquid-filled combination container 10L is performed. Alternatively, the operation of bringing the barrier container 40 into contact with the outer surface 30b of the fluorescent material placement position 39 of the container 30 may be performed before the step of adjusting the oxygen amount in the manufacturing of the liquid-filled combination container 10L. The operation of bringing the barrier container 40 into contact with the outer surface 30b of the fluorescent material placement position 39 of the container 30 may be, for example, an operation of wrapping shrink film 91 around the barrier container 40 and applying heat, or an operation of degassing the inside of the barrier container 40 to create a vacuum.

[0226] When manufacturing a 10L liquid-filled combination container, if the barrier container 40 is brought into contact with the outer surface 30b of the fluorescent material installation position 39 of the container 30 before the oxygen adjustment process, or if the oxygen adjustment process is expected to be performed after the inspection method, the following points may be noted. Care may be taken to ensure that the movement of oxygen between the oxygen-permeable portion of the container 30 and the oxygen reagent 20 is not hindered by bringing the barrier container 40 into contact with the outer surface 30b of the fluorescent material installation position 39 of the container 30. This allows, if the oxygen reagent 20 is an oxygen scavenger 21, to rapidly reduce the oxygen that has permeated the oxygen-permeable portion of the container 30 by oxygen absorption by the oxygen scavenger 21. Furthermore, if the oxygen reagent 20 is an oxygen detection material 25, the oxygen state of the space inside the barrier container 40 into which the oxygen that has permeated the oxygen-permeable portion of the container 30 flows can be detected by the oxygen detection material 25. In the example shown in Figure 13, the barrier container 40 is in contact with the outer surface 30b of the container 30 around its entire circumference, including the fluorescent material placement position 39. Therefore, the movement of oxygen-containing gas is hindered between the first space S1 located above the fluorescent material placement position 39 and the second space S2 located below the fluorescent material placement position 39 within the barrier container 40. In the example shown in Figure 13, the stopper 34 of the container 30 is oxygen-permeable. The stopper 34, which is the oxygen-permeable part of the container 30, is located in the first space S1. In this case, as shown in Figure 13, the oxygen reagent 20 may be placed in the first space S1. In this case, the movement of oxygen between the oxygen-permeable part of the container 30 and the oxygen reagent 20 is not hindered. In the example shown in Figure 13, the oxygen reagent 20 is an oxygen scavenger 21. Therefore, the oxygen that has permeated the oxygen-permeable part of the container 30 can be rapidly reduced by the oxygen absorption of the oxygen scavenger 21. Although not shown in the diagram, when the oxygen reagent 20 is placed in the second space S2, the barrier container 40 may be brought into contact with the outer surface 30b of the fluorescent material placement position 39 of the container 30, such that a gap remains between the barrier container 40 and the container 30 connecting the first space S1 and the second space S2. In this case as well, it is possible to suppress obstruction of oxygen movement between the oxygen-permeable portion of the container 30 and the oxygen reagent 20.When the oxygen reactant 20 is the deoxidizer 21, the oxygen that has permeated through the oxygen-permeable portion of the container 30 can be rapidly reduced by the oxygen absorption of the deoxidizer 21.

[0227] (Modified Example 2) The barrier container 40 may be designed such that when the container 30 is housed in the barrier container 40, the barrier container 40 naturally comes into contact with the outer surface 30b of the fluorescence material installation position 39 of the container 30. FIG. 15 is a view showing the liquid-containing combined container 10L of Modified Example 2. FIG. 15 corresponds to a cross-sectional view of the liquid-containing combined container 10L in a state where the barrier container 40 is in contact with the outer surface 30b of the fluorescence material installation position 39 of the container 30.

[0228] The barrier container 40 of the liquid-containing combined container 10L shown in FIG. 15 does not have deformable flexibility. The barrier container 40 shown in FIG. 15 is a vial. The barrier container 40 has a container body 42 and a lid 44 inserted into the opening 45 of the container body 42. The material of the container body 42 is, for example, glass or resin. The container body 42 may be a glass bottle. The opening 45 of the container body 42 has a size that can accommodate the container 30. The liquid-containing container 30L of the liquid-containing combined container 10L shown in FIG. 15 is the same as the liquid-containing container 30L shown in FIGS. 1 and 2. In the example shown in FIG. 15, the liquid-containing combined container 10L includes one oxygen reactant 20. In the example shown in FIG. 15, the oxygen reactant 20 is the deoxidizer 21. In the example shown in FIG. 15, the oxygen reactant 20 is fixed to the outer surface 30b of the container 30. In the example shown in FIG. 15, the oxygen reactant 20 is fixed to the stopper 34 of the container 30.

[0229] The barrier container 40 shown in Figure 15 is designed such that when the container 30 is placed inside the barrier container 40, the barrier container 40 automatically comes into contact with the outer surface 30b of the fluorescent material placement position 39 of the container 30. As described above, the container 30 is a vial bottle having a glass bottle body 32 and a stopper 34. The container 30 has a roughly cylindrical outer shape. The barrier container 40 also has a roughly cylindrical outer shape. As shown in Figure 15, the outer diameter w1 of the container 30 matches the inner diameter w2 of the barrier container 40. Therefore, when the container 30 is placed inside the barrier container 40, the barrier container 40 automatically comes into contact with the outer surface 30b of the fluorescent material placement position 39 of the container 30. In the liquid-filled combination container 10L shown in Figure 15, the container 30 of the liquid-filled combination container 10L is in a stationary state, particularly in an upright state. In this state, the horizontal movement of container 30 is suppressed by the barrier container 40. Furthermore, the vertical movement of container 30 is also suppressed by the barrier container 40. In the liquid-filled combination container 10L shown in Figure 15, by placing container 30 inside the barrier container 40, gravity is utilized to fix the barrier container 40 to container 30.

[0230] The barrier container 40 shown in Figure 15 can stably maintain contact between the barrier container 40 and the outer surface 30b of the container 30 where the fluorescent material is installed 39. In the barrier container 40 shown in Figure 15, the positional relationship between the fluorescent material 27, the illumination unit 81, and the sensor unit 82 can be determined by bringing the detection device 80 into contact with the part of the barrier container 40 that contacts the fluorescent material installation position 39.

[0231] Furthermore, the barrier container 40 shown in Figure 15 does not have deformable flexibility, and therefore can contain a gas while maintaining negative pressure in an atmospheric environment. Being able to contain a gas while maintaining negative pressure under atmospheric pressure means that the gas can be contained without damage while maintaining an internal pressure of 0.80 atm or higher. The barrier container 40, which can contain a gas while maintaining negative pressure under atmospheric pressure, may also be airtight when the internal pressure is 0.80 atm. The container, which can contain a gas while maintaining negative pressure under atmospheric pressure, may maintain a volume of 95% or more of its volume at an internal pressure of 0.80 atm compared to its volume at 1.0 atm. The barrier container 40 may also be able to contain a gas while maintaining positive pressure under atmospheric pressure. Being able to contain a gas while maintaining positive pressure under atmospheric pressure means that the gas can be contained without damage while maintaining an internal pressure of 1.2 atm or higher. A barrier container 40 capable of containing a gas while maintaining a positive pressure under atmospheric pressure may be airtight when the internal pressure is 1.20 atm. A container capable of containing a gas while maintaining a positive pressure under atmospheric pressure may maintain its volume at an internal pressure of 1.2 atm at 105% or less of its volume at an internal pressure of 1.0 atm. The barrier container 40 has sufficient rigidity to maintain its shape. However, the barrier container 40 may deform somewhat in the atmosphere when maintaining a negative or positive internal pressure.

[0232] Thus, when using a barrier container 40 capable of containing a gas while maintaining negative pressure in an atmospheric environment, the barrier container 40 containing the container 30 may be closed under the negative pressure atmosphere. The pressure inside the closed barrier container 40 will be less than atmospheric pressure. In this case, oxygen permeation from the container 30 to the barrier container 40 is promoted. In particular, the pressure inside the container 30 can be significantly adjusted by ensuring a large volume of the barrier container 40 or by significantly reducing the initial pressure inside the barrier container 40. As a result, the pressure inside the container 30, which was initially positive, can be adjusted to negative pressure by storing the container 30 inside the barrier container 40. This makes it possible to produce a pressure-controlled liquid container 30L without depending on the method of manufacturing the liquid L or the environment in which the liquid L is sealed into the container 30.

[0233] Furthermore, closing the barrier container 40 under negative pressure promotes oxygen permeation through the container 30. Therefore, the time required for oxygen permeation through the container 30 to reach equilibrium after closing the barrier container 40 containing the liquid container 30L can be shortened.

[0234] Negative pressure refers to pressure below atmospheric pressure (1 atm). Positive pressure refers to pressure above atmospheric pressure (1 atm). Whether or not a container is under negative pressure can be determined using a pressure gauge if one is provided. If a container is not equipped with a pressure gauge, it can also be determined using a syringe. Specifically, when the needle of a syringe is inserted into the container, it can be determined by whether or not the liquid or gas contained in the syringe flows into the container while only atmospheric pressure is applied to the syringe piston. If the liquid or gas contained in the syringe flows into the container, it is determined that the container was under negative pressure. Similarly, whether or not a container is under positive pressure can be determined using a pressure gauge, but it can also be determined using a syringe. Specifically, when the needle of a syringe is inserted into the container, it can be determined by whether or not the liquid or gas contained in the container flows into the syringe while only atmospheric pressure is applied to the syringe piston. If the liquid or gas contained in the container flows into the syringe, it is determined that the container was under positive pressure.

[0235] (Variation 3) The container 30 may be fixed to the barrier container 40. For example, the container 30 may be fixed to the barrier container 40 so that its position relative to the barrier container 40 does not change even if the orientation of the liquid-filled combination container 10L is changed. When the container 30 of the liquid-filled combination container 10L is in a stationary state, especially when the container 30 is upright, the container 30 may be fixed to the barrier container 40 by the action of gravity. For example, the container 30 may be fixed to the barrier container 40 by a first fixing member 921 that is different from the container 30 and the barrier container 40. By being fixed to the barrier container 40, the container 30 may be in contact with the outer surface 30b of the fluorescent material installation position 39 of the container 30.

[0236] Figure 16 shows a modified example of a 10L liquid-filled combination container. The barrier container 40 of the 10L liquid-filled combination container shown in Figure 16 is the same as the barrier container 40 shown in Figure 15, except for its dimensions. The liquid-filled container 30L of the 10L liquid-filled combination container shown in Figure 16 is the same as the liquid-filled container 30L shown in Figures 1 and 2. In the example shown in Figure 16, the 10L liquid-filled combination container is equipped with one oxygen reagent 20. In the example shown in Figure 16, the oxygen reagent 20 is an oxygen scavenger 21. In the example shown in Figure 16, the oxygen reagent 20 is sandwiched between the outer surface 30b of the container 30 and the inner surface of the barrier container 40. This suppresses the horizontal movement of the oxygen reagent 20. In the example shown in Figure 16, the container 30 of the 10L liquid-filled combination container is in a stationary state, particularly in an upright state. In this state, the vertical movement of the oxygen reagent 20 is suppressed by the action of gravity. This ensures that it is fixed to the outer surface 30b of container 30 and the inner surface of barrier container 40.

[0237] In the example shown in Figure 16, container 30 is fixed to the barrier container 40 by a first fixing member 921 that is different from container 30 and the barrier container 40. In the example shown in Figure 16, the inner diameter w2 of the barrier container 40 is larger than the outer diameter w1 of container 30. Therefore, simply placing container 30 in the barrier container 40 does not fix the position of the barrier container 40 relative to container 30. In this case, as in the example shown in Figure 16, container 30 may be fixed to the barrier container 40 by a first fixing member 921 that is different from container 30 and the barrier container 40. In the example shown in Figure 16, the space between container 30 and the barrier container 40 is occupied by the first fixing member 921, thereby suppressing the horizontal movement of the barrier container 40 relative to container 30. In the example shown in Figure 16, container 30 of the liquid-filled combination container 10L is in a stationary state, particularly in an upright state. In this state, vertical movement of the barrier container 40 relative to the container 30 is suppressed by the action of gravity. As a result, the container 30 is fixed to the barrier container 40. By fixing the container 30 to the barrier container 40, the barrier container 40 may be brought into contact with the outer surface 30b of the fluorescent material installation position 39 of the container 30. For example, the first fixing member 921 is provided inside the barrier container 40. The first fixing member 921 is sandwiched between the outer surface 30b of the container 30 and the inner surface of the barrier container 40, thereby fixing the container 30 to the barrier container 40 and bringing the barrier container 40 into contact with the outer surface 30b of the fluorescent material installation position 39 of the container 30.

[0238] In the example shown in Figure 16, the oxygen reagent 20 also serves as the first fixing member 921. That is, the oxygen reagent 20 is sandwiched between the outer surface 30b of the container 30 and the inner surface of the barrier container 40, thereby fixing the container 30 to the barrier container 40. Although not shown, the first fixing member 921 may be a different material from the oxygen reagent 20. As the first fixing member 921, a member that fixes the container 30 to the barrier container 40 and brings the barrier container 40 into contact with the outer surface 30b of the fluorescent material installation position 39 of the container 30 is used as appropriate, depending on the form of the container 30 and the barrier container 40.

[0239] [Second Embodiment] Next, a second embodiment will be described. In the following description and the drawings used therein, parts that can be configured in the same way as the first embodiment and variations 1 to 3 described above will be given the same reference numerals as those used for the corresponding parts in the first embodiment and variations 1 to 3 described above, and redundant explanations may be omitted. Also, if it is clear that the effects and advantages obtained in the first embodiment and variations 1 to 3 described above can also be obtained in the second embodiment, the explanation may be omitted.

[0240] Figures 17 and 18 illustrate a second embodiment of the present disclosure. The liquid-filled combination container 10L of the second embodiment, like the liquid-filled combination container 10L of the first embodiment, comprises a container 30 that contains liquid L in a storage section 31 and is oxygen-permeable, and a barrier container 40 that contains the container 30 and is oxygen-barrier.

[0241] Furthermore, in the second embodiment, the oxygen concentration inside the liquid-filled combination container 10L can be inspected by irradiating the liquid-filled combination container 10L with laser light or LED light of a wavelength attenuated according to the oxygen concentration in the optical path LA, so as to transmit the light to a portion of the container 30 away from the contact area 31a of the housing portion 31, and measuring the attenuation rate of the laser light or LED light.

[0242] Figure 17 shows an example of a liquid-filled combination container 10L according to the second embodiment. The liquid-filled combination container 10L shown in Figure 17 is the same as the liquid-filled combination container 10L shown in Figure 13, except that it does not include the fluorescent material 27. That is, the liquid-filled combination container 10L shown in Figure 17 includes a liquid-filled container 30L and a barrier container 40, as well as a shrink film 91 wrapped around the outer circumference of the barrier container 40. In the liquid-filled combination container 10L shown in Figure 17, the barrier container 40 is in contact with the outer surface 30b of the container 30 due to the thermal shrinkage of the shrink film 91 wrapped around the outer circumference of the barrier container 40. Figure 18 shows another example of a liquid-filled combination container 10L according to the second embodiment. The liquid-filled combination container 10L shown in Figure 18 is the same as the liquid-filled combination container 10L shown in Figure 14, except that it does not include the fluorescent material 27. In other words, in the liquid-filled combination container 10L shown in Figure 18, the barrier container 40 is in contact with the outer surface 30b of the container 30 by degassing the inside of the barrier container 40 to create a vacuum.

[0243] In the second embodiment, the container 30 has a first position 35a and a second position 35b that are separated from the contact area 31a of the housing 31. The container 30 is light-transmitting at least at the first position 35a and the second position 35b. The barrier container 40 is light-transmitting at least at positions that intersect the straight line connecting the first position 35a and the second position 35b. In the examples shown in Figures 17 and 18, the straight line representing the optical path LA corresponds to the straight line connecting the first position 35a and the second position 35b. The barrier container 40 is light-transmitting at least at positions that intersect the straight line representing the optical path LA. In the examples shown in Figures 17 and 18, the barrier container 40 is in contact with the outer surfaces 30b of the first position 35a and the second position 35b of the container 30. In particular, the barrier container 40 is in contact with the outer surfaces 30b of the first position 35a and the second position 35b of the container 30 at the light-transmitting positions. In this case, the attenuation rate of the laser or LED light can be measured by irradiating the liquid-filled combination container 10L with laser or LED light so as to pass through the first position 35a and the second position 35b of the container 30. The dashed line in the drawing indicates the optical path LA of the laser or LED light.

[0244] In the examples shown in Figures 17 and 18, the barrier container 40 is in contact with the container 30 over its entire circumference at a position away from the contact area 31a of the housing portion 31 of the container 30, and above the contact area 31a. In other words, the barrier container 40 is in contact with the container 30 over its entire circumference at a position in contact with the headspace HS of the container 30. In this case, the first position 35a and the second position 35b are defined as follows: The first position 35a is defined as any position away from the contact area 31a of the housing portion 31 of the container 30 and in contact with the barrier container 40. The second position 35b is defined as any position away from the contact area 31a of the housing portion 31 of the container 30 and in contact with the barrier container 40, and through which laser light or LED light that has passed through the first position 35a and the headspace HS can pass. In other words, the first position 35a and the second position 35b are located on either side of the headspace HS.

[0245] In the examples shown in Figures 17 and 18, the optical path LA of the laser or LED light passing through the first position 35a and the second position 35b is perpendicular to the wall surface of the container 30 at the first position 35a and perpendicular to the wall surface of the container 30 at the second position 35b. In other words, the first position 35a and the second position 35b are positioned such that the optical path LA of the laser or LED light passing through the first position 35a and the second position 35b is perpendicular to the wall surface of the container 30 at the first position 35a and perpendicular to the wall surface of the container 30 at the second position 35b.

[0246] The liquid-filled combination container 10L of the second embodiment further comprises at least one oxygen reagent 20 that can react with oxygen in the barrier container 40. The oxygen reagent 20 is fixed to at least one of the outer surface 30b of the container 30 and the inner surface of the barrier container 40. In the examples shown in Figures 17 and 18, the liquid-filled combination container 10L comprises one oxygen reagent 20. In the examples shown in Figures 17 and 18, the oxygen reagent 20 is an oxygen scavenger 21. In the example shown in Figure 17, the oxygen reagent 20 is fixed to the inner surface of the barrier container 40. In the example shown in Figure 18, the oxygen reagent 20 is fixed to the outer surface 30b of the container 30. In the example shown in Figure 18, the oxygen reagent 20 is fixed to the stopper 34 of the container 30.

[0247] In the second embodiment, the oxygen reagent 20 is fixed in a position that does not obstruct the transmission of laser light or LED light through the first position 35a and the second position 35b of the container 30 when inspecting the oxygen concentration inside the container 30 in the inspection method for the liquid-containing combination container 10L described later.

[0248] In the second embodiment, the oxygen reagent 20 is spaced apart from the straight line connecting the first position 35a and the second position 35b. In the examples shown in Figures 17 and 18, the straight line representing the optical path LA corresponds to the straight line connecting the first position 35a and the second position 35b. The oxygen reagent 20 is spaced apart from the straight line representing the optical path LA. In other words, the oxygen reagent 20 is not located on the straight line connecting the first position 35a and the second position 35b. As a result, by making the straight line connecting the first position 35a and the second position 35b the optical path LA, laser light or LED light can be irradiated so as to pass through the container 30.

[0249] For example, when the oxygen reagent 20 is fixed to the outer surface 30b of the container 30, the oxygen reagent 20 is fixed to a position on the outer surface 30b of the container 30 that does not overlap with the first position 35a and the second position 35b. For example, when the oxygen reagent 20 is fixed to the inner surface of the barrier container 40, the oxygen reagent 20 is fixed to a position on the inner surface of the barrier container 40 that does not overlap with the first position 35a and the second position 35b in a direction perpendicular to the inner surface of the barrier container 40.

[0250] The positional relationship between the container 30 and the oxygen reagent 20 may be predetermined. A predetermined positional relationship between the container 30 and the oxygen reagent 20 means that the relative movement of the oxygen reagent 20 relative to the container 30 is suppressed. For example, the positional relationship between the container 30 and the oxygen reagent 20 is determined by fixing the oxygen reagent 20 to the outer surface 30b of the container 30. Another example is that the positional relationship between the container 30 and the oxygen reagent 20 is determined via the barrier container 40 by fixing the oxygen reagent 20 to the inner surface of the barrier container 40, and furthermore, as described later, fixing the container 30 to the barrier container 40.

[0251] In the example shown in Figure 18, the oxygen reagent 20 is located on the second surface 34f of the stopper 34. In the example shown in Figure 18, the liquid-filled combination container 10L is placed on the mounting surface with the container 30 in an upright position. In other words, the liquid-filled combination container 10L is placed on the mounting surface with the opening 33 of the container body 32 facing upwards. In the example shown in Figure 18, the oxygen reagent 20 is located above the stopper 34.

[0252] A method for testing the oxygen concentration inside a container 30 of a liquid-filled combination container 10L according to a second embodiment will be described. The method for testing the oxygen concentration inside a liquid-filled combination container 10L is comprised of a decay rate measurement step and a measurement step. The method for testing the oxygen concentration inside a liquid-filled combination container 10L is further comprised of a step of bringing a barrier container 40 into contact with the outer surfaces 30b of the container 30 at first positions 35a and second positions 35b. The method for testing the oxygen concentration inside a liquid-filled combination container 10L is further comprised of a first standard sample measurement step and a second standard sample measurement step.

[0253] In the step of bringing the barrier container 40 into contact with the outer surfaces 30b of the first position 35a and second position 35b of the container 30, for example, a shrink film 91 is wrapped around the barrier container 40 and heat is applied, or the inside of the barrier container 40 is degassed to create a vacuum. By wrapping the shrink film 91 around the barrier container 40 and applying heat, the barrier container 40 comes into contact with the outer surfaces 30b of the first position 35a and second position 35b of the container 30, as shown in the example in Figure 17. By degassing the inside of the barrier container 40 to create a vacuum, the barrier container 40 comes into contact with the outer surfaces 30b of the first position 35a and second position 35b of the container 30, as shown in the example in Figure 18. In this step, the barrier container 40 is brought into contact with the outer surfaces 30b of the first position 35a and second position 35b of the container 30 at a position that is light-transmitting.

[0254] The specific method for bringing the barrier container 40 into contact with the outer surfaces 30b of the first position 35a and the second position 35b of the container 30 is not limited to the example described above, and a wide range of methods can be used to bring the barrier container 40 into contact with the outer surfaces 30b of the first position 35a and the second position 35b of the container 30.

[0255] It is preferable that no wrinkles are formed in the portion of the barrier container 40 that comes into contact with the outer surface 30b of the first position 35a and the second position 35b of the container 30. By preventing wrinkle formation, it is possible to suppress a decrease in the measurement accuracy of oxygen concentration due to wrinkles in the measurement process described later. For example, it is possible to suppress the reduction in the measurement accuracy of oxygen concentration caused by the irregular reflection of laser light or LED light transmitted through the first position 35a and the second position 35b of the container 30 due to wrinkles in that portion.

[0256] In the attenuation rate measurement process, laser light or LED light is irradiated onto the liquid-filled combination container 10L so as to penetrate the portion of the container 30 that is away from the contact area 31a of the housing portion 31, and the attenuation rate of the laser light or LED light is measured. In particular, when the barrier container 40 is in contact with the outer surfaces 30b of the first position 35a and the second position 35b that are away from the contact area 31a of the housing portion 31 of the container 30, laser light or LED light is irradiated onto the liquid-filled combination container 10L so as to penetrate the light-transmitting position of the barrier container 40 and the first position 35a and the second position 35b of the container 30.

[0257] The attenuation rate of laser light or LED light is measured using a measuring device 95. The measuring device 95 has a light source 951 that irradiates laser light or LED light, and a measuring instrument 952 that measures the attenuation rate of laser light or LED light. The measurement of the attenuation rate of laser light or LED light in the attenuation rate measurement process, and the measurement of oxygen concentration in the measurement process described later, are performed using a so-called headspace analyzer method. The measuring device 95 is a so-called headspace analyzer. A desktop headspace analyzer or an inline headspace analyzer may be used as the headspace analyzer. A desktop headspace analyzer is small enough to be placed on a desk and can measure the oxygen concentration inside a combined container 10L containing liquid to be measured by manually setting up the combined container 30 containing the liquid. An inline headspace analyzer is a headspace analyzer that can automatically measure the oxygen concentration inside the container 30 of the produced combined container 10L containing liquid by being incorporated into a production line that produces the combined container 10L containing liquid. The headspace analyzer used as the measuring device 95 is, for example, the Lighthouse FMS760 headspace analyzer.

[0258] In the attenuation rate measurement process, first, the light source 951 is positioned so that the laser light or LED light passes through a portion of the container 30 that is away from the contact area 31a. The measuring instrument 952 is then positioned to measure the intensity of the laser light or LED light that has passed through the portion of the container 30 that is away from the contact area 31a. In other words, the measuring instrument 952 is positioned so that the optical path LA of the laser light or LED light extends from the light source 951 to the measuring instrument 952. As an example, in the measuring device 95, the positional relationship between the light source 951 and the measuring instrument 952 is predetermined. In this case, the portion of the container 30 that is away from the contact area 31a is positioned between the light source 951 and the measuring instrument 952. In the example shown in Figures 17 and 18, the light source 951 is positioned so that the laser light or LED light passes through the first position 35a and the second position 35b of the container 30.

[0259] Next, the light source 951 is used to irradiate the container 30 with laser light or LED light so that it penetrates the portion of the container 30 that is away from the contact area 31a. Then, the measuring instrument 952 is used to measure the attenuation rate of the laser light or LED light that has penetrated the portion of the container 30 that is away from the contact area 31a. Frequency modulation spectroscopy may be used to measure the attenuation rate in the attenuation rate measurement step. That is, frequency modulation may be applied to the irradiated laser light or LED light, the light that has passed through the container 30 that is away from the contact area 31a is demodulated, and the attenuation rate may be measured by finding the difference between the light before modulation and the light after demodulation.

[0260] As an example, the laser or LED light irradiated onto the 10L liquid-filled combination container has a wavelength that is attenuated according to the oxygen concentration in the optical path LA. The wavelength of the laser or LED light includes wavelengths that are absorbed by oxygen. Therefore, the laser or LED light is attenuated according to the oxygen concentration in the optical path LA because a portion of the wavelength included in the laser or LED light is absorbed by oxygen. As an example, laser or LED light with a wavelength of 760 nm is absorbed by oxygen. Therefore, the wavelength of the laser or LED light may include a wavelength of 760 nm. From the viewpoint of improving the accuracy of oxygen concentration measurement by selectively irradiating the 10L liquid-filled combination container with light of a wavelength that is attenuated according to the oxygen concentration in the optical path LA, it is preferable that the light irradiated onto the 10L liquid-filled combination container is laser light.

[0261] "Attenuation rate" is a value that represents the ratio of the intensity of the laser light or LED light measured by the measuring instrument 952 to the intensity of the laser light or LED light emitted from the light source 951. In particular, the attenuation rate may be measured as the ratio of the intensity of the laser light or LED light at a wavelength measured by the measuring instrument 952 to the intensity at a wavelength that is thought to be attenuated according to the oxygen concentration of the optical path LA of the laser light or LED light emitted from the light source 951. For example, the attenuation rate may be measured as the ratio of the intensity of the laser light or LED light at a wavelength of 760 nm measured by the measuring instrument 952 to the intensity of the laser light or LED light at a wavelength of 760 nm to the intensity of the laser light or LED light emitted from the light source 951 at a wavelength of 760 nm.

[0262] The measuring instrument 952 may measure information other than intensity of the light emitted from the light source 951. For example, the measuring instrument 952 may measure the difference in amplitude and the difference in wavelength per period of the light emitted from the light source 951. In this case, the attenuation rate may be corrected using information other than intensity measured by the measuring instrument 952. In this case, the oxygen concentration in the container 30 may be measured based on the corrected attenuation rate in the measurement process described later.

[0263] Measuring the attenuation rate in the attenuation rate measurement process includes measuring a numerical value that changes according to the attenuation rate, for example, a numerical value that is proportional to the attenuation rate. Furthermore, measuring the oxygen concentration in container 30 based on the attenuation rate in the measurement process described later includes measuring the oxygen concentration in container 30 based on a numerical value that changes according to the attenuation rate, thereby substantially measuring the oxygen concentration in container 30 based on the attenuation rate. For example, measuring the oxygen concentration in container 30 based on the attenuation rate in the measurement process described later includes measuring the oxygen concentration in container 30 based on a numerical value that is proportional to the attenuation rate. Moreover, in the measurement process described later, the oxygen concentration may be measured by combining measuring the oxygen concentration based on the attenuation rate of light intensity and measuring the oxygen concentration based on a numerical value that changes according to the attenuation rate. This allows for more accurate measurement of the oxygen concentration. In addition, in the attenuation rate measurement process, the rate of change of light, including the attenuation rate of light intensity, may be measured. "Rate of change of light" is a measurable value related to light, which is the rate of change of a value that is considered to change according to the oxygen concentration in the optical path through which the light is irradiated. Furthermore, in the measurement process described later, the oxygen concentration may be measured based on the rate of change of light. For example, in the attenuation rate measurement process, changes in the amplitude or wavelength of light may be measured. Alternatively, changes in the amplitude or wavelength of light may be used in the measurement process to measure the oxygen concentration.

[0264] In this case, it may be necessary to measure the oxygen concentration in container 30 of the same liquid-filled combination container 10L at multiple points in time. For example, when observing the change in oxygen concentration in container 30 over time to determine whether the amount of dissolved oxygen in the liquid L contained in container 30 has sufficiently decreased, it is necessary to measure the oxygen concentration in container 30 of the same liquid-filled combination container 10L at multiple points in time. Also, when calculating the rate of decrease in oxygen concentration in container 30 based on the change in oxygen concentration in container 30 over time, it is necessary to measure the oxygen concentration in container 30 of the same liquid-filled combination container 10L at multiple points in time. Furthermore, it may be necessary to measure the oxygen concentration in container 30 of multiple liquid-filled combination containers 10L. In these cases, it is preferable that the relative positions of container 30, barrier container 40, light source 951, and measuring instrument 952 are aligned at the time of measurement of the attenuation rate. This allows for the standardization of the conditions for measuring the attenuation rate, such as the length of the optical path LA of the laser light or LED light, and improves the measurement accuracy of the oxygen concentration measured based on the attenuation rate.

[0265] In the examples shown in Figures 17 and 18, the laser or LED light passes through the container 30 and the outside of the liquid-filled combination container 10L before reaching the measuring instrument 952 from the light source 951. In this case, by aligning the positional relationship between the container 30, the barrier container 40, the light source 951, and the measuring instrument 952 at the time of attenuation rate measurement, the following effects can be obtained: The length of the optical path LA of the laser or LED light can be aligned. In particular, the distance the laser or LED light passes through the container 30 can be aligned. Also, the distance the laser or LED light passes through the outside of the liquid-filled combination container 10L can be aligned. As a result, variations in the attenuation rate measured in the attenuation rate measurement process due to the difference between the distance the laser or LED light passes through the container 30 and the distance the laser or LED light passes through the outside of the liquid-filled combination container 10L are suppressed. This allows for a more accurate correspondence between the magnitude of the attenuation rate measured in the attenuation rate measurement process and the magnitude of the oxygen concentration inside the container 30. Therefore, the measurement accuracy when measuring oxygen concentration based on the decay rate in the measurement process described later can be improved.

[0266] In the first standard sample measurement step, the first standard sample is irradiated with laser light or LED light, and the attenuation rate of the laser light or LED light is measured. Parts of the first standard sample that can be configured in the same way as the liquid-filled combination container 10L that is the subject of the inspection method are referred to by the same name, but are given different reference numerals than the corresponding parts of the liquid-filled combination container 10L. Figures 17 and 18 are denoted with reference numerals representing the configuration of the liquid-filled combination container 10L, as well as reference numerals representing the configuration of the first standard sample. The first standard sample comprises a container 301 and a barrier container 401 containing container 301, similar to the container 30 and barrier container 40 containing container 30 of the liquid-filled combination container 10L that is the subject of the inspection method.

[0267] The oxygen concentration inside the container 301 of the first standard sample is specified. For example, the container 301 of the first standard sample contains air. In this case, the oxygen concentration inside the container 301 of the first standard sample can be specified as the oxygen concentration of the air. Generally, the oxygen concentration of air is known to be close to 20.95%. Therefore, the oxygen concentration inside the container 301 containing air in the first standard sample can be considered to be 20.95%. Also, for example, the pressure of the air contained in the container 301 of the first standard sample is equal to atmospheric pressure.

[0268] The container 301 of the first standard sample may or may not contain liquid L1 in its containment section 311, which is the same liquid L contained in the containment section 31 of the container 30 of the liquid-containing combination container 10L. If the container 301 of the first standard sample contains liquid L1 in its containment section 311, the oxygen concentration of the headspace HS1 of the container 301 may be specified. Specifically, air may be contained in the headspace HS1 of the container 301, and the oxygen concentration of the headspace HS1 of the container 301 may be specified as the oxygen concentration of the air. If the container 301 of the first standard sample does not contain liquid L1 in its containment section 311, the overall oxygen concentration inside the container 301 may be specified. Specifically, air may be contained throughout the entire interior of the container 301, and the overall oxygen concentration inside the container 301 may be specified as the oxygen concentration of the air.

[0269] In the first standard sample measurement step, the first standard sample is irradiated with laser light or LED light so as to pass through the inside of the container 301, and the attenuation rate of the laser light or LED light is measured. In the first standard sample measurement step, the attenuation rate is measured using the same light source 951 and measuring instrument 952 as those used in the attenuation rate measurement step. The wavelength of the laser light or LED light irradiated onto the first standard sample in the first standard sample measurement step is the same as the wavelength of the laser light or LED light irradiated onto the liquid-filled combination container 10L in the attenuation rate measurement step. In the first standard sample measurement step, the laser light or LED light may be irradiated onto the first standard sample so as to pass through a portion of the housing portion 311 of the container 301 away from the contact area 31a1.

[0270] The first standard sample measurement step allows for the measurement of the decay rate when the oxygen concentration inside container 301 is equal to the oxygen concentration of air. In particular, by using a first standard sample containing air inside container 301, the decay rate can be measured when the oxygen concentration inside container 301 is 20.95%.

[0271] In the second standard sample measurement step, the second standard sample is irradiated with laser light or LED light, and the attenuation rate of the laser light or LED light is measured. Parts of the second standard sample that can be configured in the same way as the liquid-filled combination container 10L that is the subject of the inspection method are referred to by the same name, but are given different reference numerals than the corresponding parts of the liquid-filled combination container 10L. Figures 17 and 18 are denoted with reference numerals representing the configuration of the liquid-filled combination container 10L, as well as reference numerals representing the configuration of the second standard sample. The second standard sample comprises a container 302 and a barrier container 402 containing container 302, similar to the container 30 and the barrier container 40 containing container 30 of the liquid-filled combination container 10L that is the subject of the inspection method.

[0272] The container 302 for the second standard sample has an internal oxygen concentration lower than that of the container 301 for the first standard sample, and its internal oxygen concentration is specified. If the container 301 for the first standard sample contains air, the internal oxygen concentration of the container 302 for the second standard sample is lower than that of the air, and its internal oxygen concentration is specified.

[0273] A specific example of a method for preparing a second standard sample containing a container 302 with a specified internal oxygen concentration will be described. As an example, a specific example of a method for preparing a second standard sample containing a container 302 with a specified internal oxygen concentration of 0% will be described. First, the inside of the container 302 of the second standard sample, which contains air, is degassed to create a vacuum. Next, nitrogen gas is introduced into the container 302 of the second standard sample. The nitrogen gas is, for example, a standard gas from the National Institute of Standards and Technology (NIST). The above-described operation of degassing the inside of the container 302 of the second standard sample to create a vacuum and the operation of introducing nitrogen gas into the container 302 of the second standard sample are repeated five times. Then, the oxygen concentration inside the container 302 of the second standard sample after the above operation is considered to be 0%. In this way, a second standard sample with a specified internal oxygen concentration of 0% can be prepared.

[0274] The container 302 for the second standard sample may or may not contain a liquid L2 in its containment section 312 that is the same as the liquid L contained in the containment section 31 of the liquid-containing combination container 10L container 30. If the container 302 for the second standard sample contains liquid L2 in its containment section 312, air may be contained in the headspace HS2 of the container 302. If the container 302 for the second standard sample does not contain liquid L2 in its containment section 312, air may be contained throughout the entire interior of the container 302.

[0275] In the second standard sample measurement step, the second standard sample is irradiated with laser light or LED light so as to pass through the inside of the container 302, and the attenuation rate of the laser light or LED light is measured. In the second standard sample measurement step, the attenuation rate is measured using the same light source 951 and measuring instrument 952 as those used in the attenuation rate measurement step. The wavelength of the laser light or LED light irradiated onto the second standard sample in the second standard sample measurement step is the same as the wavelength of the laser light or LED light irradiated onto the liquid-filled combination container 10L in the attenuation rate measurement step. In the second standard sample measurement step, the laser light or LED light may be irradiated onto the second standard sample so as to pass through a portion of the container 302 that is away from the contact area 31a2.

[0276] The second standard sample measurement step allows for the measurement of the decay rate when the oxygen concentration inside container 302 is at a specific value lower than the oxygen concentration in the air. In particular, by using a second standard sample prepared by the specific method described above, in which the oxygen concentration inside container 302 is specified as 0%, the decay rate when the oxygen concentration inside container 302 is 0% can be measured.

[0277] In the measurement step, the oxygen concentration inside the container 30 is measured based on the decay rate measured in the decay rate measurement step. The measurement step of the second embodiment includes a step of calculating the oxygen concentration inside the container 30 of the liquid-filled combination container 10L from the decay rate measured in the decay rate measurement step, based on the measurement results of the first standard sample measurement step and the second standard sample measurement step. As the measurement result of the first standard sample measurement step, the relationship between the decay rate measured in the first standard sample measurement step and the oxygen concentration inside the container 301 of the first standard sample is used. As the measurement result of the second standard sample measurement step, the relationship between the decay rate measured in the second standard sample measurement step and the oxygen concentration inside the container 302 of the second standard sample is used.

[0278] Specifically, first, assuming that the oxygen concentration Y(%) is a linear function of the decay rate X(%), we derive a linear function equation representing the relationship between the oxygen concentration Y(%) and the decay rate X(%) based on the measurement results of the first and second standard sample measurement steps.

[0279] Let x1 (%) be the decay rate measured in the first standard sample measurement step. Let y1 (%) be the oxygen concentration inside container 301 in the first standard sample. Let x2 (%) be the decay rate measured in the second standard sample measurement step. Let y2 (%) be the oxygen concentration inside container 302 in the second standard sample. In this case, the linear function equation representing the relationship between oxygen concentration Y (%) and decay rate X (%) can be expressed by the following equation (1).

number

[0280] As described above, if the oxygen concentration inside container 301 in the first standard sample is assumed to be 20.95%, the value of y1 is 20.95. As described above, if the oxygen concentration inside container 301 in the second standard sample is assumed to be 0%, the value of y2 is 0. In this case, the linear function representing the relationship between oxygen concentration Y(%) and decay rate X(%) can be expressed by the following equation (2).

number

[0281] By substituting the attenuation rate (%) measured in the attenuation rate measurement process into X (%) in equation (1) or equation (2) and calculating Y (%), the oxygen concentration (%) in the container 30 of the 10L liquid-filled combination container can be calculated.

[0282] The first standard sample is not limited to the container 301 described above which air is contained inside. The first standard sample may include a container 301 with a specified internal oxygen concentration and a barrier container 401 containing the container 301. Furthermore, the second standard sample is not limited to the container 302 described above which the inside is degassed. The second standard sample may include a container 302 with an internal oxygen concentration lower than that of the first standard sample's container 301 and with a specified internal oxygen concentration, and a barrier container 402 containing the container 302. In addition, the decay rate may be measured for three or more standard samples, including the first and second standard samples, and the oxygen concentration in the container 30 of the liquid-filled combination container 10L may be calculated based on the relationship between the decay rates and oxygen concentrations of the three or more standard samples.

[0283] Furthermore, the method for determining the oxygen concentration of a standard sample, including the first and second standard samples, is not limited to the examples described above. For example, the oxygen concentration of a standard sample may be determined using the inspection method of the first embodiment described above. That is, the oxygen concentration of the standard sample container may be determined by providing a fluorescent material on the inner surface of the standard sample container, irradiating the fluorescent material with light, and measuring the fluorescence time or fluorescence intensity of the fluorescent material. Also, when determining the oxygen concentration of a standard sample, including the first and second standard samples, if laser light or LED light is irradiated so as to pass through the inside of the container 302, the oxygen concentration may be determined by the following method. A numerical value that changes according to the attenuation rate may be measured, and the oxygen concentration inside the container 30 may be measured based on that numerical value. For example, a numerical value proportional to the attenuation rate may be measured, and the oxygen concentration inside the container 30 may be measured based on that numerical value. Furthermore, the oxygen concentration may be measured by combining measuring the oxygen concentration based on the attenuation rate of light intensity and measuring the oxygen concentration based on a numerical value that changes according to the attenuation rate. This makes it possible to measure the oxygen concentration with higher accuracy. In addition, the rate of change of light, including the attenuation rate of light intensity, may be measured, and the oxygen concentration may be measured based on the rate of change of light. For example, changes in the amplitude or wavelength of light can be measured, and the oxygen concentration can be measured using these changes.

[0284] Next, the effects of the inspection method for a liquid-filled combination container 10L according to the second embodiment will be described. The inspection method of the second embodiment includes an attenuation rate measurement step, in which laser light or LED light of a wavelength attenuated according to the oxygen concentration in the optical path LA is irradiated onto the liquid-filled combination container 10L so as to penetrate a portion of the container 30 away from the contact area 31a of the housing portion 31, and the attenuation rate of the laser light or LED light is measured. Measuring the attenuation rate in the attenuation rate measurement step includes measuring a numerical value that changes according to the attenuation rate, for example, a numerical value that is proportional to the attenuation rate. In addition, the attenuation rate measurement step may also measure the rate of change of light, including the attenuation rate of the light intensity. As an example, the attenuation rate measurement step may also measure changes in the amplitude or wavelength of the light. Furthermore, the method includes a measurement step for measuring the oxygen concentration in the container 30 based on the attenuation rate measured in the attenuation rate measurement step. Furthermore, measuring the oxygen concentration in the container 30 based on the attenuation rate in the measurement step includes measuring the oxygen concentration in the container 30 substantially based on the attenuation rate by measuring the oxygen concentration in the container 30 based on a numerical value that changes according to the attenuation rate. For example, measuring the oxygen concentration in container 30 based on the attenuation rate in the measurement process includes measuring the oxygen concentration in container 30 based on a value proportional to the attenuation rate. Furthermore, in the measurement process, the oxygen concentration may be measured by combining measuring the oxygen concentration based on the attenuation rate of light intensity and measuring the oxygen concentration based on a value that changes according to the attenuation rate. In addition, the oxygen concentration may be measured based on the rate of change of light in the measurement process. As an example, the oxygen concentration may be measured using changes in the amplitude or wavelength of light in the measurement process. This makes it possible to measure and inspect the oxygen concentration in container 30 without opening the container 30.

[0285] In addition, in the inspection method of the second embodiment, with the barrier container 40 in contact with the outer surfaces 30b of the first position 35a and the second position 35b, which are away from the contact area 31a of the housing portion 31 of the container 30, laser light or LED light is irradiated onto the liquid-filled combination container 10L so as to pass through the first position 35a and the second position 35b of the container 30. Therefore, the optical path LA does not pass through the space inside the barrier container 40 that is outside the container 30 (also referred to as the barrier container space 49). This eliminates the influence of the oxygen concentration in the barrier container space 49 on the measured attenuation rate. Furthermore, it eliminates the influence of the oxygen concentration in the barrier container space 49 on the numerical value that changes according to the attenuation rate, for example, a numerical value that is proportional to the attenuation rate, which is measured in the attenuation rate measurement step. Furthermore, it eliminates the influence of the oxygen concentration in the barrier container space 49 on the rate of change of light measured in the attenuation rate measurement step. For example, the influence of changes in the amplitude and wavelength of light measured in the attenuation rate measurement process on the oxygen concentration in the barrier container space 49 can be eliminated. Also, the contact of the barrier container 40 with the outer surface 30b of the container 30 determines the positional relationship between the container 30 and the barrier container 40. Therefore, when measuring the oxygen concentration in the container 30 of the same liquid-filled combination container 10L at multiple time points, the contact of the barrier container 40 with the outer surface 30b of the container 30 allows the positional relationship between the container 30 and the barrier container 40 at the time of measurement to be aligned. Similarly, when measuring the oxygen concentration in the containers 30 of multiple liquid-filled combination containers 10L each, the positional relationship between the container 30 and the barrier container 40 at the time of measurement can be aligned. This makes it possible to standardize the measurement conditions for the attenuation rate, such as the length of the optical path LA of the laser or LED light, and improve the measurement accuracy of the oxygen concentration measured based on the attenuation rate. In addition, in the attenuation rate measurement process, the measurement conditions for numerical values ​​that change according to the attenuation rate, such as numerical values ​​proportional to the attenuation rate, can be standardized. Furthermore, the conditions for measuring the rate of change of light can be standardized in the attenuation rate measurement process. For example, the conditions for measuring changes in the amplitude and wavelength of light can be standardized in the attenuation rate measurement process.

[0286] In addition, the inspection method of the second embodiment further includes the step of bringing the barrier container 40 into contact with the outer surfaces 30b of the first position 35a and the second position 35b of the container 30. This allows laser light or LED light to be irradiated onto the liquid-filled combination container 10L while the barrier container 40 is in contact with the outer surfaces 30b of the first position 35a and the second position 35b of the container 30, as described above.

[0287] In addition, in the inspection method of the second embodiment, the wavelength of the laser light or LED light includes a wavelength of 760 nm. Laser light or LED light with a wavelength of 760 nm is attenuated according to the oxygen concentration in the optical path LA, and is less attenuated according to other factors, such as the concentration of substances other than oxygen. Therefore, by including a wavelength of 760 nm in the irradiated laser light or LED light, the measurement accuracy of the oxygen concentration in the measurement process can be improved.

[0288] In addition, the inspection method of the second embodiment further comprises a first standard sample measurement step of irradiating a first standard sample with laser light or LED light to measure the attenuation rate, and a second standard sample measurement step of irradiating a second standard sample with laser light or LED light to measure the attenuation rate. This makes it possible to measure the oxygen concentration in the container 30 of the liquid-filled combination container 10L based on the relationship between the attenuation rate and oxygen concentration in the first standard sample, and the relationship between the attenuation rate and oxygen concentration in the second standard sample.

[0289] In addition, in the inspection method of the second embodiment, in the first standard sample measurement step, the barrier container 401, light source 951, and measuring instrument 952 of the first standard sample may be arranged relative to the container 301 of the first standard sample, so as in the arrangement of the barrier container 40, light source 951, and measuring instrument 952 relative to the container 30 when laser light or LED light is irradiated onto the liquid-filled combination container 10L in the attenuation rate measurement step, and the first standard sample may be irradiated with laser light or LED light. Furthermore, in the second standard sample measurement step, the barrier container 402, light source 951, and measuring instrument 952 of the second standard sample may be arranged relative to the container 302 of the second standard sample, so as in the arrangement of the barrier container 40, light source 951, and measuring instrument 952 relative to the container 30 when laser light or LED light is irradiated onto the liquid-filled combination container 10L in the attenuation rate measurement step, and the first standard sample may be irradiated with laser light or LED light. This allows for the standardization of the measurement conditions for the attenuation rate, such as the length of the optical path LA of the laser or LED light, in the attenuation rate measurement process, the first standard sample measurement process, and the second standard sample measurement process.

[0290] For example, container 30 is transparent at least at the first position 35a and the second position 35b. Similarly, barrier container 40 is transparent at least in the portion that contacts the outer surface 30b at the first position 35a and the second position 35b. This reduces the influence of attenuation of laser or LED light as it passes through container 30 and barrier container 40 on the measured attenuation rate.

[0291] Next, the effects of the liquid-filled container 30L and the liquid-filled combination container 10L of the second embodiment on performing the inspection method described above will be explained. In the second embodiment, the oxygen reagent 20 is spaced apart from the straight line connecting the first position 35a and the second position 35b. Therefore, by making the straight line connecting the first position 35a and the second position 35b the optical path LA, laser light or LED light can be irradiated so as to pass through the container 30. As a result, the oxygen concentration inside the container 30 can be measured and inspected using the inspection method described above without opening the container 30. Furthermore, the oxygen concentration inside the container 30 can be measured and inspected without opening the barrier container 40.

[0292] In addition, the oxygen reagent 20 is fixed to at least one of the outer surface 30b of the container 30 and the inner surface of the barrier container 40. This prevents the oxygen reagent 20 from moving to a position that prevents the laser light or LED light from passing through the first position 35a and the second position 35b of the container 30. In particular, by fixing the oxygen reagent 20 in a position that does not prevent the laser light or LED light from passing through the first position 35a and the second position 35b of the container 30, the laser light or LED light can be irradiated so as to pass through the container 30 without being obstructed by the oxygen reagent 20.

[0293] In addition, the following effects can be obtained by defining the positional relationship between the container 30 and the oxygen reagent 20. The oxygen reagent 20 can be used as a marker to identify a suitable position for irradiating the container 30 with laser light or LED light. An example of a method for identifying a position for irradiating the container 30 with laser light or LED light using the oxygen reagent 20 as a marker will be described. The positional relationship between the position of the oxygen reagent 20 relative to the container 30 and a suitable position for irradiating the container 30 with laser light or LED light is determined. The position of the oxygen reagent 20 is also identified by image detection using a camera or the like. Then, a suitable position for irradiating the container 30 with laser light or LED light is identified from the positional relationship between the position of the oxygen reagent 20 relative to the container 30 and a suitable position for irradiating the container 30 with laser light or LED light, and from the position of the oxygen reagent 20 identified by image detection or the like. This makes it possible to identify a suitable position for irradiating the container 30 with laser light or LED light.

[0294] Furthermore, when the characteristic of having a defined positional relationship between the container 30 and the oxygen reagent 20 is combined with the liquid-filled combination container 10L of the first embodiment, the following effects can be obtained: The oxygen reagent 20 can be used as a marker to identify a suitable position for irradiating the container 30 with light that causes the fluorescent material 27 to fluoresce.

[0295] In addition, the oxygen reagent 20 is located on the second surface 34f side of the stopper 34. This makes it less likely for the movement of oxygen between the stopper 34 and the oxygen reagent 20 to be obstructed. In the example shown in Figure 17, the barrier container 40 is in contact with the outer surface 30b of the container 30 around the entire circumference of the outer periphery of the container 30, including the first position 35a and the second position 35b. As a result, the movement of oxygen-containing gas is obstructed between the first space S1 located above the first position 35a and the second position 35b and the second space S2 located below the first position 35a and the second position 35b within the barrier container 40. In this case, by specifying that the oxygen reagent 20 is located on the second surface 34f side of the stopper 34, the oxygen reagent 20 is placed in the first space S1. This makes it less likely for the movement of oxygen between the stopper 34 and the oxygen reagent 20 to be obstructed. Therefore, when the stopper 34 is oxygen permeable, the obstruction of oxygen movement between the stopper 34 and the oxygen absorber 21 can be suppressed. As a result, when the oxygen reactant 20 is the oxygen absorber 21, the oxygen that has permeated through the stopper 34 can be rapidly reduced by the oxygen absorption of the oxygen absorber 21. When the oxygen reactant 20 is the oxygen sensing material 25, the oxygen state of the space in the barrier container 40 into which the oxygen that has permeated through the oxygen permeable part of the container 30 flows can be detected by the oxygen sensing material 25.

[0296] The common features and effects of the liquid-filled combination container 10L of the first embodiment and the liquid-filled combination container 10L of the second embodiment will be described.

[0297] The liquid-filled combination container 10L of the first embodiment and the liquid-filled combination container 10L of the second embodiment share the common feature that the oxygen reagent 20 is fixed to at least one of the outer surface 30b of the container 30 and the inner surface of the barrier container 40.

[0298] In the first embodiment of the liquid-filled combination container 10L, the above features prevent the oxygen reagent 20 from moving to a position that obstructs the irradiation of light that causes the fluorescent material 27 to fluoresce. In the second embodiment of the liquid-filled combination container 10L, the above features prevent the oxygen reagent 20 from moving to a position that obstructs the transmission of laser light or LED light through the first position 35a and the second position 35b of the container 30. Thus, both the first embodiment of the liquid-filled combination container 10L and the second embodiment of the liquid-filled combination container 10L have the common effect of preventing the oxygen reagent 20 from moving to a position that obstructs the irradiation of light that irradiates the container 30 for measuring the oxygen concentration.

[0299] In the first embodiment of the liquid-filled combination container 10L, the barrier container 40 is in contact with the outer surface 30b of the fluorescent material installation position 39 of the container 30. By the barrier container 40 being in contact with the outer surface 30b of the fluorescent material installation position 39 of the container 30, it becomes easier to determine the positional relationship between the fluorescent material installation position 39 of the container 30 and the barrier container 40. This makes it easier to determine the optical path of the light emitted from the illumination unit 81 that passes through the barrier container 40 and the fluorescent material installation position 39 of the container 30 to fluoresce the fluorescent material 27. Specifically, when measuring the oxygen concentration in the container 30 of the same liquid-filled combination container 10L at multiple time points, the positional relationship between the fluorescent material installation position 39 of the container 30 and the barrier container 40 can be aligned at the time of measurement. Similarly, when measuring the oxygen concentration in the containers 30 of multiple liquid-filled combination containers 10L, the positional relationship between the fluorescent material installation position 39 of the container 30 and the barrier container 40 can be aligned at the time of measurement. This allows the optical path of the light emitted from the lighting unit 81, which passes through the fluorescent material installation positions 39 in the barrier container 40 and container 30 and fluoresces the fluorescent material 27, to be aligned.

[0300] On the other hand, in the liquid-filled combination container 10L of the second embodiment, the barrier container 40 is in contact with the outer surfaces 30b of the first position 35a and the second position 35b of the container 30. By the barrier container 40 being in contact with the outer surfaces 30b of the first position 35a and the second position 35b of the container 30, it becomes easier to determine the positional relationship between the first position 35a and the second position 35b of the container 30 and the barrier container 40. This makes it easier to determine the optical path LA of the laser light or LED light emitted from the light source 951 that passes through the barrier container 40 and the first position 35a and the second position 35b of the container 30 and reaches the measuring instrument 952. Specifically, when measuring the oxygen concentration in the container 30 of the same liquid-filled combination container 10L at multiple time points, the positional relationship between the first position 35a and the second position 35b of the container 30 and the barrier container 40 can be aligned at the time of measurement. Similarly, when measuring the oxygen concentration in a container 30 containing multiple liquids in a 10L combination container, the positional relationship between the first position 35a and the second position 35b of the container 30 and the barrier container 40 at the time of measurement can be aligned. This aligns the optical path LA of the laser or LED light emitted from the light source 951, which passes through the barrier container 40 and the first position 35a and the second position 35b of the container 30 and reaches the measuring instrument 952.

[0301] As described above, the liquid-filled combination container 10L of the first embodiment and the liquid-filled combination container 10L of the second embodiment share the common feature that the barrier container 40 is in contact with at least a portion of the outer surface 30b of the container 30. Furthermore, the liquid-filled combination container 10L of the first embodiment and the liquid-filled combination container 10L of the second embodiment share the common effect that the optical path of the light irradiated onto the container 30 for measuring the oxygen concentration can be easily determined due to the above-mentioned feature.

[0302] When container 30 is upright within the barrier container 40, the oxygen reagent 20 may be used to adjust the vertical position of container 30 within the barrier container 40. For example, the oxygen reagent 20 is placed below the upright container 30. In this case, container 30 can be positioned higher than when the oxygen reagent 20 is not placed below it. This allows for adjustment of the positional relationship between container 30 and the device used to measure oxygen concentration, such as the light source 951 and measuring instrument 952.

[0303] The oxygen reagent 20 may be placed above the upright container 30. In this case, as described above, the oxygen reagent 20 can be easily used as a marker to identify a suitable position for irradiating the container 30 with laser light or LED light. Furthermore, the oxygen reagent 20 can be easily used as a marker to identify a suitable position for irradiating the container 30 with light that will cause the fluorescent material 27 to fluoresce.

[0304] In addition, a pressing member that holds the container 30 is brought close to the combination container 10L containing liquid from above, deforming the flexible barrier container 40 to hold the container 30 between the pressing member and the mounting surface, and then the oxygen concentration inside the container 30 is measured. In this case, because the vertical dimensions of the upright container 30 are small, the pressing member may not be able to contact the container 30, and the container 30 may not be able to be held between the pressing member and the mounting surface. In this case, the oxygen reagent 20 may be placed above the upright container 30. This allows the pressing member to come into contact with the oxygen reagent 20, and the force from the pressing member to the container 30 is transmitted to the container 30 via the oxygen reagent 20. As a result, the container 30 can be held between the pressing member and the mounting surface together with the oxygen reagent 20.

[0305] It is possible to make various modifications to the second embodiment described above. Hereinafter, modifications of the second embodiment will be described with reference to the drawings as necessary. In the following description and the drawings used therein, parts that can be configured similarly to the second embodiment will be given the same reference numerals as those used for the corresponding parts in the second embodiment, and redundant explanations may be omitted. Furthermore, if it is clear that the effects and advantages obtained in the second embodiment can also be obtained in the modifications, the explanation may be omitted.

[0306] (Modification 4) The barrier container 40 may be designed such that when the container 30 is placed inside the barrier container 40, the barrier container 40 automatically comes into contact with the outer surfaces 30b of the first position 35a and the second position 35b of the container 30. Figure 19 shows a liquid-filled combination container 10L according to Modification 4. Figure 19 corresponds to a cross-sectional view of the liquid-filled combination container 10L with the barrier container 40 in contact with the outer surfaces 30b of the first position 35a and the second position 35b of the container 30.

[0307] The liquid-filled combination container 10L shown in Figure 19 is the same as the liquid-filled combination container 10L shown in Figure 15, except that it does not include the fluorescent material 27. Similar to the liquid-filled combination container 10L shown in Figure 15, the container 30 is a vial bottle having a glass bottle body 32 and a stopper 34. The container 30 has a substantially cylindrical outer shape. The barrier container 40 also has a substantially cylindrical outer shape. As shown in Figure 19, the outer diameter w1 of the container 30 matches the inner diameter w2 of the barrier container 40. Therefore, when the container 30 is placed inside the barrier container 40, the barrier container 40 naturally comes into contact with the outer surfaces 30b of the first position 35a and the second position 35b of the container 30.

[0308] The barrier container 40 shown in Figure 19 can stably maintain a state in which the barrier container 40 is in contact with the outer surfaces 30b of the first position 35a and the second position 35b of the container 30. In the barrier container 40 shown in Figure 19, the influence of the oxygen concentration in the barrier container space 49 on the measured decay rate can be eliminated by the barrier container 40 being in contact with the outer surfaces 30b of the first position 35a and the second position 35b of the container 30. Furthermore, the positional relationship between the container 30 and the barrier container 40 can be determined.

[0309] (Variation 5) In the second embodiment and modification 4 described above, a liquid-filled combination container 10L is shown in which the barrier container 40 is in contact with the outer surfaces 30b of the first position 35a and the second position 35b of the container 30. In the second embodiment and modification 4 described above, an inspection method is shown in which laser light or LED light is irradiated onto the liquid-filled combination container 10L while the barrier container 40 is in contact with the outer surfaces 30b of the first position 35a and the second position 35b of the container 30. However, the liquid-filled combination container 10L and the inspection method for the liquid-filled combination container 10L are not limited thereto.

[0310] The first position 35a and the second position 35b through which the laser light or LED light is transmitted are not particularly limited, as long as the oxygen reagent 20 is spaced apart from the straight line connecting these positions. In the liquid-filled combination container 10L, the barrier container 40 does not have to be in contact with the outer surface 30b of the first position 35a and the second position 35b of the container 30. In other words, the first position 35a and the second position 35b of the container 30 may be set to positions where the barrier container 40 does not come into contact with the outer surface 30b. In the inspection method for the liquid-filled combination container 10L, the laser light or LED light may be irradiated onto the liquid-filled combination container 10L while the barrier container 40 is not in contact with the outer surface 30b of the container 30. In the inspection method for the liquid-filled combination container 10L, the laser light or LED light may be irradiated onto the liquid-filled combination container 10L so as to transmit the light through the position of the container 30 that is not in contact with the barrier container 40. In this case, when measuring the oxygen concentration in container 30 of the same liquid-filled combination container 10L at multiple time points, or when measuring the oxygen concentration in container 30 of multiple liquid-filled combination containers 10L, the inspection method is performed as follows: The relative positions of container 30, barrier container 40, light source 951, and measuring instrument 952 are aligned, and laser light or LED light is irradiated onto the liquid-filled combination container 10L. This standardizes the conditions for measuring the attenuation rate, such as the length of the optical path LA of the laser light or LED light, and improves the measurement accuracy of the oxygen concentration measured based on the attenuation rate.

[0311] In Modification 5, the container 30 is fixed to the barrier container 40. Figure 20 shows an example of irradiating the liquid-filled combination container 10L with laser light or LED light in the inspection method for the liquid-filled combination container 10L of Modification 5. Figure 21 shows another example of irradiating the liquid-filled combination container 10L with laser light or LED light in the inspection method for the liquid-filled combination container 10L of Modification 5. In the examples shown in Figures 20 and 21, the container 30 is fixed to the barrier container 40 by a second fixing member 922 that is different from the container 30 and the barrier container 40. As an example, the container 30 is fixed to the barrier container 40 at least while the laser light or LED light is irradiated to the liquid-filled combination container 10L. Although not shown, the container 30 may also be fixed to the barrier container 40 by being bonded to the inner surface of the barrier container 40 with an adhesive or the like. A liquid-filled combination container 10L in which the outer surface 30b of container 30 and the inner surface of barrier container 40 are in contact, as shown in Figure 19, is also included in the category of liquid-filled combination containers 10L in which container 30 is fixed to barrier container 40. Because container 30 is fixed to barrier container 40, the positional relationship between container 30 and barrier container 40 can be aligned, allowing for measurement of oxygen concentration. Specifically, when measuring the oxygen concentration in container 30 of the same liquid-filled combination container 10L at multiple time points, or when measuring the oxygen concentration in container 30 of multiple liquid-filled combination containers 10L, the positional relationship between container 30 and barrier container 40 can be aligned, allowing for measurement of oxygen concentration.

[0312] The barrier container 40 of the liquid-filled combination container 10L shown in Figures 20 and 21 is the same as the barrier container 40 shown in Figure 16. The liquid-filled container 30L of the liquid-filled combination container 10L shown in Figures 20 and 21 is the same as the liquid-filled container 30L shown in Figures 1 and 2, except that it does not include the fluorescent material 27. In the examples shown in Figures 20 and 21, the liquid-filled combination container 10L includes one oxygen reagent 20. In the examples shown in Figures 20 and 21, the oxygen reagent 20 is an oxygen scavenger 21. In the example shown in Figure 20, the oxygen reagent 20 is fixed to the outer surface 30b of the container 30. In the example shown in Figure 20, the oxygen reagent 20 is fixed to the stopper 34 of the container 30.

[0313] In the examples shown in Figures 20 and 21, the position of the barrier container 40 relative to the container 30 is fixed by a second fixing member 922, which is different from the container 30 and the barrier container 40. This allows the positional relationship between the container 30 and the barrier container 40 to be aligned.

[0314] In the example shown in Figure 20, the second fixing member 922 is a tray-shaped container. A container that accommodates the container 30 and is housed in the barrier container 40, such as the tray-shaped container shown in Figure 20, is referred to as the intermediate container 50. The second fixing member 922 shown in Figure 20 has a bottom portion 922a, a side portion 922b, and a flange portion 922c. The side portion 922b is connected to the periphery of the bottom portion 922a at the first end 922d. The side portion 922b is connected to the flange portion 922c at the second end 922e, which is located on the opposite side of the first end 922d. In this case, the material of the second fixing member 922 is, for example, the same as the material of the container 30 or the barrier container 40.

[0315] In the example shown in Figure 20, the second fixing member 922 is sandwiched between the outer surface 30b of the container 30 and the inner surface of the barrier container 40, thereby fixing the position of the barrier container 40 relative to the container 30. The second fixing member 922 contacts the outer surface 30b of the container 30 at its bottom portion 922a and side portion 922b, and contacts the inner surface of the barrier container 40 at its flange portion 922c. The container 30 is housed in the intermediate container 50 and is supported and stationary by the intermediate container 50. In particular, the container 30 is upright within the barrier container 40. In the example shown in Figure 20, the entire second fixing member 922 (intermediate container 50) is located below the first position 35a and the second position 35b of the container 30, which is upright within the barrier container 40.

[0316] In the example shown in Figure 21, the oxygen reagent 20 also serves as the second fixing member 922. That is, the oxygen reagent 20 is sandwiched between the outer surface 30b of the container 30 and the inner surface of the barrier container 40, thereby fixing the position of the barrier container 40 relative to the container 30. In the example shown in Figure 21, the oxygen reagent 20 is an oxygen scavenger 21. In the example shown in Figure 21, the oxygen reagent 20 is sandwiched between the outer surface 30b of the container 30 and the inner surface of the barrier container 40. This suppresses the horizontal movement of the oxygen reagent 20. In the example shown in Figure 21, the container 30 of the liquid-filled combination container 10L is in a stationary state, particularly in an upright state. In this state, the vertical movement of the oxygen reagent 20 is suppressed by the action of gravity. This fixes it to the outer surface 30b of the container 30 and the inner surface of the barrier container 40.

[0317] In Modification 5, the portions of the container 30 and the barrier container 40 that transmit laser light or LED light are transparent. This reduces the influence of attenuation of the laser light or LED light as it passes through the container 30 and the barrier container 40 on the measured attenuation rate.

[0318] In Modified Example 5, when performing the first standard sample measurement step, the position of the barrier container 401 of the first standard sample relative to the container 301 of the first standard sample may be fixed by the second fixing member 922, and the first standard sample may be irradiated with laser light or LED light. In Modified Example 5, when performing the second standard sample measurement step, the position of the barrier container 402 of the second standard sample relative to the container 302 of the second standard sample may be fixed by the second fixing member 922, and the second standard sample may be irradiated with laser light or LED light. This makes it possible to standardize the conditions for measuring the attenuation rate, such as the length of the optical path LA of the laser light or LED light, in the attenuation rate measurement step, the first standard sample measurement step, and the second standard sample measurement step.

[0319] (Experimental variation 6) The form of the intermediate container 50 is not limited to the form shown in Figure 20. Figure 22A shows an example of irradiating the liquid-filled combination container 10L with laser light or LED light in the inspection method for the liquid-filled combination container 10L of Modification 6. The liquid-filled combination container 10L shown in Figure 22A is the same as the barrier container 40 shown in Figure 20, except that the form of the intermediate container 50 is different.

[0320] In the example shown in Figure 22A, a portion of the intermediate container 50 is located above the first position 35a and second position 35b of the container 30, which is upright within the barrier container 40. Therefore, the intermediate container 50 covers the first position 35a and second position 35b of the container 30 from the outer circumference of the container 30. As shown in Figure 22A, the intermediate container 50 has an intermediate container light-transmitting portion 51 that intersects the straight line connecting the first position 35a and the second position 35b of the container 30 and allows light to pass through. In the example shown in Figure 22A, the straight line indicating the optical path LA corresponds to the straight line connecting the first position 35a and the second position 35b. In the example shown in Figure 22A, the intermediate container 50 has a pair of intermediate container light-transmitting portions 51. The form of the intermediate container light-transmitting portion 51 is not particularly limited as long as it allows light to pass through. As an example, the intermediate container light-transmitting portion 51 is made of a light-transmitting material. The intermediate container light-transmitting portion 51 may also be a through-hole provided in the wall surface of the intermediate container 50. If the intermediate container light-transmitting portion 51 is a through hole, the intermediate container light-transmitting portion 51 is considered to intersect the straight line connecting the first position 35a and the second position 35b of the container 30 when the straight line passing through the through hole.

[0321] Because the intermediate container 50 has an intermediate container light-transmitting portion 51, even when the intermediate container 50 covers the first position 35a and the second position 35b of the container 30, laser light or LED light can be irradiated so as to pass through the first position 35a and the second position 35b of the container 30.

[0322] (Example 7) The barrier container 40 does not need to be fixed to the container 30. Figure 22B shows an example of irradiating the liquid-filled combination container 10L with laser light or LED light in the inspection method for the liquid-filled combination container 10L of Modification 7. The liquid-filled combination container 10L shown in Figure 22B is the same as the liquid-filled combination container 10L shown in Figure 17, except that it does not have a shrink film 91 and the barrier container 40 is not in contact with the outer surfaces 30b of the first position 35a and second position 35b of the container 30.

[0323] In the example shown in Figure 22B, the barrier container 40 is not fixed to the container 30. Even in the liquid-filled combination container 10L shown in Figure 22B, the oxygen concentration inside the container 30 can be measured based on the measured attenuation rate by irradiating the liquid-filled combination container 10L with laser light or LED light and measuring the attenuation rate of the laser light or LED light. In particular, if the influence of oxygen located outside the container 30 on the measured attenuation rate is sufficiently small compared to the influence of oxygen located inside the container 30, the measurement accuracy of the oxygen concentration can be sufficiently high even if the barrier container 40 is not fixed to the container 30. The case where the influence of oxygen located outside the container 30 on the measured attenuation rate is sufficiently small compared to the influence of oxygen located inside the container 30 is, for example, when the oxygen concentration outside the container 30 is sufficiently small compared to the oxygen concentration inside the container 30.

[0324] In the example shown in Figure 22B, the optical path LA passes through the inside of the container 30 and also through the barrier container space 49 and the outside of the barrier container 40. Therefore, the measured attenuation rate is affected by the oxygen inside the container 30 and by the oxygen inside the barrier container space 49 and outside the barrier container 40. In this case, if the influence of the oxygen inside the barrier container space 49 and outside the barrier container 40 on the attenuation rate is sufficiently small compared to the influence of the oxygen located inside the container 30, the measurement accuracy of the oxygen concentration can be sufficiently high even if the barrier container 40 is not fixed to the container 30.

[0325] Although not shown in the figures, the feature that the barrier container 40 is not fixed to the container 30 may be incorporated into the liquid-filled combination container 10L equipped with the fluorescent material 27 of the first embodiment. In this case as well, the oxygen concentration inside the container 30 can be measured based on the measured fluorescence time or fluorescence intensity by irradiating the fluorescent material 27 with light that causes it to fluoresce and measuring the fluorescence time or fluorescence intensity of the fluorescent material 27. In particular, if the influence of oxygen located outside the container 30 on the fluorescence time or fluorescence intensity of the fluorescent material 27 being measured is sufficiently small compared to the influence of oxygen located inside the container 30, the measurement accuracy of the oxygen concentration can be sufficiently high.

[0326] (Variation 8) The liquid-filled combination container 10L may further comprise an outer container 55 that houses the barrier container 40. Figure 22C shows an example of irradiating the liquid-filled combination container 10L with laser light or LED light in the inspection method of the liquid-filled combination container 10L of Modification 8. The liquid-filled combination container 10L shown in Figure 22C is the same as the liquid-filled combination container 10L shown in Figure 22B, except that it comprises an outer container 55. The outer container 55 may support the container 30 and the barrier container 40. The container 30 may be placed still by being supported by the outer container 55.

[0327] As shown in Figure 22C, the outer container 55 has a light-transmitting portion 56 that intersects the straight line connecting the first position 35a and the second position 35b of the container 30 and allows light to pass through. In the example shown in Figure 22C, the straight line indicating the optical path LA corresponds to the straight line connecting the first position 35a and the second position 35b. In the example shown in Figure 22C, the outer container 55 has a pair of light-transmitting portions 56.

[0328] In the example shown in Figure 22C, the outer container 55 has an outer container body 57 and a light-transmitting portion 56 provided on the outer container body 57. For example, the outer container body 57 does not transmit light. The material of the outer container body 57 is, for example, paper. The outer container body 57 is, for example, a paper box.

[0329] The form of the light-transmitting portion 56 is not particularly limited as long as it allows light to pass through. For example, the light-transmitting portion 56 is made of a light-transmitting material. The light-transmitting portion 56 may also be a through-hole provided in the outer container body 57. When the light-transmitting portion 56 is a through-hole, the light-transmitting portion 56 is considered to intersect the straight line connecting the first position 35a and the second position 35b of the container 30 when the straight line passing through the through-hole.

[0330] Because the outer container 55 has a light-transmitting portion 56, even when the barrier container 40 is equipped with an outer container 55, laser light or LED light can be irradiated so as to pass through the first position 35a and the second position 35b of the container 30.

[0331] (Extreme variation 9) The form of the barrier container 40 is not limited to the form described above. Figure 23A is a perspective view showing an example of the barrier container 40 of Modification 9. The barrier container 40 shown in Figure 23A is closed by joining films to form a seal portion 43, similar to the barrier container 40 shown in Figure 4. The form of the barrier container 40 shown in Figure 23A is the same as the barrier container 40 shown in Figure 4, except for the points described later. The barrier container 40 shown in Figure 23A has a seal portion through hole 41f provided in the seal portion 43.

[0332] The side of the barrier container 40 opposite to the bottom side shown in Figure 23A is referred to as the upper end side of the barrier container 40. In the barrier container 40 shown in Figure 23A, the seal through hole 41f is provided in the portion of the seal 43 located on the upper end side of the barrier container 40.

[0333] The barrier container 40 has a sealing through-hole 41f, which allows the liquid-filled combination container 10L to be transported using the sealing through-hole 41f. For example, the liquid-filled combination container 10L can be suspended from the hook-shaped member by passing the tip of the hook-shaped member through the sealing through-hole 41f. The liquid-filled combination container 10L can be transported by moving the hook-shaped member while the liquid-filled combination container 10L is suspended from it. The barrier container 40 may have multiple sealing through-holes 41f. In this case, when suspending the liquid-filled combination container 10L using the sealing through-holes 41f, the tips of multiple hook-shaped members may be passed through each of the multiple sealing through-holes 41f. In the example shown in Figure 23A, the barrier container 40 has two sealing through-holes 41f, a first sealing through-hole 41f1 and a second sealing through-hole 41f2. In this case, the first hook-shaped member may be passed through the first seal through hole 41f1, and the second hook-shaped member may be passed through the second seal through hole 41f2.

[0334] By suspending a liquid-filled combination container 10L by passing the tip of a hook-shaped member through the seal through-hole 41f of the barrier container 40, and measuring the oxygen concentration inside the container 30, the following effects can be obtained: The position of the container 30 inside the barrier container 40 is determined by the action of gravity. Therefore, when measuring the oxygen concentration inside the container 30 of the same liquid-filled combination container 10L at multiple points in time, the position of the container 30 inside the barrier container 40 at the time of measurement can be aligned. Similarly, when measuring the oxygen concentration inside the containers 30 of multiple liquid-filled combination containers 10L, the position of the containers 30 inside the barrier container 40 at the time of measurement can be aligned. This makes it possible to standardize the measurement conditions for measuring the oxygen concentration inside the container 30 and improve the accuracy of oxygen concentration measurement. In particular, by passing the tip of each of the multiple hook-shaped members through each of the multiple seal through-holes 41f, the liquid-filled combination container 10L is stably supported by the hook-shaped members. Therefore, when the 10L liquid-filled combination container is suspended, the position of the container 30 within the barrier container 40 is more stably determined. This allows for improved accuracy in measuring oxygen concentration.

[0335] As shown in Figure 4, the barrier container 40 does not necessarily have a through-hole 41f for the sealing portion. The barrier container 40 shown in Figure 4 and the barrier container 40 shown in Figure 23A can be suspended by the first member and the second member by sandwiching the sealing portion 43 between the first member and the second member. By suspending the barrier container 40 by the first member and the second member, the position of the container 30 inside the barrier container 40 is determined by the action of gravity. This improves the accuracy of oxygen concentration measurement.

[0336] The container 30 may be left stationary by suspending the liquid-filled combination container 10L. That is, by suspending the liquid-filled combination container 10L, the position of the container 30 within the barrier container 40 is determined, and the liquid level of the liquid L contained in the storage section 31 may be stabilized.

[0337] (Variation 10) In the first embodiment, the second embodiment, and each of the modifications described above, examples were given in which the oxygen reagent 20 is fixed to at least one of the outer surface 30b of the container 30 and the inner surface of the barrier container 40. However, the liquid-filled combination container 10L is not limited to this. The oxygen reagent 20 does not have to be fixed to either the outer surface 30b of the container 30 or the inner surface of the barrier container 40.

[0338] Figure 23B is a perspective view showing an example of a liquid-filled combination container 10L of Modification 10. The barrier container 40 of the liquid-filled combination container 10L shown in Figure 23B is the same as the barrier container 40 shown in Figure 23A, except for the points described later. The oxygen reagent 20 is not fixed to the inner surface of the barrier container 40 shown in Figure 23B. An oxygen reagent containment section 49a for containing the oxygen reagent 20 is partitioned off in a part of the barrier container 40 shown in Figure 23B. The oxygen reagent containment section 49a is partitioned off in a part of the barrier container space 49. The liquid-filled combination container 10L shown in Figure 23B further comprises a container 30 containing liquid L and an oxygen reagent 20. The liquid-filled combination container 10L shown in Figure 23B comprises an oxygen scavenger 21 and an oxygen detection material 25 as the oxygen reagent 20.

[0339] The combination container 10L containing liquid shown in Figure 23B allows for the measurement of the oxygen concentration inside the container 30 by the following method. Two appropriate positions on the container 30 are designated as the first position 35a and the second position 35b. Next, laser light or LED light is shone onto the combination container 10L containing liquid, passing through the first position 35a and the second position 35b, and the attenuation rate of the laser light or LED light is measured. The oxygen concentration inside the container 30 is then determined from the measured attenuation rate.

[0340] As an example, the containment section of the barrier container 40 is divided into multiple parts, including an oxygen reagent containment section 49a and a container containment section 49b that contains a container 30 containing liquid L. The containment section of the barrier container 40 shown in Figure 23B is divided into two parts: an oxygen reagent containment section 49a and a container containment section 49b. The containment section of the barrier container 40 is divided in such a way that oxygen can move between the oxygen reagent containment section 49a and the container containment section 49b, but the container 30 and the oxygen reagent 20 cannot move between the oxygen reagent containment section 49a and the container containment section 49b.

[0341] In the barrier container 40 shown in Figure 23B, the first main film 41a and the second main film 41b are joined at the seal portion 43 and at the divided seal portion 47. The divided seal portion 47 divides the housing portion of the barrier container 40. In the example shown in Figure 23B, the housing portion of the barrier container 40 is divided by the divided seal portion 47 into an oxygen reagent housing portion 49a and a container housing portion 49b. The divided seal portion 47 is provided with a gap 47a in which the first main film 41a and the second main film 41b are not joined. The width of the gap is smaller than the minimum width of the container 30 and the oxygen reagent 20. Oxygen can move between the oxygen reagent housing portion 49a and the container housing portion 49b through the gap 47a of the divided seal portion 47. Movement of the container 30 housed in the container housing portion 49b to the oxygen reagent housing portion 49a is prevented by the divided seal portion 47. The movement of the oxygen reagent 20 contained in the oxygen reagent containment section 49a to the container containment section 49b is prevented by the divided seal section 47.

[0342] The method for dividing the containment portion of the barrier container 40 into multiple parts, including the oxygen reagent containment portion 49a, is not limited to the method of providing a dividing seal portion 47. For example, the containment portion of the barrier container 40 may be divided by forming multiple through holes that penetrate the first main film 41a and the second main film 41b, and then deforming and interlocking the first main film 41a and the second main film 41b around the through holes.

[0343] In the liquid-filled combination container 10L shown in Figure 23B, container 30 is in an upright position. In the liquid-filled combination container 10L shown in Figure 23B, the oxygen reagent container 49a is located below the container container 49b. The positional relationship between the oxygen reagent container 49a and the container container 49b is not limited to the example shown in Figure 23B. Although not shown, in the liquid-filled combination container 10L with container 30 in an upright position, the oxygen reagent container 49a may be located above the container container 49b. Although not shown, in the liquid-filled combination container 10L with container 30 in an upright position, the oxygen reagent container 49a and the container container 49b may be aligned horizontally.

[0344] The oxygen reagent 20 is housed in the oxygen reagent housing section 49a, so that it is positioned at a location separated from the straight line connecting the first position 35a and the second position 35b. In other words, the oxygen reagent 20 housed in the oxygen reagent housing section 49a is not located on the straight line connecting the first position 35a and the second position 35b. Therefore, by making the straight line connecting the first position 35a and the second position 35b the optical path LA, laser light or LED light can be irradiated so as to pass through the container 30.

[0345] As shown in Figure 23B, if the containment section of the barrier container 40 is divided in such a way that the container 30 and the oxygen reagent 20 cannot move between the oxygen reagent containment section 49a and the container containment section 49b, the following effects can be obtained in particular: The oxygen reagent 20 can be prevented from moving to a position that prevents the laser light or LED light from passing through the first position 35a and the second position 35b of the container 30.

[0346] Although not shown in the figures, the combination container 10L containing the liquid and fluorescent material 27 of the first embodiment may also be characterized in that the oxygen reagent 20 is not fixed to the inner surface of the barrier container 40, and an oxygen reagent containment section 49a for containing the oxygen reagent 20 is partitioned within a part of the barrier container 40. That is, in the combination container 10L containing the liquid and fluorescent material 27, an oxygen reagent containment section 49a for containing the oxygen reagent 20 may be partitioned within a part of the barrier container 40. For example, the combination container 10L containing the liquid and fluorescent material shown in Figure 23B may be provided with a fluorescent material 27 on the inner surface 30a of the container 30 at a fluorescent material installation position 39 away from the contact area 31a that comes into contact with the liquid L.

[0347] In such a liquid-filled combination container 10L, the oxygen reagent 20 is housed in the oxygen reagent containment section 49a, so that it is positioned not between the fluorescent material installation position 39 and the light transmission position 40b. Therefore, by allowing light to pass through the fluorescent material installation position 39 and the light transmission position 40b, the fluorescent material 27 can be irradiated with light from outside the barrier container 40. In such a liquid-filled combination container 10L, the oxygen concentration inside the container 30 can be measured by irradiating the fluorescent material 27 with light that causes it to fluoresce and measuring the fluorescence time or fluorescence intensity of the fluorescent material 27, based on the measured fluorescence time or fluorescence intensity.

[0348] In particular, the following effects can be obtained when the containment section of the barrier container 40 of the liquid-filled combination container 10L equipped with a fluorescent material 27 is divided such that the container 30 and the oxygen reagent 20 cannot move between the oxygen reagent containment section 49a and the container containment section 49b. The movement of the oxygen reagent 20 to a position that obstructs the irradiation of the fluorescent material 27 with light can be suppressed.

[0349] The features described above for the liquid-filled combination container 10L shown in Figure 23B can be applied to the liquid-filled combination container 10L equipped with the fluorescent material 27, provided that they do not contradict each other.

[0350] (Variation 11) In the modified example 10 described above, a liquid-filled combination container 10L was described in which the containment section of the barrier container 40 is divided so that the container 30 and the oxygen reagent 20 cannot move between the oxygen reagent containment section 49a and the container containment section 49b. However, the liquid-filled combination container 10L is not limited to this.

[0351] Figure 23C is a cross-sectional view showing an example of a liquid-filled combination container 10L according to Modification 11. The liquid-filled combination container 10L shown in Figure 23C is the same as the liquid-filled combination container 10L shown in Figure 20, except for the points described later. In the liquid-filled combination container 10L shown in Figure 23C, the intermediate container 50 partitions an oxygen reagent containment section 49a containing the oxygen reagent 20 within a part of the barrier container 40. The oxygen reagent 20 is contained in the oxygen reagent containment section 49a partitioned by the intermediate container 50. The liquid-filled combination container 10L shown in Figure 23C comprises an oxygen scavenger 21 and an oxygen detection material 25 as the oxygen reagent 20.

[0352] The container 30 of the liquid-filled combination container 10L shown in Figure 23C is in a stationary state, particularly in an upright state. The intermediate container 50 of the liquid-filled combination container 10L shown in Figure 23C further has a first side portion 922f of the housing section, a second side portion 922g of the housing section, and a bottom portion 922h of the housing section. The first side portion 922f of the housing section is a plate-shaped portion parallel in the vertical direction. At its upper end, the first side portion 922f of the housing section is connected to the end of the flange portion 922c opposite to the end that connects to the side portion 922b. The bottom portion 922h of the housing section is a plate-shaped portion parallel in the horizontal direction. At one end, the bottom portion 922h of the housing section is connected to the lower end of the first side portion 922f of the housing section. The second side portion 922g of the housing section is a plate-shaped portion parallel in the vertical direction. The second side portion 922g of the housing section is connected at its lower end to the end of the bottom portion 922h of the housing section that is opposite to the end that connects to the first side portion 922f of the housing section. The first side portion 922f, the second side portion 922g, and the bottom portion 922h of the housing section may be provided around the entire circumference of the outer circumference of the flange portion 922c, or they may be provided on a part of the outer circumference of the flange portion 922c. The oxygen reagent housing section 49a is partitioned by the first side portion 922f, the second side portion 922g, and the bottom portion 922h of the housing section.

[0353] In the liquid-filled combination container 10L shown in Figure 23C, when the container 30 is stationary, particularly upright, gravity is utilized to house the oxygen reagent 20 in the oxygen reagent housing section 49a. In the modified example 11, the oxygen reagent 20 is housed in the oxygen reagent housing section 49a, thereby positioning it at a distance from the straight line connecting the first position 35a and the second position 35b.

[0354] If the oxygen reagent 20 contained in the oxygen reagent containment section 49a includes an oxygen detection material 25, the intermediate container 50 may have a visibility-permitting section 52 that allows the display section 26 of the oxygen detection material 25 to be visible from the outside of the intermediate container 50. In the example shown in Figure 23C, the visibility-permitting section 52 is provided on the second side surface 922g of the containment section. The form of the visibility-permitting section 52 is not particularly limited as long as it allows the display section 26 of the oxygen detection material 25 contained in the oxygen reagent containment section 49a to be visible. As an example, the visibility-permitting section 52 is made of a transparent material. The visibility-permitting section 52 may also be a through hole or notch provided in the wall surface of the intermediate container 50. If the visibility-permitting section 52 is provided on the second side surface 922g of the containment section, the oxygen detection material 25 may be contained with the display section 26 facing the second side surface 922g of the containment section, as shown in Figure 23C. The oxygen detection material 25 may be placed in the oxygen reagent containment section 49a at a position closer to the second side surface 922g of the containment section than to the oxygen absorber 21. This makes the display section 26 easily visible from the outside of the liquid-filled combination container 10L.

[0355] Although not shown in the figures, the liquid-filled combination container 10L may be further equipped with an intermediate container 50, and the intermediate container 50 may partition the oxygen reagent containment section 49a, as described in the first embodiment of the liquid-filled combination container 10L equipped with the fluorescent material 27. That is, the liquid-filled combination container 10L equipped with the fluorescent material 27 may further be equipped with an intermediate container 50, and the intermediate container 50 may partition the oxygen reagent containment section 49a. For example, the liquid-filled combination container 10L shown in Figure 23C may be equipped with a fluorescent material 27 provided on the inner surface 30a of the fluorescent material installation position 39 of the containment section 31 of the container 30, away from the contact area 31a that comes into contact with the liquid L.

[0356] [Third Embodiment] Next, a third embodiment will be described. In the following description and the drawings used therein, parts that can be configured in the same way as the embodiments and modified examples described above will be given the same reference numerals as those used for the corresponding parts in the embodiments and modified examples described above, and redundant explanations may be omitted. Also, if it is clear that the effects and advantages obtained in the embodiments and modified examples described above can also be obtained in the third embodiment, the explanation may be omitted.

[0357] In the inspection method of the third embodiment, the oxygen concentration inside the barrier container 40 of the liquid-filled combination container 10L is measured. The oxygen concentration inside the barrier container 40 refers to the oxygen concentration in the space inside the barrier container 40 that is outside the container 30, i.e., the barrier container space 49 described above. Figure 24 is a diagram illustrating an example of the inspection method of the third embodiment of this disclosure. Figure 25 is a diagram illustrating another example of the inspection method of the third embodiment of this disclosure.

[0358] The liquid-filled combination container 10L shown in Figure 24 is the same as the liquid-filled combination container 10L shown in Figure 13, except that it does not have a shrink film 91 and the fluorescent material 27 is provided on the inner surface of the barrier container 40. That is, the liquid-filled combination container 10L shown in Figure 24 comprises a con...

Claims

1. A method for inspecting a liquid-containing combination container comprising: a container having oxygen permeability and containing a liquid in its containment section; a barrier container having oxygen barrier properties and containing the aforementioned container; at least one oxygen reagent capable of reacting with oxygen in the barrier container; and a fluorescent material whose fluorescence time or fluorescence intensity differs depending on the ambient oxygen concentration, The fluorescent material is provided on the inner surface of the container's housing portion at a location where the fluorescent material is installed, away from the contact area that comes into contact with the liquid. The container has light transmittance at least at the location where the fluorescent material is installed. The barrier container has light-transmitting positions that are light-transmitting, The inspection method for the liquid-filled combination container includes an acquisition step of measuring the oxygen concentration inside the container at a first time and a second time after the first time using a method for measuring the oxygen concentration inside the container, and obtaining a first oxygen concentration, which is the oxygen concentration inside the container at the first time, and a second oxygen concentration, which is the oxygen concentration inside the container at the second time. The method includes a selection step in which, when the second oxygen concentration is 100 times or more the detection limit and 0.99 times or more and 1.01 times or less the first oxygen concentration, or when the second oxygen concentration is above the detection limit and less than 100 times the detection limit and 0.9 times or more and 1.1 times or less the first oxygen concentration, or when the second oxygen concentration is below the detection limit and the first oxygen concentration is below the detection limit, the oxygen saturation solubility in the liquid contained in the container is determined based on the second oxygen concentration, and the amount of oxygen dissolved in the liquid is determined based on the determined oxygen saturation solubility, The method for measuring the oxygen concentration in the container is as follows: The arrangement step involves arranging the oxygen reagent so that it is not located between the fluorescent material installation position and the light transmission position. A fluorescence measurement step involves irradiating the fluorescent material with light that causes the fluorescent material to fluoresce, passing it through the light transmission position of the barrier container and the fluorescent material installation position of the container, and measuring the fluorescence time or fluorescence intensity of the fluorescent material. The measurement step includes measuring the oxygen concentration in the container based on the fluorescence time or fluorescence intensity of the fluorescent material measured in the fluorescence measurement step, The container comprises a container body having an opening and a stopper for closing the opening. The stopper has oxygen permeability, An inspection method wherein the stopper includes a first surface facing the container body and a second surface located on the opposite side of the first surface.

2. A method for inspecting a liquid-containing combination container comprising: a container having oxygen permeability and containing a liquid in its containment section; a barrier container having oxygen barrier properties and containing the aforementioned container; at least one oxygen reagent capable of reacting with oxygen in the barrier container; and a fluorescent material whose fluorescence time or fluorescence intensity differs depending on the ambient oxygen concentration, The fluorescent material is provided on the inner surface of the container's housing portion at a location where the fluorescent material is installed, away from the contact area that comes into contact with the liquid. The container has light transmittance at least at the location where the fluorescent material is installed. The barrier container has light-transmitting positions that are light-transmitting, The inspection method for the liquid-containing combination container includes the steps of measuring the oxygen concentration inside the container at a first measurement time and a second measurement time after the first measurement time using the method for measuring the oxygen concentration inside the container, and obtaining the oxygen concentration inside the container at the first measurement time and the oxygen concentration inside the container at the second measurement time, A step of determining the oxygen saturation solubility in the liquid contained in the container at the first measurement time based on the oxygen concentration in the container at the first measurement time, and determining a first oxygen solubility amount, which is the amount of oxygen dissolved in the liquid at the first measurement time, based on the determined oxygen saturation solubility. A step of determining the oxygen saturation solubility in the liquid contained in the container at the second measurement time based on the oxygen concentration in the container at the second measurement time, and determining the second oxygen solubility amount, which is the amount of oxygen dissolved in the liquid at the second measurement time, based on the determined oxygen saturation solubility. A step of calculating the rate of decrease in the oxygen dissolution amount of the liquid based on the first oxygen dissolution amount and the second oxygen dissolution amount, and determining whether the rate of decrease is equal to or greater than a target value, The process includes determining whether the oxygen concentration in the barrier container is below a target value, The method for measuring the oxygen concentration in the container is as follows: The arrangement step involves arranging the oxygen reagent so that it is not located between the fluorescent material installation position and the light transmission position. A fluorescence measurement step involves irradiating the fluorescent material with light that causes the fluorescent material to fluoresce, passing it through the light transmission position of the barrier container and the fluorescent material installation position of the container, and measuring the fluorescence time or fluorescence intensity of the fluorescent material. The measurement step includes measuring the oxygen concentration in the container based on the fluorescence time or fluorescence intensity of the fluorescent material measured in the fluorescence measurement step, The container comprises a container body having an opening and a stopper for closing the opening. The stopper has oxygen permeability, An inspection method wherein the stopper includes a first surface facing the container body and a second surface located on the opposite side of the first surface.

3. The inspection method according to claim 1, wherein the acquisition step includes a step of vibrating the container at a time between the first time and the second time.

4. The inspection method according to claim 1, wherein the acquisition step includes a step of determining whether the oxygen concentration in the barrier container is below a target value.

5. A method for manufacturing a liquid-filled combination container, comprising an inspection step of inspecting the liquid-filled combination container by the inspection method described in claim 1 or 2.

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